TWI893199B - Composite pattern manufacturing method, resin composition, laminate manufacturing method, and semiconductor device manufacturing method - Google Patents

Abstract

The present invention provides a method for producing a composite pattern capable of obtaining a composite pattern with a high aspect ratio, a resin composition used in the composite pattern production method, a method for producing a laminate including the composite pattern production method, and a method for producing a semiconductor device including the composite pattern production method or the laminate production method. The composite pattern production method includes a first film formation step for obtaining a first pattern using a first resin composition, a first exposure step, a first development step, a second film formation step for obtaining a second pattern, a second exposure step, a second development step, and a modification step for modifying the first and second patterns simultaneously. The first resin composition contains a specific resin.

Description

Composite pattern manufacturing method, resin composition, laminate manufacturing method, and semiconductor device manufacturing method

The present invention relates to a method for manufacturing a composite pattern, a resin composition, a method for manufacturing a laminate, and a method for manufacturing a semiconductor device.

Polyimide and polybenzoxazole possess excellent heat resistance and insulation properties, making them suitable for a wide range of applications. While these applications are not particularly limited, for example, in semiconductor devices for practical applications, patterns containing these resins can be used as insulating films, sealants, or protective films. Furthermore, patterns containing these resins are also used as base films or cover films for flexible substrates.

For example, in the aforementioned applications, polyimide, polybenzoxazole, and polyamidoimide can be used in the form of a resin composition containing a polyimide precursor, a polybenzoxazole precursor, or a polyamidoimide precursor. For example, such a resin composition can be applied to a substrate by coating, and then, if necessary, exposed, developed, or modified to form a cured product of the polyimide precursor, polybenzoxazole precursor, or polyamidoimide precursor on the substrate. Resin compositions can be applied using known coating methods, and fine patterns and complex shapes can be formed through development. This allows for a high degree of design freedom in the cured product, resulting in excellent manufacturing versatility. Considering this superior manufacturing versatility, in addition to the high performance inherent in polyimide, polybenzoxazole, or polyamidoimide, methods for producing cured products using resin compositions containing polyimide precursors, polybenzoxazole precursors, or polyamidoimide precursors are expected to see further expansion in industrial applications.

For example, Patent Document 1 describes a substrate for a multi-layer wiring board characterized in that a metal layer having interlayer conductive bumps is formed on one surface of the substrate, and an insulating resin material having adhesive properties is applied to the area other than the top of the bump, thereby forming an insulating adhesive layer with the top of the bump exposed or protruding. Patent document 2 describes a method for manufacturing a semiconductor device, which includes the steps of providing a temporary carrier, mounting a semiconductor chip on the temporary carrier, depositing a sealant on the semiconductor chip and the temporary carrier, forming a first insulating layer on the semiconductor chip and the sealant, forming a plurality of first through-holes penetrating the first insulating layer and the semiconductor chip during the process of mounting the semiconductor chip on the temporary carrier, forming a plurality of second through-holes penetrating the first insulating layer and the sealant during the process of mounting the semiconductor chip on the temporary carrier, depositing a conductive material in the first through-hole to form a conductive through silicon via (TSV). The process includes forming a conductive through-mold via (TMV) by depositing a conductive material in the second through-hole, forming a first interconnect structure on the first insulating layer and electrically connecting the first interconnect structure to the conductive TSV and the conductive TMV, removing the temporary carrier, and forming a second interconnect structure on the semiconductor chip and the encapsulant on the side opposite to the first interconnect structure and electrically connecting the second interconnect structure to the conductive TSV and the conductive TMV. Patent Document 3 describes a semiconductor device comprising: a base layer having a first semiconductor chip, the first semiconductor chip having at least one conductive contact on a first side of the first semiconductor chip; a first redistribution layer contacting the at least one conductive contact and extending beyond a boundary of the first semiconductor chip; a second semiconductor chip having a first side and a second side and having at least one conductive contact on the first side; and an adhesive layer disposed between the first side of the first semiconductor chip and the second side of the second semiconductor chip, with the second semiconductor chip disposed directly on the adhesive layer.

[Patent Document 1] Japanese Patent Application Publication No. 2005-183880 [Patent Document 2] U.S. Patent Application Publication No. 2011/0204505 [Patent Document 3] U.S. Patent Application Publication No. 2014/0015131

In conventional methods for producing a cured product using a resin composition containing a polyimide precursor, a polybenzoxazole precursor, or a polyamidoimide precursor, it is required to increase the aspect ratio of a pattern formed by the cured product.

The object of the present invention is to provide a method for manufacturing a composite pattern that can obtain a composite pattern with a high aspect ratio, a resin composition used in the above-mentioned method for manufacturing a composite pattern, a method for manufacturing a laminate including the above-mentioned method for manufacturing a composite pattern, and a method for manufacturing a semiconductor device including the above-mentioned method for manufacturing a composite pattern or the above-mentioned method for manufacturing a laminate.

Representative embodiments of the present invention are described below. <1> A method for producing a composite pattern, comprising: a first film-forming step of applying a first resin composition to a substrate to form a first photosensitive film; a first exposure step of selectively exposing the first photosensitive film; a first development step of developing the exposed first photosensitive film to form a first pattern; a second film-forming step of applying a second resin composition to form a second photosensitive film on the first pattern and on the area where the first pattern was removed by the first development step; a second exposure step of selectively exposing the second photosensitive film; a second development step of developing the exposed second photosensitive film to form a second pattern; and The step of modifying the first and second patterns simultaneously. The first resin composition comprises resin A. The resin A is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, and a polyamideimide precursor having a polyamideimide structure. <2> The method for producing a composite pattern according to <1>, wherein the resin A comprises a polymerizable group. <3> The method for producing a composite pattern according to <1> or <2>, wherein the ratio of the cyclization rate of the resin A in the first pattern after the second development step to the cyclization rate of the resin A in the first pattern after the first development step is 1.1 times or less. <4> A method for producing a composite pattern, comprising: a first film-forming step of applying a first resin composition to a substrate to form a first photosensitive film; a first exposure step of selectively exposing the first photosensitive film; a first development step of developing the exposed first photosensitive film to form a first pattern; a second film-forming step of applying a second resin composition to form a second photosensitive film on the first pattern and on the area where the first pattern was removed by the first development step; a second exposure step of selectively exposing the second photosensitive film; a second development step of developing the exposed second photosensitive film to form a second pattern; and A step of modifying the first pattern and the second pattern simultaneously; The second pattern is formed so as to cover at least a portion of the first pattern; In the substrate, the portion of the first photosensitive film that contacts the portion removed in the first developing step comprises a region that contacts the second pattern and a region that does not contact the second pattern. <5> The method for producing a composite pattern according to any one of <1> to <4>, wherein the first resin composition comprises a polymerizable compound. <6> The method for producing a composite pattern according to <5>, wherein the first resin composition comprises a trifunctional or higher-functional polymerizable compound as the polymerizable compound. <7> The method for producing a composite pattern according to any one of <1> to <6>, wherein the second resin composition comprises resin B. <8> The method for producing a composite pattern according to <7>, wherein the resin B is at least one selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamide imide precursor, a polyamide imide precursor having a polyamide imide structure, and an epoxy resin. <9> The method for producing a composite pattern as described in any one of <1> to <8>, wherein the residual film rate of the first pattern after the second development step is applied is 70% or more. <10> The method for producing a composite pattern as described in any one of <1> to <9>, wherein the first resin composition does not contain a colorant. <11> The method for producing a composite pattern as described in any one of <1> to <10>, wherein the modification step is a heating step of heating the first pattern and the second pattern at once. <12> The method for producing a composite pattern as described in any one of <7> to <11>, wherein the resin A and the resin B are resins containing repeating units represented by the same structural formula. <13> The method for producing a composite pattern according to any one of <1> to <12>, wherein the ratio S2/S1 of the dissolution rate S1 of the first photosensitive film in the developer in the first developing step to the dissolution rate S2 of the second photosensitive film in the developer in the second developing step is 1.05 or greater. <14> A first resin composition for forming the first photosensitive film in the method for producing a composite pattern according to any one of <1> to <13>. <15> A second resin composition for forming the second photosensitive film in the method for producing a composite pattern according to any one of <1> to <13>. <16> A method for manufacturing a laminate, comprising applying the steps of the composite pattern manufacturing method described in any one of <1> to <13> a plurality of times. <17> The method for manufacturing a laminate as described in <16>, further comprising: A metal layer forming step of forming a metal layer on a layer composed of the composite pattern, wherein the metal layer forming step is included between the steps of the composite pattern manufacturing method applied a plurality of times. <18> A method for manufacturing a semiconductor device, comprising the composite pattern manufacturing method described in any one of <1> to <13> or the laminate manufacturing method described in <16> or <17>. [Effects of the Invention]

According to the present invention, there are provided a method for manufacturing a composite pattern capable of obtaining a composite pattern with a high aspect ratio, a resin composition used in the above-mentioned method for manufacturing a composite pattern, a method for manufacturing a laminate including the above-mentioned method for manufacturing a composite pattern, and a method for manufacturing a semiconductor device including the above-mentioned method for manufacturing a composite pattern or the above-mentioned method for manufacturing a laminate.

The following describes the main embodiments of the present invention. However, the present invention is not limited to the embodiments described. In this specification, numerical ranges indicated by the symbol "～" indicate a range that includes the numerical values before and after the symbol "～" as the lower and upper limits, respectively. In this specification, the term "step" refers not only to independent steps but also to steps that cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved. In the notation of groups (atomic radicals) in this specification, the notation noting "substituted" and "unsubstituted" includes both groups (atomic radicals) without substituents and groups (atomic radicals) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure," unless otherwise specified, includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and actinic radiation such as electron beams. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid," and "(meth)acryl" means both or either "acryl" and "methacryl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. Furthermore, the term "solids concentration" refers to the mass percentage of components other than the solvent relative to the total mass of the composition. Unless otherwise specified, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) and are defined as polystyrene-equivalent values. In this specification, for example, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined using an HLC-8220GPC (manufactured by TOSOH CORPORATION) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by TOSOH CORPORATION) in series. These molecular weights are measured using THF (tetrahydrofuran) as the eluent, unless otherwise specified. However, when THF is not suitable as an eluent, such as when the solubility is low, NMP (N-methyl-2-pyrrolidone) can be used. Furthermore, unless otherwise specified, GPC measurements utilize a UV (ultraviolet) detector with a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting a laminate is described as "upper" or "lower," it suffices that other layers exist above or below the reference layer in question. In other words, a third layer or a third element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Furthermore, unless otherwise specified, the direction in which layers are stacked relative to a substrate is referred to as "upper," or when a resin composition layer is present, the direction from the substrate toward the resin composition layer is referred to as "upper," and the opposite direction is referred to as "lower." In addition, these vertical directions are used for convenience in this specification. In actual embodiments, the "upper" direction in this specification may differ from the vertically upward direction. In this specification, unless otherwise specified, each component contained in a composition may include two or more compounds that meet the requirements of that component. Furthermore, unless otherwise specified, the content of each component in a composition refers to the total content of all compounds that meet the requirements of that component. In this specification, unless otherwise specified, the temperature is 23°C, the pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, the combination of preferred embodiments is considered a more preferred embodiment.

(Method for Producing a Composite Pattern) In a first aspect of the method for producing a composite pattern of the present invention, the method for producing a composite pattern comprises a first film forming step of applying a first resin composition to a substrate to form a first photosensitive film, a first exposure step of selectively exposing the first photosensitive film, a first development step of developing the exposed first photosensitive film to form a first pattern, a second film forming step of applying a second resin composition to form a second photosensitive film on the first pattern and on the area where the first pattern was removed by the first development step, and a second film forming step of selectively exposing the second photosensitive film. The method further comprises a second exposure step of performing a photosensitive exposure, a second development step of developing the exposed second photosensitive film to form a second pattern, and a modification step of modifying the first pattern and the second pattern at once. The first resin composition comprises resin A, and the resin A is at least one resin selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamide imide precursor, and a polyamide imide precursor having a polyamide imide structure. In a second aspect of the method for producing a composite pattern of the present invention, the method for producing a composite pattern comprises a first film forming step of applying a first resin composition to a substrate to form a first photosensitive film, a first exposure step of selectively exposing the first photosensitive film, a first developing step of developing the exposed first photosensitive film to form a first pattern, and a first developing step of forming a first pattern on the first pattern. A second film forming step comprises applying a second resin composition to the area where the first pattern was removed in the first developing step to form a second photosensitive film; a second exposing step comprises selectively exposing the second photosensitive film to light; a second developing step comprises developing the exposed second photosensitive film to form a second pattern; and a modifying step comprises modifying the first and second patterns simultaneously. The second pattern is formed so as to cover at least a portion of the first pattern. In the substrate, the portion of the first photosensitive film that contacts the portion removed in the first developing step comprises an area in contact with the second pattern and an area not in contact with the second pattern.

In the present invention, a composite pattern refers to a pattern comprising at least a first pattern and a second pattern. The first and second patterns may or may not be in contact with each other, but contact is preferred. Preferably, the top of the first pattern and the bottom of the second pattern are in contact with each other at least partially. Furthermore, a composite pattern may further include a third pattern, a fourth pattern, and so on.

The aspect ratio of a composite pattern is the ratio of the pattern's height to its width. The pattern's height is measured using an ellipsometer and used as the film thickness. The pattern's width is determined by measuring the maximum line width for line patterns, the maximum diameter for pillar patterns, the maximum pore width for groove patterns, and the maximum pore diameter for hole patterns. The width is determined by cutting the pattern and observing the cross-section with a scanning electron microscope.

The composite pattern manufacturing method of the present invention produces a pattern with a high aspect ratio. The mechanism for achieving this effect is not yet clear, but it can be speculated as follows.

The composite pattern production method of the present invention employs a method in which a modification step is performed in a single step after the film formation, exposure, and development steps are repeated multiple times. This method enables the formation of patterns with high aspect ratios, particularly fine grooves or holes. When forming composite patterns using conventional methods that repeat the film formation, exposure, development, and modification steps multiple times, the formation of high-aspect-ratio patterns is difficult due to the shrinkage of the cured product caused by the modification. For example, when stacking patterns to form a high-aspect-ratio pattern, the number of shrinkages caused by the modification varies across the pattern, making it difficult to achieve a high-aspect-ratio pattern. According to the present invention, by modifying both the first and second photosensitive films simultaneously, it is believed that high-aspect-ratio patterns can be formed. Furthermore, by forming the second photosensitive film overlying the first pattern after forming the first pattern, the line width of the first pattern is increased, and the second pattern is formed even in areas where the first pattern does not exist, thereby enabling the formation of a denser pattern.

Patent Document 1 does not describe a modification step for modifying both the first and second photosensitive films simultaneously. The following describes the method for producing the composite pattern of the present invention in detail. Unless otherwise specified, the first film formation step, first exposure step, first development step, second film formation step, second exposure step, second development step, modification step, and other steps are identical in the first and second aspects.

<First Film Formation Step> The composite pattern production method of the present invention includes a first film formation step in which a first resin composition is applied to a substrate to form a first photosensitive film. The details of the first resin composition used in the present invention will be described later.

[Substrate] The type of substrate can be appropriately determined depending on the intended use. Examples include semiconductor substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates and metal layers formed of metals, such as those formed by electroplating or deposition); paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; cast substrates; and electrode plates for plasma display panels (PDPs). In the present invention, semiconductor substrates, Cu substrates, and cast substrates are particularly preferred, with silicon substrates, Cu substrates, and cast substrates being even more preferred. Furthermore, a bonding layer or oxide layer, such as one formed from hexamethyldisilazane (HMDS), may be provided on the surface of the substrate. Furthermore, the substrate may be subjected to a dehydration baking treatment. For example, when forming a bonding layer formed from HMDS on a substrate, examples include heating the substrate at 120°C (dehydration baking) while allowing HMDS vapor to contact the substrate, or heating the substrate at 120°C (dehydration baking) and then allowing HMDS vapor to contact the substrate after heating. Furthermore, the substrate may be treated with oxygen plasma. The shape of the substrate is not particularly limited and may be circular or rectangular. The dimensions of the substrate are, for example, a circular substrate with a diameter of 100 to 450 mm, preferably 200 to 450 mm. For a rectangular substrate, the length of the short side is, for example, 100 to 1000 mm, preferably 200 to 700 mm. Also, the substrate can be a plate-shaped substrate (substrate), preferably a panel-shaped substrate.

When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer composed of a cured product) or the surface of a metal layer, the resin layer and the metal layer serve as a base material.

As a method of applying the first resin composition to the substrate, coating is preferred.

Specific examples of applicable methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet coating. From the perspective of film thickness uniformity, spin coating, slit coating, spray coating, or ink jet coating is more preferred. From the perspective of film thickness uniformity and productivity, spin coating and slit coating are particularly preferred. By adjusting the solid content concentration of the first resin composition and coating conditions according to the method, a film of desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the substrate shape. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. Spin coating can be applied at a rotation speed of 500 to 3,500 rpm for approximately 10 seconds to 3 minutes. Alternatively, a method can be employed in which a coating film previously applied to a dummy support using the aforementioned application method is transferred onto the substrate. Regarding the transfer method, the present invention can also preferably utilize the production methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Laid-Open No. 2006-023696 or paragraphs 0096-0108 of Japanese Patent Application Laid-Open No. 2006-047592. In addition, a step of removing excess film from the edges of the substrate may be performed. Examples of such steps include edge bead rinse (EBR) and backside rinse. Also, a pre-wetting step may be employed: before applying the first resin composition to the substrate, various solvents may be applied to the substrate to improve its wettability, and then the first resin composition may be applied.

<First Drying Step> After the first film-forming step (layer-forming step), the first photosensitive film may be subjected to a step (first drying step) of drying the formed film (layer) to remove the solvent. That is, the composite pattern manufacturing method of the present invention may include a first drying step of drying the film formed in the first film-forming step. The first drying step is preferably performed after the first film-forming step and before the first exposure step. The drying temperature of the film in the first drying step is preferably 50-150°C, more preferably 70-130°C, and even more preferably 90-110°C. Drying may be performed under reduced pressure. The drying time can be exemplified as 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.

<First Exposure Step> The first photosensitive film is provided in a first exposure step of selectively exposing the first photosensitive film. That is, the composite pattern manufacturing method of the present invention includes a first exposure step of selectively exposing the first photosensitive film formed by the first film forming step. Selective exposure refers to exposing a portion of the film. Furthermore, by selective exposure, exposed areas (exposed portions) and unexposed areas (non-exposed portions) are formed on the film. The exposure amount is not particularly limited as long as it can cure the first resin composition. For example, when converted to exposure energy at a wavelength of 365 nm, 50 to 10,000 mJ/ ^cm2 is preferred, and 200 to 8,000 mJ/ ^cm2 is more preferred.

The exposure wavelength can be appropriately determined within the range of 190-1,000nm, with 240-550nm being optimal.

Regarding the exposure wavelength, in terms of its relationship with the light source, we can cite (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (g, h, i-ray (three wavelengths), (4) excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beam, (7) YAG laser second harmonic wave 532nm, third harmonic wave 355nm, etc. Regarding the first resin composition, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, high exposure sensitivity can be obtained. In addition, the exposure method is not particularly limited, as long as at least a portion of the film composed of the first resin composition is exposed, and exposure using a mask, exposure based on laser direct imaging method, etc. can be cited.

<First Post-Exposure Heating Step> The first photosensitive film may be subjected to a post-exposure heating step (first post-exposure heating step). That is, the composite pattern manufacturing method of the present invention may include a first post-exposure heating step of heating the first photosensitive film exposed in the first exposure step. The first post-exposure heating step can be performed after the first exposure step and before the first development step. The heating temperature in the first post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C. The heating time in the first post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes. The heating rate during the first post-exposure heating step is preferably 1-12°C/minute, more preferably 2-10°C/minute, and even more preferably 3-10°C/minute, from the initial heating temperature to the maximum heating temperature. The heating rate can be appropriately varied during the heating process. The heating method during the first post-exposure heating step is not particularly limited; known heating plates, ovens, infrared heaters, and the like can be used. Heating is preferably performed in an environment with a low oxygen concentration by circulating an inert gas such as nitrogen, helium, or argon.

<First Development Step> The exposed first photosensitive film is subjected to a first development step in which it is developed using a developer to form a pattern. That is, the composite pattern production method of the present invention includes a first development step in which the first photosensitive film exposed in the first exposure step is developed to form a first pattern. During development, one of the exposed and unexposed portions of the film is removed, forming the first pattern. Preferably, this development is performed using a developer. Herein, development in which the unexposed portions of the film are removed by development is referred to as negative development, and development in which the exposed portions of the film are removed by development is referred to as positive development.

[Developer] The developer used in the first developing step can be an alkaline aqueous solution or a developer containing an organic solvent.

When the developer is an alkaline aqueous solution, examples of the saline compounds that can be contained in the alkaline aqueous solution include inorganic bases, primary amines, secondary amines, tertiary amines, quaternary ammonium salts, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, dimethylethanolamine, diethyl ... Preferred are tetrapropylamine, tetrabutylamine hydroxide, tetrapentylamine hydroxide, tetrahexylamine hydroxide, tetraoctylamine hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine. More preferred is TMAH. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass % based on the total amount of the developer.

When the developer contains an organic solvent, the organic solvent includes, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxy methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate and ethyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like; and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and as ketones, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like are preferably mentioned. Examples of the preferred hydrocarbons include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of the preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole; and cyclic terpenes such as limonene; examples of the preferred sulfoxides include dimethyl sulfoxide; examples of the preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and examples of the preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the developer contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is preferred. A developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.

When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or greater, more preferably 70% by mass or greater, even more preferably 80% by mass or greater, and particularly preferably 90% by mass or greater. Furthermore, the above content may be 100% by mass.

The developer may further contain other components. Examples of such other components include known surfactants and defoaming agents.

[Developer Supply Method] As long as the desired pattern can be formed, there are no particular limitations on the developer supply method. Examples include immersing the film-formed substrate in the developer, flood development using a nozzle to supply developer to the film formed on the substrate, and continuous developer supply. The type of nozzle is not particularly limited, and examples include direct current nozzles, shower nozzles, and mist nozzles. From the perspectives of developer permeability, removal of non-image areas, and manufacturing efficiency, it is preferable to supply the developer using a DC nozzle or a continuous spray nozzle. From the perspective of developer permeability to the image area, the spray nozzle method is more preferred. Alternatively, the following steps can be employed: after continuously supplying developer using a DC nozzle, the substrate is rotated to remove the developer from the substrate. After drying the developer by rotation, the developer is continuously supplied again using a DC nozzle, and then the substrate is rotated to remove the developer from the substrate. This step can also be repeated multiple times. Furthermore, the developer solution supply method in the first development step may include a step of continuously supplying the developer solution onto the substrate, a step of holding the developer solution on the substrate in a substantially stationary state, a step of vibrating the developer solution on the substrate using ultrasound or the like, or a combination of these methods.

The developing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

In the first development step, the pattern may be cleaned (rinsed) with a rinse solution after treatment with the developer. Alternatively, a rinse solution may be supplied before the developer in contact with the pattern has completely dried.

[Rinse Solution] When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse solution. When the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, an organic solvent different from water or the organic solvent contained in the developer) can be used as the rinse solution.

When the rinsing liquid contains an organic solvent, the organic solvent includes, for example, esters, preferably ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxy methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-alkoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), methyl 2-alkoxypropionate and ethyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ester, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like; and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like; and as ketones, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like are preferably mentioned. Examples of the preferred hydrocarbons include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone; examples of the preferred cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole; and cyclic terpenes such as limonene; examples of the preferred sulfoxides include dimethyl sulfoxide; examples of the preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol; and examples of the preferred amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.

When the rinse solution contains an organic solvent, the organic solvent may be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, with cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being even more preferred, and cyclohexanone and PGMEA being even more preferred.

When the rinse solution contains an organic solvent, the organic solvent preferably accounts for 50% by mass or more of the rinse solution, more preferably 70% by mass or more of the rinse solution, and even more preferably 90% by mass or more of the rinse solution. Alternatively, the organic solvent may account for 100% by mass of the rinse solution.

The rinse solution may further contain other ingredients. Examples of other ingredients include known surfactants and defoaming agents.

[Rinsing Liquid Supply Method] There are no particular limitations on the method for supplying the rinsing liquid, as long as the desired pattern can be formed. Examples include immersing the substrate in the rinsing liquid, applying the rinsing liquid over the substrate, supplying the rinsing liquid onto the substrate using a showerhead, and continuously supplying the rinsing liquid onto the substrate using a direct current nozzle. From the perspectives of rinse liquid permeability, removal of non-image areas, and manufacturing efficiency, the rinse liquid can be supplied using a shower nozzle, a direct current nozzle, or a mist nozzle. Continuous supply using a mist nozzle is preferred, and from the perspective of rinse liquid permeability into the image area, supply using a mist nozzle is even more preferred. The type of nozzle is not particularly limited, and examples include direct current nozzles, shower nozzles, and mist nozzles. Specifically, the rinsing step preferably involves supplying or continuously supplying the rinsing liquid to the exposed film using a direct current nozzle, and more preferably, supplying the rinsing liquid using a mist nozzle. Additionally, the rinsing liquid supply method in the rinsing step can include continuously supplying the rinsing liquid to the substrate, maintaining the rinsing liquid substantially stationary on the substrate, vibrating the rinsing liquid on the substrate using ultrasound or the like, or a combination of these methods.

The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.

<Second Film Formation Step> The composite pattern production method of the present invention includes a second film formation step of applying a second resin composition to form a second photosensitive film on the first pattern and on the area where the first pattern was removed in the first development step. The details of the second resin composition used in the present invention will be described later.

As a method for applying the second resin composition, the same method as the method for applying the first resin composition in the above-mentioned first film formation step can be cited, and the preferred embodiment is also the same.

<Second Drying Step> The second photosensitive film may be subjected to a step (second drying step) of drying the formed film (layer) to remove the solvent after the second film formation step (layer formation step). That is, the composite pattern manufacturing method of the present invention may include a second drying step of drying the film formed in the second film formation step. Preferably, the second drying step is performed after the second film formation step and before the second exposure step. The drying method in the second drying step can be the same as that in the first drying step, and the preferred embodiments are also the same.

<Second Exposure Step> The second photosensitive film is provided in a second exposure step in which the second photosensitive film is selectively exposed. That is, the composite pattern manufacturing method of the present invention includes a second exposure step in which the second photosensitive film formed in the second film formation step is selectively exposed. The exposure method in the second exposure step can be the same as that in the first exposure step, and the preferred embodiments are also the same.

<Second Post-Exposure Heating Step> The second photosensitive film may be subjected to a post-exposure heating step (second post-exposure heating step). That is, the composite pattern manufacturing method of the present invention may include a second post-exposure heating step of heating the second photosensitive film exposed in the second exposure step. The second post-exposure heating step can be performed after the second exposure step and before the second development step. The heating method in the second post-exposure heating step can be the same as that in the first post-exposure heating step, and preferred embodiments are also the same.

<Second Development Step> The exposed second photosensitive film is subjected to a second development step in which it is developed using a developer to form a pattern. That is, the composite pattern production method of the present invention includes a second development step in which the second photosensitive film exposed in the second exposure step is developed to form a second pattern. The development removes one of the exposed and unexposed portions of the film, thereby forming the second pattern. Preferably, the development is performed using a developer. The development method in the second development step can be the same as that in the first development step, and preferred embodiments are also the same.

In a second aspect of the composite pattern of the present invention, the second pattern is formed so as to cover at least a portion of the first pattern. In this aspect, the second pattern only needs to cover at least a portion of the first pattern, and preferably covers the entire top and side surfaces of the first pattern. Furthermore, in this second aspect, the portion of the first photosensitive film on the substrate that contacts the portion removed in the first development step includes regions that contact the second pattern and regions that do not. In other words, after the second pattern is formed, at least a portion of the substrate is exposed. According to this aspect, for example, a finer pattern than the first pattern achieved by the shrinkage effect of the second photosensitive film can be formed on the side of the first pattern, for example, a finer pattern with an aspect ratio of 3:1 or greater can be formed. In the first aspect of the composite pattern of the present invention, the second pattern can be formed so as to cover at least a portion of the first pattern. Furthermore, in the first aspect of the composite pattern of the present invention, the second pattern can be formed so as to contact only the top surface of the first pattern, or can also be formed so as to contact surfaces other than the top display surface of the first pattern. The position of this second pattern can be adjusted by adjusting the exposure conditions and exposure position in the second exposure step, the development method in the second development step, etc.

From the perspective of forming a high-aspect-ratio composite pattern, the ratio of the cyclization ratio of Resin A in the first pattern after the second development step (cyclization ratio 2) to the cyclization ratio of Resin A in the first pattern after the first development step (cyclization ratio 1) (cyclization ratio 2/cyclization ratio 1) is preferably 1.1 times or less, more preferably 1.07 times or less, and even more preferably 1.05 times or less. The lower limit of the cyclization ratio is not particularly limited; for example, it is 1.0 times or greater. Here, cyclization ratio 1 refers to the cyclization ratio of Resin A in the first pattern after the first development step and before the second development step. Resin A will be described later. The cyclization rate of Resin A was calculated by the method described in the Examples below.

From the perspective of forming a high-aspect-ratio composite pattern, the residual film ratio of the first pattern after forming the second pattern (after the second development step) is preferably 70% or higher. The residual film ratio is preferably 70% or higher, and more preferably 85% or higher. The upper limit of the residual film ratio is not particularly limited and can be 100%. The residual film ratio is calculated using the method described in the Examples below.

When producing high-aspect-ratio composite patterns, from the perspective of suppressing residue generation, the ratio (S2/S1) of the dissolution rate (S1) of the first photosensitive film in the developer solution during the first development step to the dissolution rate (S2) of the second photosensitive film in the developer solution during the second development step is preferably 1.05 or greater. S2/S1 is preferably 1.07 or greater, and more preferably 1.10 or greater. There is no particular upper limit for S2/S1, but a ratio of 2 or less is preferred.

<Modification Step> The method for producing a composite pattern of the present invention includes a modification step of modifying the first and second patterns simultaneously. Preferably, the modification step involves heating the first and second patterns simultaneously. Through this modification step, a composite pattern comprising the first and second patterns can be formed. In the present invention, "modifying the first and second patterns simultaneously" means that the modification step does not substantially include a step of modifying only the first pattern prior to the modification step. In other words, there is no intentional step of modifying only the first pattern prior to the modification step. However, after forming the first pattern, the steps for forming the second pattern are not subject to this limitation regarding reactions caused by unreacted components that may be contained in the first pattern. For example, the following aspects can be cited as modification steps. ・The step of simultaneously heating the first and second patterns to perform the modification ・The step of simultaneously heating the first and second patterns in stages to perform the modification ・The step of simultaneously heating the first and second patterns two or more times to perform the modification ・The step of simultaneously heating the first and second patterns in stages to perform the modification As described above, as long as the step of modifying the first and second patterns is performed simultaneously, that is, as long as the first and second patterns are modified at the same stage and under the same conditions, the same modification step may be applied multiple times, and different modification steps may be combined and applied.

[Heating Step] The first pattern obtained by the first developing step and the second pattern obtained by the second developing step (or, if rinsing is performed, the post-rinsing pattern, respectively) can be subjected to a heating step for heating these patterns at once. That is, the method for producing a composite pattern of the present invention can include a heating step for heating the first pattern obtained by the first developing step and the second pattern obtained by the second developing step at once. During the heating step, a resin such as a polyimide precursor undergoes cyclization to form a resin such as a polyimide. Furthermore, a crosslinking reaction may also occur with unreacted crosslinking groups that may be present in the first and second resin compositions. The heating temperature (maximum heating temperature) in the heating step is preferably 50-450°C, more preferably 150-350°C, even more preferably 150-250°C, even more preferably 160-250°C, and particularly preferably 160-240°C.

The heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the first pattern and/or the second pattern by utilizing the action of the base generated from the base generator by heating.

During the heating step, heating is preferably performed at a rate of 1-12°C/minute from the starting temperature to the maximum heating temperature. This rate is more preferably 2-10°C/minute, and even more preferably 3-10°C/minute. A rate of 1°C/minute or higher ensures productivity while preventing excessive volatilization of the acid or solvent. A rate of 12°C/minute or lower alleviates residual stress in the composite pattern. In addition, in a fast-heating oven, a rate of 1-8°C/second, more preferably 2-7°C/second, and even more preferably 3-6°C/second, from the starting temperature to the maximum heating temperature is preferred.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the heating step to the maximum heating temperature. For example, when the first or second resin composition of the present invention is applied to a substrate and then dried, this refers to the temperature of the dried film (layer). For example, heating is preferably performed from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

The heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

In particular, when forming multi-layer laminates, from the perspective of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher. The upper limit of the above temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

Heating can be performed in stages. For example, the following steps can be performed: heating from 25°C to 120°C at 3°C/minute and holding at 120°C for 60 minutes, then heating from 120°C to 180°C at 2°C/minute and holding at 180°C for 120 minutes. Furthermore, as described in U.S. Patent No. 9,159,547, simultaneous treatment with UV irradiation is also preferred. These pretreatment steps can improve membrane properties. The pretreatment step can be performed for a short period of time, from approximately 10 seconds to 2 hours, preferably from 15 seconds to 30 minutes. Pretreatment can be performed in two or more stages. For example, the first stage can be performed at a temperature between 100 and 150°C, followed by a second stage at a temperature between 150 and 200°C. Furthermore, heating can be followed by cooling. In this case, a cooling rate of 1 to 5°C/minute is preferred.

To prevent decomposition of certain resins, the heating step is preferably performed in a low-oxygen environment, such as under reduced pressure with an inert gas such as nitrogen, helium, or argon. An oxygen concentration of 50 ppm (volume ratio) or less is preferred, and 20 ppm (volume ratio) or less is even more preferred. The heating method used in the heating step is not particularly limited; examples include a hot plate, infrared furnace, electric oven, hot air oven, and infrared oven.

[Post-Development Exposure Step] The first pattern obtained in the first development step and the second pattern obtained in the second development step (when rinsing is performed, each is referred to as a post-development exposure step) can be provided in the post-development exposure step of the pattern after the development step, either in place of the aforementioned heating step, or in addition to the aforementioned heating step. That is, the composite pattern production method of the present invention can include a post-development exposure step of exposing the first pattern obtained in the first development step and the second pattern obtained in the second development step. The method for producing a composite pattern of the present invention may include a heating step and a post-development exposure step as a modification step, or may include only one of the heating step and the post-development exposure step as a modification step. In the post-development exposure step, for example, cyclization reactions of polyimide precursors, etc., can be promoted by sensitization with a photoalkali generator, or acid-degradable group removal reactions can be promoted by sensitization with a photoacid generator. In the post-development exposure step, at least a portion of the first and second patterns may be exposed, but preferably, all of the first and second patterns are exposed. The exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/ ^cm² , and more preferably 100 to 15,000 mJ/ ^cm² , calculated as exposure energy at the wavelength to which the photosensitive compound is sensitive. The post-development exposure step can be performed using the same light source as in the exposure step described above, preferably broadband light.

The composite pattern production method of the present invention may further include a third film formation step of applying a third resin composition to form a third photosensitive film on the second pattern and on the areas where the second pattern was removed by the second development step; a third exposure step of selectively exposing the third photosensitive film; and a third development step of developing the exposed third photosensitive film to form a third pattern. According to this aspect, a three-layer composite pattern can be obtained, including not only the first and second patterns but also the third pattern. The third film formation step, the third exposure step, and the third development step can be performed using the same methods as the second film formation step, the second exposure step, and the second development step, respectively, and preferred embodiments are the same. A third drying step may be included after the third film formation step, and a third post-exposure heating step may be included after the third exposure step. The third drying step can be performed by the same method as the second drying step, and the third post-exposure heating step can be performed by the same method as the second post-exposure heating step. Furthermore, in addition to the third film formation step, the third exposure step, and the third development step, a fourth film formation step, a fourth exposure step, and a fourth development step may be further included to provide a composite pattern having four or more layers. Furthermore, the third film formation step, the third exposure step, the third development step, etc. can be performed after the modification step, but preferably before the modification step.

<Metal Layer Formation Step> The composite pattern obtained in the modification step can be subjected to a metal layer formation step of forming a metal layer on the composite pattern. That is, the composite pattern manufacturing method of the present invention preferably includes a metal layer formation step of forming a metal layer on the composite pattern obtained in the modification step.

The metal layer is not particularly limited, and existing metals can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Application Publication No. 2007-157879, Japanese National Publication No. 2001-521288, Japanese Patent Application Publication No. 2004-214501, Japanese Patent Application Publication No. 2004-101850, U.S. Patent No. 7,888,181B2, and U.S. Patent No. 9,177,926B2 can be utilized. For example, photolithography, PVD (physical deposition), CVD (chemical vapor deposition), liftoff, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods that combine sputtering, photolithography, and etching, and those that combine photolithography and electrolytic plating can be cited. Preferred electrolytic plating methods include electrolytic plating using copper sulfate plating solutions or copper cyanide plating solutions.

The thickness of the metal layer is preferably 0.01 to 50 μm, more preferably 1 to 10 μm, at the thickest portion.

<Applications> Examples of applications for the composite pattern manufacturing method and composite patterns of the present invention include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, interlayer insulating films for TSV (through silicon via) and TMV (through mold via) applications, and stress buffer films. Examples include sealing films, substrate materials (base films or cover films for flexible printed circuit boards, interlayer insulating films), and the formation of patterns by etching on insulating films for practical mounting applications such as those described above. For information on these applications, see, for example, "Advanced Functionality and Application Technology of Polyimides" by Science & Technology Co., Ltd., April 2008; "Fundamentals and Development of Polyimide Materials" by Masaaki Kakimoto, CMC Technical Library, November 2011; and "Latest Polyimides: Fundamentals and Applications" by the Japan Polyimide and Aromatic Polymer Research Society, NTS, August 2010.

Furthermore, the composite pattern manufacturing method or the composite pattern of the present invention can also be used in the manufacture of offset printing plates or screen printing plates, the use of molded parts in etching, and the manufacture of protective varnishes and dielectric layers in electronics, especially microelectronics.

<Compound Pattern> The composite pattern produced by the composite pattern manufacturing method of the present invention is not particularly limited in form and can be in the form of a film, rod, sphere, or pellet, depending on the intended use. In the present invention, the composite pattern is preferably in the form of a film. Furthermore, through pattern processing, the shape of the composite pattern can be selected based on the intended use, such as forming a protective film on the wall, forming through-holes for electrical conduction, adjusting resistance, electrostatic capacitance, or internal stress, or providing heat dissipation. The composite pattern preferably has a film thickness of 0.5 μm or greater and 150 μm or less.

<Characteristics of the Composite Pattern> When the first resin composition and/or the second resin composition include, as resin A and/or resin B, at least one member selected from the group consisting of the aforementioned polyimide precursors, polyimide precursors containing a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors containing a polybenzoxazole structure, polyamidoimide precursors, and polyamidoimide precursors containing a polyamidoimide structure, the cyclization rate in the composite pattern is preferably 70% or greater, more preferably 80% or greater, and even more preferably 90% or greater. The elongation at break of the composite pattern is preferably 30% or higher, more preferably 40% or higher, and even more preferably 50% or higher. The glass transition temperature (Tg) of the composite pattern is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher. If the composite pattern has two or more glass transition temperatures, the lower temperature is preferably within the above range.

(Laminar Body and Laminate Manufacturing Method) A laminate refers to a structure having multiple layers composed of the composite pattern of the present invention. The laminate of the present invention includes two or more layers composed of the composite pattern, and may also include three or more layers. Of the two or more layers comprising the composite pattern included in the laminate, at least one is formed using the composite pattern forming method of the present invention. From the perspective of suppressing shrinkage of the composite pattern or deformation of the composite pattern associated with such shrinkage, it is also preferred that all of the layers comprising the composite pattern included in the laminate be formed using the composite pattern manufacturing method of the present invention.

That is, the method for manufacturing the laminate of the present invention preferably includes the method for manufacturing the composite pattern of the present invention, and more preferably includes repeating the steps of the method for manufacturing the composite pattern of the present invention multiple times.

The laminate of the present invention preferably includes two or more layers comprising a composite pattern, and preferably includes a metal layer between any of the layers comprising the composite pattern. The metal layer is preferably formed by the metal layer forming step described above. That is, the laminate manufacturing method of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer comprising the composite pattern between multiple steps of the composite pattern manufacturing method. Preferred embodiments of the metal layer forming step are as described above. A preferred example of the laminate is a laminate having a layered structure comprising at least three layers, stacked in this order: a layer comprising a first composite pattern, a metal layer, and a layer comprising a second composite pattern. Preferably, both the layer comprising the first composite pattern and the layer comprising the second composite pattern are composite pattern layers obtained using the composite pattern forming method of the present invention. The first and second resin compositions used to form the layer comprising the first composite pattern and the first and second resin compositions used to form the layer comprising the second composite pattern may have the same composition or different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a redistribution layer.

<Lamination Step> The laminate manufacturing method of the present invention preferably includes a lamination step. The lamination step refers to a series of steps comprising performing the various steps of the composite pattern manufacturing method of the present invention again on the surface of the pattern (resin layer) or metal layer. The composite pattern manufacturing method of the present invention may be performed multiple times before including the metal layer formation step.

When a further layering step is performed after the lamination step, a surface activation treatment step may be performed after the composite pattern manufacturing method of the present invention or after the metal layer formation step described above. An example of the surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.

The above-mentioned lamination step is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, in the case of a resin layer (composite pattern layer)/metal layer/resin layer/metal layer/resin layer/metal layer, a structure of 2 or more resin layers and 20 or less resin layers is preferred, and a structure of 2 or more resin layers and 9 or less is even more preferred. The composition, shape, film thickness, etc. of each of the above-mentioned layers may be the same or different.

In the present invention, after providing a metal layer, a composite pattern obtained by the composite pattern manufacturing method of the present invention is further formed to cover the metal layer. The steps of laminating a layer (resin layer) composed of the composite pattern obtained by the composite pattern manufacturing method of the present invention and forming a metal layer are alternately performed, thereby enabling the alternate lamination of the layer (resin layer) composed of the composite pattern obtained by the composite pattern manufacturing method of the present invention and the metal layer.

(Surface Activation Step) The method for manufacturing the laminate of the present invention preferably includes a surface activation step of performing a surface activation treatment on at least a portion of the metal layer and the layer comprising the composite pattern. This surface activation step is typically performed after the metal layer formation step, but it can be performed after the modification step and then after the layer comprising the composite pattern is surface activated. The surface activation treatment can be performed only on at least a portion of the metal layer, only on at least a portion of the layer comprising the composite pattern, or on at least a portion of both the metal layer and the layer comprising the composite pattern. The surface activation treatment is preferably performed on at least a portion of the metal layer, and preferably on a portion or all of the area of the metal layer where the layer comprising the composite pattern is formed on the surface. As described above, by performing a surface activation treatment on the surface of the metal layer, the adhesion between the metal layer and the layer comprising the composite pattern disposed on the surface can be improved. Furthermore, the surface activation treatment is preferably performed on a portion or all of the layer comprising the composite pattern. As described above, by performing a surface activation treatment on the surface of the layer comprising the composite pattern, the adhesion between the metal layer and the resin layer disposed on the surface of the metal layer comprising the composite pattern can be improved. In particular, when negative tone development is performed, and the layer composed of the composite pattern is cured, it is less likely to be damaged by the surface treatment, and adhesion is easily improved. Specifically, the surface activation treatment can be selected from plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , and _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment by immersing in aqueous hydrochloric acid solution to remove the oxide film followed by immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

(Semiconductor Device Manufacturing Method) The present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing the composite pattern of the present invention or a method for manufacturing the laminate of the present invention. Specific examples of semiconductor devices using the composite pattern of the present invention to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213-0218 and Figure 1 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

(First Resin Composition) The first resin composition of the present invention is used to form the first photosensitive film in the method for producing a composite pattern of the present invention. In the first aspect of the method for producing a composite pattern of the present invention, the first resin composition comprises at least one resin selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamideimide precursor, and a polyamideimide precursor having a polyamideimide structure, namely, resin A. In the first aspect of the composite pattern manufacturing method of the present invention, the first resin composition preferably includes the aforementioned resin A. The following describes in detail the components included in the first resin composition of the present invention.

<Resin A> Resin A is at least one resin selected from the group consisting of polyimide precursors, polyimide precursors containing a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors containing a polybenzoxazole structure, polyamidoimide precursors, and polyamidoimide precursors containing a polyamidoimide structure. Preferably, Resin A is at least one resin selected from the group consisting of polyimide precursors and polyimide precursors containing a polyimide structure.

Resin A preferably has a polymerizable group, and more preferably, a radically polymerizable group. When Resin A has a radically polymerizable group, the first resin composition of the present invention preferably contains a radical polymerization initiator, as described below, and more preferably contains both a radical polymerization initiator and a radical crosslinker, as described below. A sensitizer, as described below, may further be included, if desired. For example, such a first resin composition of the present invention can form a negative photosensitive film. Also, Resin A may contain a polarity-converting group such as an acid-degradable group. When Resin A has an acid-degradable group, the first resin composition of the present invention preferably contains a photoacid generator, as described below. For example, the first resin composition of the present invention can be used to form a chemically amplified, positive-type photosensitive film or a negative-type photosensitive film.

Furthermore, it is preferable that the first resin composition does not contain a colorant. The absence of a colorant in the first resin composition may result in excellent light transmittance and a good pattern shape.

[Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably comprises a repeating unit represented by the following formula (2). [Chemical Formula 1] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or -NH-, preferably an oxygen atom. In formula (2), ^R111 represents a divalent organic group. Examples of the divalent organic group include linear or branched aliphatic groups, cyclic aliphatic groups, and groups containing aromatic groups. Preferably, they are linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 3 to 20 carbon atoms, or groups composed of combinations thereof. More preferably, they are groups containing aromatic groups having 6 to 20 carbon atoms. The linear or branched aliphatic groups may be substituted with a group containing a heteroatom in the alkyl group in the chain, and the cyclic aliphatic and aromatic groups may be substituted with a group containing a heteroatom in the alkyl group of a ring member. Preferred embodiments of the present invention include groups represented by -Ar- and -Ar-L-Ar-, with -Ar-L-Ar- being particularly preferred. Ar is independently an aromatic group, and L is a single bond, an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a divalent group composed of a combination of two or more of the foregoing. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a diamine containing an aromatic group having 6 to 20 carbon atoms is even more preferred. The linear or branched aliphatic group may be substituted with a group containing a heteroatom in the alkyl group in the chain, and the cyclic aliphatic group and aromatic group may be substituted with a group containing a heteroatom in the alkyl group of a ring member. As examples of the group containing an aromatic group, the following groups can be cited.

【Chemical formula 2】 In the formula, A represents a single bond or a divalent group. Preferably, it is a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, _-SO₂- , and _-NHCO- , or a combination thereof. More preferably, it is a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with fluorine atoms, -O-, -C(=O)-, -S-, or -SO₂-. Even more preferably, it is _-CH₂- , -O-, -S-, _-SO₂- , -C(CF₃) _{₂- ,} or -C( _CH₃ ) _₂- . In the formula, * represents a bonding site to another structure.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexane, Hexylmethane and isophoronediamine; m-phenylenediamine or p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfonium and 3,3'-diaminodiphenylsulfonium, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroxyanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5, 5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-Bis(4-aminophenyl)octafluorobutane, 1,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy)benzene At least one diamine selected from the group consisting of: 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfonium, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotolidine, and 4,4’-diaminoquaternaryl.

Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred.

Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the perspective of the flexibility of the resulting organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Ar is independently an aromatic group, and L is an aliphatic alkyl group having 1 to 10 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, or -NHCO-, or a divalent group composed of a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic alkyl group having 1 or 2 carbon atoms that may be substituted with fluorine atoms, -O-, -CO-, -S-, or -SO ₂ -. The aliphatic alkyl group herein is preferably an alkylene group.

From the perspective of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the perspective of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 3] In formula (51), ^R50 to ^R57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). Examples of the monovalent organic group represented by ^R50 to ^R57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 4] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). Examples of diamines that impart the structure of formula (51) or (61) include 2,2'-dimethyl-p-benzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These can be used alone or in combination of two or more.

R ¹¹⁵ in formula (2) represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with another structure. [Chemical Formula 5] In formula (5), R ¹¹² is a single bond or a divalent linking group, preferably a single bond or a divalent linking group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ -, and -NHCO-, and combinations thereof, more preferably a single bond or a divalent linking group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, and -SO ₂ -, and even more preferably a divalent linking group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and -SO ₂ -.

Specifically, R ¹¹⁵ can include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. The polyimide precursor may contain only one tetracarboxylic dianhydride residue or two or more tetracarboxylic dianhydride residues, as a structure corresponding to R ^115. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 6] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane Dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Furthermore, as a preferred example, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

In formula (2), at least one of R ¹¹¹ and R ¹¹⁵ may have an OH group. More specifically, R ¹¹¹ can be exemplified by a residual group of a diaminophenol derivative.

In formula (2), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group preferably comprises a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group. Furthermore, preferably, at least one of R ¹¹³ and R ¹¹⁴ comprises a polymerizable group, and more preferably, both comprise polymerizable groups. It is also preferred that at least one of R ¹¹³ and R ¹¹⁴ comprises two or more polymerizable groups. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, or the like, and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, cyclobutyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. Preferred free radical polymerizable groups in the polyimide precursor include groups having an ethylenically unsaturated bond. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl groups), (meth)acrylamido groups, (meth)acryloyloxy groups, and groups represented by the following formula (III). Groups represented by the following formula (III) are preferred.

【Chemical formula 7】

In formula (III), R ²⁰⁰ represents a hydrogen atom, a methyl group, an ethyl group, or a hydroxymethyl group, preferably a hydrogen atom or a methyl group. In formula (III), * represents a bonding site to another structure. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, a cycloalkylene group, or a polyalkyleneoxy group. Preferred examples of R ²⁰¹ include alkylene groups such as vinyl, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, 1,2-butanediyl, 1,3-butanediyl, _-CH₂CH (OH) _CH₂- , and polyalkoxyene groups. More preferred are alkylene groups such as vinyl and propylene, -CH₂CH(OH) _CH₂- , cyclohexyl, and polyalkoxyene groups. Even _more preferred are alkylene groups such as vinyl and propylene, or polyalkoxyene groups. In the present invention, a polyalkoxyene group refers to an alkoxyene group directly bonded to two or more groups. The alkylene groups in the multiple alkoxyene groups contained in the polyalkoxyene group may be the same or different. When a polyalkoxyl group comprises multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group can be random, block-like, or alternating. The carbon number of the alkoxyl group (including the carbon number of the substituent, if the alkylene group has a substituent) is preferably 2 or greater, more preferably 2-10, more preferably 2-6, even more preferably 2-5, even more preferably 2-4, particularly preferably 2 or 3, and most preferably 2. Furthermore, the alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, and halogen atoms. Furthermore, the number of alkoxyl groups in the polyalkoxyl group (the number of repetitions of the polyalkoxyl group) is preferably 2-20, more preferably 2-10, and even more preferably 2-6. From the perspective of solvent solubility and solvent resistance, polyalkyleneoxy groups are preferably polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or groups comprising multiple polyethyleneoxy groups bonded to multiple propoxy groups. Polyethyleneoxy groups or polypropyleneoxy groups are more preferred, and polyethyleneoxy groups are even more preferred. In the aforementioned groups comprising multiple polyethyleneoxy groups bonded to multiple propoxy groups, the polyethyleneoxy and propoxy groups may be arranged randomly, in blocks, or in an alternating pattern. Preferred aspects of the number of repetitions of polyethyleneoxy groups and the like in these groups are as described above.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

In formula (2), at least one of R ¹¹³ and R ¹¹⁴ may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it decomposes by the action of an acid to produce an alkaline-soluble group such as a phenolic hydroxyl group or a carboxyl group. An acetal group, an acetal group, a silyl group, a silyl ether group, or a tertiary alkyl ester group is preferred. From the perspective of exposure sensitivity, an acetal group or a ketal group is more preferred. Specific examples of the acid-decomposable group include a tertiary butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tertiary butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuryl is preferred.

Furthermore, the polyimide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyimide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamines include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

The repeating units represented by formula (2) are preferably repeating units represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having repeating units represented by formula (2-A). By including repeating units represented by formula (2-A) in the polyimide precursor, the exposure latitude can be further increased. Formula (2-A) [Chemical Formula 8] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), respectively, and their preferred ranges are also the same. R ¹¹² has the same meaning as R ¹¹² in formula (5), and its preferred range is also the same.

The polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). Furthermore, in addition to the repeating unit represented by formula (2), the polyimide precursor may also contain other types of repeating units.

As one embodiment of the polyimide precursor of the present invention, the content of the repeating units represented by formula (2) is 50 mol% or more of the total repeating units. More preferably, the total content is 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor, excluding the terminal repeating units, may be repeating units represented by formula (2).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. Furthermore, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The molecular weight dispersity of the polyimide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited; for example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is even more preferred. In this specification, molecular weight dispersion is calculated as weight-average molecular weight/number-average molecular weight. When the first resin composition comprises multiple polyimide precursors as resin A, it is preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of at least one polyimide precursor fall within the aforementioned ranges. Furthermore, it is also preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of the multiple polyimide precursors, calculated as a single resin, fall within the aforementioned ranges.

[Polyimide Precursor Containing a Polyimide Structure] As the polyimide precursor containing a polyimide structure, a resin in which a portion of the repeating units represented by formula (2) in the polyimide precursor are ring-closed to form an imide structure is also preferred. The imidization rate (also referred to as "ring closure rate") in the polyimide precursor containing a polyimide structure is preferably 25% or less, more preferably 10% or less, and even more preferably 5% or less. The lower limit of the imidization rate is not particularly limited and may be greater than 0%. For example, the imidization rate can be measured by the following method. The infrared absorption spectrum of the polyimide precursor was measured to determine the peak intensity P1, an absorption peak at around 1377 cm ^-1 attributed to the imide structure. The polyimide was then heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was again measured to determine the peak intensity P2 at around 1377 cm ^-1 . The obtained peak intensities P1 and P2 can be used to determine the imidization rate of the polyimide precursor according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[Polybenzoxazole Precursor] The polybenzoxazole precursor used in the present invention is not particularly limited in structure, but preferably comprises repeating units represented by the following formula (3). [Chemical Formula 9] In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and their preferred ranges are also the same. That is, at least one is preferably a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As a divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As an aliphatic group, a linear aliphatic group is preferred. R ¹²¹ is preferably a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

Preferred dicarboxylic acid residues include those containing an aliphatic group and those containing an aromatic group, with those containing an aromatic group being more preferred. Preferred dicarboxylic acids containing an aliphatic group include those containing a linear or branched (preferably linear) aliphatic group, and those composed of a linear or branched (preferably linear) aliphatic group and two -COOH groups are more preferred. The linear or branched (preferably linear) aliphatic group preferably has 2 to 30 carbon atoms, more preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. Examples of dicarboxylic acids containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetrafluorohexanedioic ... Methyl pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid), and further dicarboxylic acid represented by the following formula, etc.

【Chemical formula 10】 (Wherein, Z is a alkyl group with 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of a group having the following aromatic group and two -COOH groups is more preferred.

【Chemical formula 11】 In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * independently represents a bonding site with other structures.

Specific examples of dicarboxylic acids containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, it has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same. ¹²² is preferably a group derived from a bisaminophenol derivative. Examples of the group derived from a bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfonium, 4,4'-diamino-3,3'-dihydroxydiphenylsulfonium, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2- Bis-(4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, those having the following aromatic groups are preferred.

【Chemical formula 12】 In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , or -NHCO-; * and # each represent a bonding site to another structure. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. Furthermore, ^R122 is preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the nitrogen atom to which R 122 in formula (3) is bonded, or that two * are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the oxygen atom to which R 122 in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

The diaminophenol derivative is preferably a compound represented by formula (As). [Chemical Formula 13]

In formula (As), _R1 is an organic group selected from a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or the group represented by the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

【Chemical formula 14】 (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by formula (As) above.)

In the above formula (As), it is particularly preferred to have a substituent at the adjacent position of the phenolic hydroxyl group, i.e., at _R3 , because this brings the carbonyl carbon of the amide bond and the hydroxyl group closer together and further enhances the cyclization rate during curing at low temperatures.

In the above formula (As), it is preferable that R ₂ is an alkyl group and R ₃ is an alkyl group because high transparency to i-rays and a high cyclization rate during curing at a low temperature can be maintained.

Furthermore, in the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of alkylene groups and substituted alkylene groups for _R1 include linear or branched alkyl groups having 1 to 8 carbon atoms. Among these, -CH2-, -CH(CH3)-, and -C( _{CH3 ) 2-} are particularly _preferred from the perspectives of maintaining high transparency to i-rays and a high cyclization rate during low-temperature curing while maintaining sufficient solubility in solvents and providing a well-balanced polybenzoxazole precursor.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), reference can be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of JP-A-2013-256506, the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese Patent Application Laid-Open No. 2013-256506, which are incorporated herein by reference. However, the present invention is not limited thereto.

In addition to the repeating units of formula (3), the polybenzoxazole precursor may also contain other types of repeating units. From the perspective of suppressing the warp associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as the other type of repeating unit.

【Chemical formula 15】 In formula (SL), Z has structures a and b. R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining groups are hydrogen atoms or organic groups having 1 to 30 carbon atoms and may be the same or different. The polymerization of structures a and b can be block or random. The molar percentage of Z is 5 to 95 molar percent for structures a, 95 to 5 molar percent for structures b, and 100 molar percent for a + b.

In formula (SL), preferred examples of Z include those in structure b where R ^5s and R ^6s are phenyl groups. Furthermore, the molecular weight of the structure represented by formula (SL) is preferably 400-4,000, and more preferably 500-3,000. By setting the molecular weight within this range, the elastic modulus of the polybenzoxazole prodiol after dehydration and ring closure can be more effectively reduced, while achieving both the effect of suppressing warp and the effect of improving solvent solubility.

When the diamine residue represented by formula (SL) is included as another type of repeating unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating unit. Examples of such tetracarboxylic acid residues include R ¹¹⁵ in formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and even more preferably 22,000 to 28,000. Furthermore, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200. The molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or greater, more preferably 1.5 or greater, and even more preferably 1.6 or greater. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited. For example, it is preferably 2.6 or less, more preferably 2.5 or less, even more preferably 2.4 or less, even more preferably 2.3 or less, and even more preferably 2.2 or less. When the first resin composition comprises a plurality of polybenzoxazole precursors as resin A, it is preferred that at least one of the polybenzoxazole precursors have a weight-average molecular weight, number-average molecular weight, and dispersion within the above-mentioned ranges. Furthermore, it is also preferred that the weight-average molecular weight, number-average molecular weight, and dispersion calculated for the plurality of polybenzoxazole precursors as a single resin are all within the above-mentioned ranges.

[Polybenzoxazole Precursor Containing a Polybenzoxazole Structure] The oxazolidation rate (also known as the "ring closure rate") of the polybenzoxazole precursor containing a polybenzoxazole structure is preferably 25% or less, and more preferably 10% or less. The lower limit is not particularly limited and may be greater than 0%. For example, the oxazolidation rate can be measured by the following method. The infrared absorption spectrum of the polybenzoxazole precursor is measured, and the peak intensity Q1 of the absorption peak at around 1650 ^cm⁻¹ originating from the amide structure of the precursor is determined. Next, the absorption intensity of the aromatic ring observed at around 1490 ^cm⁻¹ is normalized. After heat treating the polybenzoxazole precursor at 350°C for 1 hour, the infrared absorption spectrum was measured again. The peak intensity Q2 near 1650 cm ^-1 was determined and normalized to the absorption intensity of the aromatic ring observed near 1490 cm ^-1 . The obtained peak intensities Q1 and Q2 can be used to calculate the oxazolidation rate of the polybenzoxazole precursor according to the following formula: Oxazolidation rate (%) = (Peak intensity Q1 standard value / Peak intensity Q2 standard value) × 100

[Polyamide-imide precursor] The polyamide-imide precursor preferably comprises a repeating unit represented by the following formula (PAI-2). [Chemical Formula 16] In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A 2 represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group formed by combining two or more of these groups via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups. -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups is more preferred. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogenated alkylene group include fluorine, chlorine, bromine, and iodine, with fluorine being preferred. The halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms. However, halogenation is preferred. Preferred examples of halogenated alkylene groups include (bistrifluoromethyl)methylene. Preferred arylene groups include phenylene or naphthylene, more preferred phenylene, and even more preferred 1,3-phenylene or 1,4-phenylene.

Furthermore, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. Chlorination is preferred as the halogenation method. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups in the tricarboxylic acid compound can be anhydrided. Examples of the halogenated tricarboxylic acid compound used in the production of polyamide imide precursors include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.

Specifically, the tricarboxylic acid compound is preferably a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group. More preferably, the tricarboxylic acid compound contains an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds formed by linking phthalic acid (or phthalic acid) and benzoic acid via a single bond, -O-, _-CH2- , -C( _CH3 ) _2- , -C( _CF3 ) _2- , _-SO2- , or a phenylene group. These compounds may be compounds in which two carboxyl groups are anhydrided (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride chloride).

In formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in formula (2), respectively, and preferred embodiments thereof are also the same.

The polyamide imide precursor may further contain other repeating units. Examples of other repeating units include the repeating unit represented by the above formula (2) and the repeating unit represented by the following formula (PAI-1). [Chemical Formula 17]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. Examples of R ¹¹⁶ in formula (PAI-1) include linear or branched aliphatic groups, cyclic aliphatic groups, aromatic groups, heteroaromatic groups, and groups formed by combining two or more of these groups via a single bond or a linking group. Preferred are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms, and groups formed by combining two or more of these groups via a single bond or a linking group. More preferred are aromatic groups having 6 to 20 carbon atoms, and groups formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups. -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of these groups is more preferred. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms. Examples of the halogenated alkylene group include fluorine, chlorine, bromine, and iodine, with fluorine being preferred. The halogenated alkylene group may have hydrogen atoms, or all hydrogen atoms may be substituted with halogen atoms. However, halogenation is preferred. Preferred examples of halogenated alkylene groups include (bistrifluoromethyl)methylene. Preferred arylene groups include phenylene or naphthylene, more preferred phenylene, and even more preferred 1,3-phenylene or 1,4-phenylene.

Furthermore, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound. The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, for example, preferably chlorinated. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. As the dicarboxylic acid compound or dicarboxylic acid dihalide compound that can be halogenated and used for the production of polyamide imide precursors, linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds can be cited. Such dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used alone or in combination of two or more.

Specifically, the dicarboxylic acid compound or dicarboxylic acid dihalide compound is preferably a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group. More preferably, the dicarboxylic acid compound or dicarboxylic acid dihalide compound contains an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group.

Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, and octafluoroadipic acid. Acid, hexadecanedioic acid, 1,9-nonanediacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, triundecanoic acid, dotriaconedioic acid, diglycolic acid, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-biphenylcarboxylic acid, 4,4'-dicarboxydiphenyl ether, benzophenone-4,4'-dicarboxylic acid, and the like. Specific examples of dicarboxylic acid dihalide compounds include compounds having a structure in which two carboxyl groups are halogenated among the specific examples of dicarboxylic acid compounds described above.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in formula (2), and preferred embodiments are also the same.

The polyamide-imide precursor preferably has fluorine atoms in its structure. The fluorine atom content in the polyamide-imide precursor is preferably 10% by mass or more, and more preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, the polyamide imide precursor can be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

As an embodiment of the polyamide-imide precursor of the present invention, the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2) is 50 mol% or more of the total repeating units. The total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably greater than 90 mol%. The upper limit of the total content is not particularly limited, and all repeating units in the polyamide-imide precursor, excluding the terminal units, may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by formula (2). Another embodiment of the polyamide-imide precursor of the present invention includes an embodiment in which the combined content of the repeating units represented by formula (PAI-2) and the repeating units represented by formula (PAI-1) is 50 mol% or greater of the total repeating units. This combined content is more preferably 70 mol% or greater, even more preferably 90 mol% or greater, and particularly preferably greater than 90 mol%. There is no particular upper limit to this combined content; all repeating units in the polyamide-imide precursor, excluding the terminal repeating units, may be repeating units represented by formula (PAI-2) or any repeating units represented by formula (PAI-1).

The weight average molecular weight (Mw) of the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more preferably 10,000 to 50,000. Furthermore, the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000. The molecular weight dispersity of the polyamide-imide precursor is preferably 1.5 or greater, more preferably 1.8 or greater, and even more preferably 2.0 or greater. The upper limit of the molecular weight dispersion of the polyamide-imide precursor is not particularly limited. For example, 7.0 or less is preferred, 6.5 or less is more preferred, and 6.0 or less is even more preferred. Furthermore, when the first resin composition comprises a plurality of polyamide-imide precursors as resin A, it is preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of at least one polyamide-imide precursor are within the above-mentioned ranges. Furthermore, it is also preferred that the weight-average molecular weight, number-average molecular weight, and dispersion of the plurality of polyamide-imide precursors as a single resin are also within the above-mentioned ranges.

[Polyamidoimide Precursor Containing a Polyamidoimide Structure] The polyamidoimide precursor containing a polyamidoimide structure is preferably a resin in which a portion of the repeating units represented by formula (PAI-2) in the polyamidoimide precursor are ring-closed to form an imide structure. The imidization rate (also referred to as "ring closure rate") in the polyamidoimide precursor containing a polyamidoimide structure is preferably 25% or less, more preferably 10% or less, and even more preferably 5% or less. The lower limit of the imidization rate is not particularly limited; it may be greater than 0%. The imidization rate can be measured, for example, by the following method. The infrared absorption spectrum of the polyamide-imide precursor was measured to determine the peak intensity P1, an absorption peak at around 1377 cm ^- 1 attributed to the imide structure. The polyimide was then heat-treated at 350°C for 1 hour, and the infrared absorption spectrum was again measured to determine the peak intensity P2 at around 1377 cm ^-1 . The obtained peak intensities P1 and P2 can be used to determine the imidization rate of the polyamide-imide precursor according to the following formula: Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

[Methods for producing polyimide precursors, etc.] For example, polyimide precursors, etc. can be produced by the following methods: a method of reacting tetracarboxylic dianhydride with a diamine at low temperature; a method of reacting tetracarboxylic dianhydride with a diamine at low temperature to produce polyamide, followed by esterification with a condensing agent or an alkylating agent; a method of producing a diester from tetracarboxylic dianhydride and an alcohol, followed by reacting the diester in the presence of a diamine and a condensing agent; a method of producing a diester from tetracarboxylic dianhydride and an alcohol, followed by halogenation of the resulting dicarboxylic acid with a halogenating acid, and then reacting the resulting dicarboxylic acid with a diamine. Of these production methods, the method of producing a diester from tetracarboxylic dianhydride and an alcohol, followed by halogenation of the resulting dicarboxylic acid with a halogenating acid, and then reacting the resulting dicarboxylic acid with a diamine is more preferred. Examples of the condensing agent include dicyclohexanecarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agent include sulfinyl chloride, oxalyl chloride, and phosphonyl chloride. In the production method of a polyimide precursor, etc., it is preferred to use an organic solvent during the reaction. The organic solvent may be one or two or more. The organic solvent can be appropriately determined depending on the raw materials, and examples include pyridine, diethylene glycol dimethyl ether (DGE), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the production method of a polyimide precursor, etc., it is preferred to add a saline compound during the reaction. The saline compound may be one or two or more. The salt compound can be appropriately determined according to the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.

-Capping Agents- To further improve storage stability when manufacturing polyimide precursors, it is preferable to block the carboxylic anhydride, anhydride derivative, or amine group remaining at the end of the polyimide precursor resin. Examples of capping agents for blocking carboxylic anhydride and anhydride derivatives remaining at the end of the resin include monoalcohols, phenols, thiols, thiophenols, and monoamines. Considering reactivity and film stability, monoalcohols, phenols, and monoamines are preferred. Preferred monohydric alcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropyl alcohol, 2-butanol, cyclohexanol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as tertiary butanol and adamantanol. Preferred phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and the like. Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-Carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple end-capping agents. Furthermore, when blocking the amine groups at the resin terminals, compounds having functional groups reactive with the amine groups can be used. Preferred blocking agents for amine groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride. Preferred carboxylic acid chloride compounds include acetyl chloride, acryloyl chloride, propionyl chloride, methacryloyl chloride, neopentanoyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyl chloride, stearyl chloride, and benzoyl chloride.

-Solid Precipitation- The production of polyimide precursors, etc., may include a solid precipitation step. Specifically, after filtering out any water-absorbing byproducts of the dehydration condensation agent present in the reaction solution, the resulting polymer component is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof to precipitate the polymer component. This solid is then dried to obtain the polyimide precursor, etc. To increase the degree of purity, the polyimide precursor, etc., may be repeatedly subjected to redissolution, reprecipitation, and drying. An ion exchange resin may also be used to remove ionic impurities.

[Content] The content of Resin A in the first resin composition of the present invention is preferably 20% by mass or greater, more preferably 30% by mass or greater, even more preferably 40% by mass or greater, and even more preferably 50% by mass or greater, relative to the total solids content of the first resin composition. Furthermore, the content of Resin A in the first resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, relative to the total solids content of the first resin composition. The first resin composition of the present invention may contain only one type of Resin A, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

Furthermore, the first resin composition of the present invention preferably comprises at least two resins. Specifically, the first resin composition of the present invention may comprise a total of two or more resins A and other resins described below, or may comprise two or more resins A, but comprising two or more resins A is preferred. When the first resin composition of the present invention comprises two or more resins A, for example, it is preferred that it comprises a polyimide precursor, wherein the polyimide precursor is derived from two or more polyimide precursors having different dianhydride structures (R ¹¹⁵ represented by the above formula (2)).

<Other Resins> The first resin composition of the present invention may contain the aforementioned resin A and another resin different from resin A (hereinafter referred to as "other resin"). Examples of such other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylate resins, (meth)acrylamide resins, urethane resins, butyraldehyde resins, styrene resins, polyether resins, and polyester resins. For example, by further adding a (meth)acrylate resin, a first resin composition with excellent coatability can be obtained, and a composite pattern with excellent solvent resistance can be obtained. For example, by adding a (meth)acrylic resin to the first resin composition instead of or in addition to the polymerizable compound described below, the coatability of the first resin composition and the solvent resistance of the composite pattern can be improved. The (meth)acrylic resin has a weight-average molecular weight of 20,000 or less and a high polymerizable group content (for example, a molar content of polymerizable groups of 1× ^10-3 mol/g or more per gram of the resin).

When the first resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or greater, more preferably 0.05% by mass or greater, even more preferably 1% by mass or greater, even more preferably 2% by mass or greater, even more preferably 5% by mass or greater, and even more preferably 10% by mass or greater, relative to the total solids content of the first resin composition. Furthermore, the content of the other resins in the first resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solids content of the first resin composition. Furthermore, as one preferred aspect of the first resin composition of the present invention, it can also be configured such that the content of other resins is low. In the above aspect, the content of other resins relative to the total solids content of the first resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the above content is not particularly limited; it can be 0% by mass or more. The first resin composition of the present invention may contain only one other resin or two or more. When containing two or more other resins, the total amount is preferably within the above range.

<Polymerizable Compound> The first resin composition of the present invention preferably contains a polymerizable compound. Furthermore, the first resin composition preferably contains a polymerizable compound having two or more functional groups, and containing a polymerizable compound having three or more functional groups is also a preferred embodiment. Examples of the polymerizable compound include free radical crosslinking agents and other crosslinking agents.

[Free Radical Crosslinking Agent] The first resin composition of the present invention preferably contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. Preferred free radical polymerizable groups are groups containing ethylenically unsaturated bonds. Examples of groups containing such ethylenically unsaturated bonds include vinyl, allyl, vinylphenyl, (meth)acryl, cis-butylenediimide, and (meth)acrylamide. Among these, (meth)acryl, (meth)acrylamide, and vinylphenyl are preferred groups containing such ethylenically unsaturated bonds. From the perspective of reactivity, (meth)acryl is more preferred.

The free radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more ethylenically unsaturated bonds. The free radical crosslinking agent may have three or more ethylenically unsaturated bonds. Compounds having two or more ethylenically unsaturated bonds are preferably compounds having 2 to 15 ethylenically unsaturated bonds, more preferably compounds having 2 to 10 ethylenically unsaturated bonds, and even more preferably compounds having 2 to 6 ethylenically unsaturated bonds. Furthermore, from the perspective of the film strength of the obtained composite pattern, it is also preferred that the first resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above-mentioned ethylenically unsaturated bonds.

The molecular weight of the free radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the free radical crosslinking agent is preferably 100 or more.

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid), or their esters and amides. Preferred are esters of unsaturated carboxylic acids with polyol compounds, and amides of unsaturated carboxylic acids with polyamine compounds. Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or thiohydrides with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, are also preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electrophilic substituents such as isocyanate or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, as well as substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogen or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, are also preferred. As another example, compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, and allyl ethers can be used in place of the unsaturated carboxylic acids. For specific examples, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Laid-Open No. 2016-027357, the contents of which are incorporated herein.

Furthermore, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher at normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trihydroxymethylpropane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating. Esterified compounds; (meth)acrylic acid urethanes described in Japanese Patent Publication Nos. 48-041708, 50-006034, and 51-037193; polyester acrylates described in Japanese Patent Publication Nos. 48-064183, 49-043191, and 52-030490; polyfunctional acrylates or methacrylates such as epoxy acrylates that are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. Compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond, such as epoxypropyl (meth)acrylate, can also be cited.

In addition to the above, preferred radical crosslinking agents include compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, as described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, and cardo resins.

Other examples include the specific unsaturated compounds described in Japanese Patent Publication Nos. 46-043946, 01-040337, and 01-040336, and the vinylphosphonic acid compounds described in Japanese Patent Application Laid-Open No. 02-025493. Furthermore, compounds containing perfluoroalkyl groups described in Japanese Patent Application Laid-Open No. 61-022048 can also be used. Furthermore, those described as photocurable monomers and oligomers in "Journal of the Adhesion Society of Japan," vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Laid-Open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are incorporated into this specification.

In addition, compounds described as formula (1) and formula (2) together with their specific examples in Japanese Patent Application Laid-Open No. 10-062986 can also be used as free radical crosslinking agents. These compounds are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the resulting compound.

Furthermore, the compounds described in paragraphs 0104 to 0131 of Japanese Patent Application Laid-Open No. 2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

As the radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which the (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues are preferred. These oligomers can also be used.

Examples of commercially available free radical crosslinking agents include SR-494, a tetrafunctional acrylate having four vinyloxy chains, manufactured by Sartomer Company, Inc.; SR-209, 231, and 239, bifunctional methacrylates having four vinyloxy chains, manufactured by Sartomer Company, Inc.; DPCA-60, a hexafunctional acrylate having six pentyloxy chains, TPA-330, a trifunctional acrylate having three isobutyloxy chains, manufactured by Nippon Kayaku Co., Ltd.; urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.); NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300; and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.). Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION.), etc.

Preferred free radical crosslinking agents include urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Furthermore, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent may be one having an acid group such as a carboxyl group or a phosphoric acid group. Among free radical crosslinking agents having an acid group, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred. More preferred are free radical crosslinking agents obtained by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to obtain acid groups. Particularly preferred are free radical crosslinking agents obtained by reacting unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to obtain acid groups, wherein the aliphatic polyhydroxy compound is a compound such as neopentatyritol or dipentatyritol. Examples of commercially available products include polyacid-modified acrylic oligomers M-510 and M-520 manufactured by TOAGOSEI CO., LTD.

The preferred acid value of a radical crosslinking agent containing an acid group is 0.1 to 300 mgKOH/g, particularly preferably 1 to 100 mgKOH/g. A free radical crosslinking agent with an acid value within this range provides excellent workability during production and, consequently, excellent developability. Furthermore, it exhibits good polymerizability. The acid value is measured in accordance with JIS K 0070:1992.

From the perspective of pattern resolution and film stretchability, a bifunctional methacrylate or acrylate is preferably used as the first resin component. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol diacrylate. Dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO (ethylene oxide) adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates with urethane bonds, and bifunctional methacrylates with urethane bonds. Two or more of these may be used in combination as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate with a polyethylene glycol chain formula weight of approximately 200. From the viewpoint of suppressing warping associated with controlling the elastic modulus of the composite pattern, the first resin composition of the present invention can preferably use a monofunctional free radical crosslinking agent as the free radical crosslinking agent. Preferred monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and other (meth)acrylic acid derivatives; N-vinyl pyrrolidone, N-vinyl caprolactam, and other N-vinyl compounds; and allyl glycidyl ether. Monofunctional radical crosslinking agents with a boiling point of 100°C or higher at normal pressure are also preferred to suppress volatility before exposure. In addition, examples of bifunctional or higher-functional free radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

When a free radical crosslinking agent is present, its content is preferably greater than 0% by mass and less than 60% by mass relative to the total solids content of the first resin composition of the present invention. The lower limit is more preferably 5% by mass or greater. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

The free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used simultaneously, the total amount thereof is preferably within the above range.

[Other Crosslinking Agents] The first resin composition of the present invention preferably contains a crosslinking agent other than the free radical crosslinking agent described above. In the present invention, the "other crosslinking agent" refers to a crosslinking agent other than the free radical crosslinking agent described above. Preferably, the compound has multiple groups within its molecule that react with the photoacid generator or photoalkali generator (forming covalent bonds with other compounds in the composition or their reaction products). More preferably, the compound has multiple groups within its molecule that react with an acid or base (forming covalent bonds with other compounds in the composition or their reaction products). The acid or base is preferably one generated from a photoacid generator or photoalkali generator during the exposure step. Other crosslinking agents are preferably compounds having at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl groups, and more preferably compounds having a structure in which at least one group selected from the group consisting of acyloxymethyl, hydroxymethyl, and alkoxymethyl groups is directly bonded to a nitrogen atom. Other crosslinking agents include, for example, compounds having a structure in which an amino-containing compound such as melamine, acetylene carbamide, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde, or formaldehyde is reacted with an alcohol, and the hydrogen atom of the amino group is replaced with an acyloxymethyl, hydroxymethyl, or alkoxymethyl group. The production method of these compounds is not particularly limited, as long as they have the same structure as the compounds produced by the above-described methods. Alternatively, these compounds may be oligomers formed by self-condensation of hydroxymethyl groups. Among the amino-containing compounds described above, crosslinking agents using melamine are referred to as melamine-based crosslinking agents, those using acetylene carbamide, urea, or alkylene urea are referred to as urea-based crosslinking agents, those using alkylene urea are referred to as alkylene urea-based crosslinking agents, and those using benzoguanamine are referred to as benzoguanamine-based crosslinking agents. Among these, the first resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group consisting of the acetylene urea-based crosslinking agents and melamine-based crosslinking agents described below.

Compounds containing at least one of the alkoxymethyl and acyloxymethyl groups of the present invention include, as structural examples, compounds in which the alkoxymethyl or acyloxymethyl group is directly substituted on an aromatic group, a nitrogen atom of the following urea structure, or a triazole. The alkoxymethyl or acyloxymethyl group in these compounds preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms. The total number of alkoxymethyl and acyloxymethyl groups in these compounds is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6. The molecular weight of these compounds is preferably 1500 or less, and preferably 180 to 1200.

【Chemical formula 18】

R ₁₀₀ represents an alkyl group or an acyl group. R ₁₀₁ and R ₁₀₂ each independently represent a monovalent organic group and may be bonded to each other to form a ring.

Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic group include compounds of the following general formula.

【Chemical formula 19】

In the formula, X represents a single bond or a divalent organic group, each R ₁₀₄ independently represents an alkyl group or an acyl group, R ₁₀₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a group that decomposes by the action of an acid to form an alkaline-soluble group (for example, a group that is liberated by the action of an acid, a group represented by -C(R ⁴ ) ₂ COOR ⁵ (R ⁴ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents a group that is liberated by the action of an acid). R ₁₀₅ independently represents an alkyl group or an alkenyl group, a, b, and c independently represent 1 to 3, d represents 0 to 4, e represents 0 to 3, f represents 0 to 3, a + d is 5 or less, b + e is 4 or less, and c + f is 4 or less. Examples of ^R₅ in the group represented by -C( ^R₄ ) _₂COOR₅ include -C(R₃)(R₃)(R₃)(OR₃), -C( _R₃ )(R₃)( _OR₃ ), and -C(R₁)( _R₂ )( _OR₃ ). In the formula, _R₃₆ to ^R₃₆ independently represent an alkyl group, _a cycloalkyl group, _an aryl group, _an aralkyl group, or _an alkenyl group. _R₃₆ and _R₃₆ may be bonded to form a ring. The alkyl group is preferably an alkyl group having 1 to ₁₀ carbon atoms, and more preferably an alkyl _group having 1 to 5 carbon atoms. The alkyl group may be linear or branched. As the above-mentioned cycloalkyl group, a cycloalkyl group having 3 to 12 carbon atoms is preferred, and a cycloalkyl group having 3 to 8 carbon atoms is more preferred. The above-mentioned cycloalkyl group may be a monocyclic structure or a polycyclic structure such as a condensed ring. The above-mentioned aryl group is preferably an aromatic alkyl group having 6 to 30 carbon atoms, and a phenyl group is more preferred. As the above-mentioned aralkyl group, an aralkyl group having 7 to 20 carbon atoms is preferred, and an alkyl group having 7 to 16 carbon atoms is more preferred. The above-mentioned aralkyl group refers to an aryl group substituted by an alkyl group, and the preferred aspects of the alkyl and aryl groups are the same as the preferred aspects of the above-mentioned alkyl and aryl groups. The above-mentioned alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, and an alkenyl group having 3 to 16 carbon atoms is more preferred. In addition, these groups may further have known substituents within the scope of obtaining the effects of the present invention.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

Preferred such groups include tertiary alkyl ester groups, acetal groups, cumyl ester groups, and enol ester groups. More preferred are tertiary alkyl ester groups and acetal ester groups.

Specific examples of compounds having an alkoxymethyl group include the following structures. Examples of compounds having an acyloxymethyl group include compounds obtained by replacing the alkoxymethyl group in the following compounds with an acyloxymethyl group. Examples of compounds having an alkoxymethyl group or an acyloxymethyl group in the molecule include the following compounds, but are not limited thereto.

【Chemical formula 20】

【Chemical formula 21】

Compounds containing at least one of an alkoxymethyl group and an acyloxymethyl group can be commercially available or synthesized by known methods. From the perspective of heat resistance, compounds in which the alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a tricyclic ring are preferred.

Specific examples of melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.

Specific examples of urea-based crosslinking agents include monohydroxymethylated acetylene carbamide, dihydroxymethylated acetylene carbamide, trihydroxymethylated acetylene carbamide, tetrahydroxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetramethoxymethylated acetylene carbamide, monomethoxymethylated acetylene carbamide, dimethoxymethylated acetylene carbamide, trimethoxymethylated acetylene carbamide, tetraethoxymethylated acetylene carbamide, monopropoxymethylated acetylene carbamide, dipropoxymethylated acetylene carbamide, tripropoxymethylated acetylene carbamide, tetrapropoxymethylated acetylene carbamide, monobutoxymethylated acetylene carbamide, dibutoxymethylated acetylene carbamide, tributoxymethylated acetylene carbamide, or tetrabutoxymethylated acetylene carbamide. Urea-based crosslinkers such as bismethoxymethyl urea, bisethoxymethyl urea, bispropoxymethyl urea, and bisbutoxymethyl urea; Ethylene urea-based crosslinkers such as monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea; Propylene urea-based crosslinkers such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

Furthermore, as the compound having at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzene hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl Ketone, methoxymethylbenzoic acid methoxymethylbenzene, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetris[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercially available products can be used. Preferred commercially available products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM- PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark, hereinafter the same) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (all manufactured by SANWA Chemical Co., Ltd.), etc.

Furthermore, the first resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds, and benzoxazolium compounds as another crosslinking agent.

-Epoxy Compounds (Compounds Containing Epoxy Groups)- Epoxy compounds preferably contain two or more epoxy groups per molecule. Epoxy groups undergo crosslinking reactions below 200°C and do not induce dehydration reactions due to crosslinking, thus minimizing film shrinkage. Therefore, the inclusion of epoxy compounds effectively suppresses low-temperature curing and warping of the first resin composition of the present invention.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group containing 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

Examples of epoxy compounds include bisphenol A epoxy resins; bisphenol F epoxy resins; alkylene glycol epoxy resins or polyol hydrocarbon epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexylene glycol diglycidyl ether, and trihydroxymethylpropane triglycidyl ether; polyalkylene glycol epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing polysiloxanes such as polymethyl (glycidoxypropyl) siloxane. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) HP-4770, EPICL ON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740 (the above are trade names, DIC Corporation), RIKARESIN (registered trademark) BEO-20E, RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, CELLOXIDE (registered trademark) 2081, CELLOXIDE (registered trademark) 2000, EHPE3150, EPOLEAD (registered trademark) GT401, EPOLEAD (registered trademark) PB4700, EPOLEAD (registered trademark) PB3600 (the above are trade names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (all trade names, manufactured by Nippon Kayaku Co., Ltd.). The following compounds can also be preferably used.

【Chemical formula 22】

Where n is an integer from 1 to 5, and m is an integer from 1 to 20.

In the above structure, considering both heat resistance and improved elongation, n is preferably 1 to 2 and m is preferably 3 to 7.

[Oxycyclobutane compounds (compounds containing an oxocyclobutyl group)] Examples of oxocyclobutane compounds include compounds containing two or more oxocyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxocyclobutane, 1,4-bis{[(3-ethyl-3-oxocyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxocyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxocyclobutyl)methyl]ester. As a specific example, the ARON OXETANE series (e.g., OXT-121, OXT-221) manufactured by TOAGOSEI CO., LTD. can be preferably used. These can be used alone or in combination of two or more.

-Benzoxazone compounds (compounds containing a benzoxazolyl group)- Benzoxazone compounds are preferred because they do not degas during curing due to the cross-linking reaction caused by the ring-opening addition reaction, which in turn reduces thermal shrinkage and suppresses warping.

Preferred examples of benzoxazolium compounds include P-d-type benzoxazolium, F-a-type benzoxazolium (trade names, manufactured by Shikoku Chemicals Corporation), benzoxazolium adducts of polyhydroxystyrene resins, and novolac-type dihydrobenzoxazolium compounds. These may be used alone or in combination of two or more.

The content of the other crosslinking agent is preferably 0.1-30 mass %, more preferably 0.1-20 mass %, even more preferably 0.5-15 mass %, and particularly preferably 1.0-10 mass %, relative to the total solids content of the first resin composition of the present invention. The other crosslinking agent may be present in a single species or in two or more species. When two or more other thermal crosslinking agents are present, their total content is preferably within the above range.

[Polymerization Initiator] The first resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible region is preferred. Alternatively, an activator that reacts with a photoexcited sensitizer to generate active radicals may be used.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorbance of at least about 50 L·mol ^-1 ·cm ^-1 within a wavelength range of approximately 240 to 800 nm (preferably 330 to 500 nm). The molar absorbance of the compound can be measured using known methods. For example, it is preferably measured using a UV-visible spectrophotometer (Varian Cary-5 spectrophotometer) using an ethyl acetate solvent at a concentration of 0.01 g/L.

Any known compound can be used as a photoradical polymerization initiator. Examples include alkyl halides (e.g., compounds having a trioxane skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron aromatic complexes. For details of these, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated into this specification. In addition, reference can be made to paragraphs 0065 to 0111 of Japanese Patent Application No. 2014-130173, compounds described in Japanese Patent No. 6301489, and MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the peroxide-based photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Patent Application Publication No. 2019-167313 are incorporated into this specification.

Examples of ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Application Laid-Open No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, and the contents of these initiators are incorporated into this specification.

As α-hydroxyketone-based initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the α-aminoketone-based initiator, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As aminoacetophenone-based initiators, compounds described in Japanese Patent Application Laid-Open No. 2009-191179, whose maximum absorption wavelength matches a light source having a wavelength of 365 nm or 405 nm, can also be used, and the contents of such compounds are incorporated into this specification.

Examples of acylphosphine oxide-based initiators include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide. Furthermore, Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins B.V.), IRGACURE-819, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784, IRGACURE-727, and IRGACURE-784EG (all manufactured by BASF), and Keycure VIS 813 (manufactured by King Brother Chem Co., Ltd.).

Oxime compounds are particularly preferred as photoradical polymerization initiators. Oxime compounds can effectively increase exposure latitude. Oxime compounds are particularly preferred because they have a wider exposure latitude (exposure margin) and also function as photohardening accelerators.

Specific examples of oxime compounds include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), compounds described in J.C.S. Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Japanese Patent Application No. 6065596, compounds described in International Publication No. 2 The compounds described in 015/152153, the compounds described in International Publication No. 2017/051680, the compounds described in JP-A-2017-198865, the compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and the compounds described in International Publication No. 2013/167515 are incorporated into this specification.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the first resin composition of the present invention, it is particularly preferred to use an oxime compound as a photoradical polymerization initiator (oxime-based photoradical polymerization initiator). Oxime-based photoradical polymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

【Chemical formula 23】

Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (all manufactured by BASF) and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, a photoradical polymerization initiator 2 described in Japanese Patent Application Publication No. 2012-014052) are also preferably used. TR-PBG-304 and TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.), ADEKA ARKLS NCI-730, NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used. DFI-091 (manufactured by Daito Chemix Corporation) and SpeedCure PDO (manufactured by SARTOMER ARKEMA) can also be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 24]

Oxime compounds having a fluorene ring can also be used as photoradical polymerization initiators. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese Patent Application Publication No. 2014-137466 and Japanese Patent No. 06636081, the contents of which are incorporated herein.

As a photoradical polymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring in a naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013/083505, the contents of which are incorporated herein.

Oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and compound (C-3) described in paragraph 0101 of JP-A-2013-164471, all of which are incorporated herein.

As a photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is preferably a dimer. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Publication No. 2014-137466, and paragraphs 0007 to 0025 of Japanese Patent Application No. 4223071, all of which are incorporated herein. Another example of an oxime compound having a nitro group is ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

Oxime compounds having a hydroxyl substituent bonded to a carbazole skeleton can also be used as photoradical polymerization initiators. Examples of such photopolymerization initiators include the compounds described in International Publication No. 2019/088055, the contents of which are incorporated herein.

As a photopolymerization initiator, an oxime compound having an aromatic ring group ^ArOX1 with an electron-withdrawing group introduced into the aromatic ring (hereinafter also referred to as the oxime compound OX) can also be used. Examples of the electron-withdrawing group possessed by the aromatic ring group ^ArOX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. Acyl and nitro groups are preferred. From the perspective of easily forming a film with excellent light resistance, acyl groups are more preferred, and benzoyl groups are even more preferred. The benzoyl group may have a substituent. The substituent is preferably a halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclooxy group, alkenyl group, alkylthiohydrogen group, arylthiohydrogen group, acyl group or amino group; more preferably, an alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, alkylthiohydrogen group, arylthiohydrogen group or amino group; and even more preferably, an alkoxy group, alkylthiohydrogen group or amino group.

The oxime compound OX is preferably at least one selected from the group consisting of a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). [Chemical Formula 25] wherein ^RX1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthiohydrogen group, an arylthiohydrogen group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, an aminoformyl group, or an aminosulfonyl group; ^RX2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclicoxy group, an alkylthiohydrogen group, an arylthiohydrogen group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyloxy group, or an amino group; ^RX3 to ^RX14 each independently represent a hydrogen atom or a substituent; wherein ^RX10 to RX14 At least one of ^X14 is an electron-withdrawing group.

In the above formula, ^RX12 is an electron-withdrawing group, and ^RX10 , ^RX11 , ^RX13 , and ^RX14 are preferably hydrogen atoms.

Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.

As the most preferable oxime compound, there can be mentioned the oxime compound having a specific substituent described in Japanese Patent Application Laid-Open No. 2007-269779 and the oxime compound having a thioaryl group described in Japanese Patent Application Laid-Open No. 2009-191061, and the contents thereof are incorporated into the present specification.

From the perspective of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl triphosphine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadienyl-benzene-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl-substituted coumarin compounds.

More preferred photoradical polymerization initiators are trihalogenomethyl triphosphine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. It is further preferred to use at least one compound selected from the group consisting of trihalogenomethyl triphosphine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds. It is even more preferred to use metallocene compounds or oxime compounds.

Furthermore, photoradical polymerization initiators that can be used include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-aminophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-aminopropanone-1, quinones formed by condensation of alkyl anthraquinones with aromatic rings, benzoin ether compounds such as benzoin alkyl ethers, benzoin compounds such as benzoin and alkyl benzoins, and benzyl derivatives such as benzyl dimethyl ketal. Compounds represented by the following formula (I) can also be used.

【Chemical formula 26】

In formula (I), R ¹⁰⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, or a phenyl group or biphenyl group substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms; R ¹⁰¹ is a group represented by formula (II) or the same group as R ¹⁰⁰ ; and R ¹⁰² to R ¹⁰⁴ are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

【Chemical formula 27】

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Furthermore, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used as the photoradical polymerization initiator, and the contents thereof are incorporated into this specification.

As photoradical polymerization initiators, bifunctional, trifunctional, or higher-functional photoradical initiators can be used. By using such photoradical polymerization initiators, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, thereby achieving excellent sensitivity. Furthermore, when using a compound with an asymmetric structure, crystallinity is reduced, resulting in increased solubility in solvents, etc., making precipitation less likely over time and thereby improving the temporal stability of the first resin composition. Specific examples of bifunctional or trifunctional or higher-functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015/004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017/033680, and compound (E) and compound (B) described in JP-A-2013-522445. (G), Cmpd 1 to 7 described in International Publication No. 2016/034963, the oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of Japanese Patent Application Laid-Open No. 2017-167399, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, and the oxime ester photoinitiator described in Japanese Patent No. 6469669, the contents of which are incorporated into this specification.

When a photopolymerization initiator is included, its content is preferably 0.1-30 mass%, more preferably 0.1-20 mass%, even more preferably 0.5-15 mass%, and even more preferably 1.0-10 mass%, relative to the total solids content of the first resin composition of the present invention. A single photopolymerization initiator may be included, or two or more may be included. When two or more photopolymerization initiators are included, the total amount is preferably within the above range. In addition, a photopolymerization initiator may also function as a thermal polymerization initiator, and therefore, crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, hot plate, or the like.

[Sensitizer] The first resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes electronically excited. When the electronically excited sensitizer comes into contact with a thermal radical polymerization initiator or a photoradical polymerization initiator, electron transfer, energy transfer, and heat generation occur. This chemically decomposes the thermal radical polymerization initiator or the photoradical polymerization initiator, generating free radicals, acids, or bases. As sensitizers, compounds that can be used include benzophenone, michler's ketone, coumarin, pyrazole azo, aniline azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxocyanine, pyrazolotriazole azo, pyridone azo, cyanine, phenathiophene, pyrrolopyrazoloazo methine, phthalocyanine, benzopyran, and indigo. As the sensitizer, for example, there can be mentioned Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-dimethylaminophenylallylidenedihydroindanone, Methylaminophenylenedihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethyl Oxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylic acid ethyl ester), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-methylbenzophenone, isoamyl dimethylaminobenzoate , isoamyl diethylaminobenzoate, 2-benzylbenzimidazole, 1-phenyl-5-benzyltetrazole, 2-benzylbenzothiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzylaniline, N-methylacetaniline, 3',4'-dimethylacetaniline, etc. Sensitizing dyes may also be used. For details on sensitizing dyes, reference may be made to paragraphs 0161 to 0163 of Japanese Patent Application Laid-Open No. 2016-027357, which is incorporated herein by reference.

When the first resin composition includes a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, relative to the total solids content of the first resin composition. The sensitizer may be used alone or in combination of two or more.

[Chain Transfer Agent] The first resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005), pages 683-684. Examples of chain transfer agents include compounds containing -SS-, _-SO2 -S-, -NO-, SH, PH, SiH, and GeH within the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds containing thiocarbonylthio groups used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These compounds generate free radicals by donating hydrogen to low-activity free radicals or by deprotonating them through oxidation. In particular, thiol compounds can be preferably used.

Furthermore, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used as chain transfer agents, and the contents thereof are incorporated into this specification.

When the first resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the first resin composition of the present invention. The chain transfer agent may be a single type or two or more types. When two or more types of chain transfer agents are present, the total amount thereof is preferably within the above range.

[Photoacid Generator] The first resin composition of the present invention preferably contains a photoacid generator. The photoacid generator is a compound that generates at least one of a Brünster acid and a Lewis acid upon irradiation with light of 200 nm to 900 nm. The irradiated light preferably has a wavelength of 300 nm to 450 nm, more preferably 330 nm to 420 nm. When used alone or in combination with a sensitizer, a photoacid generator that can generate an acid upon exposure is preferred. Preferred examples of the acid generated include hydrogen halides, carboxylic acids, sulfonic acids, sulfinic acids, thiosulfinic acids, phosphoric acid, phosphoric acid monoesters, phosphoric acid diesters, boron derivatives, phosphorus derivatives, antimony derivatives, halogen peroxides, and sulfonamides.

Examples of photoacid generators used in the first resin composition of the present invention include quinonediazide compounds, oximesulfonate compounds, organic halogenated compounds, organic borate compounds, disulfonate compounds, and onium salt compounds. From the perspectives of sensitivity and storage stability, organic halogenated compounds, oximesulfonate compounds, and onium salt compounds are preferred. From the perspectives of mechanical properties of the resulting film, oxime esters are preferred.

Examples of quinonediazide compounds include quinonediazide sulfonic acid ester-bonded with a mono- or polyvalent hydroxyl compound, quinonediazide sulfonic acid sulfonic acid ester-bonded with a mono- or polyvalent amino compound, and quinonediazide sulfonic acid ester-bonded and/or sulfonamide-bonded with a polyhydroxypolyamino compound. These polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds do not necessarily require all functional groups to be substituted with quinonediazide; preferably, at least 40 mol% of the total functional groups are substituted with quinonediazide. By containing this quinone diazide compound, a first resin composition can be obtained that is sensitive to general ultraviolet light, namely, i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from mercury lamps.

Specific examples of the hydroxyl compounds include phenol, trihydroxybenzophenone, 4-methoxyphenol, isopropyl alcohol, octanol, tert-butyl alcohol, cyclohexanol, naphthol, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, and Methylene Tris-FR-CR. -FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PF P, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (these are trade names, manufactured by ASAHI YUKIZAI CORPORATION), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), novolac resin, etc., but the present invention is not limited thereto.

Specific examples of the amino compound include aniline, methylaniline, diethylamine, butylamine, 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl sulfide, but the present invention is not limited thereto.

Specific examples of the polyhydroxypolyamino compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but the present invention is not limited thereto.

Among them, esters containing phenol compounds and 4-naphthoquinonediazidesulfonyl groups are preferred as quinonediazide compounds. This can achieve higher sensitivity and higher resolution than i-ray exposure.

The content of the quinonediazide compound used in the first resin composition of the present invention is preferably 1 to 50 parts by mass, and more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin. Setting the quinonediazide compound content within this range is preferred because it allows for a contrast between exposed and unexposed areas, thereby achieving higher sensitivity. A sensitizer or the like may be further added as needed.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it contains an oxime sulfonate group. Preferred are oxime sulfonate compounds represented by the following formula (OS-1), the later-described formula (OS-103), the formula (OS-104), or the formula (OS-105).

【Chemical formula 28】

In formula (OS-1), ^X3 represents an alkyl group, an alkoxy group, or a halogen atom. When there are multiple ^X3 groups, they may be the same or different. The alkyl group and alkoxy group in ^X3 may have a substituent. The alkyl group in ^X3 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in ^X3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in ^X3 is preferably a chlorine atom or a fluorine atom. In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the multiple ^X3 groups may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an amine benzoyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In formula (OS-1), m3 is 3, ^X3 is methyl, the substitution position of ^X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl, or p-tolyl.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, the contents of which are incorporated herein.

【Chemical formula 29】

In Formulas (OS-103) to (OS-105), ^Rs1 represents an alkyl group, an aryl group, or a heteroaryl group. When multiple ^Rs2 groups exist, some of them independently represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom. When multiple ^Rs6 groups exist, some of them independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxysulfonyl group. Xs represents O or S, ns represents 1 or 2, and ms represents an integer from 0 to 6. In Formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms), or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by ^Rs1 may have known substituents as long as the effects of the present invention are achieved.

In Formulas (OS-103) to (OS-105), ^Rs2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), more preferably a hydrogen atom or an alkyl group. When two or more ^Rs2 are present in a compound, one or two of them are preferably alkyl groups, aryl groups, or halogen atoms, more preferably one is an alkyl group, aryl group, or halogen atom, and particularly preferably one is an alkyl group and the rest are hydrogen atoms. The alkyl or aryl group represented by ^Rs2 may have known substituents as long as the effects of the present invention are achieved. In Formulas (OS-103), (OS-104), and (OS-105), Xs represents O or S, preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In Formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1. When Xs is S, ns is preferably 2. In Formulas (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and alkoxy group (preferably having 1 to 30 carbon atoms) represented by ^Rs6 may have a substituent. In Formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110), or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 30]

In Formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group, or a heteroaryl group; R ^t7 represents a hydrogen atom or a bromine atom; R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group; R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group; and R ^t2 represents a hydrogen atom or a methyl group. In Formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, with a hydrogen atom being preferred.

In formulae (OS-106) to (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group, or a chlorophenyl group. An alkyl group having 1 to 8 carbon atoms, a halogen atom, or a phenyl group is preferred. An alkyl group having 1 to 8 carbon atoms is more preferred. An alkyl group having 1 to 6 carbon atoms is further preferred. A methyl group is particularly preferred.

In Formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. Furthermore, the stereostructure (E,Z) of the oxime may be any of the above-mentioned oxime sulfonate compounds or a mixture. Specific examples of the oxime sulfonate compounds represented by Formulas (OS-103) to (OS-105) include the compounds described in paragraphs 0088 to 0095 of JP-A-2011-209692 and paragraphs 0168 to 0194 of JP-A-2015-194674, the contents of which are incorporated herein.

Other preferred embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formula (OS-101) and formula (OS-102).

【Chemical formula 31】

In Formula (OS-101) or (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl group. More preferably, R ^u9 is a cyano group or an aryl group, and even more preferably, R ^u9 is a cyano group, a phenyl group, or a naphthyl group. In Formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group. In Formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H-, or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In Formula (OS-101) or Formula (OS-102), R ^u1 to R ^u4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonyl group, a cyano group, or an aryl group. Two of ^{R u1} to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring with a benzene ring. R ^u1 to R ^u4 are preferably a hydrogen atom, a halogen atom, or an alkyl group. Furthermore, at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, it is preferred that all of R ^u1 to R ^u4 are hydrogen atoms. Each of the above substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). Furthermore, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any of the above-mentioned oxime sulfonate compounds, or a mixture thereof. Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraphs 0102 to 0106 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated herein. Among the above compounds, the following b-9, b-16, b-31, and b-33 are preferred. [Chemical Formula 32] Commercially available products include WPAG-336 (manufactured by FUJIFILM Wako Pure Chemical Corporation), WPAG-443 (manufactured by FUJIFILM Wako Pure Chemical Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, the compound represented by the following structural formula can also be cited as a preferred example. [Chemical Formula 33]

Specific examples of organic halogenated compounds include Wakabayashi et al., "Bull Chem. Soc Japan," 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Application Laid-Open No. 48-36281, Japanese Patent Application Laid-Open No. 55-32070, Japanese Patent Application Laid-Open No. 60-239736, Japanese Patent Application Laid-Open No. 61-169835, Japanese Patent Application Laid-Open No. 61-169837, Japanese Patent Application Laid-Open No. 62-58241, Japanese Patent Application Laid-Open No. 62-212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, and M.P. Hutt's "Journal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970) and the like are incorporated into this specification. In particular, preferred examples include trihalomethyl-substituted oxazole compounds: S-triadium compounds. More preferred are s-triadium derivatives in which at least one mono-, di-, or trihalomethyl-substituted methyl group is bonded to the s-triadium ring. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triadium, 2,4,6-tris(dichloromethyl)-s-triadium, 2,4,6-tris(trichloromethyl)-s-triadium, 2-methyl-4,6-bis(trichloromethyl)-s-triadium, 2-n-butyl-4,6-bis(trichloromethyl)-s-triadium, 2 -(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-phenyl-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trisinium, 2-[1-(p-methoxyphenyl)] )-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trithionyl, 2-phenylvinyl-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-isopropoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trithionyl, 2-(4-naphthoxynaphthalene) )-4,6-bis(trichloromethyl)-s-trithionyl, 2-phenylthio-4,6-bis(trichloromethyl)-s-trithionyl, 2-benzylthio-4,6-bis(trichloromethyl)-s-trithionyl, 2,4,6-tris(dibromomethyl)-s-trithionyl, 2,4,6-tris(tribromomethyl)-s-trithionyl, 2-methyl-4,6-bis(tribromomethyl)-s-trithionyl, 2-methoxy-4,6-bis(tribromomethyl)-s-trithionyl, etc.

Specific examples of the organic borate compounds include Japanese Patent Application Laid-Open No. 62-143044, Japanese Patent Application Laid-Open No. 62-150242, Japanese Patent Application Laid-Open No. 9-188685, Japanese Patent Application Laid-Open No. 9-188686, Japanese Patent Application Laid-Open No. 9-188710, Japanese Patent Application Laid-Open No. 2000-131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application Laid-Open No. 2002-116539, and Kunz, Martin "Rad Tech '98. Proceedings April Organic borates described in "Chicago" et al., 19-22, 1998, organic borate salts described in Japanese Patent Application Laid-Open No. 6-157623, Japanese Patent Application Laid-Open No. 6-175564, Japanese Patent Application Laid-Open No. 6-175561, organic boron-zinc complexes or organic boron-oxygenated zirconium complexes described in Japanese Patent Application Laid-Open No. 6-175554, Japanese Patent Application Laid-Open No. 6-175553, organic boron tinctures described in Japanese Patent Application Laid-Open No. 6-175553 Complexes, organoboron phosphonium complexes described in Japanese Patent Application Laid-Open No. 9-188710, organoboron-transfer metal coordination complexes described in Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Application Laid-Open No. 7-128785, Japanese Patent Application Laid-Open No. 7-140589, Japanese Patent Application Laid-Open No. 7-306527, Japanese Patent Application Laid-Open No. 7-292014, etc., the contents of which are incorporated into this specification.

Examples of the disulfide compounds include compounds described in Japanese Patent Application Laid-Open No. 61-166544 and Japanese Patent Application Laid-Open No. 2002-328465, and diazodisulfide compounds.

Examples of the above-mentioned onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. Diazo salts described in al, Polymer, 21,423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Application Laid-Open No. 4-365049, etc., phosphonium salts described in U.S. Patent No. 4,069,055, U.S. Patent No. 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, iodine salts described in Japanese Patent Application Laid-Open No. 2-150848, Japanese Patent Application Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390 , 214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J.V. Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), and onium salts such as arsenic salts and pyridinium salts described in C.S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), are incorporated into this specification.

Examples of onium salts include those represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 34] In formula (RI-I), _Ar11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 2 to 12 carbon atoms, an alkylamide group having 1 to 12 carbon atoms, an arylamide group having 6 to 20 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a sulfursulfate ion, or a sulfate ion. In view of stability, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, a sulfonate ion, and a sulfinate ion are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 1 to 20 carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms in an alkyl group, an alkylamide group or an arylamide group having 1 to 12 carbon atoms in an alkyl group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, such as a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, sulfursulfate ion, or sulfate ion. From the perspectives of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, and carboxylate ion are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group having 6 to 20 carbon atoms, which may have 1 to 6 substituents, or an alkyl group, alkenyl group, or alkynyl group. From the perspectives of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, a monoalkylamino group having 1 to 12 carbon atoms, a dialkylamino group having an alkyl group with 1 to 12 carbon atoms, an alkylamide group or an arylamide group having an alkyl group with 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, such as a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a sulfursulfate ion, or a sulfate ion. In view of stability and reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion is preferred.

As specific examples of preferred photoacid generators, the following can be cited. [Chemical Formula 35] 【Chemical formula 36】 【Chemical formula 37】 【Chemical formula 38】

The photoacid generator is preferably used in an amount of 0.1-20 mass% relative to the total solids content of the first resin composition, more preferably 0.5-18 mass%, even more preferably 0.5-10 mass%, even more preferably 0.5-3 mass%, and even more preferably 0.5-1.2 mass%. The photoacid generator may be used singly or in combination. When using multiple types, the total amount is preferably within the above range. In addition, it is also preferred to use a sensitizer to impart sensitivity to the desired light source.

<Base Generator> The first resin composition of the present invention may contain a base generator. Here, a base generator refers to a compound capable of generating a base through physical or chemical action. Preferred base generators for the first resin composition of the present invention include thermal base generators and photobase generators. In particular, when the first resin composition contains a precursor of a cyclized resin, it is particularly preferred that the first resin composition contain a base generator. By including a thermal base generator in the first resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, thereby improving the mechanical properties and chemical resistance of the composite pattern. For example, the performance of the composite pattern as an interlayer insulating film for a redistribution layer included in a semiconductor package is improved. The base generator can be either ionic or non-ionic. Examples of bases generated from the base generator include diamines and tertiary amines. The base generator of the present invention is not particularly limited, and known base generators can be used. Examples of known base generators include aminoformyl oxime compounds, aminoformylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, aminoimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, pyridinium salts, α-lactone ring derivative compounds, aminoimide compounds, o-xylylenediamine derivative compounds, and acyloxyimide compounds. Specific examples of non-ionic base generators include compounds represented by Formula (B1), Formula (B2), or Formula (B3). [Chemical Formula 39]

In Formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 are each independently an organic group, a halogen atom, or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 cannot simultaneously be hydrogen atoms. Furthermore, ^Rb1 , ^Rb2 , and ^Rb3 do not have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms in a hydrocarbon system. Therefore, this is not limited to the case where the carbon atom to which the bond is formed forms a carbonyl group, that is, when it forms an amide group together with the nitrogen atom.

In formulas (B1) and (B2), at least one of ^Rb1 , ^Rb2 , and ^Rb3 preferably comprises a cyclic structure, and at least two of them more preferably comprise a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, with a monocyclic ring or a condensed ring of two monocyclic rings being preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, with a 6-membered ring being more preferred. The monocyclic ring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), alkenyl groups (preferably having 2-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), aryl groups (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-10 carbon atoms), or aralkyl groups (preferably having 7-25 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). These groups may have substituents within the scope of the present invention. ^Rb1 and ^Rb2 may bond to each other to form a ring. The formed ring is preferably a 4-7 membered nitrogen-containing heterocyclic ring. In particular, ^Rb1 and ^Rb2 are preferably linear, branched, or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), and even more preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms), aralkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), An aralkenyl group (preferably having 8-24 carbon atoms, more preferably 8-20, and even more preferably 8-16 carbon atoms), an alkoxy group (preferably having 1-24 carbon atoms, more preferably 2-18 carbon atoms, and even more preferably 3-12 carbon atoms), an aryloxy group (preferably having 6-22 carbon atoms, more preferably 6-18 carbon atoms, and even more preferably 6-12 carbon atoms), or an aralkyloxy group (preferably having 7-23 carbon atoms, more preferably 7-19 carbon atoms, and even more preferably 7-12 carbon atoms). Among these, cycloalkyl groups (preferably having 3-24 carbon atoms, more preferably 3-18 carbon atoms, and even more preferably 3-12 carbon atoms), aralkenyl groups, and aralkyloxy groups are preferred. ^Rb3 may further have a substituent within the scope of achieving the effects of the present invention.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 40]

In the formula, ^Rb11 and ^Rb12 and ^Rb31 and ^Rb32 have the same meanings as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), and may have a substituent within a range that allows the effects of the present invention to be exerted. Among them, ^Rb13 is preferably an aralkyl group.

^Rb33 and ^Rb34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), preferably an aryl group.

The compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a). [Chemical Formula 41]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atom, alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms), alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms), aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms), aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms), preferably hydrogen atom or methyl group. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 12 carbon atoms), or an aralkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 12 carbon atoms), among which an aryl group is preferred.

【Chemical formula 42】

In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group along the linking chain connecting adjacent oxygen atoms and carbon atoms, and represents a hydrocarbon group having three or more atoms along the linking chain. Furthermore, ^RN1 and ^RN2 each independently represent a monovalent organic group.

In this specification, "linking chain" refers to the chain of atoms on the path connecting two atoms or groups of atoms that connect the two connecting targets at the shortest distance (the smallest number of atoms). For example, in the compound represented by the following formula, L is composed of a phenylene vinyl group, which has a vinyl group as a saturated alkyl group, and the linking chain is composed of 4 carbon atoms. The number of atoms on the linking chain path (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "linking chain length") is 4. [Chemical Formula 43]

The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is even more preferably 4 or greater. From the perspective of rapid progress of the intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, with 4 being the most preferred. Specific examples of preferred compounds as base generators include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020/066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018/038002.

Furthermore, it is also preferred that the base generator comprises a compound represented by the following formula (N1). [Chemical Formula 44]

In formula (N1), R ^N1 and R ^N2 each independently represent a monovalent organic group, R ^C1 represents a hydrogen atom or a protecting group, and L represents a divalent linking group.

L is a divalent linking group, preferably a divalent organic group. The linking group chain length is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The chain length refers to the number of atoms in the atomic arrangement that forms the shortest path between the two carbonyl groups in the formula.

In formula (N1), ^RN1 and ^RN2 each independently represent a monovalent organic group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), preferably a alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms), and specifically, an aliphatic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms) or an aromatic alkyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms) can be mentioned, with the aliphatic alkyl group being preferred. When aliphatic alkyl groups are used as ^RN1 and ^RN2 , the resulting base has a high basicity and is preferred. Furthermore, aliphatic alkyl groups and aromatic alkyl groups may have substituents, and may have oxygen atoms in the aliphatic alkyl chain, in the aromatic ring, or in the substituent. In particular, embodiments in which the aliphatic alkyl group has an oxygen atom in the alkyl chain are exemplified.

Examples of the aliphatic alkyl group constituting ^RN1 and ^RN2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. For example, linear or branched chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, dibutyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl. The carbon number of the cyclic alkyl group is preferably 3 to 12, and more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The carbon number of the group in the combination of a chain alkyl group and a cyclic alkyl group is preferably 4 to 24, more preferably 4 to 18, and even more preferably 4 to 12. Examples of the group in the combination of a chain alkyl group and a cyclic alkyl group include cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, methylcyclohexylmethyl, and ethylcyclohexylethyl. The carbon number of the alkyl group having an oxygen atom in the chain is preferably 2 to 12, more preferably 2 to 6, and even more preferably 2 to 4. The alkyl group containing an oxygen atom in the chain can be chain or cyclic, and can be linear or branched. From the perspective of increasing the boiling point of the base generated by decomposition described later, ^RN1 and ^RN2 are preferably alkyl groups with 5 to 12 carbon atoms. However, in formulations where adhesion to metal layers (e.g., copper) is important, groups containing cyclic alkyl groups and alkyl groups with 1 to 8 carbon atoms are preferred.

^RN1 and ^RN2 may be linked to form a ring structure. When forming a ring structure, an oxygen atom or the like may be present in the ring. The ring structure formed by ^RN1 and ^RN2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferred. As the cyclic structure formed, a 5-membered or 6-membered ring containing the nitrogen atom in formula (N1) is preferred, and examples thereof include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidinyl ring, an imidazolidinyl ring, a pyrazolidinyl ring, a piperidine ring, a piperonyl ring, and a quinolinyl ring. Preferred examples include a pyrroline ring, a pyrrolidinyl ring, a piperidine ring, a piperonyl ring, and a quinolinyl ring.

R ^C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.

As the protecting group, a protecting group that is decomposed by the action of an acid or a base is preferred, and a protecting group that is decomposed by an acid can be preferably exemplified.

Specific examples of protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups containing an oxygen atom in the chain. Examples of chain or cyclic alkyl groups include methyl, ethyl, isopropyl, tertiary butyl, and cyclohexyl groups. Examples of chain alkyl groups containing an oxygen atom in the chain include alkoxyalkyl groups, more specifically methoxymethyl (MOM) and ethoxyethyl (EE). Examples of cyclic alkyl groups containing an oxygen atom in the chain include epoxy, epoxypropyl, cyclobutyl, tetrahydrofuryl, and tetrahydropyranyl (THP).

The divalent linking group constituting L is not particularly limited, but a alkyl group is preferred, and an aliphatic alkyl group is more preferred. The alkyl group may have a substituent and may have atoms other than carbon atoms in the alkyl chain. More specifically, a divalent alkyl linking group that may have an oxygen atom in the chain is preferred, a divalent aliphatic alkyl group that may have an oxygen atom in the chain, a divalent aromatic alkyl group, or a combination of a divalent aliphatic alkyl group that may have an oxygen atom in the chain and a divalent aromatic alkyl group that may have an oxygen atom in the chain is more preferred, and a divalent aliphatic alkyl group that may have an oxygen atom in the chain is even more preferred. These groups preferably do not have an oxygen atom. The carbon number of the divalent alkyl linking group is preferably 1-24, more preferably 2-12, and even more preferably 2-6. The carbon number of the divalent aliphatic alkyl group is preferably 1-12, more preferably 2-6, and even more preferably 2-4. The carbon number of the divalent aromatic alkyl group is preferably 6-22, more preferably 6-18, and even more preferably 6-10. The carbon number of the group comprising a combination of a divalent aliphatic alkyl group and a divalent aromatic alkyl group (e.g., an arylene alkyl group) is preferably 7-22, more preferably 7-18, and even more preferably 7-10.

Specifically, preferred linking groups include linear or branched chain alkylene groups, cyclic alkylene groups, combinations of chain and cyclic alkylene groups, alkylene groups containing an oxygen atom in the chain, linear or branched chain alkenylene groups, cyclic alkenylene groups, arylene groups, and arylene alkylene groups. Preferably, the linear or branched chain alkylene group has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. Preferably, the cyclic alkylene group has 3 to 12 carbon atoms, and even more preferably 3 to 6. The carbon number of the group in the combination of a chain alkylene group and a cyclic alkylene group is preferably 4-24, more preferably 4-12, and even more preferably 4-6. Alkylene groups containing oxygen atoms in the chain may be chain or cyclic, and may be straight or branched. Alkylene groups containing oxygen atoms in the chain preferably have 1-12 carbon atoms, more preferably 1-6, and even more preferably 1-3 carbon atoms.

The number of carbon atoms in a linear or branched alkenylene group is preferably 2-12, more preferably 2-6, and even more preferably 2-3. The number of carbon atoms in a linear or branched alkenylene group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The number of carbon atoms in a cyclic alkenylene group is preferably 3-12, more preferably 3-6. The number of carbon atoms in a cyclic alkenylene group is preferably 1-6, more preferably 1-4, and even more preferably 1-2. The number of carbon atoms in an arylene group is preferably 6-22, more preferably 6-18, and even more preferably 6-10. The carbon number of the arylene and alkylene groups is preferably 7 to 23, more preferably 7 to 19, and even more preferably 7 to 11. Preferred among these are chain alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, chain alkenylene groups, arylene groups, and arylene alkylene groups. More preferred are 1,2-vinyl groups, propanediyl groups (especially 1,3-propanediyl), cyclohexanediyl groups (especially 1,2-cyclohexanediyl), vinylene groups (especially cis-vinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and vinyloxyvinyl groups (especially 1,2-vinyloxy-1,2-vinyl groups).

The following examples can be cited as alkali generators, but the present invention should not be construed as being limitative thereof.

【Chemical formula 45】

The molecular weight of the non-ionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. As a lower limit, it is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Specific examples of preferred compounds as ionic base generators include, for example, the compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.

As specific examples of ammonium salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 46]

As specific examples of imine salts, the following compounds can be cited, but the present invention is not limited thereto. [Chemical Formula 47]

When the first resin composition of the present invention contains a base generator, the content of the base generator is preferably 0.1 to 50 parts by mass per 100 parts by mass of the resin in the first resin composition of the present invention. The lower limit is preferably 0.3 parts by mass or greater, and even more preferably 0.5 parts by mass or greater. The upper limit is preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. The amount may be 5 parts by mass or less, or even 4 parts by mass or less. One or more base generators may be used. When two or more types are used, the total amount is preferably within the above range.

<Solvent> The first resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfones, amides, ureas, and alcohols.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), etc. esters, etc.)), alkyl 2-alkoxypropionates (for example, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

Preferred examples of the ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate acetate, ethyl thiocyanate acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

Preferred examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.

Preferred examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfoxides, for example, dimethyl sulfoxide can be preferably mentioned.

Preferred amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formyl isocyanate, and N-acetyl isocyanate.

Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol, and diacetone alcohol.

Regarding solvents, mixing two or more solvents is preferred from the perspective of improving the coating surface properties.

In the present invention, one solvent selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, propylene glycol methyl ether acetate, levulinone, and dihydrolevulinone, or a mixed solvent consisting of two or more of these is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone or the simultaneous use of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred.

From the perspective of coating properties, the solvent content is preferably such that the total solids concentration of the first resin composition of the present invention is 5 to 80 mass%, more preferably 5 to 75 mass%, even more preferably 10 to 70 mass%, and even more preferably 20 to 70 mass%. The solvent content can be adjusted based on the desired coating thickness and coating method.

The first resin composition of the present invention may contain only one solvent or two or more. When containing two or more solvents, it is preferred that the total amount of the solvents be within the above range.

<Metal Adhesion Improver> The first resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having sulfonamide structures, compounds having thiourea structures, phosphoric acid derivatives, β-ketoester compounds, and amino compounds.

[Silane coupling agent] Examples of silane coupling agents include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Laid-Open No. 2014-191002, the compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, and the compounds described in paragraphs 0064 to 0065 of Japanese Patent Application Laid-Open No. 2014-191252. The compounds described in paragraphs 0060-0061 of the publication, the compounds described in paragraphs 0045-0052 of Japanese Patent Application Publication No. 2014-041264, the compounds described in paragraph 0055 of International Publication No. 2014/097594, and the compounds described in paragraphs 0067-0078 of Japanese Patent Application Publication No. 2018-173573 are incorporated into this specification. Furthermore, as described in paragraphs 0050-0058 of Japanese Patent Application Publication No. 2011-128358, it is also preferred to use two or more different silane coupling agents. Furthermore, the following compounds are also preferred as silane coupling agents. In the following formula, Me represents a methyl group and Et represents an ethyl group.

【Chemical formula 48】

As other silane coupling agents, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediaminetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Oxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding agents] Examples of aluminum-based bonding agents include tris(ethyl acetylacetate)aluminum, tris(acetylacetone)aluminum, and diisopropyl acetylacetate aluminum.

Furthermore, as other metal adhesion improvers, the compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Laid-Open No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Laid-Open No. 2013-072935 can also be used, and these contents are incorporated into this specification.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass per 100 parts by mass of resin A. By setting the content above the lower limit, the adhesion between the pattern and the metal layer is improved. By setting the content below the upper limit, the heat resistance and mechanical properties of the pattern are improved. The metal adhesion improver may be used alone or in combination of two or more. When using two or more, the total content is preferably within the above range.

<Migration Inhibitor> The first resin composition of the present invention preferably further comprises a migration inhibitor. The inclusion of a migration inhibitor effectively inhibits the migration of metal ions from the metal layer (metal wiring) into the film.

Migration inhibitors are not particularly limited, and examples thereof include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, phenoxyethanol ring, 2H-pyranyl ring, 6H-pyranyl ring, triazole ring), compounds having thiourea and thiohydrin groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole; and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions can be used.

Other migration inhibitors that can be used include the rust preventive described in paragraph 0094 of Japanese Patent Application Laid-Open No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Laid-Open No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2011-059656, the compounds described in paragraphs 0114, 0116, and 0118 of Japanese Patent Application Laid-Open No. 2012-194520, and the compound described in paragraph 0166 of International Publication No. 2015/199219. These contents are incorporated into this specification.

Specific examples of migration inhibitors include the following compounds.

【Chemical formula 49】

When the first resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, relative to the total solid content of the first resin composition of the present invention.

The number of migration inhibitors may be one or more. When two or more migration inhibitors are used, the total amount thereof is preferably within the above range.

<Polymerization Inhibitor> The first resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, and metal compounds.

As specific compounds of the polymerization inhibitor, preferably used are p-hydroquinone, o-hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso Phenylhydroxylamine first onium salt, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N- Sulfurpropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 2,2 ,6,6-tetramethylpiperidinyl 1-oxyl free radical, phenathiophene, phenoxathiophene, 1,1-diphenyl-2-picrylhydrazyl, dibutyl dithiocarbonate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide), etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used, and the contents are incorporated into this specification.

When the first resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20 mass %, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %, relative to the total solid content of the first resin composition of the present invention.

The polymerization inhibitor may be used alone or in combination. When two or more polymerization inhibitors are used, the total amount thereof is preferably within the above range.

<Acid Scavenger> The performance of the first resin composition of the present invention degrades over time from exposure to heating, so it is preferable to contain an acid scavenger. Here, an acid scavenger refers to a compound capable of scavenging generated acid by its presence in the system. Compounds with low acidity and high pKa are preferred. Preferred acid scavengers include compounds having an amine group, with primary amines, diamines, tertiary amines, ammonium salts, and tertiary amides being preferred. Primary amines, diamines, tertiary amines, and ammonium salts are preferred, with diamines, tertiary amines, and ammonium salts being even more preferred. Preferred examples of acid scavengers include compounds having an imidazole structure, a diazabicyclic structure, an onium structure, a tertiary alkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having hydroxyl and/or ether bonds, and aniline derivatives having hydroxyl and/or ether bonds. When having an onium structure, the acid scavenger is preferably a salt selected from cations selected from ammonium, diazo, iodonium, coronium, phosphonium, pyridinium, and the like, and an anion of an acid having a lower acidity than the acid generated by the acid generator.

Examples of acid scavengers having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4,0]undec-7-ene. Examples of acid scavengers having an onium structure include tetrabutylamine hydroxide, triarylcosium hydroxide, benzylmethylcosium hydroxide, and cosium hydroxides having a 2-oxoalkyl group, specifically triphenylcosium hydroxide, tri(tertiarybutylphenyl)cosium hydroxide, bis(tertiarybutylphenyl)iodonium hydroxide, benzylmethylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide. Examples of acid scavengers having a tertiary alkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine. Examples of acid scavengers with an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Examples of acid scavengers with a pyridine structure include pyridine and 4-methylpyridine. Examples of alkylamine derivatives with hydroxyl and/or ether bonds include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of aniline derivatives with hydroxyl and/or ether bonds include N,N-bis(hydroxyethyl)aniline.

Specific examples of preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabiscycloundecene), DABCO (1,4-diazabiscyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N -Methyldicyclohexylamine, trioctylamine, N-ethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetrabutyl-1,6-hexanediamine, quinone triamine, diaminocyclohexyl, bis(2-methoxyethyl)amine, piperidine, methylpiperidine, piperidine, tropane, N-phenylbenzylamine, 1,2-diphenylamineethane, 2-aminoethanol, toluidine, aminophenol, hexylaniline, phenylenediamine, phenylethylamine, dibenzylamine, pyrrole, N-methylpyrrole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, amino-amino-piperidin, aminoalkyl-amino-piperidin, etc.

These acid scavengers may be used singly or in combination. The composition of the present invention may or may not contain an acid scavenger. However, when present, the acid scavenger content is generally 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the total solids content of the composition.

The preferred ratio of acid generator to acid scavenger is 2.5 to 300 (molar ratio). Specifically, a molar ratio of 2.5 or higher is preferred for sensitivity and resolution, while a ratio of 300 or lower is preferred to prevent the problem of coarsening the relief pattern over time during post-exposure heat treatment, which can lead to a decrease in resolution. The molar ratio of acid generator to acid scavenger is more preferably 5.0 to 200, and even more preferably 7.0 to 150.

<Other Additives> The first resin composition of the present invention may be blended with various additives as needed, within the scope of achieving the effects of the present invention. These additives include surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, UV absorbers, organic titanium compounds, antioxidants, anti-agglomeration agents, phenolic compounds, other polymer compounds, plasticizers, and other additives (e.g., defoaming agents, flame retardants, etc.). By appropriately incorporating these ingredients, the film's physical properties can be adjusted. For information on these ingredients, see, for example, paragraphs 0183 and thereafter of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013/0034812) and paragraphs 0101-0104 and 0107-0109 of Japanese Patent Application Publication No. 2008-250074, the contents of which are incorporated herein. When these additives are blended, their combined blending amount is preferably 3% by mass or less of the solid content of the first resin composition of the present invention.

[Surfactant] A variety of surfactants can be used, including fluorine-based surfactants, silicone-based surfactants, hydrocarbon-based surfactants, and others. Surfactants can be nonionic, cationic, or anionic.

By including a surfactant in the first resin composition of the present invention, the liquid properties (particularly fluidity) of the resulting coating liquid can be further enhanced, further improving coating thickness uniformity and liquid conservation. Specifically, when a film is formed using a composition containing a surfactant, the interfacial tension between the coated surface and the coating liquid is reduced, thereby improving wettability and coating properties. Consequently, a film with uniform thickness and minimal thickness variations can be formed.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE F482, MEGAFACE F554, MEGAFACE F780, RS-72-K (all manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171, Novec FC4430, Novec FC4432 (all manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (the above is ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA Solutions Inc.), etc. Fluorine-based surfactants may also include compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and in paragraphs 0117 to 0132 of JP-A-2011-132503, the contents of which are incorporated herein. Block polymers may also be used as fluorine-based surfactants. Specific examples include compounds described in JP-A-2011-89090, the contents of which are incorporated herein. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds (comprising repeating units derived from a (meth)acrylate compound having fluorine atoms and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkoxy groups (preferably vinyloxy or propoxy)). The following compounds can also be exemplified as fluorine-based surfactants used in the present invention. [Chemical Formula 50]

The weight-average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. Regarding fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups in the side chains can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, which are incorporated herein. Commercially available products include MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content of the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in achieving uniform thickness of the coating film and saving liquid, and also have good solubility in the composition.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon surfactants include PIONIN A-76, NEWKALGEN FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by TAKEMOTO OIL & FAT CO., LTD.).

Examples of non-ionic surfactants include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid esters. Commercially available products include PLURONIC (registered trademark) L10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, and NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD.), OLFIN E1010, and Surfynol 104, 400, and 440 (manufactured by Nissin Chemical Industry Co., Ltd.).

Specific examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 77, No. 90, and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

A single surfactant may be used, or a combination of two or more may be used. The surfactant content is preferably 0.001-2.0% by mass, and more preferably 0.005-1.0% by mass, relative to the total solids content of the composition.

[Higher Fatty Acid Derivatives] To prevent polymerization hindrance caused by oxygen, a higher fatty acid derivative such as behenic acid or behenamide may be added to the first resin composition of the present invention so that it is localized on the surface of the first resin composition during the drying process after coating.

Furthermore, as higher fatty acid derivatives, compounds described in paragraph 0155 of International Publication No. 2015/199219 can also be used, and the contents thereof are incorporated into this specification.

When the first resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solids content of the first resin composition of the present invention. The higher fatty acid derivative may be a single type or two or more types. When two or more types are present, the total content of the higher fatty acid derivative is preferably within the above range.

[Thermal Polymerization Initiator] The first resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates free radicals using thermal energy, thereby initiating or accelerating the polymerization reaction of a polymerizable compound. Adding a thermal radical polymerization initiator can also advance the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance. Furthermore, the aforementioned photopolymerization initiator may also have the ability to initiate polymerization by heat and may be added as a thermal polymerization initiator.

Specific examples of thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Laid-Open No. 2008-063554, the contents of which are incorporated herein.

When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass%, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%, relative to the total solids content of the first resin composition of the present invention. The thermal polymerization initiator may be present in a single species or in two or more species. When two or more thermal polymerization initiators are present, the total amount is preferably within the above range.

[Ultraviolet Absorber] The composition of the present invention may contain a UV absorber. Examples of UV absorbers include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and tris(III)-based UV absorbers. Examples of salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based UV absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. -5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of trisinium-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium. (2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and other mono(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, 2 ,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-trisinium, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium and other bis(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4- Tris(hydroxyphenyl) tris(hydroxyphenyl) compounds such as 2-(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(hydroxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(hydroxyphenyl)-2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(hydroxyphenyl)-2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(hydroxy ...

In the present invention, each of the aforementioned UV absorbers may be used alone or in combination of two or more. The composition of the present invention may or may not contain a UV absorber. However, when included, the UV absorber content is preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.1% by mass, relative to the total solids content of the composition of the present invention.

[Organic Titanium Compound] The first resin composition of this embodiment may contain an organic titanium compound. By containing an organic titanium compound, the first resin composition can form a resin layer with excellent chemical resistance even when curing at low temperatures.

Examples of usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown below in I) to VII). I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are particularly preferred, as they provide excellent storage stability of the first resin composition and yield a good cured pattern. Specific examples include titanium bis(triethanolamine)diisopropoxy, titanium di(n-butoxy)bis(2,4-pentanedioate), titanium diisopropoxybis(2,4-pentanedioate), titanium diisopropoxybis(tetramethylpimelate), and titanium diisopropoxybis(ethyl acetylacetate). II) Tetraalkoxytitanium compounds: for example, tetrakis(n-butoxy)titanium, tetrakis(2-ethylhexyloxy)titanium, tetrakis(isobutoxy)titanium, tetrakis(isopropoxy)titanium, tetrakis(methoxy)titanium, tetrakis(methoxypropoxy)titanium, tetrakis(n-nonoxy)titanium, tetrakis(n-propoxy)titanium, tetrakis(stearyloxy)titanium, tetrakis[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanium cyclopentadiene compounds: Examples include pentamethylcyclopentadienyltrimethoxytitanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium. IV) Titanium monoalkoxy compounds: Examples include tris(dioctyl phosphate)isopropoxytitanium and tris(dodecylbenzenesulfonate)isopropoxytitanium. V) Titanium oxide compounds: Examples include bis(glutarate)oxide, bis(tetramethylpimelate)oxide, and titanium phthalocyanine oxide. VI) Titanium tetraacetylacetonate compounds: Examples include titanium tetraacetylacetonate. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among these, the preferred organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the perspective of exhibiting better chemical resistance. In particular, titanium diisopropoxybis(ethyl acetylacetate), tetra(n-butoxy)titanium, and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When incorporating an organic titanium compound, the incorporation amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of resin A. A blending amount of 0.05 parts by mass or greater effectively exhibits excellent heat resistance and chemical resistance in the resulting cured pattern. On the other hand, a blending amount of 10 parts by mass or less improves the storage stability of the composition.

[Antioxidant] The composition of the present invention may contain an antioxidant. Including an antioxidant as an additive can improve the tensile properties of the cured film and its adhesion to metal materials. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (at the adjacent position) are preferred. Preferred substituents include substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms. Furthermore, compounds having a phenolic group and a phosphite group in the same molecule are also preferred antioxidants. Furthermore, phosphorus-based antioxidants can also be preferably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tetriblyldibenzo[d,f][1,3,2]dioxaphosphinylcycloheptadien-2-yl)oxy]ethyl]amine, and bis(2,4-di-tetriblyl-6-methylphenyl)ethyl phosphite. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used as antioxidants, and this disclosure is incorporated herein. Furthermore, the composition of the present invention may contain a potential antioxidant, if desired. Potential antioxidants include compounds in which the site where the antioxidant is activated is protected by a protecting group. These protecting groups are removed by heating at 100-250°C or at 80-200°C in the presence of an acid/base catalyst, allowing the compound to activate its antioxidant activity. Examples of potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and JP-A-2017-008219, the contents of which are incorporated herein. Commercially available potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). As examples of preferred antioxidants, there are 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and the compound represented by formula (3).

【Chemical formula 51】

In general formula (3), ^R₅ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R₆ represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ^R₇ represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

The compound represented by formula (3) inhibits the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it inhibits metal oxidation by providing a rust-proofing effect on metal materials.

To enable simultaneous action on both the resin and the metal material, k is preferably an integer of 2 to 4. Examples of R ⁷ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof. The group may further have a substituent. Among these, alkyl ether groups and -NH- are preferred from the perspectives of solubility in developer solutions and metal adhesion. From the perspectives of interaction with the resin and metal adhesion through metal complex formation, -NH- is more preferred.

The compounds represented by the general formula (3) include the following compounds as examples, but are not limited to the following structures.

【Chemical formula 52】

【Chemical formula 53】

【Chemical formula 54】

【Chemical formula 55】

The antioxidant addition amount is preferably 0.1 to 10 parts by weight relative to the resin, and more preferably 0.5 to 5 parts by weight. An addition amount of 0.1 parts by weight or greater facilitates achieving tensile properties and improved adhesion to metal materials, even in high-temperature and high-humidity environments. Furthermore, an addition amount of 10 parts by weight or less enhances the sensitivity of the first resin composition, for example, through interaction with the photosensitizer. A single antioxidant may be used, or two or more may be used. When two or more antioxidants are used, their combined amount is preferably within the above range.

[Anti-aggregating agent] The first resin composition of this embodiment may contain an anti-aggregating agent as needed. Examples of such anti-aggregating agents include sodium polyacrylate.

In the present invention, a single anti-aggregating agent may be used alone, or two or more may be used in combination. The composition of the present invention may or may not contain an anti-aggregating agent. However, when included, the anti-aggregating agent content is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass, relative to the total solids content of the composition of the present invention.

[Phenolic Compound] The first resin composition of this embodiment may contain a phenolic compound as needed. Examples of phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, and BisRS-26X (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and BIP-PC, BIR-PC, BIR-PTBP, and BIR-BIPC-F (all trade names, manufactured by Asahi Yukizai Corporation).

In the present invention, a phenolic compound may be used alone or in combination of two or more. The composition of the present invention may or may not contain a phenolic compound. When the composition of the present invention contains a phenolic compound, the content of the phenolic compound is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solids content of the composition of the present invention.

[Other Polymer Compounds] Examples of other polymer compounds include silicone resins, (meth)acrylic acid copolymers, novolac resins, cresol novolac resins, polyhydroxystyrene resins, and copolymers thereof. Other polymer compounds may be modified products having introduced crosslinking groups such as hydroxymethyl, alkoxymethyl, and epoxy groups.

In the present invention, other polymer compounds may be used singly or in combination. The composition of the present invention may or may not contain other polymer compounds. However, when included, the content of the other polymer compounds is preferably 0.01% by mass to 30% by mass, and more preferably 0.02% by mass to 20% by mass, relative to the total solids content of the composition of the present invention.

<Properties of the First Resin Composition> The viscosity of the first resin composition of the present invention can be adjusted according to the solids concentration of the first resin composition. From the perspective of coating film thickness, the viscosity is preferably 1,000 ^mm² /s to 12,000 ^mm² /s, more preferably 2,000 ^mm² /s to 10,000 ^mm² /s, and even more preferably 2,500 ^mm² /s to 8,000 ^mm² /s. Within this range, a highly uniform coating film is easily obtained. For example, if the coating speed is 1,000 mm ² /s or more, it is difficult to coat the film with the required thickness for the interlayer insulation film for the redistribution layer. If the coating speed is 12,000 mm ² /s or less, a coating with excellent coating surface appearance can be obtained.

<Restrictions on Substances Contained in the First Resin Composition> The first resin composition of the present invention preferably has a moisture content of less than 2.0 mass%, more preferably less than 1.5 mass%, and even more preferably less than 1.0 mass%. If the moisture content is less than 2.0%, the storage stability of the first resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

From the perspective of insulation, the metal content of the first resin composition of the present invention is preferably less than 5 parts per million (ppm), more preferably less than 1 ppm, and even more preferably less than 0.5 ppm. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, excluding metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total content of these metals is preferably within the above range.

Furthermore, as a method for reducing the amount of metal impurities accidentally contained in the first resin composition of the present invention, there can be cited a method comprising selecting a raw material having a low metal content as the raw material constituting the first resin composition of the present invention, filtering the raw material constituting the first resin composition of the present invention through a filter, lining the interior of an apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions that minimize contamination.

Considering applications as semiconductor materials, the first resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the perspective of wiring corrosion resistance. In particular, the halogen atom content in the form of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of halogen atoms include chlorine and bromine atoms. It is preferred that the total content of chlorine and bromine atoms, or the total content of chlorine and bromine ions, is within the above-mentioned ranges. Preferred methods for adjusting the halogen atom content include ion exchange treatment.

Conventional containers can be used as containers for the first resin composition of the present invention. Furthermore, to prevent contaminants from entering the raw materials or the first resin composition of the present invention, it is also preferable to use a multilayer bottle having an inner wall composed of six layers of six different resins, or a bottle having a seven-layer structure composed of six different resins. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

<Preparation of the First Resin Composition> The first resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by conventionally known methods. Mixing can be performed using a stirring blade, a ball mill, or a rotary tumbler. The temperature during mixing is preferably 10-30°C, more preferably 15-25°C.

Furthermore, for the purpose of removing foreign matter such as dust or particles from the first resin composition of the present invention, it is preferred to perform filtration using a filter. Regarding the pore size of the filter, for example, 5 μm or less can be cited, 1 μm or less is preferred, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, HDPE (high-density polyethylene) is more preferred. The filter can be used after being pre-cleaned with an organic solvent. In the filtering step of the filter, a plurality of filters can be used in series or in parallel. When using a plurality of filters, filters with different pore sizes or materials can be used in combination. For example, a connection configuration could be: a 1μm pore size HDPE filter as the first stage, and a 0.2μm pore size HDPE filter as the second stage, connected in series. Furthermore, various materials can be filtered multiple times. Multiple filtration cycles can be used as cyclic filtration. Furthermore, filtration can be performed after applying pressure. When applying pressure, for example, the applied pressure can be 0.01 MPa to 1.0 MPa, preferably 0.03 MPa to 0.9 MPa, more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal using an adsorbent can also be performed. Filtering and impurity removal using an adsorbent can also be combined. Known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the first resin composition filled in the bottle can be further degassed by placing it under reduced pressure.

(Second Resin Composition) The second resin composition of the present invention is used to form the second photosensitive film in the composite pattern manufacturing method of the present invention.

The second resin composition preferably includes resin B as the resin. More preferably, resin B includes at least one resin selected from the group consisting of polyimide precursors, polyimide precursors containing a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors containing a polybenzoxazole structure, polyamidoimide precursors, polyamidoimide precursors containing a polyamidoimide structure, and epoxy resins. The polyimide precursor, the polyimide precursor containing a polyimide structure, the polybenzoxazole precursor, the polybenzoxazole precursor containing a polybenzoxazole structure, the polyamide imide precursor, and the polyamide imide precursor containing a polyamide imide structure in the resin B are respectively The polyimide precursor, polyimide precursor containing a polyimide structure, polybenzoxazole precursor, polybenzoxazole precursor containing a polybenzoxazole structure, polyamidoimide precursor, and polyamidoimide precursor containing a polyamidoimide structure are the same, and the preferred embodiments are also the same.

The epoxy resin in the resin B is not particularly limited, and examples thereof include novolac epoxy resins, bisphenol epoxy resins, glycidylamine epoxy resins, glycidyl ether epoxy resins, trisphenol methane epoxy resins, trisphenol propane epoxy resins, alkyl-modified trisphenol methane epoxy resins, epoxy resins containing tris(II) nuclei, and dicyclopentadiene epoxy resins. Arane-type epoxy resins such as pentadiene-modified phenol-type epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, phenol-aralkyl-type epoxy resins having at least either a phenylene skeleton or a biphenylene skeleton, and naphthol-aralkyl-type epoxy resins having at least either a phenylene skeleton or a biphenylene skeleton, and aliphatic epoxy resins. When the second resin composition includes an epoxy resin, the epoxy compounds listed above for the polymerizable compounds can be used.

The details of the components contained in the second resin composition of the present invention and the physical properties of the second resin composition are the same as those of the first resin composition, and the preferred embodiments are also the same.

In the method for producing a composite pattern of the present invention, the first resin composition and the second resin composition are preferably resin compositions containing repeating units represented by the same structural formula. That is, resins A and B preferably contain repeating units represented by the same structural formula, but may also contain two or more repeating units represented by the same structural formula. When resins A and B contain repeating units represented by the same structural formula, the preferred content of repeating units represented by the same structural formula is, for example, 30 mol% or more of the total repeating units, preferably 50 mol% or more. Furthermore, when containing two or more repeating units represented by the same structural formula, the total content thereof may be within the above range. The upper limit is not particularly limited, but may be, for example, 100 mol% or less. This aspect is believed to reduce the impact of shrinkage during curing, making it easier to form a composite pattern with a high aspect ratio. Furthermore, a composite pattern with excellent adhesion between the first and second patterns may be obtained. [Examples]

The present invention is further described below with reference to the following examples. The materials, amounts, ratios, processing details, and steps described in the following examples are subject to modification without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are by mass.

<Synthesis Example 1: Synthesis of Polymer P-1> 7.76 g (25 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 6.23 g (25 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride were placed in a reaction vessel, followed by 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the reaction heat subsided, the mixture was cooled to room temperature and then allowed to stand for 16 hours. Next, under ice cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexanecarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, 3 ml of ethanol was added and stirred for 1 hour. Subsequently, 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, resulting in a reaction solution. This solution was added to 3 liters of ethanol, yielding a precipitate containing a crude polymer. The precipitate containing the resulting crude polymer was filtered and dissolved in 200 ml of tetrahydrofuran to obtain a crude polymer solution. The crude polymer solution was added dropwise to 3 liters of water to obtain a precipitate. The precipitate was filtered and then vacuum-dried to obtain a powdered polymer P-1. The weight-average molecular weight (Mw) of the polymer was measured and found to be 23,000. Polymer P-1 is a resin having the following structure. The subscripts in parentheses represent the molar ratio of each repeating unit. [Chemical Formula 56]

<Synthesis Example 2: Synthesis of Polymer P-2> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ and converted to a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 5. Polymer P-2 was obtained in the same manner as in Synthesis Example 5. The weight-average molecular weight of polymer P-2 was 29,000. Polymer P-2 is a resin having the following structure: [Chemical Formula 57]

<Synthesis Example 3: Synthesis of Polymer P-3> 15.5 g (50 mmol) of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a reaction vessel, followed by 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexanecarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, while stirring, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes. After stirring at room temperature for 2 hours, 3 ml of ethanol was added and stirred for 1 hour. Subsequently, 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration, yielding a reaction solution. The resulting reaction solution was added to 3 liters of ethanol, yielding a precipitate containing a crude polymer. The resulting precipitate containing the crude polymer was filtered and dissolved in 200 ml of tetrahydrofuran to yield a crude polymer solution. The resulting crude polymer solution was added dropwise to 3 liters of water to yield a precipitate. The resulting precipitate was filtered and vacuum dried to obtain a powdered polymer, P-3. The weight-average molecular weight (Mw) of the polymer P-3 was determined to be 27,000. Polymer P-3 is a resin having the following structure: [Chemical Formula 58]

<Synthesis Example 4: Synthesis of Polymer P-4> 14.7 g (50 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was placed in a reaction vessel, followed by 13.4 g of 2-hydroxyethyl methacrylate (HEMA) and 100 ml of γ-butyrolactone. While stirring at room temperature, 7.91 g of pyridine was added to obtain a reaction mixture. After the exotherm due to the reaction subsided, the mixture was cooled to room temperature and allowed to stand for 16 hours. Next, under ice cooling, a solution of 20.6 g (99.9 mmol) of dicyclohexanecarbodiimide (DCC) dissolved in 30 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 9.3 g (46 mmol) of 4,4'-diaminodiphenyl ether (DADPE) in 350 ml of γ-butyrolactone was added over 60 minutes while stirring. Purification and drying were then carried out using the same methods as in Synthesis Example 1 to obtain polymer P-4. The weight-average molecular weight (Mw) of this polymer was measured to be 28,000. Polymer P-4 is a resin having the following structure: [Chemical Formula 59]

<Synthesis Example 5: Synthesis of Polymer P-5> 20.0 g (64.5 mmol) of 4,4'-oxyphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a reaction mixture containing the diester of 4,4'-oxyphthalic anhydride and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to -5°C, and 16.12 g (135.5 mmol) of _SOCl₂ was added over 2 hours while maintaining the temperature at -5±2°C. Next, a solution of 11.32 g (60.0 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was adjusted to a temperature range of -5 to 0°C and added dropwise to the reaction mixture over 2 hours. The reaction mixture was allowed to react at 0°C for 1 hour, after which 70 g of ethanol was added and stirred at room temperature for 1 hour. The reaction mixture was then added to 5 liters of water, and the polyimide precursor was precipitated. The mixture was then centrifuged at 5,000 rpm for 15 minutes. The precipitate was filtered, placed in 4 liters of water, stirred again for 30 minutes, and then filtered again. The resulting precipitate was then dried at 45°C under reduced pressure for two days to obtain polymer P-5. The weight average molecular weight of polymer P-5 was 31,000. Polymer P-5 is a resin having the following structure: [Chemical Formula 60]

<Synthesis Example 6: Synthesis of Polymer P-6> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate. The resulting diester was then chlorinated with _SOCl₂ . The 4,4'-diaminodiphenyl ether was dissolved in N-methylpyrrolidone using the same method as in Synthesis Example 5, but with the amount reduced by 2%. The reaction was repeated to convert the 4,4'-diaminodiphenyl ether into a polyimide precursor. Polymer P-6 was obtained using the same method as in Synthesis Example 5. The weight-average molecular weight of polymer P-6 was 18,000. [Chemical Formula 61]

<Synthesis Example 7: Synthesis of Polymer P-7> To a reaction vessel containing 60 g of N-methylpyrrolidone, 13.9 g (38 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added and stirred to dissolve. Next, 10.7 g (40 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes at a temperature between 0 and 5°C, followed by stirring for 60 minutes. The reaction solution was then poured into 3 liters of water to obtain a precipitate. The precipitate was washed with pure water and dried to obtain Polymer P-7 (polybenzoxazole precursor). The weight-average molecular weight of Polymer P-7 was 32,000.

<Synthesis Example 8: Synthesis of Polymer P-8> Under a dry nitrogen stream, 100 g of N-methylpyrrolidone, 32.96 g (90 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2.18 g (20 mmol) of m-aminophenol were added. After stirring at room temperature to dissolve, 20.04 g (75 mmol) of dodecanedioic acid dichloride was added dropwise over 10 minutes while maintaining the reaction solution temperature between -10 and 0°C. Then, 7.38 g (25 mmol) of 4,4'-diphenylether dicarboxylic acid chloride was added. Stirring was continued at room temperature for 3 hours. The reaction solution was poured into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and then dried in a 50°C ventilation dryer for three days to obtain a powder of a polybenzoxazole precursor (polymer P-8). The weight-average molecular weight of polymer P-8 was 31,000.

<Synthesis Example 9: Synthesis of Polymer P-9> Under a dry nitrogen stream, 88.64 g (180 mmol) of a dicarboxylic acid diester composed of 4,4'-dicarboxydiphenyl ether and 1-hydroxybenzotriazole, 65.93 g (180 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 12.00 g (20 mmol) of ED-600 (trade name, manufactured by Huntsman International LLC.), and 800 g of NMP were reacted at 25°C for 30 minutes. The mixture was then heated in an oil bath and allowed to react at 80°C for 8 hours. Subsequently, 12.31 g (75 mmol) of 5-norbornene-2,3-dicarboxylic anhydride was added as a capping agent. The mixture was stirred at 80°C for a further 3 hours before the reaction was terminated. After the reaction, the solution was cooled to room temperature, the reaction mixture was filtered, and poured into 2 L of a 3/1 (volume ratio) mixture of water and isopropyl alcohol to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain polymer P-9 (polybenzoxazole precursor). The weight-average molecular weight of polymer P-9 was 28,000.

<Examples and Comparative Examples> The components listed in the following table were mixed to obtain each composition. Specifically, the contents of the components listed in the table were set to the amounts listed in the "parts by mass" column. The resulting compositions were pressure-filtered through a polytetrafluoroethylene filter with a pore size of 0.2 μm. In the table, "-" indicates that the composition does not contain that component.

【Table 1】 Component 1 Component 2 Component 3 Composition 4 Composition 5 Component 6 Composition 7 Composition 8 Composition 9 Composition 10 Composition 11 Composition 12 Resin P-1 35 - - - - - - - - - - - P-2 - - 33.42 - - - - - - - - - P-3 - - - 33.66 - - - - - - - - P-4 - 35 - - - - - - - - - - P-5 - - - - 36.79 - - - - - - - P-6 - - - - - 36.79 36.79 36.79 - - - - P-7 - - - - - - - - - - 35.55 - P-8 - - - - - - - - 32.86 - - P-9 - - - - - - - - - 32.86 - - P-10 - - - - - - - - - - - 9 P-11 - - - - - - - - - - - 13 P-12 - - - - - - - - - - - 15.5 polymerizable compounds B-1 4 4 - - - - - - - - - - B-2 - 1.11 5.01 - 0.53 - - - - - - - B-3 - - - 6.73 - - - - 5.24 - - B-4 - - - 3.29 - - - - - 3.29 - - B-5 - - - 1.64 - - - - - 1.64 - - B-6 - - 6.69 - 5 5.53 5 5 - 6.57 - - B-7 - - - - - - - - 1 - 7.1 - B-8 - - - - - - 0.53 - - - - - B-9 - - - - - - - 0.53 - - - - B-10 - - - - - - - - - - - 10.5 Polymerization initiator C-1 - 1.6 - 0.17 - - - - - - - - C-2 - - 0.17 - - - - - - 1.31 - - C-3 - - - - 1.29 1.29 1.29 1.29 - - - - C-4 1.31 - - - - - - - - - - - C-5 - - 1.34 - - - - - - - - - C-6 - - - - - - - - 6.57 - 3.56 - C-7 1.4 - - - - - - - - - - - C-8 - - - - - - - - - - - 1.5 Metal adhesion improver D-1 - - - 1.68 - - - - 1.58 1.58 - 0.3 D-2 - - 1 - - - - - - - - - D-3 - - - - 0.73 0.73 0.73 0.73 - - - - D-4 0.7 0.7 - - - - - - - - - - migration inhibitors E-1 0.01 0.01 0.33 0.33 0.12 0.12 0.12 0.12 0.07 0.07 0.36 - polymerization inhibitors F-1 0.1 0.1 - 0.1 0.1 0.1 0.1 0.1 - 0.1 - - F-2 - - 0.1 - - - - - - - - - surfactants G-1 - - - - - - - - 0.1 0.1 0.33 0.2 Alkali generators H-1 - - - - 1.03 1.03 1.03 1.03 - - - - additives I-1 - - 0.14 - - - - - - - - - I-2 2.4 2.4 - - - - - - - - - - I-3 1 1 - - - - - - - - - - solvent J-1 - - - 47.5 43.53 43.53 43.53 43.53 52.58 52.48 53.1 50 J-2 - - - - 10.88 10.88 10.88 10.88 - - - - J-3 11.5 11.5 - - - - - - - - - - J-4 42.58 42.58 51.8 4.9 - - - - - - - -

The details of each ingredient listed in the table are as follows.

[Resin] P-1 to P-9: P-1 to P-9 synthesized above P-10: Bisphenol A epoxy resin (LX-01, manufactured by Daiso Industries Co., Ltd.) P-11: Aliphatic epoxy resin (CEL2021, manufactured by Daicel Corporation) P-12: Multifunctional epoxy resin (VG-3101L, manufactured by Printec Corporation)

[Polymerizable compounds] ・B-1: Polyethylene glycol methacrylate G4 (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・B-2: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・B-3: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD.) ・B-4: TML-BPA (manufactured by Honshu Chemical Industry Co., Ltd.) ・B-5: CELLOXIDE 2021P (manufactured by Daicel Corporation) ・B-6: Tetraethylene glycol dimethacrylate ・B-7: Compound with the following structure ・B-8: Trihydroxymethylpropane triacrylate (CAS: 15625-89-5) ・B-9: Dipentatriol hexaacrylate ・B-10: PR-53365 (manufactured by Sumitomo Bakelite Co., Ltd.) 【Chemical formula 62】

[Polymerization Initiator] C-1: Irgacure OXE-01 (manufactured by BASF) C-2: Irgacure OXE-02 (manufactured by BASF) C-3: Irgacure 784 (manufactured by BASF) C-4: CPI-210S (manufactured by San-Apro Ltd.) C-5: Lambson G-1820 C-6: A compound obtained by diazonaphthoquinoneizing the hydroxyl group of TrisP-PA (α,α,α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene) with 1,2-naphthoquinone-2-diazolidine-4-sulfonyl chloride C-7: 1-Phenyl-2-[(benzoyloxy)imino]-1-propanone C-8: Irgacure 290 (made by BASF)

[Metal Adhesion Improver] D-1: KBM-403 (Shin-Etsu Chemical Co., Ltd.) D-2: γ-Ureidopropyltriethylsilane D-3: N-[3-(Triethoxysilyl)propyl]butenylamine D-4: N-(3-Triethoxysilyl)propyl-2-methylaminobenzoic acid

[Migration Inhibitor] ・E-1: 5-Aminotetrazole

[Polymerization Inhibitor] F-1: 2MeHQ (methoxyhydroquinone) F-2: TAOBN (1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-N,N-dioxide)

[Surfactant] ・G-1: MEGAFACE F444 (manufactured by DIC Corporation)

[Thermoalkali Generator] ・H-1: 1-[4-(2-hydroxyethyl)-1-piperidinyl]-3-(2-hydroxyphenyl)-1-propanone

[Additives] ・I-1: Compound with the following structure ・I-2: N-phenyldiethanolamine ・I-3: Compound with the following structure [Chemical Formula 63]

[Solvent] ・J-1: GBL (γ-butyrolactone) ・J-2: DMSO (dimethyl sulfoxide) ・J-3: EL (ethyl lactate) ・J-4: NMP (N-methyl-2-pyrrolidone)

(Evaluation) <Fabrication of Composite Patterns> In each example, a first photosensitive layer (first photosensitive film) with a uniform thickness of 20 μm was formed on the silicon wafer by spin coating the first composition listed in the table. The film was dried on a hot plate at 100°C for 5 minutes. This first photosensitive layer was then exposed to UV light at 400 mJ/ ^cm² through a photomask having a groove pattern with a 1 μm scale (with each pitch being 8 times the groove size) ranging from 5 μm to 25 μm (first exposure step). The exposed first photosensitive layer was developed with cyclopentanone and rinsed with PGMEA to form the first pattern (first development step). After development, the second composition listed in the table was applied by spin coating onto the first pattern and the areas where the first pattern had been removed in the first development step. The film was dried on a hot plate at 100°C for 5 minutes to form a second photosensitive layer (second photosensitive film) with a uniform thickness of 20 μm. The second photosensitive layer was then irradiated with UV light at 400 mJ/ ^cm² through the photomask, overlapping the exposed areas of the first photosensitive layer (second exposure step). The exposed second photosensitive layer was developed with cyclopentanone and rinsed with PGMEA, forming a second pattern (second development step). In the examples where a composition is listed in the "Third Resin Composition" column, a third pattern is formed on the second pattern using the same method as used to form the second pattern. Subsequently, the first and second patterns are heated in a furnace at the heating temperature and for the time specified in the "Curing Conditions" column (modification step), thereby obtaining a composite pattern. In Comparative Example 1, the pattern formation was performed in the same manner as in the Example, except that only the first pattern was formed and the second pattern was not. Furthermore, in Comparative Example 2, the composite pattern is formed in the same manner as in the Example, except that the modification step is performed after the first and second development steps, respectively.

<Measurement of the Cyclization Ratio> The cyclization ratio was determined by measuring the first pattern (the pattern formed by the first photosensitive composition) using infrared absorption spectroscopy after both the first and second development steps. The cyclization ratio of Resin A contained in the first pattern was calculated. First, after patterning the first photosensitive composition, the cyclization ratio of Resin A in the first pattern after the first development step (Cyclization Ratio 1) was measured using infrared absorption spectroscopy. Next, after patterning the second photosensitive composition, the cyclization rate (cyclization rate 2) of Resin A in the first pattern after the second development step was measured by infrared absorption spectroscopy in the portion where the second photosensitive composition pattern remained but the first photosensitive composition pattern remained. When the first photosensitive composition includes a polyimide precursor, the peak intensity P1 of the absorption peak at approximately 1377 ^cm⁻¹ , attributed to the imide structure, in the first pattern was determined after patterning the first photosensitive composition (after the first development step described above). Next, after patterning the second photosensitive composition (after the aforementioned second development step), the infrared absorption spectrum of the portion where the second photosensitive composition pattern remained but the first photosensitive composition pattern remained was measured, and the peak intensity P2 around 1377 cm ^-1 was determined. Similarly, when the first photosensitive composition was a polybenzoxazole precursor, the peak intensity P1 around 1554 cm ^-1 , an absorption peak derived from the benzoxazole structure, was determined. Next, after patterning the second photosensitive composition, the infrared absorption spectrum of the portion where the second photosensitive composition pattern remained but the first photosensitive composition pattern remained was measured, and the peak intensity P2 around 1554 cm ^-1 was determined. For all resins, the obtained peak intensities P1 and P2 were used to calculate the cyclization ratio using the following formula. The results are reported in the "Cyclization Ratio" column of the table below. Cyclization Ratio (%) = (Peak Intensity P2 / Peak Intensity P1) × 100. "<1.1" indicates a ratio less than 1.1, and ">1.5" indicates a ratio greater than 1.5.

<Determination of Residual Film Ratio> After forming the first pattern and the second pattern, the residual film ratio of the first pattern was measured using cross-sectional SEM (scanning electron microscope cross-sectional observation). The height of the pattern after the first pattern was formed was designated T1, and the height of the first pattern after the second pattern was formed was designated T2. The residual film ratio was defined using the following formula: Residual Film Ratio (%) = (T1/T2) × 100 A was assigned a residual film ratio of 70% or higher, and B was assigned a residual film ratio of less than 70%.

<Dissolution Rate Ratio Measurement> After preparing the first and second photosensitive films, the dissolution rates were measured using an RDA-790 manufactured by Litho Tech Japan Corporation. Cyclopentanone was used for solvent development, and a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution was used for alkaline development. The dissolution rate of the first photosensitive film was designated R1, and the dissolution rate of the second photosensitive film was designated R2. The dissolution rate ratio was calculated using the following formula. The evaluation results, dissolution rate ratio = (R2/R1), are reported in the "Dissolution Rate Ratio" column of the table. A: A dissolution rate ratio of 1.05 or greater is marked. B: A dissolution rate ratio of less than 1.05 or 1.0 or greater is marked. C: A dissolution rate ratio of less than 1.0 is marked.

<Aspect Ratio Measurement> Aspect ratio was measured using cross-sectional SEM. The total residual film (pattern height) after pattern formation of the first, second, or third photosensitive composition was defined as T3, and the minimum trench or contact hole line width obtained at this point was defined as D1. The aspect ratio was calculated using the following formula. Aspect Ratio = T3 / D1 Based on the calculated aspect ratio, evaluation was performed according to the following evaluation criteria. The evaluation results are reported in the "Aspect Ratio" column in the table. -Evaluation Criteria- Aspect ratios of 9 or greater are rated S, Aspect ratios of 6 or greater but less than 9 are rated A, Aspect ratios of 4.5 or greater but less than 6 are rated B, Aspect ratios of 3 or greater but less than 4.5 are rated C, Aspect ratios less than 3 are rated D.

【Table 2】 1. Resin composition Thickness of the first resin composition Second resin composition Second resin composition film thickness 3. Resin composition Thickness of the third resin composition Circularization rate Film residue rate Dissolution rate ratio Aspect ratio Hardening conditions Example 1 Component 1 24um Component 2 24um - - <1.1 A B B 240℃/30 minutes Example 2 Component 3 24um Composition 4 24um - - <1.1 A B B 240℃/30 minutes Example 3 Component 5 24um Component 6 24um - - <1.1 A A S 240℃/30 minutes Example 4 Composition 7 24um Composition 8 24um - - <1.1 A B A 240℃/30 minutes Example 5 Composition 8 24um Composition 8 24um - - <1.1 A B A 240℃/30 minutes Example 6 Composition 10 24um Composition 9 24um - - <1.1 A B B 240℃/30 minutes Example 7 Component 1 24um Composition 5 24um - - <1.1 A B C 240℃/30 minutes Example 8 Composition 5 24um Composition 11 24um - - <1.1 A B B 240℃/30 minutes Example 9 Composition 5 24um Composition 12 24um - - <1.1 A B B 240℃/30 minutes Example 10 Composition 5 24um Component 6 24um Component 6 10um <1.1 A A S 240℃/30 minutes Example 11 Composition 5 20um Component 6 20um - - <1.1 A A A 200℃/120 minutes Example 12 Composition 5 15um Component 6 15um - - <1.1 A A B 200℃/120 minutes Example 13 Component 1 24um Component 1 24um - - <1.1 A B A 240℃/30 minutes Comparative example 1 Component 1 48um - - - - <1.1 Unable to use 1st level judgment D 240℃/30 minutes Comparative example 2 Component 1 24um Component 1 24um - - >1.5 B B D 240℃/30 minutes each

From the above results, it can be seen that the composite pattern manufacturing method according to the present invention can obtain a composite pattern with a high aspect ratio.

<Example 101> The first resin composition used in Example 3 was applied in layers to the surface of a copper thin layer on a resin substrate having a copper thin layer formed thereon by spin coating. The film was dried on a hot plate at 100°C for 300 seconds to form a first photosensitive film. The film thickness after drying was set to 24 μm. The first photosensitive film was then exposed using a stepper (CANON FPA3000 i5). Exposure was performed at a wavelength of 365 nm through a mask having a groove pattern with a size of approximately 5 μm formed in the above example. After exposure, the film was heated at 120°C for 300 seconds. After heating, the film was developed with cyclopentanone and rinsed with PGMEA to obtain the first pattern. Next, a second photosensitive film was formed by spin coating the second resin composition used in Example 1 on the first pattern and the areas where the first pattern had been removed in the first development step. The film was dried on a hot plate at 100°C for 300 seconds. The film thickness after drying was set to 24μm. The second photosensitive film was then exposed and developed using the same method as the first photosensitive film to obtain the second pattern. Then, the temperature was raised at a rate of 10°C/minute in a nitrogen atmosphere to 240°C. After reaching this temperature, the temperature was maintained for 30 minutes to cure the first and second patterns, thereby forming an interlayer insulating film for the redistribution layer, which consisted of a composite pattern. This interlayer insulating film for redistribution layers exhibits excellent insulation properties. Furthermore, semiconductor devices fabricated using this interlayer insulating film for redistribution layers have been confirmed to function normally.

without.

Claims (17)

A method for producing a composite pattern comprises: a first film forming step of applying a first resin composition to a substrate to form a first photosensitive film; a first exposure step of selectively exposing the first photosensitive film; a first developing step of developing the exposed first photosensitive film to form a first pattern; and a first developing step of removing the first pattern and the first photosensitive film formed by the first developing step. The second film forming step comprises applying a second resin composition to the area of the first pattern to form a second photosensitive film; performing a second exposure step on the second photosensitive film to selectively expose the second photosensitive film; performing a second development step on the exposed second photosensitive film to form a second pattern; and performing a modification step on the first pattern and the second pattern to modify the first pattern and the second pattern at the same time, wherein the modification step is to heat the first pattern and the second pattern at the same time. The heating step of the pattern and the second pattern, the first resin composition comprises resin A, and the resin A is selected from the group consisting of polyimide precursor, polyimide precursor comprising a polyimide structure, polybenzoxazole precursor, polybenzoxazole precursor comprising a polybenzoxazole structure, polyamide imide precursor and polyamide imide precursor comprising a polyamide imide structure. At least one of the second resin compositions comprises resin B, wherein resin B is selected from the group consisting of a polyimide precursor, a polyimide precursor having a polyimide structure, a polybenzoxazole precursor, a polybenzoxazole precursor having a polybenzoxazole structure, a polyamidoimide precursor, a polyamidoimide precursor having a polyamidoimide structure, and an epoxy resin. The method for producing a composite pattern as described in claim 1, wherein the resin A has a polymerizable group. The method for producing a composite pattern as described in claim 1 or claim 2, wherein the ratio of the cyclization rate of the resin A in the first pattern after the second development step to the cyclization rate of the resin A in the first pattern after the first development step is 1.1 times or less. The method for producing a composite pattern as described in claim 1 or claim 2, wherein the first resin composition comprises a polymerizable compound. The method for producing a composite pattern as described in claim 4, wherein the first resin composition comprises a trifunctional or higher-functional polymerizable compound as the polymerizable compound. A method for producing a composite pattern comprises: a first film forming step of applying a first resin composition to a substrate to form a first photosensitive film; a first exposure step of selectively exposing the first photosensitive film; a first development step of developing the exposed first photosensitive film to form a first pattern; and removing the first pattern and the first development step. A second film forming step of applying a second resin composition to the area of the first pattern to form a second photosensitive film; a second exposure step of selectively exposing the second photosensitive film; a second development step of developing the exposed second photosensitive film to form a second pattern; and a modification step of simultaneously modifying the first pattern and the second pattern, wherein the modification step is performed by heating the first pattern and the second pattern at the same time. In the heating step of the first pattern and the second pattern, the first resin composition comprises a polymerizable compound, the second resin composition comprises resin B, and the resin B is selected from the group consisting of polyimide precursors, polyimide precursors comprising a polyimide structure, polybenzoxazole precursors, polybenzoxazole precursors comprising a polybenzoxazole structure, polyamide imide precursors, and At least one of the group consisting of a polyamide-imide precursor and an epoxy resin having a polyamide-imide structure is provided; the second pattern is formed so as to cover at least a portion of the first pattern; and the portion of the first photosensitive film in the substrate that contacts the portion removed in the first development step includes an area in contact with the second pattern and an area not in contact with the second pattern. The method for producing a composite pattern as described in claim 6, wherein the first resin composition comprises a trifunctional or higher-functional polymerizable compound as the polymerizable compound. The method for producing a composite pattern as described in claim 1, claim 2, or claim 6, wherein the residual film rate of the first pattern before the second development step is applied is 70% or more. The method for producing a composite pattern as described in claim 1, claim 2, or claim 6, wherein the first resin composition does not contain a colorant. The method for producing a composite pattern as described in claim 1, claim 2, or claim 6, wherein the resin A and the resin B contain repeating units represented by the same structural formula. The method for producing a composite pattern as described in claim 1, claim 2, or claim 6, wherein the ratio S2/S1 of the dissolution rate S1 of the first photosensitive film in the developer in the first developing step to the dissolution rate S2 of the second photosensitive film in the developer in the second developing step is greater than 1.05. A first resin composition is used to form the first photosensitive film in the method for manufacturing the composite pattern described in claim 1 to claim 11. A second resin composition used to form the second photosensitive film in the method for manufacturing the composite pattern described in claim 1 to claim 11. A method for manufacturing a laminate, comprising applying the steps of the method for manufacturing a composite pattern described in any one of claims 1 to 11 multiple times. The method for manufacturing a laminate as described in claim 14 further comprises: a metal layer forming step of forming a metal layer on the layer composed of the composite pattern, wherein the metal layer forming step is included between the steps of applying the manufacturing method of the composite pattern multiple times. A method for manufacturing a semiconductor device, comprising the method for manufacturing the composite pattern described in any one of claims 1 to 11. A method for manufacturing a semiconductor device, comprising the method for manufacturing a multilayer body according to claim 14 or claim 15.