TWI901645B - Photosensitive resin composition, pattern manufacturing method, photosensitive film, cured product, laminate and device - Google Patents

Abstract

This invention provides a photosensitive resin composition, a method for manufacturing a pattern formed by the photosensitive resin composition, a photosensitive film formed by the photosensitive resin composition, a cured form of the photosensitive film, a laminate comprising layers composed of the cured form, and an element comprising the cured form or the laminate. The photosensitive resin composition comprises at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide, and polybenzoxazole, an organometallic complex, and a sensitizer having a condensed ring structure.

Description

Methods for manufacturing photosensitive resin compositions and patterns, photosensitive films, curing agents, laminates and components.

This invention relates to a photosensitive resin composition, a method for manufacturing a pattern, a photosensitive film, a curing material, a laminate, and an element.

Polyimide or polybenzoxazole possesses excellent heat resistance and insulation properties, making it suitable for a wide range of applications. While there are no particular limitations on these applications, for example, in the practical installation of semiconductor components, it can be used as an insulating film, sealing material, or protective film. Furthermore, it can also be used as a base film or cover film for flexible substrates.

For example, in the above-described applications, polyimide or polybenzoxazole is used in the form of a photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. For example, such a photosensitive resin composition is applied to a substrate by coating or the like to form a photosensitive film, and then, as needed, exposure, development, heating, etc., are performed, thereby forming a cured product on the substrate. The aforementioned polyimide precursor and polybenzoxazole precursor are, for example, cyclized by heating, becoming polyimide and polybenzoxazole, respectively, in the cured product. Photosensitive resin compositions can be applied using known coating methods, thus offering excellent manufacturing adaptability, such as a high degree of design freedom in terms of shape, size, and application location. Considering this excellent manufacturing adaptability, in addition to the high performance of polyimide and polybenzoxazole, there is growing anticipation for the expansion of industrial applications for these photosensitive resin compositions.

For example, Patent 1 describes a photosensitive resin composition characterized by comprising a polyimide precursor with a specific structure, a photopolymerization initiator, a sensitizer, an inhibitor for maintaining stability, and a solvent containing a photosensitizer. Patent 2 describes a positive-type photosensitive resin composition characterized by comprising a polyimide precursor with a specific structure, a compound containing an ethylene oxide group with a specific structure, a photosensitizer that decomposes to produce acid upon exposure to active light such as ultraviolet light, a sensitizer that promotes the decomposition of the photosensitizer, and a solvent. Patent document 3 describes a polyamide composition characterized by mixing (A) a polyamide with a specific structure, (B) an organic titanium compound in which the weight of the polyamide relative to (A) is 0.3 to 10% by weight, and (C) a solvent.

[Patent Document 1] Japanese Patent Application Publication No. 2003-186187 [Patent Document 2] Japanese Patent Application Publication No. 2001-290270 [Patent Document 3] Japanese Patent Application Publication No. 2004-091572

When forming patterns composed of photosensitive resins, it is necessary to improve the resolution and drug resistance of the obtained patterns.

The purpose of this invention is to provide a photosensitive resin composition with excellent resolution and drug resistance of the obtained pattern, a method for manufacturing a pattern composed of the photosensitive resin composition, a photosensitive film formed from the photosensitive resin composition, a cured form of the photosensitive film, a laminate comprising layers composed of the cured form, and an element comprising the cured form or the laminate.

The following are examples of representative embodiments of the present invention. <1> A photosensitive resin composition comprising: at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, polyimide, and polybenzoxazole; an organometallic complex; and a sensitizer having a condensed ring structure. <2> The photosensitive resin composition as described in <1>, wherein the sensitizer comprises at least one atom selected from the group consisting of nitrogen and sulfur atoms as a ring member in the condensed ring structure. <3> The photosensitive resin composition as described in <1> or <2>, wherein the sensitizer comprises at least one structure selected from the group consisting of acridinone, thiotonone, and acridinium structures as a condensed ring structure. <4> The photosensitive resin composition as described in any one of <1> to <3>, wherein the content of the sensitizer is 0.5 to 5.0 parts by weight relative to 1 part by weight of the organometallic complex. <5> The photosensitive resin composition as described in any one of <1> to <4>, wherein the organometallic complex is a metallocene compound. <6> A photosensitive resin composition as described in any one of <1> to <5>, wherein the metal contained in the organometallic complex is selected from at least one metal of the group consisting of titanium, zirconium, and iron. <7> A photosensitive resin composition as described in any one of <1> to <6>, wherein the organometallic complex has photoradical polymerization initiation capability. <8> A method for manufacturing a pattern, comprising: a film forming process, applying a photosensitive resin composition as described in any one of <1> to <7> to a substrate to form a photosensitive film; an exposure process, exposing the photosensitive film; and a developing process, developing the exposed photosensitive film to obtain the pattern. <9> A method for manufacturing a pattern as described in <8>, wherein the exposure light used in the above-described exposure process includes light with a wavelength of 150-450 nm. <10> A method for manufacturing a pattern as described in <8> or <9>, further comprising: a heating process, heating the pattern obtained by the above-described developing process to harden the pattern. <11> A photosensitive film formed from any one of the photosensitive resin compositions described in <1> to <7>. <12> A cured material, which is a cured form of the photosensitive film described in <11>. <13> The cured material described in <12> used as an interlayer insulating film for a rewiring layer. <14> A laminate comprising two or more layers composed of the hardened material described in <12> or <13>, wherein a metal layer is interposed between any of the layers composed of the hardened material. <15> An element comprising the hardened material described in <12> or <13>, or the laminate described in <14>. [Invention Effects]

According to the present invention, a photosensitive resin composition with excellent resolution and drug resistance of the obtained pattern is provided, a method for manufacturing the pattern composed of the photosensitive resin composition, a photosensitive film formed from the photosensitive resin composition, a cured form of the photosensitive film, a laminate comprising layers composed of the cured form, and an element comprising the cured form or the laminate.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments shown. In this specification, the numerical range indicated by the "~" symbol represents the range including the lower and upper limits of the values recorded before and after the "~". In this specification, the term "process" not only refers to an independent process, but also includes processes that cannot be clearly distinguished from other processes, as long as the desired function of the process can be achieved. Regarding the marking of group (atomic group) in this specification, the markings without indication of substitution and non-substitution include both unsubstituent group (atomic group) and substituent group (atomic group). For example, "alkyl" includes not only unsubstituent alkyl (unsubstituted alkyl) but also substituent alkyl (substituted alkyl). In this instruction manual, unless otherwise specified, "exposure" includes exposure using light, as well as exposure using particle beams such as electron beams and ion beams. Furthermore, examples of light used for exposure include brightline light from mercury lamps, far-ultraviolet light (represented by excimer lasers), extreme ultraviolet light (EUV light), X-rays, and active light or radiation such as electron beams. In this instruction manual, "(meth)acrylate" refers to either or both "acrylate" and "methacrylate," "(meth)acrylic acid" refers to either or both "acrylic acid" and "methacrylic acid," and "(meth)acrylyl" refers to either or both "acrylyl" and "methacrylyl." In this instruction manual, in the structural formula, Me represents methyl, Et represents ethyl, Bu represents butyl, and Ph represents phenyl. In this specification, total solids content represents the total mass of the components after removing the solvent from the total composition. Furthermore, in this specification, solids concentration is the mass percentage of all components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are based on gel osmosis chromatography (GPC) and are defined as polystyrene conversion values. In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, using an HLC-8220 GPC (manufactured by TOSOH CORPORATION) with guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, these molecular weights will be measured using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, the detection in GPC measurements will use a UV (ultraviolet) detector at a wavelength of 254 nm. In this specification, when the positional relationship of the layers constituting the laminate is described as "upper" or "lower," other layers may exist above or below the reference layer in a plurality of layers. That is, a third layer or third element may be sandwiched between the reference layer and the other layers, and the reference layer does not need to be in contact with the other layers. Furthermore, unless otherwise specified, the direction of the stacked layers on the substrate is referred to as "upper," or, in the presence of a photosensitive film, the direction from the substrate towards the photosensitive film is referred to as "upper," and the opposite direction as "lower." Moreover, this vertical orientation is for convenience in this specification; in actual practice, the "upper" direction in this specification may differ from the vertical orientation. In this specification, unless otherwise specified, each component included in the composition may contain two or more compounds that conform to that component. Furthermore, unless otherwise specified, the content of each component in the composition represents the total content of all compounds that conform to 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 preferred configuration is considered a better configuration.

(Photosensitive Resin Composition) The photosensitive resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides and polybenzoxazoles (hereinafter also referred to as "specific resins"), an organometallic complex, and a sensitizer having a condensed ring structure.

The photosensitive resin composition of this invention is preferably used to form a photosensitive film for exposure and development, and preferably to form a film for exposure and development using a developing solution containing an organic solvent. As for the above-described exposure method, the above-described developing solution, and the above-described developing method, for example, the exposure method described in the exposure process of the manufacturing method in the following figures, and the developing solution and developing method described in the developing process can be used.

The photosensitive resin composition of this invention produces patterns with excellent resolution and drug resistance. The mechanism by which these effects are achieved is not yet clear, but can be hypothesized as follows.

For example, as described in Patent 1 and Patent 2, a sensitizer is used in a photosensitive resin composition containing a specific resin for the purpose of improving exposure sensitivity. Furthermore, Patent 3 describes how the use of an organotitanium compound in the composition improves drug resistance. In this case, the inventors, through in-depth research, discovered that by simultaneously using an organometallic complex and a sensitizer with a condensed ring structure in a photosensitive resin composition, the resolution of the obtained pattern is improved. The mechanism by which these effects are achieved is not yet fully understood, but it is hypothesized as follows: By including organometallic complexes and sensitizers with specific structures in the photosensitive resin composition, the electronic state of the sensitizer changes. For example, the sensitivity of the sensitizer is increased by reducing the LUMO (Lowest Unoccupied Molecular Orbital), thereby improving the resolution of the obtained pattern. This is believed to be because the interaction between the metal sites contained in the organometallic complexes and the sensitizer, along with the increased planarity of the condensed ring structure of the sensitizer, simultaneously alters its electronic state. Furthermore, it was discovered that by simultaneously using an organometallic complex and a sensitizer with a condensed ring structure in the photosensitive resin composition, the drug resistance of the obtained pattern was improved. The mechanism by which this effect is achieved is not yet clear, but it is hypothesized that specific resins interact with both the organometallic complex and the sensitizer with the condensed ring structure within the obtained pattern, thereby enhancing drug resistance. Due to the excellent chemical resistance of the pattern, for example, when further applying other photosensitive resin compositions containing solvents to form a laminate on a pattern formed from the photosensitive resin composition of this invention, the dissolution of the pattern can be inhibited even when the pattern comes into contact with the developer or other photosensitive resin compositions. Furthermore, according to the present invention, for example, it is believed that a pattern exhibiting excellent drug resistance can be obtained by suppressing solubility in polar solvents such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), alkaline aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solution, acidic aqueous solutions such as dilute sulfuric acid aqueous solution and dilute hydrochloric acid aqueous solution, mixtures of the above-mentioned polar solvents and alkaline aqueous solutions, or mixtures of the above-mentioned polar solvents and acidic aqueous solutions. Furthermore, since the planarity is improved and LUMO and other properties are reduced, the photosensitive film formed from the photosensitive resin composition of the present invention tends to exhibit excellent exposure sensitivity when exposed using a photomask or when exposed based on direct laser imaging.

The following is a detailed description of the components contained in the photosensitive resin composition of the present invention.

<Specific Resin> The photosensitive resin composition of the present invention comprises at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor. As a specific resin, it is preferable that the photosensitive resin composition of the present invention comprises polyimide or a polyimide precursor, and more preferably, it comprises a polyimide precursor. Furthermore, it is preferable that the specific resin has free radical polymerizable groups. When a specific resin has free radical polymerizable groups, it is preferable that the photosensitive resin composition includes a photoradical polymerization initiator (described later) as a photosensitizer; it is even more preferable that it includes both the photoradical polymerization initiator and the free radical crosslinker (described later); and it is further preferable that it includes both the photoradical polymerization initiator and the free radical crosslinker (described later) as a photosensitizer and the sensitizer (described later). For example, a negative photosensitive film can be formed from such a photosensitive resin composition. Furthermore, the specific resin may have polar conversion groups such as acid-degrading groups. When a specific resin has acid-degrading groups, it is preferable that the photosensitive resin composition includes a photoacid generator as a photosensitizer. For example, such photosensitive resins can form chemically amplified, i.e., positive or negative photosensitive layers.

[Polyimide Precursor] The type of polyimide precursor used in this invention is not particularly limited, but it is preferable to include repeating units represented by the following formula (2). Formula (2) [Chemical Formula 1] In equation (2), ^A1 and ^A2 represent oxygen atoms or NH atoms independently, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 represent hydrogen atoms or monovalent organic groups independently.

In formula (2), ^A1 and ^A2 independently represent an oxygen atom or NH, with an oxygen atom being preferred. In formula (2), ^R111 represents a divalent organic group. Examples of divalent organic groups include linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups. It is preferred to have linear or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 6 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups composed of combinations thereof. It is even more preferred to have groups containing aromatic groups with 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, the case of a group represented by -Ar-L-Ar- can be shown. In this group, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can be replaced by a fluorine atom, or a group consisting of -O-, -CO-, -S-, _-SO2- , or -NHCO-, or a combination of two or more of the above. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of diamines used in the manufacture of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, diamines containing linear or branched aliphatic groups with 2 to 20 carbon atoms, cyclic aliphatic groups with 6 to 20 carbon atoms, aromatic groups with 6 to 20 carbon atoms, or groups composed of combinations thereof, are preferred; diamines containing groups composed of aromatic groups with 6 to 20 carbon atoms are even more preferred. Examples of aromatic groups include the following aromatic groups.

[Chemical Formula 2] In the formula, A is preferably a single bond or a group selected from aliphatic hydrocarbons with 1 to 10 carbon atoms that can be substituted by fluorine atoms, or a combination of -O-, -C(=O)-, -S-, _-SO₂- , -NHCO-, or the like. A single bond or a group selected from alkyl groups with 1 to 3 carbon atoms that can be substituted by fluorine atoms, or a group selected from -O-, -C(=O)-, -S-, or _-SO₂- , is even more preferred. _-CH₂- , -O-, -S-, _-SO₂- , -C( _CF₃ ) _₂- , or -C( _CH₃ ) _₂- are further preferred. * indicates a bonding site with other structures.

As a diamine, specific examples include those selected from 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'- Dimethylcyclohexylmethane and isophorone diamine; 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'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ketone or 3,3'-diaminodiphenyl ketone, 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) phosphate, bis(4-amino-3-hydroxyphenyl) phosphate, 4,4'-diamino-p-terphenyl, 4, 4’-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] guanidine, bis[4-(3-aminophenoxy)phenyl] guanidine, bis[4-(2-aminophenoxy)phenyl] guanidine, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3’-dimethyl-4,4’-diaminodiphenyl guanidine, 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'-diaminooctafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 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)furan, 4,4'-dimethyl-3,3'-diaminodiphenyl sulfonium, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminophen, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzoniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)hexafluoropropane, 1,5-bis(4-aminophenyl)decafluoropentane, 1,7-bis(4-aminophenyl)tetrafluoroheptane, 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 The diamine selected from the following: 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfonium, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl sulfonium, 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'-hexafluorobitoluidine, and 4,4'-diaminotetraphenyl.

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

Alternatively, the diamine having two or more alkyl diol units on the main chain as described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 may be preferred.

From the viewpoint of the flexibility of the obtained organic membrane, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon of 1 to 10 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, _-SO₂- , or -NHCO-, or a combination of two or more of the above. It is preferable that Ar is an alkylene group, and it is preferable that L is an aliphatic hydrocarbon of 1 or 2 carbon atoms that can be substituted with a fluorine atom, or a group consisting of -O-, -CO-, -S-, or _-SO₂- . It is preferable that the aliphatic hydrocarbon group here is an alkylene group.

From the perspective of i-ray transmittance, R ¹¹¹ is preferably represented by a divalent organic group as shown in formula (51) or formula (61). In particular, from the perspective of i-ray transmittance and availability, the 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, and at least one of ^R50 to ^R57 is a fluorine atom, a methyl group, or a trifluoromethyl group. Examples of monovalent organic groups among ^R50 to ^R57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and fluorinated alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). [Chemical Formula 4] In formula (61), R ⁵⁸ and R ⁵⁹ are each independently a fluorine atom or a trifluoromethyl atom. Examples of diamine compounds endowed with 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. One or more of these compounds may be used.

In addition, the following diamines can also be used more effectively. [Formula 5]

In formula (2), R ¹¹⁵ represents a tetravalent organic group. A tetravalent organic group containing an aromatic ring is preferred, and a group represented by formula (5) or formula (6) below is even more preferred. In formula (5) or formula (6), * independently represents the bonding site with other structures. [Formula 6] In formula (5), R ¹¹² represents a single bond or a group consisting of an aliphatic hydrocarbon of carbon number 1 to 10 that can be substituted by a fluorine atom, -O-, -CO-, -S-, -SO _2- and -NHCO-, and a combination thereof, preferably a single bond or a group consisting of an alkyl group of carbon number 1 to 3 that can be substituted by a fluorine atom, -O-, -CO-, -S- and -SO _2- , and even more preferably a divalent 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 the tetracarboxylic acid residue remaining after removing the anhydride group from a tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more may be used. It is preferred that the tetracarboxylic dianhydride be represented by the following formula (O). [Chemical Formula 7] In equation (O), R ¹¹⁵ represents a tetravalent organic group. The meaning of the preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in equation (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include those selected from pyromellitic dianhydride (PMDA), 3,3’,4,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-diphenyl sulfide tetracarboxylic dianhydride, 3,3’,4,4’-diphenyl sulfide 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’-oxophthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)propane. Alkane dianhydrides, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydrides, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydrides, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic acid dianhydrides, 1,4,5,6-naphthalenetetracarboxylic acid dianhydrides, 2,2',3,3'-diphenyltetracarboxylic acid dianhydrides, 3,4,9,10-perylenetetracarboxylic acid dianhydrides, 1,2,4,5-naphthalenetetracarboxylic acid dianhydrides, 1,4,5,8-naphthalenetetracarboxylic acid dianhydrides, 1,8,9,10-phenanthrenetetracarboxylic acid dianhydrides, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydrides, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydrides, 1,2,3,4-benzenetetracarboxylic acid dianhydrides, and alkyl and alkoxy derivatives of the like having 1 to 6 carbon atoms.

As a better example, one could also cite the tetracarboxylic acid dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , the residual group of a diaminophenol derivative can be cited.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is even more preferable that both contain polymerizable groups. As a polymerizable group, it is a group capable of cross-linking reactions through the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of polymerizable groups include groups having ethylene unsaturated bonds, alkoxymethyl, hydroxymethyl, acetoxymethyl, epoxy, oxacyclobutyl, benzoxazolyl, block isocyanate, hydroxymethyl, and amino groups. As a free radical polymerizable group in polyimide precursors, etc., a group having an ethylene unsaturated bond is preferred. Examples of groups having ethylene-like unsaturated bonds include vinyl, (methyl)allyl, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[Chemical Formula 8]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. In formula (III), * indicates a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkyl group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ -, or a polyalkylene group. Examples of preferred R ²⁰¹ include ethylene, propylene, trimethylene, tetramethylene, 1,2-butadiene, 1,3-butadiene, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, and polyalkylene group. Ethylene, propylene, trimethylene, -CH ₂ CH(OH)CH ₂ -, and polyalkylene group are more preferred, with polyalkylene group being even more preferred. In this invention, polyalkylene oxide refers to a group formed by the direct bonding of two or more alkylene oxides. The alkylene groups of the plurality of alkylene oxides contained in the polyalkylene oxide can be the same or different. When the polyalkylene oxide contains a plurality of alkylene oxides with different alkylene groups, the arrangement of the alkylene oxides in the polyalkylene oxide can be random, block-shaped, or alternating. It is preferred that the number of carbon atoms in the aforementioned alkylene group (including the number of carbon atoms of the substituents when the alkylene group has substituents) is 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is the most preferred. Furthermore, the aforementioned alkylene group can have substituents. Examples of preferred substituents include alkyl, aryl, and halogen atoms. Furthermore, the number of alkoxy groups (the repetition number of the polyalkoxy group) in the polyalkoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups bonded by a plurality of ethyleneoxy groups and a plurality of alkoxy groups are preferred as polyvinyloxy or polypropyleneoxy groups, with polyvinyloxy being even more preferred. In the groups formed by the bonding of a plurality of ethyleneoxy groups and a plurality of alkoxy groups, the ethyleneoxy and alkoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the repetition number of the ethyleneoxy groups in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are each independently a hydrogen atom or a monovalent organic group. Examples of monovalent organic groups include aromatic groups and aralkyl groups with an acid group bonded to one, two, or three (preferably one) carbon atom constituting the aryl group. Specifically, examples include aromatic groups with 6 to 20 carbon atoms having an acid group, and aralkyl groups with 7 to 25 carbon atoms having an acid group. More specifically, examples include phenyl groups having an acid group and benzyl groups having an acid group. An OH group is preferred as the acid group. It is also preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl, or 4-hydroxybenzyl.

From the perspective of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ being monovalent organic groups is preferred. As a monovalent organic group, it is preferable to include straight-chain or branched alkyl groups, cyclic alkyl groups, or aromatic groups, with alkyl groups substituted with aromatic groups being even more preferred. It is preferable that the alkyl group has 1 to 30 carbon atoms. The alkyl group can be any of straight-chain, branched, or cyclic. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, dibutyl, tributyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy, 2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy. Cyclic alkyl groups can be monocyclic or polycyclic. Examples of monocyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alkyl groups include adamantyl, norcamphenyl, camphenyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, camphenyl, dicyclohexyl, and pinenyl. Among these, cyclohexyl is the most suitable from the perspective of achieving both high sensitivity. Furthermore, as for alkyl groups substituted with aromatic groups, straight-chain alkyl groups substituted with aromatic groups (described later) are preferred. As an aromatic group, specifically, it refers to substituted or unsubstituted benzene rings, naphthyl rings, pentanene rings, indene rings, azulene rings, heptanene rings, indene rings, perylene rings, fused pentaphenyl rings, acenaphthene rings, phenanthrene rings, anthracene rings, fused tetraphenyl rings, cyclopentadiene rings, triphenylene rings, fumonisin rings, biphenyl rings, pyrrole rings, furan rings, thiophene rings, imidazole rings, azirazole rings, thiazole rings, pyridine rings, and pyridine rings. The following rings are available: pyrimidine ring, pyridinium ring, indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, pyridinium ring, naphthidine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, caffeine ring, acridine ring, caffeine ring, thiathrone ring, chromene ring, pyridinium ring, caffeine-thiazoline ring, or caffeine-pyridinium ring. Benzene rings are preferred.

In formula (2), if R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugated salt with a tertiary amine compound having ethylene unsaturated bonds. N,N-dimethylaminopropyl methacrylate is an example of a tertiary amine compound having such ethylene unsaturated bonds.

At least one of R ¹¹³ and R ¹¹⁴ can be a polar conversion group such as an acid-degradable group. As an acid-degradable group, it is not particularly limited as long as it decomposes under the action of an acid to produce an alkaline-soluble group such as a phenolic hydroxyl group or a carboxyl group. Acetaldehyde, ketaldehyde, silicone, silicone ether, and tertiary alkyl ester groups are preferred, with acetal being more desirable from the perspective of exposure sensitivity. Specific examples of acid-degradable groups include tertiary butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, tertiary butoxycarbonylmethyl, and trimethyl silicone ether. From the perspective of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl are preferred.

Furthermore, it is preferable that the polyimide precursor contains fluorine atoms in its structural units. It is preferable that the content of fluorine atoms in the polyimide precursor is 10% by mass or more, and preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, polyimide precursors can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

The repeating unit represented by formula (2) is preferably the repeating unit represented by formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in this invention is a precursor having a repeating unit represented by formula (2-A). By adopting this structure, the exposure tolerance can be further expanded. Formula (2-A) [Chemical Formula 9] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 represent divalent organic groups independently, ^R113 and ^R114 represent hydrogen atoms or monovalent organic groups independently, and at least one of ^R113 and ^R114 is a group containing polymerizable groups, preferably both of which are polymerizable groups.

The meanings of ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 are the same as those of ^A1 , ^A2 , ^R111 , ^R113 , and ^R114 in equation (2), and their preferred ranges are also the same. The meaning of ^R112 is the same as that of ^R112 in equation (5), and its preferred range is also the same.

Polyimide precursors may contain one or more repeating structural units represented by formula (2). They may also contain structural isomers of repeating units represented by formula (2). Furthermore, in addition to the repeating units of formula (2) above, polyimide precursors may obviously contain other types of repeating structural units.

As an embodiment of the polyimide precursor of the present invention, it can be exemplified that the polyimide precursor of the repeating unit represented by formula (2) is 50 mol% or more, further 70 mol% or more, and especially 90 mol% or more of the total repeating unit.

The weight-average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. 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 dispersion of the above-mentioned polyimide precursor is preferably 2.5 or higher, more preferably 2.7 or higher, and even more preferably 2.8 or higher. There is no particular upper limit to the molecular weight dispersion of the polyimide precursor. For example, 4.5 or less is preferred, 4.0 or less is better, 3.8 or less is even better, 3.2 or less is even better, 3.1 or less is even better, 3.0 or less is still even better, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is calculated using the weight average molecular weight / number average molecular weight.

[Polyimide] The polyimide used in this invention can be an alkaline-soluble polyimide or a polyimide soluble in a developing solution primarily composed of an organic solvent. In this specification, alkaline-soluble polyimide means that at least 0.1 g of polyimide can be dissolved in 100 g of a 2.38% (w/w) tetramethylammonium aqueous solution at 23°C. From a pattern-forming point of view, dissolving at least 0.5 g of polyimide is preferred, and dissolving at least 1.0 g of polyimide is further preferred. There is no particular upper limit to the above-mentioned dissolution amount, but less than 100 g is preferred. Furthermore, considering the strength and insulation properties of the obtained organic membrane, polyimides with multiple amide structures in the main chain are preferred. In this specification, "main chain" refers to the relatively longest bond in the polymer molecule constituting the resin, and "side chain" refers to all other bond chains.

-Fluorine Atoms- From the viewpoint of the strength of the obtained organic membrane, it is preferable that the polyimide contains fluorine atoms. It is preferable that the fluorine atoms are contained, for example, in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later, and it is even more preferable that they are contained as fluorinated alkyl groups in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later. It is preferable that the amount of fluorine atoms relative to the total mass of the polyimide is 1 to 50 mol/g, and even more preferable that it is 5 to 30 mol/g.

-Silicon Atoms- From the viewpoint of the strength of the obtained organic film, it is preferable that polyimide contains silicon atoms. It is preferable that the silicon atoms are included, for example, in R ¹³¹ , a repeating unit represented by the following formula (4), and even more preferably, in R ¹³¹ , a repeating unit represented by the following formula (4), as an organic modified (poly)siloxane structure. Furthermore, the aforementioned silicon atoms or the aforementioned organic modified (poly)siloxane structure may be included in the side chain of polyimide, but it is preferable that they are included in the main chain of polyimide. It is preferable that the amount of silicon atoms relative to the total mass of polyimide is 0.01 to 5 mol/g, and even more preferably 0.05 to 1 mol/g.

-Ethylene Unsaturated Bonds- From the perspective of the strength of the obtained organic membrane, it is preferable that polyimide has ethylene unsaturated bonds. Polyimide can have ethylene unsaturated bonds at the main chain end or in the side chain, with the latter being preferred. The aforementioned ethylene unsaturated bonds are preferably free radical polymerizable. It is preferable that the ethylene unsaturated bond is contained in ^R132 or R131 in the repeating unit represented by the following formula (4), and it is even more preferable that the group having the ethylene unsaturated bond is contained in ^R132 or ^R131 in the repeating unit represented by the following formula (4). Among these, it is preferable that the ethylene unsaturated bond is contained in ^R131 in the repeating unit represented by the following formula (4), and it is even more preferable that the group having the ethylene unsaturated bond is contained ^{in R131 in} the repeating unit represented by the following formula (4). Examples of groups having ethylene-like unsaturated bonds include vinyl, allyl, vinylphenyl and other substituted vinyl groups that are directly bonded to the aromatic ring, (meth)acrylamide, (meth)acryloxy and groups represented by the following formula (IV).

[Chemical Formula 10]

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, with methyl being preferred.

In formula (IV), R ²¹ represents an alkyl group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyl group having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and especially preferably 2 or 3 carbon atoms; preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and especially preferably 1 to 3 carbon atoms), or a group consisting of two or more of these.

Of these, it is preferable that ^R21 is represented by any one of the groups in formulas (R1) to (R3), with the group represented by formula (R1) being more preferred. [Chemical Formula 11] In formulas (R1) to (R3), L represents a single bond or a alkyl group having 2 to 12 carbon atoms, a (poly)alkylene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these bonds; X represents an oxygen atom or a sulfur atom; * represents a bonding site with other structures; and ● represents a bonding site with the oxygen atom bonded to R ²⁰¹ in formula (III). In formulas (R1) to (R3), the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in L is the same as the preferred state of the alkyl group having 2 to 12 carbon atoms or the (poly)alkylene group having 2 to 30 carbon atoms in R ²¹ above. In formula (R1), it is preferred that X is an oxygen atom. In formulas (R1) to (R3), the meaning of * is the same as that of * in formula (IV), and the preferred state is also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide with a hydroxyl group, such as a phenolic hydroxyl group, with a compound having an isocyanate group and an ethylene-unsaturated bond (e.g., ethyl 2-isocyanate methacrylate). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide with a carboxyl group with a compound having a hydroxyl group and an ethylene-unsaturated bond (e.g., ethyl 2-hydroxymethacrylate). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide with a hydroxyl group, such as a phenolic hydroxyl group, with a compound having an epoxypropyl group and an ethylene-unsaturated bond (e.g., glyoxypropyl methacrylate). From the viewpoint of solvent solubility and solvent resistance, polyvinyloxy, polypropyleneoxy, polytrimethyleneoxy, polytetramethethyleneoxy, or groups bonded by a plurality of ethyleneoxy groups and a plurality of propoxy groups are preferred as polyvinyloxy groups, with polyvinyloxy or polypropyleneoxy being more preferred, and polyvinyloxy being even more preferred. In the aforementioned groups formed by the bonding of a plurality of ethyleneoxy and propoxy groups, the ethyleneoxy and propoxy groups can be arranged randomly, can form blocks, or can be arranged in alternating patterns. The preferred state of the repetition of the ethyleneoxy groups in these groups is as described above.

In formula (IV), * indicates a bonding site with other structures, preferably a bonding site with the polyimide backbone.

The amount of ethylene unsaturated bonds relative to the total mass of polyimide is preferably 0.05–10 mol/g, and more preferably 0.1–5 mol/g. Furthermore, from a manufacturing suitability perspective, the amount of ethylene unsaturated bonds relative to the total mass of polyimide is preferably 0.0001–0.1 mol/g, and more preferably 0.0005–0.05 mol/g.

- Crosslinking groups other than ethylene unsaturated bonds - Polyimide may have crosslinking groups other than ethylene unsaturated bonds. Examples of crosslinking groups other than ethylene unsaturated bonds include cyclic ether groups such as epoxy and oxocyclobutyl, alkoxymethyl groups such as methoxymethyl, hydroxymethyl, etc. Crosslinking groups other than ethylene unsaturated bonds are preferably included, for example, in the repeating unit represented by formula (4) described later. The amount of crosslinking groups other than ethylene unsaturated bonds relative to the total mass of polyimide is preferably ^0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g. Furthermore, from the perspective of manufacturing suitability, the amount of cross-linking groups other than ethylene unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and even more preferably 0.001 to 0.05 mol/g.

-Polar switching group- Polyimide can have polar switching groups such as acid-degrading groups. The acid-degrading groups in polyimide are the same as those described in R ¹¹³ and R ¹¹⁴ of the above formula (2), and the preferred state is also the same.

-Acid Value- When using polyimide in alkaline developing, from the viewpoint of improving developing properties, an acid value of 30 mg KOH/g or higher is preferred, 50 mg KOH/g or higher is more preferred, and 70 mg KOH/g or higher is even more preferred. Furthermore, an acid value of 500 mg KOH/g or lower is preferred, 400 mg KOH/g or lower is more preferred, and 200 mg KOH/g or lower is even more preferred. Furthermore, when using polyimide in developing solutions with organic solvents as the main component (e.g., "solvent developing" described below), an acid value of 2–35 mg KOH/g is preferred, 3–30 mg KOH/g is more preferred, and 5–20 mg KOH/g is even more preferred. The acid values mentioned above are determined by well-known methods, for example, by the method described in JIS K 0070:1992. Furthermore, considering both stability and development, acid groups contained in polyimide with pKa values of 0 to 10 are preferred, and those with pKa values of 3 to 8 are even better. pKa is the equilibrium constant Ka expressed by the negative common logarithm pKa, taking into account the dissociation reaction of hydrogen ions released by the acid. In this specification, unless otherwise specified, pKa is set to a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, the values described in the "5th Revised Edition of Chemical Handbook: Fundamentals" compiled by the Chemical Society of Japan can be consulted. Furthermore, when the acid group is a polybasic acid such as phosphoric acid, the above-mentioned pKa is the first dissociation constant. As such an acid group, it is preferable that the polyimide contains at least one group selected from the group consisting of carboxyl and phenolic hydroxyl groups, and it is even more preferable that it contains phenolic hydroxyl groups.

-Phenolic hydroxyl group- From the viewpoint of achieving an appropriate development speed for alkaline-based developing solutions, it is preferable that polyimide has a phenolic hydroxyl group. Polyimide may have a phenolic hydroxyl group at the end of the main chain or on the side chain. It is preferable that the phenolic hydroxyl group is included, for example, in R ¹³² or R ¹³¹ in the repeating unit represented by formula (4) described later. It is preferable that the amount of phenolic hydroxyl group relative to the total mass of polyimide is 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.

The polyimide used in this invention is not particularly limited as long as it is a polymeric compound having an imine ring. It is preferred to contain a repeating unit represented by formula (4) below, and even more preferred to contain a repeating unit represented by formula (4) and have polymerizable groups. Formula (4) [Chemical Formula 12] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When polymerizable groups are present, the polymerizable groups can be located on at least one of R ¹³¹ and R ¹³² , or they can be located at the end of the polyimide as shown in formula (4-1) or formula (4-2) below. Formula (4-1) [Chemical Formula 13] In formula (4-1), R ¹³³ is a polymerizable group, and the meanings of the other groups are the same as in formula (4). Formula (4-2) [Chemical Formula 14] At least one of R ¹³⁴ and R ¹³⁵ is a polymeric group, and if it is not a polymeric group, it is an organic group. The meanings of the other groups are the same as in equation (4).

The meaning of polymerizable groups is the same as that of polymerizable groups described in the above-mentioned polyimide precursors, etc. R ¹³¹ represents a divalent organic group. As a divalent organic group, examples can be the same as R ¹¹¹ in formula (2), and the preferred range is also the same. Furthermore, as R ¹³¹ , the diamine residue remaining after the amino group of the diamine is removed can be given. As a diamine, aliphatic, cyclic aliphatic or aromatic diamines can be given. As a specific example, the example of R ¹¹¹ in formula (2) of the polyimide precursor can be given.

From the perspective of more effectively suppressing warping during firing, R ¹³¹ is preferably a diamine residue having at least two alkyl diol units in the main chain. More preferably, it contains a total of two or more diamine residues of any one or both of ethylene glycol and propylene glycol chains in one molecule, and even more preferably, it does not contain diamine residues of aromatic rings.

Examples of diamines comprising one or more of ethylene glycol or propylene glycol chains include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane-2-amine, 1-(1-(1-(1-(2-aminopropoxy)propane-2-yl)oxy)propane-2-amine, but are not limited to these.

R ¹³² represents a tetravalent organic group. As a tetravalent organic group, it can be exemplified as the same as R ¹¹⁵ in equation (2), and the preferred range is also the same. For example, the four connecting bonds of the tetravalent organic group exemplified as R ¹¹⁵ are partially bonded to the four -C (=O)- in the above equation (4) to form a condensation ring.

Furthermore, R ¹³² can be exemplified by the tetracarboxylic acid residue remaining after the removal of the anhydride group from a tetracarboxylic acid dianhydride. As a specific example, R ¹¹⁵ in formula (2) of a polyimide precursor can be cited. From the viewpoint of the strength of the organic membrane, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferred that at least one of R ¹³¹ and R ¹³² has an OH group. More specifically, as R ¹³¹ , 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, and (DA-1) to (DA-18) above are preferred examples, and as R ¹³² , (DAA-1) to (DAA-5) above are more preferred examples.

Furthermore, it is preferable that the polyimide contains fluorine atoms in its structural units. It is preferable that the content of fluorine atoms in the polyimide is 10% by mass or more, and preferably 20% by mass or less.

Furthermore, to improve adhesion to the substrate, polyimide can be copolymerized with aliphatic groups having a silicate structure. Specifically, examples of diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

Furthermore, in order to improve the storage stability of the composition, it is preferable to seal the main chain end of the polyimide with end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monochlorodimethylamine compounds, and monoactive ester compounds. Among these, the use of monoamines is preferred. Preferred compounds for monoamines 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, and 1-carboxy-5-aminonaphthalene. -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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different terminal groups can be introduced by reacting multiple end-capping agents.

-Lipidification Rate (Ring-Closing Rate)- Considering the strength and insulation properties of the obtained organic membrane, a lipidification rate (also known as "ring-closing rate") of 70% or higher for polyimide is preferred, 80% or higher is even better, and 90% or higher is still preferable. There is no specific upper limit to the above lipidification rate; below 100% is acceptable. For example, the lipidification rate can be determined using the following method: Measure the infrared absorption spectrum of the polyimide and determine the peak intensity P1 near the absorption peak originating from the lipid structure, i.e., around 1377 ^cm⁻¹ . Then, after heat-treating the polyimide at 350°C for 1 hour, measure the infrared absorption spectrum again and determine the peak intensity P2 near 1377 ^cm⁻¹ . Using the obtained peak intensities P1 and P2, the amide ratio of polyimide can be calculated according to the following formula: Imidization ratio (%) = (peak intensity P1 / peak intensity P2) × 100

Polyimide may include all repeating structural units of formula (4) above containing one type of R ¹³¹ or R ¹³² , or may include repeating units of formula (4) above containing two or more different types of R ¹³¹ or R ^132. In addition to repeating units of formula (4) above, polyimide may also contain other types of repeating structural units.

Polyimides can be produced, for example, by reacting tetracarboxylic dianhydrides with diamine compounds (partially replaced by monoamines, i.e., end-capping agents) at low temperatures; by reacting tetracarboxylic dianhydrides (partially replaced by acid anhydrides, monochloro compounds, or monoactive ester compounds, i.e., end-capping agents) with diamine compounds at low temperatures; by obtaining diesters from tetracarboxylic dianhydrides and alcohols and then reacting them in the presence of diamines (partially replaced by monoamines, i.e., end-capping agents) and condensing agents; and by reacting tetracarboxylic dianhydrides with diamines. Polyimide precursors are obtained by methods such as obtaining diesters from dianhydrides and alcohols, chlorinating the remaining dicarboxylic acid, and reacting it with a diamine (partially replacing a monoamine, i.e., a capping agent). These precursors are then synthesized using conventional amideration reactions, employing either complete amideration or a method that stops the amideration reaction midway and introduces a partial amider structure. Further synthesis is achieved by mixing the fully amiderated polymer with its polyimide precursor to introduce a partial amider structure. Commercially available polyimides include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation).

Regarding the weight-average molecular weight (Mw) of polyimides, 4,000–100,000, 5,000–70,000 are preferred, 8,000–50,000 are more preferred, and 10,000–30,000 are even more preferred. By setting the weight-average molecular weight to 5,000 or higher, the flexural strength of the cured film can be improved. For organic films with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more polyimides are contained, it is preferable that at least one polyimide has a weight-average molecular weight within the above range.

[Polybenzoxazole precursor] The polybenzoxazole precursor used in this invention is not particularly limited in its structure, but preferably contains repeating units represented by the following formula (3). Formula (3) [Chemical Formula 15] In equation (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ represent hydrogen atoms or monovalent organic groups, respectively.

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

As a dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, with dicarboxylic acid residues containing aromatic groups being more preferred. As a dicarboxylic acid containing an aliphatic group, dicarboxylic acids containing straight-chain or branched (preferably straight-chain) aliphatic groups are preferred, and dicarboxylic acids composed of a straight-chain or branched (preferably straight-chain) aliphatic group and two -COOH groups are more preferred. The number of carbon atoms in the straight-chain or branched (preferably straight-chain) aliphatic group is preferably 2-30, more preferably 2-25, further preferably 3-20, even more preferably 4-15, and particularly preferably 5-10. The straight-chain aliphatic group is preferably an alkyl 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, and 2,2,6,6-tetramethylhimelic acid. Diacid, 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, hexadecanedioic acid , behenedioic acid, triacontanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octadecanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diethylene glycol acid, and dicarboxylic acid represented by the following formula, etc.

[Chemical Formula 16] (In the formula, Z represents an hydrocarbon with 1 to 6 carbon atoms, and n represents an integer from 1 to 6.)

As a dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic group is preferred, and a dicarboxylic acid consisting only of the following aromatic group and 2 -COOH groups is even more preferred.

[Chemical Formula 17] In the formula, A represents a divalent group selected from the group including _-CH2- , -O-, -S-, _-SO2- , -CO-, -NHCO-, -C( _CF3 ) _2- and -C( _CH3 ) _2- , and * represents the bonding site with other structures independently.

Specific examples of dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid and 4,4'-dicarboxylic diphenyl ether and terephthalic acid.

In equation (3), R ¹²² represents a tetravalent organic group. As a tetravalent organic group, its meaning is the same as that of R ¹¹⁵ in equation (2) above, and the preferred range is also the same. Furthermore, R... Group ¹²² is preferably derived from a diaminophenol derivative. Examples of groups derived from diaminophenol derivatives include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl phosphate, 4,4'-diamino-3,3'-dihydroxydiphenyl phosphate, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 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 diaminophenols can be used alone or in combination.

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

[Chemical Formula 18] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , and -NHCO-, and * and # represent the bonding sites with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, with hydrogen atom or alkyl group being preferred, and hydrogen atom or alkyl group being even more preferred. Furthermore, ^R122 is also preferred as the structure represented by the above formula. When R ¹²² is represented by the above formula, it is preferable that any two of the four asterisks and # are bonded to nitrogen atoms in R ¹²² in formula (3) and the other two are bonded to oxygen atoms in R ¹²² in formula (3). It is even better that two asterisks are bonded to oxygen atoms in R ¹²² in formula (3) and two # are bonded to nitrogen atoms in R ¹²² in formula (3), or two asterisks are bonded to nitrogen atoms in R ¹²² in formula (3) and two # are bonded to oxygen atoms in R ¹²² in formula (3). The bonding sites of the oxygen atoms bonded by ¹²² and the two # are more preferably the bonding sites of the nitrogen atoms bonded by ^R in equation (3).

[Chemical Formula 19]

In formula (As), _R1 is a hydrogen atom, an alkyl group, a substituted alkyl group, -O-, -S-, _-SO₂- , -CO-, -NHCO-, a single bond, or an organic group selected from the group consisting of the following formulas (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acetoxy group, or a cyclic alkyl group, which may be the same or different. _R3 is any one of a hydrogen atom, a straight-chain or branched alkyl group, an alkoxy group, an acetoxy group, or a cyclic alkyl group, which may be the same or different.

[Chemical Formula 20] (In formula (A-sc), * indicates an aromatic ring bonded to the aminophenol group of the diaminophenol derivative represented by formula (As) above.)

It is believed that in the above formula (As), the presence of a substituent at the position adjacent to the phenolic hydroxyl group, i.e., at _R3, would bring the carbonyl carbon of the amide bond closer to the hydroxyl group, and would be particularly advantageous from the perspective of further improving the effect of high cyclization rate when hardened at low temperature.

Furthermore, in the above formula (As), the case where _R2 is an alkyl group and _R3 is an alkyl group can maintain the effect of high transparency to i-rays and the effect of increasing cyclization rate when hardening at low temperature, which is therefore better.

Furthermore, in the above formula (As), it is even more preferable that _R1 is an alkylene group or a substituted alkylene group. As specific examples of alkylene groups and substituted alkylene groups related to _R1 , linear or branched alkyl groups having 1 to 8 carbon atoms can be cited. Among them, from the viewpoint of maintaining high transparency to i-rays and high cyclization rate when curing at low temperatures, while having sufficient solubility in solvents and being able to obtain a polybenzoxazole precursor with excellent balance, _-CH2- , -CH( _CH3 )-, and -C( _CH3 ) _2- are more preferred.

As a method for manufacturing the diaminophenol derivative represented by the above formula (A-s), for example, reference can be made to paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Publication No. 2013-256506, the contents of which are incorporated herein by reference.

As a specific example of the structure of a diaminophenol derivative represented by the above formula (A-s), the contents described in paragraphs 0070 to 0080 of Japanese Patent Application Publication No. 2013-256506 are provided, and such contents are incorporated in this specification. Of course, it is not limited to such examples.

In addition to the repeating unit of formula (3) above, polybenzoxazole precursors may also contain other types of repeating structural units. From the viewpoint of suppressing warping associated with ring closure, it is preferable to include a diamine residue represented by formula (SL) as another type of repeating structural unit.

[Chemical Formula 21] In formula (SL), Z has an a-structure and a b-structure. ^R1s is a hydrogen atom or an hydrocarbon with 1 to 10 carbon atoms, ^R2s is an hydrocarbon with 1 to 10 carbon atoms, at least one of ^R3s , ^R4s , ^R5s , and ^R6s is an aromatic group, and the remaining part is a hydrogen atom or an organic group with 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a-structure and the b-structure can be block polymerization or random polymerization. Regarding the molar percentage of the Z part, the a-structure is 5 to 95 molars, the b-structure is 95 to 5 molars, and a+b is 100 molars.

In formula (SL), Z is preferably represented by ^R5s and ^R6s being 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 the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, while simultaneously achieving both anti-buckling and improved solvent solubility.

When a diamine residue represented by formula (SL) is included as another type of repeating structural unit, it is also preferable to further include a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic acid dianhydride as a repeating structural unit. As an example of such a tetracarboxylic acid residue, R ¹¹⁵ in formula (2) can be cited.

For example, when used in the compositions described later, 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 dispersion of the above-mentioned polybenzoxazole precursor is preferably 1.4 or higher, more preferably 1.5 or higher, and even more preferably 1.6 or higher. There is no particular upper limit to the molecular weight dispersion of polybenzo[a]azole precursors. For example, 2.6 or less is preferred, 2.5 or less is better, 2.4 or less is even better, 2.3 or less is even better, and 2.2 or less is even better.

[Polybenzoxazole] As for polybenzoxazole, there is no particular limitation as long as it is a polymeric compound having a benzoxazole ring. Compounds represented by formula (X) are preferred, and compounds represented by formula (X) and having polymerizable groups are even more preferred. As for the polymerizable groups, free radical polymerizable groups are preferred. Furthermore, compounds represented by formula (X) and having polar conversion groups such as acid-decomposing groups can also be used. [Chemical Formula 22] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When a polymerizable or acid-degradable polar conversion group is present, the polymerizable or acid-degradable polar conversion group may be located on at least one of R ¹³³ and R ¹³⁴ , or it may be located at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2) below. Formula (X-1) [Chemical Formula 23] In formula (X-1), at least one of ^R135 and ^R136 is a polymerizable group or an acid-degradable polar conversion group, or an organic group if it is not a polymerizable group or an acid-degradable polar conversion group. The meanings of the other groups are the same as in formula (X). Formula (X-2) [Chemical Formula 24] In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-degradable group, and the rest are substituents. The meanings of other groups are the same as in formula (X).

The meaning of polar conversion groups such as polymerizable groups or acid-degradable groups is the same as that of polar conversion groups such as polymerizable groups or acid-degradable groups described in the polymerizable groups of the above-mentioned polyimide precursors.

R ¹³³ represents a divalent organic group. Examples of divalent organic groups include aliphatic or aromatic groups. As a specific example, R ¹²¹ in formula (3) of the polybenzoxazole precursor can be given. Furthermore, the meaning of the preferred example is the same as that of R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. An example of a tetravalent organic group is R ¹²² in formula (3) of a polybenzoxazole precursor. Furthermore, its preferred meaning is the same as R ^122. For example, the four bonds of the tetravalent organic group exemplified by R ¹²² bond with the nitrogen and oxygen atoms in formula (X) above to form a condensed ring. For example, when R ¹³⁴ is an organic group, the following structure is formed. [Formula 25]

A benzoxazole saturation rate of 85% or higher is preferred, and 90% or higher is even better. With a saturation rate of 85% or higher, the shrinkage of the closed-ring membrane (which occurs during saturation by heating) is reduced, and warping can be effectively suppressed.

Polybenzoxazole may include all repeating structural units of formula (X) above containing one type of R ¹³¹ or R ¹³² , or may include repeating structural units of formula (X) above containing two or more different types of R ¹³¹ or R ^132. Furthermore, in addition to repeating units of formula (X) above, polybenzoxazole may also include other types of repeating structural units.

For example, a polybenzoxazole precursor can be obtained by reacting a diaminophenol derivative with a dicarboxylic acid containing R ¹³³ , or a dicarboxylic acid dichloride selected from the above dicarboxylic acid, or a dicarboxylic acid derivative thereof. The precursor can then be acetazoleized using a conventional acetazole reaction method to obtain polybenzoxazole. Furthermore, in the case of a dicarboxylic acid, to improve the reaction yield, an active ester-type dicarboxylic acid derivative, such as 1-hydroxy-1,2,3-benzotriazole, can be used as a pre-reacted derivative to increase the reaction yield.

The weight-average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight-average molecular weight to 5,000 or higher, the flexural strength of the cured film can be improved. For organic films with excellent mechanical properties, a weight-average molecular weight of 20,000 or higher is particularly preferred. Furthermore, when two or more polybenzoxazoles are contained, it is preferable that at least one polybenzoxazole has a weight-average molecular weight within the above range.

[Manufacturing Method of Polyimide Precursors, etc.] Polyimide precursors, etc., can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or its derivative is halogenated with a halogenating agent before reacting with the diamine. In the manufacturing method of the polyimide precursor, it is preferable to use an organic solvent during the reaction. One or more organic solvents can be used. The organic solvent can be appropriately selected depending on the raw materials; examples include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimides can be manufactured by cyclizing polyimide precursors through methods such as thermal cyclization, chemical cyclization (e.g., by using a catalyst to promote the cyclization reaction), or they can be synthesized directly.

Furthermore, it is preferable to use a non-halogenated catalyst instead of the aforementioned halogenated agents for synthesis. As the aforementioned non-halogenated catalyst, known amide catalysts that do not contain halogen atoms can be used without particular restriction; examples include borooxytrimer compounds, N-hydroxyl compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds. Examples of carbodiimide compounds include N,N'-diisopropylcarbodiimide and N,N'-dicyclohexylcarbodiimide.

-End- Capping Agents- In order to further improve storage stability, it is better to seal the ends of polyimide precursors, etc., with end-capping agents such as acid anhydrides, monocarboxylic acids, monochlorodiphenyl compounds, and monoactive ester compounds. Monoamines are preferred as end-capping agents. Examples of 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, and 1-carboxy-5-aminonaphthalene. -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-aminobenzenethiophenol, 3-aminobenzenethiophenol, 4-aminobenzenethiophenol, etc. Two or more of these can be used, or multiple different terminal groups can be introduced by reacting multiple end-capping agents.

-Solid Precipitation- The manufacture of polyimide precursors, etc., may include a process for precipitating solids. Specifically, the polyimide precursor, etc., in the reaction solution is precipitated in water and dissolved in a solvent soluble in the polyimide precursor, such as tetrahydrofuran, thereby causing solid precipitation. Subsequently, by drying the polyimide precursor, etc., powdered polyimide precursors, etc., can be obtained.

[Content] The content of the specific resin in the composition of the present invention, relative to the total solid content of the composition, is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and even more preferably 50% by mass or more. Furthermore, the content of the resin in the composition of the present invention, relative to the total solid content of the composition, is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less. The composition of the present invention may contain only one specific resin, or it may contain two or more. When containing two or more, the total amount within the above-mentioned range is preferred.

Furthermore, it is preferable that the photosensitive resin composition of the present invention contains at least two types of resins. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more specific resins and other resins described below, or it may contain two or more specific resins, with the inclusion of two or more specific resins being preferable. When the photosensitive resin composition of the present invention contains two or more specific resins, it is preferable, for example, to contain a polyimide precursor, which is derived from two or more polyimide precursors with different structures of dianhydrides (R ¹¹⁵ mentioned in formula (2) above).

<Organometallic Complexes> The photosensitive resin composition of this invention comprises organometallic complexes. Organometallic complexes are any organic complex compounds containing metal atoms. It is preferable to have complex compounds containing both metal atoms and organic groups; compounds in which the organic groups are coordinated with the metal atoms are more preferred; and metallocene compounds are even more preferred. In this invention, metallocene compounds refer to organometallic complexes containing two cyclopentadienyl anionic derivatives, which may have substituents, as n5-ligands. The aforementioned organic groups are not particularly limited; hydrocarbon groups or groups composed of hydrocarbon groups and heteroatoms are preferred. As heteroatoms, oxygen, sulfur, and nitrogen atoms are preferred. In this invention, it is preferable that at least one of the organic groups is a cyclic group, and more preferably that at least two are cyclic groups. The aforementioned cyclic groups are preferably selected from 5-membered and 6-membered ring cyclic groups, with 5-membered ring cyclic groups being more preferred. The aforementioned cyclic groups can be hydrocarbon rings or heterocyclic rings, but hydrocarbon rings are preferred. As a 5-membered ring cyclic group, cyclopentadienyl is preferred. Furthermore, it is preferable that the organometallic complex used in this invention contains 2 to 4 cyclic groups per molecule.

The metals contained in the organometallic complex are not particularly limited, but it is preferable to be metals that conform to Group 4 elements, more preferably to be selected from at least one metal in the group including titanium, zirconium and ruthenium, even more preferably to be selected from at least one metal in the group including titanium and zirconium, and titanium is particularly preferred.

Organometallic complexes can contain two or more metal atoms, or they can contain only one metal atom, but it is preferable to contain only one metal atom. When organometallic complexes contain two or more metal atoms, they can contain only one type of metal atom or two or more types of metal atoms.

Organometallic compounds are preferably titanium diacene, zirconium diacene, or ferrocene, with titanium diacene or zirconium diacene being more preferred, and titanium diacene being even more preferred.

The organometallic complex exhibiting photoradical polymerization initiation capability is also one of the preferred embodiments of the present invention. In the present invention, photoradical polymerization initiation capability refers to the ability to generate free radicals capable of initiating free radical polymerization upon light irradiation. For example, when a composition containing a free radical crosslinker and an organometallic complex is irradiated with light in the wavelength region absorbed by the organometallic complex and the wavelength region not absorbed by the free radical crosslinker, the presence or absence of photoradical polymerization initiation capability can be confirmed by observing whether the free radical crosslinker disappears. Confirmation of disappearance can be made using an appropriate method, such as IR determination (infrared spectrophotometry) or HPLC determination (high-performance liquid chromatography), depending on the type of free radical crosslinker. When organometallic complexes possess photoradical polymerization initiation capabilities, metallocene compounds are preferred, with titanium diacene, zirconium diacene, or titanium diacene being even better, titanium diacene or zirconium diacene being further preferred, and titanium diacene being particularly preferred. When the organometallic complex does not possess photoradical polymerization initiation ability, it is preferable that the organometallic complex is selected from at least one compound from the group consisting of titanium diacene compounds, tetraalkoxy titanium compounds, nitrified titanium compounds, chelated titanium compounds, zirconium diacene compounds, and titanium diacene compounds; it is even more preferable that it is selected from at least one compound from the group consisting of titanium diacene compounds, zirconium diacene compounds, and titanium diacene compounds; it is further preferable that it is selected from at least one compound from the group consisting of titanium diacene compounds and zirconium diacene compounds; and titanium diacene compounds are particularly preferred.

The molecular weight of organometallic complexes is preferably 50 to 2,000, and even better if it is 100 to 1,000.

As organometallic complexes, compounds represented by the following formula (P) are preferably exemplified. [Formula 26] In formula (P), M is a metallic element, and R are each and each independently a substituent. Preferably, R are each independently selected from aromatic groups, alkyl groups, halogen atoms, and alkyl sulfonyloxy groups.

In formula (P), the metallic element represented by M is preferably titanium, zirconium, or iron, with titanium or zirconium being more preferred, and titanium being even more preferred. The aromatic group in R of formula (P) can be an aromatic group having 6 to 20 carbon atoms, with aromatic hydrocarbons having 6 to 20 carbon atoms being preferred, such as phenyl, 1-naphthyl, or 2-naphthyl. The alkyl group in R of formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, with alkyl groups having 1 to 10 carbon atoms being more preferred, such as methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. Examples of halogen atoms in R include F, Cl, Br, and I. As for the alkyl group constituting the alkylsulfonyloxy group in R, alkyl groups with 1 to 20 carbon atoms are preferred, and alkyl groups with 1 to 10 carbon atoms are even more preferred, such as methyl, ethyl, propyl, octyl, isopropyl, tributyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. R may further have substituents. Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acetyl, alkoxycarbonyl, aryloxycarbonyl, acetyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino, etc.

Specific examples of organometallic complexes are not particularly limited, but may include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetoacetate)titanium, diisopropoxybis(acetoacetone)titanium, and the following compounds. [Chemical Formula 27]

In addition, compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 may be used, but are not limited thereto.

The content of the organometallic complex relative to the total solids of the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more. The upper limit is preferably 25% by mass or less. One or more organometallic complexes can be used. When two or more are used, the total amount within the above range is preferred.

<Sensitizer with Condensed Ring Structure> The photosensitive resin composition of this invention includes a sensitizer with a condensed ring structure (hereinafter also referred to as a "specific sensitizer"). In this invention, a condensed ring structure refers to a structure in which two ring structures share two atoms and one bond. One or both of the aforementioned two ring structures can further form a condensed ring structure with other ring structures. The specific sensitizer may have at least one condensed ring structure, or may contain a plurality of them. Furthermore, the condensation ring structure in a specific sensitizer can be a structure formed by the linear condensation of multiple ring structures such as those in benzene series hydrocarbons; it can also be a structure formed by the non-linear condensation of multiple ring structures such as phenanthrene structures; or it can be a structure formed by the condensation of multiple ring structures such as pyrene structures with other multiple ring structures. Of these, a condensed ring structure formed by the condensation of 2 to 6 ring structures is preferred, a ring structure formed by the condensation of 2 to 4 ring structures is more preferred, a ring structure formed by the condensation of 2 or 3 ring structures is further preferred, and a ring structure formed by the condensation of 3 ring structures is particularly preferred. The above-mentioned ring structures are not particularly limited, but 5-membered or 6-membered ring structures are preferred. Furthermore, in the above-mentioned ring structures, at least one ring structure containing a nitrogen atom (described later) or a ring structure containing a sulfur atom is preferred.

The specific sensitizer can be a sensitizer of the photosensitizer described later, and it is preferable to be a compound of the above-mentioned organometallic complex that has the ability to initiate photoradical polymerization or a sensitizer that has a sensitizing effect on the free radical polymerization initiator described later.

It is preferable that a specific sensitizer has a maximum absorption wavelength in the wavelength range of 250 nm to 550 nm, and even more preferably in the wavelength range of 300 nm to 450 nm. For example, the aforementioned maximum absorption wavelength can be determined using a spectrophotometer and a known method.

Preferably, the condensed ring structure in a particular sensitizer includes at least one atom selected from the group consisting of nitrogen and sulfur atoms as a ring member. The inclusion of at least one atom selected from the group consisting of nitrogen and sulfur atoms as a ring member means that at least one of the at least two ring structures forming the condensed ring structure includes at least one atom selected from the group consisting of nitrogen and sulfur atoms as a ring member. Examples of ring structures containing a nitrogen atom as a ring member include pyrrolidine rings, pyrrole rings, imidazolide rings, azirazole rings, tetrahydrothiazolium rings, isotetrahydrothiazolium rings, triazole rings, tetraazole rings, piperidine rings, piperazine rings, pyridine rings, diazine rings, triazine rings, and 4-piperidinone rings. Examples of ring structures containing a sulfur atom as a ring member include thiophene rings, tetrahydrothiophene rings, tetrahydrothiazolium rings, isotetrahydrothiazolium rings, dithiazolide rings, and 4-tetrahydrothiaranone rings. The ring is not particularly limited to forming a condensed ring structure with a ring structure that includes at least one atom selected from the group including nitrogen and sulfur atoms as ring members. It can be a ring structure that includes at least one atom selected from the group including nitrogen and sulfur atoms as ring members, but a hydrocarbon ring structure is preferred, an aromatic hydrocarbon ring structure is more preferred, and a benzene ring structure is even more preferred.

Considering resolution, exposure sensitivity, and drug resistance, it is preferable that the specific sensitizer includes at least one structure selected from the group consisting of acridinone, thiatonone, and acridinium structures as a condensed ring structure. The specific sensitizer may include only one structure selected from the group consisting of acridinone, thiatonone, and acridinium structures, or it may include two or more structures. When two or more structures are included, these structures may be the same or different. Furthermore, it is preferable that the specific sensitizer is a compound represented by any one of the following formulas (1-1), (2-1), and (3-1). [Formula 28] In formula (1-1), formula (2-1) or formula (3-1), ^R11 to ^R19 each independently represent a hydrogen atom or a substituent, at least two of ^R11 to ^R19 can bond to form a ring structure, ^R21 to ^R28 each independently represent a hydrogen atom or a substituent, at least two of ^R21 to ^R28 can bond to form a ring structure, and ^R31 to ^R39 each independently represent a hydrogen atom or a substituent, at least two of ^R31 to ^R39 can bond to form a ring structure.

In formula (1-1), ^R11 to ^R18 independently represent a hydrogen atom or a substituent, with hydrogen, hydrocarbon, or halogen atom being preferred. The hydrocarbon can be any of an aliphatic or aromatic hydrocarbon, but alkyl or aromatic hydrocarbons are preferred, with alkyl being even more preferred. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, with phenyl or naphthyl being more preferred, and phenyl being even more preferred. The halogen atom is preferably a fluorine, chlorine, bromine, or iodine atom, with chlorine or bromine being even more preferred. In formula (1-1), R ¹⁹ represents a hydrogen atom or a substituent, preferably a hydrogen atom, an hydrocarbon atom, or a halogen atom, with a hydrogen atom or a hydrocarbon atom being more preferred. In formula (1-1), the preferred states of the hydrocarbon atom and halogen atom in R ¹⁹ are the same as the preferred states of the hydrocarbon atom and halogen atom in R ¹¹ to R ^18. In this invention, at least two of R ¹¹ to R ¹⁹ can bond to form a ring structure, but a state in which none of R ¹¹ to R ¹⁹ forms a ring structure is also a preferred state.

In formula (2-1), R ²¹ to R ²⁸ independently represent a hydrogen atom or a substituent, with hydrogen atom, hydrocarbon atom, or halogen atom being preferred, hydrogen atom or halogen atom being more preferred, and hydrogen atom being particularly preferred. The hydrocarbon atom can be any of aliphatic or aromatic hydrocarbons, but alkyl or aromatic hydrocarbons are preferred, and alkyl is even more preferred. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, and alkyl group having 1 to 4 carbon atoms is even more preferred. The aromatic hydrocarbon atom is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, phenyl or naphthyl is more preferred, and phenyl is even more preferred. The halogen atom is preferably a fluorine atom, chlorine atom, bromine atom, or iodine atom, with chlorine or bromine atom being even more preferred. In this invention, at least two of R ²¹ to R ²⁸ can be bonded to form a ring structure, but the state in which none of R ²¹ to R ²⁸ form a ring structure is also one of the better states.

In formula (3-1), R ³¹ to R ³⁸ independently represent a hydrogen atom or a substituent, with hydrogen, hydrocarbon, or halogen atom being preferred. As the aforementioned hydrocarbon, any aliphatic or aromatic hydrocarbon is preferred, but alkyl or aromatic hydrocarbons are preferred. As the aforementioned alkyl group, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 4 carbon atoms are more preferred. As the aforementioned aromatic hydrocarbon group, aromatic hydrocarbon groups having 6 to 30 carbon atoms are preferred, phenyl or naphthyl are more preferred, and phenyl is even more preferred. As the aforementioned halogen atom, fluorine, chlorine, bromine, or iodine atoms are preferred, with chlorine or bromine atoms being more preferred. In formula (3-1), R ³⁹ represents a hydrogen atom or a substituent, preferably a hydrogen atom, an hydrocarbon group, or a halogen atom, with a hydrogen atom or a hydrocarbon group being more preferred. In formula (3-1), the preferred states of the hydrocarbon group and halogen atom in R ³⁹ are the same as the preferred states of the hydrocarbon group and halogen atom in R ³¹ to R ^38. In this invention, at least two of R ³¹ to R ³⁹ can bond to form a ring structure, but a state in which none of R ³¹ to R ³⁹ forms a ring structure is also a preferred state.

Furthermore, certain sensitizers may also be compounds comprising the following structures as part of their structure: structures in which at least one of ^R11 - ^R19 , ^R21 - ^R28 , and ^R31 - ^R39 in any of the structures represented by formulas (1-1), (2-1), and (3-1) serves as a bonding site with other structures. For example, as shown in formula (3-2) below, examples can be given of compounds in which ^R39 in the structure represented by formula (3-1) serves as a bonding site with other structures. [Chemical Formula 29] In formula (3-2), the meanings of R ³¹ to R ³⁸ are independently the same as those of R ³¹ to R ³⁸ in formula (3-1) above, and the preferred states are also the same. In formula (3-2), L represents a linking group with an m-valence, which is preferably an hydrocarbon with a substituent in the m-valence. For example, L can be an hydrocarbon or a group consisting of -O-, C(=O)-, -S-, -S(=O) _2- , or a combination of two or more of these. It is preferred that the group contains at least a hydrocarbon, and more preferably a hydrocarbon. The hydrocarbon can be an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group represented by a combination of these, but a saturated aliphatic hydrocarbon is preferred. In equation (3-2), m represents an integer greater than 2, and it is preferable to use an integer between 2 and 10.

The molecular weight of a specific sensitizer is preferably 100-2,000, and even better if it is 150-1,000.

Specific examples of certain sensitizers are not particularly limited, but can include 2,4-dimethylthiatonone, N-phenyldiethanolamine, ethyl 7-(diethylamino)coumarin-3-carboxylate, 2,4-diethylthiatonone, 2-chlorothiatonone, 2,4-diisopropylthiatonone, acridine, N-methyl acridine, N-butyl acridine, N-butyl-chloro acridine, 9-phenyl acridine, 1,7-bis(9,9'-acidine)heptane, p-dimethylaminobenzyldihydroindene, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylvinyl)isonaphthothiazole, 3 3’-Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 2-benzimidazole, 2-benzimidazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, dibenzothiophene, benzo[b]naphtho[1,2-d]thiophene, benzo[b]naphtho[1,2-d]thiophene, 4-phenyldibenzothiophene, etc.

The content of the specific sensitizer relative to the total solids content of the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass. The lower limit is preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1.0% by mass or more. The upper limit is preferably 25% by mass or less. One or more organometallic compounds can be used. When two or more are used, the total amount is preferably within the above range.

Furthermore, relative to 1 part by weight of the above-mentioned organometallic complex, the content of the specific sensitizer is preferably 0.5 to 5.0 parts by weight, more preferably 0.6 to 3.0 parts by weight, and even more preferably 0.75 to 2.0 parts by weight.

<Other Resins> The composition of this invention may include the specific resin described above and other resins different from the specific resin (hereinafter also referred to as "other resins"). Examples of other resins include polyamide-imide, polyamide-imide precursors, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, and acrylic resins. For example, by further adding acrylic resins, a composition with excellent coatability can be obtained, and an organic film with excellent solvent resistance can also be obtained. For example, by replacing the crosslinker described later or by adding an acrylic resin with a weight average molecular weight of less than 20,000 and a high polymeric group value to the composition, the coatability of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and still more preferably 10% by mass or more. Furthermore, the content of other resins in the composition of the present invention relative to the total solid content of the composition is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, even more preferably 60% by mass or less, and still more preferably 50% by mass or less. Furthermore, as one of the preferred embodiments of the composition of the present invention, it is also possible to design an embodiment with a low content of other resins. In the above embodiments, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, more preferably 15% by mass or less, further 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; 0% by mass or more is acceptable. The composition of the present invention may contain only one type of other resin, or it may contain two or more types. When containing two or more types, it is preferable that the total amount is within the above range.

<Soluble> The photosensitive resin composition of this invention preferably contains a solvent. Any known solvent can be used. The solvent is preferably an organic solvent. Examples of organic solvents include esters, ethers, ketones, cyclic hydrocarbons, monoxides, amides, ureas, and alcohols.

Examples of 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetic acid, ethyl alkoxyacetic acid, butyl alkoxyacetic acid (e.g., methyl methoxyacetic acid, ethyl methoxyacetic acid, butyl methoxyacetic acid, methyl ethoxyacetic acid, ethyl ethoxyacetic acid, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., methyl 3-alkoxypropionic acid, ethyl 3-alkoxypropionic acid, etc. (e.g., methyl 3-methoxypropionic acid, ethyl 3-methoxypropionic acid, methyl 3-ethoxypropionic acid, ethyl 3-ethoxypropionic acid). Alkyl esters of 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 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 (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred.

As ethers, preferred examples include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl 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, and propylene glycol monopropyl ether acetate.

As ketones, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, L-glucanone, and dihydro-L-glucanone are among the better choices.

As cyclic hydrocarbons, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene are preferred examples.

As for ionoids, dimethyl ionoids can be cited as a better example.

Among the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-methoxy-N,N-dimethylpropionic acid, N-methoxy-N,N-dimethylpropionic acid, and N-acetylatedotropine are considered as better choices.

Among ureas, N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone are considered better options.

Examples of 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, from the perspective of improving coating properties, it is better to mix two or more forms.

In this invention, a solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celusoacetate, 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, and propylene glycol methyl ether acetate, or a mixture of two or more solvents, is preferred. The simultaneous use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Furthermore, combinations of N-methyl-2-pyrrolidone with ethyl lactate, diacetone alcohol with ethyl lactate, and cyclopentanone with γ-butyrolactone are also preferred.

Regarding the solvent content, from a coating properties perspective, it is preferable that the total solids concentration of the photosensitive resin composition of this invention is 5-80% by mass, more preferably 5-75% by mass, further preferably 10-70% by mass, and even more preferably 40-70% by mass. The solvent content can be adjusted according to the required coating thickness and coating method.

The solvent may contain only one type or more than two types. When there are more than two types of solvents, it is preferable that their total amount is within the above range.

<Photosensitive Agent> The composition of this invention preferably includes a photosensitizer. The photosensitizer does not contain any compound that is an organometallic complex as described above and has photoradical polymerization initiation ability. As a photosensitizer, a photopolymerization initiator is preferred.

[Photopolymerization Initiator] The composition of this invention preferably includes a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular limitations 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, it can be an active agent that interacts with a photosensitive agent and generates active free radicals.

In this invention, compounds that conform to organometallic complexes do not conform to photosensitizers and photoradical polymerization initiators.

When the composition of the present invention possesses photoradical polymerization initiation ability, it is also preferable that the composition of the present invention substantially does not contain any free radical polymerization initiators other than the aforementioned organometallic chelates. "Substantially does not contain any free radical polymerization initiators other than the aforementioned organometallic chelates" means that the content of free radical polymerization initiators other than the aforementioned organometallic chelates in the composition of the present invention is preferably 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass. Furthermore, when the composition of the present invention contains organometallic chelates possessing free radical polymerization initiation ability, it is also preferable that the composition of the present invention contains the aforementioned organometallic chelates and other photoradical polymerization initiators. When the composition of the present invention contains organometallic chelates and other photoradical polymerization initiators, the content of organometallic chelates relative to the total content of the organometallic chelates and other photoradical polymerization initiators is preferably 20-80% by mass, and more preferably 30-70% by mass. Furthermore, the oxime compounds described later are preferred as the other photoradical polymerization initiators.

The photoradical polymerization initiator preferably contains at least one compound having a molar absorptivity of at least about 50 L/ ^mol⁻¹ / ^cm⁻¹ in the range of about 300–800 nm (preferably 330–500 nm). The molar absorptivity of the compound can be determined using known methods. For example, it is preferable to determine it using a UV-Vis spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, any known compound can be used. Examples include halogenated hydrocarbon derivatives (such as compounds with a trihalomethane skeleton, compounds with a diazole skeleton, compounds with a trihalomethane skeleton, etc.), acetyphosphine compounds such as acetyphosphine oxide, hexaaryl diimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron-aromatic hydrocarbon complexes. For details regarding these contents, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, which are incorporated herein by reference.

As a ketone compound, for example, the compound described in paragraph 0087 of Japanese Patent Application Publication No. 2015-087611, the contents of which are incorporated herein by reference. KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferred in commercially available products.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and amide phosphine compounds are preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators disclosed in Japanese Patent Application Publication No. 10-291969 and amide phosphine oxide-based initiators disclosed in Japanese Patent No. 4225898 can be used.

As a hydroxyacetophenone initiator, it can use IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF).

As an aminoacetophenone-based initiator, it can be used in commercially available products such as IRGACURE 907, IRGACURE 369 and IRGACURE 379 (all manufactured by BASF).

As an aminoacetophenone-based initiator, compounds described in Japanese Patent Application Publication No. 2009-191179, which have extremely high absorption wavelengths and are matched with light sources of wavelengths such as 365 nm or 405 nm, can also be used.

Examples of phosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Additionally, commercially available products such as IRGACURE-819 and IRGACURE-TPO (both manufactured by BASF) can be used.

Oxime compounds are preferred as photoradical polymerization initiators. Using oxime compounds can further and more effectively improve exposure tolerance. Oxime compounds are particularly advantageous because they offer a wider exposure tolerance (residual exposure) and also act as photocuring accelerators.

As specific examples of oxime compounds, compounds disclosed in Japanese Patent Application Publication No. 2001-233842, Japanese Patent Application Publication No. 2000-080068, and Japanese Patent Application Publication No. 2006-342166 may be used.

Preferred oxime compounds include, for example, compounds with the following structures: 3-benzoxylidene-iminobutane-2-one, 3-acetoxylidene-iminobutane-2-one, 3-propoxylidene-iminobutane-2-one, 2-acetoxylidene-iminopentane-3-one, 2-acetoxylidene-1-phenylpropane-1-one, 2-benzoxylidene-1-phenylpropane-1-one, 3-(4-toluenesulfonoxy)iminobutane-2-one, and 2-ethoxycarbonyloxylidene-1-phenylpropane-1-one. In the compositions of the present invention, it is particularly preferred to use the oxime compound as a photoradical polymerization initiator (oxime-based photopolymerization initiator). Oxime-based photopolymerization initiators have a >C=N-O-C(=O)- linker in the molecule.

[Chemical Formula 30]

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 disclosed in Japanese Patent Application Publication No. 2012-014052) are also suitable. Furthermore, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO.,LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) are also suitable. Additionally, DFI-091 (manufactured by DAITO CHEMIX Co.,Ltd.) is also suitable. Furthermore, oxime compounds with the following structure can also be used. [Formula 31]

Oxime compounds with cyclohexane can also be used as photopolymerization initiators. Specific examples of oxime compounds with cyclohexane include the compound disclosed in Japanese Patent Application Publication No. 2014-137466 and the compound disclosed in Japanese Patent No. 06636081.

As a photopolymerization initiator, oxime compounds with at least one benzene ring having a carbazole ring forming the naphthalene ring skeleton can also be used. Specific examples of such oxime compounds include the compound described in International Publication No. 2013/083505.

Oxime compounds containing fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Patent Application Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Patent Application Publication No. 2013-164471.

As the best oxime compounds, examples include the oxime compounds with specific substituents shown in Japanese Patent Application Publication No. 2007-269779, and the oxime compounds with thioaryl groups shown in Japanese Patent Application Publication No. 2009-191061.

From the perspective of exposure sensitivity, photoradical polymerization initiators are preferably selected from the group consisting of trihalomethane trihalomethane compounds, benzyl dimethyl ketone compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acetophosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazolium dimers, onium salts, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadienyl-benzene-iron complexes and their salts, halomethanediazole compounds, and 3-aryl-substituted coumarin compounds.

The preferred free radical polymerization initiator is a trihalomethane trihalomethane compound, an α-amino ketone compound, an oxime compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazolium dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. It is further preferred that at least one compound is selected from the group consisting of trihalomethane trihalomethane compounds, α-amino ketone compounds, oxime compounds, triarylimidazolium dimers, and benzophenone compounds. It is even more preferred that a metallocene compound or an oxime compound is used. An oxime compound is even more preferred.

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

[Chemical Formula 32]

In formula (I), ^RI00 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, 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 interrupted by one or more oxygen atoms, and a phenyl or biphenyl group having at least one substituted alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms. ^RI01 is a group represented by formula (II) or is the same group as ^RI00 . ^RI02 to ^RI04 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 33]

In the formula, ^RI05 to ^RI07 are the same as ^RI02 to ^RI04 in the above formula (I).

Furthermore, the photoradical polymerization initiator can also be the compound described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. The photopolymerization initiator may be contained in only one type or in two or more types. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range.

[Photosensitive Acid Generator] Furthermore, it is preferable that the composition of the present invention includes a photosensitive acid generator as a photosensitizer. By containing a photosensitive acid generator, for example, acid is generated in the exposed portion of the photosensitive film, thereby increasing the solubility of the exposed portion in the developing solution (e.g., an alkaline aqueous solution), and a positive pattern in which the exposed portion is removed by the developing solution can be obtained. Alternatively, it is also possible to configure the composition to contain a photosensitive acid generator and a crosslinking agent other than the free radical crosslinking agent described later. For example, by utilizing the acid generated in the exposed portion to promote the crosslinking reaction of the crosslinking agent, the exposed portion is less likely to be removed by the developing solution than the non-exposed portion. According to this configuration, a negative pattern can be obtained.

As a photoacid generator, there are no particular limitations as long as acid is generated through exposure. Examples include quinone diazonium compounds, diazonium salts, phosphonium salts, strontium salts, monazine salts, succinates, oxime sulfonates, diazonium, diazonium, and sulfonate compounds such as orthonitrobenzyl sulfonate.

Examples of quinone diazonium compounds include those in which the sulfonic acid of the quinone diazonium is bonded to a polyhydroxy compound via an ester bond, those in which the sulfonic acid of the quinone diazonium is bonded to a polyamine compound via a sulfonamide bond, and those in which the sulfonic acid of the quinone diazonium is bonded to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond. In this invention, for example, it is preferable that at least 50 mol% of the functional groups of such polyhydroxy compounds and polyamine compounds are replaced by quinone diazonium compounds.

In this invention, 5-naphthoquinone diazonium sulfonate and 4-naphthoquinone diazonium sulfonate are both preferred as quinone diazonium compounds. The 4-naphthoquinone diazonium sulfonate compound has absorption in the i-ray region of a mercury lamp, and is therefore suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazonium sulfonate compound extends to the g-ray region of a mercury lamp, and is therefore suitable for g-ray exposure. In this invention, the 4-naphthoquinone diazonium sulfonate compound and the 5-naphthoquinone diazonium sulfonate compound are preferred depending on the wavelength of the exposure. Furthermore, it may contain naphthoquinone disulfonate compounds having 4-naphthoquinone disulfonyl and 5-naphthoquinone disulfonyl groups in the same molecule, or it may contain both 4-naphthoquinone disulfonate compounds and 5-naphthoquinone disulfonate compounds.

The aforementioned naphthoquinone diazonium compounds can be synthesized by esterification of compounds with phenolic hydroxyl groups and quinone diazonium sulfonic acid compounds, and can be synthesized by known methods. By using these naphthoquinone diazonium compounds, resolution, sensitivity, and film residue are further improved. Examples of the aforementioned naphthoquinone diazonium compounds include, for example, 1,2-naphthoquinone-2-diazazo-5-sulfonic acid or 1,2-naphthoquinone-2-diazazo-4-sulfonic acid, salts or esters of these compounds.

Examples of compounds that are onium salts or sulfonates include those described in paragraphs 0064 to 0122 of Japanese Patent Application Publication No. 2008-013646.

Photonic acid generators containing an oxime sulfonate group (hereinafter also referred to as "oxime sulfonate compounds") are preferred. There are no particular restrictions on the presence of an oxime sulfonate group in the oxime sulfonate compound; oxime sulfonate compounds represented by the following formula (OS-1), the formula described later (OS-103), the formula (OS-104), or the formula (OS-105) are preferred.

[Chemical Formula 34]

In formula (OS-1), ^X3 represents an alkyl, alkoxy, or halogen atom. When there are multiple ^X3 atoms, they can be the same or different. The alkyl and alkoxy atoms in ^X3 can have substituents. As the alkyl group in ^X3 , a straight-chain or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in ^X3 , a straight-chain or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in ^X3 , a chlorine or fluorine atom is preferred. In formula (OS-1), m3 represents an integer from 0 to 3, with 0 or 1 being preferred. When m3 is 2 or 3, the multiple ^X3 atoms can be the same or different. In formula (OS-1), R ³⁴ represents an alkyl or 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 that can be substituted with W, a naphthyl group that can be substituted with W, or an orthoamine benzoic acid group that can 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, or 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, ^X3 is substituted at an ortho position, and ^R34 is preferably a straight-chain alkyl group with 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorborneolmethyl or p-tolyl.

As specific examples of oxime sulfonate compounds represented by formula (OS-1), the following compounds described in Japanese Patent Application Publication No. 2011-209692, paragraphs 0064 to 0068, and Japanese Patent Application Publication No. 2015-194674, paragraphs 0158 to 0167, are illustrated in this specification.

[Chemical Formula 35]

In formulas (OS-103) to (OS-105), ^Rs1 represents alkyl, aryl, or heteroaryl; when present in multiples, some ^Rs2 independently represent hydrogen, alkyl, aryl, or halogen atoms; when present in multiples, some ^Rs6 independently represent halogen, alkyl, alkoxy, sulfonic acid, aminosulfonyl, or alkoxysulfonyl; 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 (preferably with 1 to 30 carbons), aryl (preferably with 6 to 30 carbons), or heteroaryl (preferably with 4 to 30 carbons) represented by Rs1 may have a substituent T.

In formulas (OS-103) to (OS-105), ^Rs2 is preferably a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms), or an aryl group (preferably with 6 to 30 carbon atoms), with hydrogen or alkyl being more preferred. In some compounds where two or more ^Rs2 are present, it is preferred that one or two are alkyl, aryl, or halogen atoms, more preferred that one is an alkyl, aryl, or halogen atom, and especially preferred that one is an alkyl group and the remainder are hydrogen atoms. The alkyl or aryl group represented by ^Rs2 may have a substituent T. In formulas (OS-103), (OS-104), or (OS-105), Xs represents O or S, with O being more preferred. In the above equations (OS-103) to (OS-105), the ring system containing Xs is a 5-member ring or a 6-member ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2. When Xs is O, ns being 1 is preferred; and when Xs is S, ns being 2 is preferred. 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 R ^s6 may have substituents. In formulas (OS-103) to (OS-105), ms represents an integer from 0 to 6, with integers from 0 to 2 being preferred, 0 or 1 being more preferred, and 0 being particularly preferred.

Furthermore, the compound represented by formula (OS-103) is preferably represented by formula (OS-106), formula (OS-110), or formula (OS-111); the compound represented by formula (OS-104) is preferably represented by formula (OS-107); and the compound represented by formula (OS-105) is preferably represented by formula (OS-108) or formula (OS-109). [Chemical Formula 36]

In formulas (OS-106) to (OS-111), ^Rt1 represents an alkyl, aryl, or heteroaryl group; ^Rt7 represents a hydrogen atom or a bromine atom; ^Rt8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl, bromomethyl, bromoethyl, methoxymethyl, phenyl, or chlorophenyl; ^Rt9 represents a hydrogen atom, a halogen atom, a methyl or methoxy group; and ^Rt2 represents a hydrogen atom or a methyl group. In formulas (OS-106) to (OS-111), ^Rt7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.

In formulas (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. It is preferred that the alkyl group having 1 to 8 carbon atoms or a halogen atom or a phenyl group has 1 to 8 carbon atoms, even more preferred, and alkyl group having 1 to 6 carbon atoms is even more preferred. Methyl is particularly preferred.

In formulas (OS-106) to (OS-111), ^Rt9 represents a hydrogen atom, a halogen atom, a methyl group, or a methoxy group, with a hydrogen atom being preferred. ^Rt2 represents a hydrogen atom or a methyl group, with a hydrogen atom being preferred. Furthermore, the stereostructure (E, Z) of the oxime can be any of the above-mentioned oxime sulfonate compounds, or a mixture thereof. Specific examples of oxime sulfonate compounds represented by formulas (OS-103) to (OS-105) are the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674, the contents of which are incorporated herein by reference.

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

[Chemical Formula 37]

In formula (OS-101) or (OS-102), ^Ru9 represents a hydrogen atom, alkyl, alkenyl, alkoxy, alkoxycarbonyl, acetyl, aminomethyl, aminosulfonyl, sulfonyl, cyano, aryl, or heteroaryl. It is preferred that ^Ru9 is cyano or aryl, and it is further preferred that ^Ru9 is cyano, phenyl, or naphthyl. In formula (OS-101) or (OS-102), ^Ru2a represents an alkyl or aryl group. In formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, ^-NRu5- , _-CH2- , ^-CRu6H- , or ^CRu6Ru7- , where ^Ru5 to ^Ru7 each independently represent an alkyl or aryl group ^.

In formula (OS-101) or formula (OS-102), ^Ru1 to ^Ru4 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, a amide group, a sulfonyl group, a cyano group, or an aryl group. Two of ^Ru1 to ^Ru4 can be bonded to each other to form a ring. In this case, the ring can condense to form a condensed ring together with the benzene ring. It is preferred that ^Ru1 to ^Ru4 are hydrogen atoms, halogen atoms, or alkyl groups, and it is also preferred that at least two of ^Ru1 to ^Ru4 are bonded to each other to form an aryl group. It is preferred that all of ^Ru1 to ^Ru4 are hydrogen atoms. All of the above substituents can be further substituented.

The compound represented by formula (OS-101) is preferably represented by formula (OS-102). Furthermore, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring can be any one of the above-mentioned oxime sulfonate compounds, or a mixture thereof. Specific examples of compounds represented by formula (OS-101) are 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 by reference. Among the above-mentioned compounds, b-9, b-16, b-31, and b-33 are preferred.

In addition, commercially available products can be used as photosensitive acid generators. Examples of commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250, Omnicat 270 (both manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF Corporation), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, compounds represented by the following structural formula can also be cited as better examples. [Formula 38]

As a photoacid generator, it can also be used with organic halogenated compounds. As organic halogenated compounds, specific examples include Wakabayashi et al.'s "Bull Chem. Soc Japan" 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, and M.P. Hutt's "Jurnal of Heterocyclic Compounds described in Chemistry 1 (No. 3), (1970), etc., especially trihalomethane-substituted oxazole compounds: S-trihalomethane compounds. More preferably, S-trihalomethane derivatives are formed by at least one mono, di, or trihalomethane-substituted methyl group bonded to an S-trihalomethane ring. Specifically, examples include 2,4,6-tris(monochloromethyl)-S-trihalomethane, 2,4,6-tris(dichloromethyl)-S-trihalomethane, 2,4,6-tris(trichloromethyl)-S-trihalomethane, 2-methyl-4,6-bis(trichloromethyl)-S-trihalomethane, 2-n-butyl-4,6-bis(trichloromethyl)-S-trihalomethane, 2 -(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl) [2,4-Butadienyl]-4,6-bis(trichloromethyl)-s-tris-tris-2-styryl-4,6-bis(trichloromethyl)-s-tris-2-styryl-2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-tris-2-styryl-2-(p-isopropoxystyryl)-4,6-bis(trichloromethyl)-s-tris-2-styryl-2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tris-2-styryl-2-(4-naphthoxynaphthyl) 4,6-bis(trichloromethyl)-s-tris, 2-phenylthio-4,6-bis(trichloromethyl)-s-tris, 2-benzylthio-4,6-bis(trichloromethyl)-s-tris, 2,4,6-tris(dibromomethyl)-s-tris, 2,4,6-tris(tribromomethyl)-s-tris, 2-methyl-4,6-bis(tribromomethyl)-s-tris, 2-methoxy-4,6-bis(tribromomethyl)-s-tris, etc.

Organic borate compounds can also be used as photoacid generators. Examples of organic borate compounds include, for instance, Japanese Patent Application Publication Nos. 62-143044, 62-150242, 9-188685, 9-188686, 9-188710, 2000-131837, 2002-107916, Japanese Patent No. 2764769, and Japanese Patent Application No. 2000-310808, as well as Kunz, Martin, “Rad Tech’98. Proceeding April”. Organic borates described in publications such as "19-22, 1998, Chicago", organic borosilicates or organic borosilicate oxo-sterilites described in Japanese Patent Application Publication Nos. 6-157623, 6-175564, and 6-175561, and organic borosilicate oxo-sterilites described in Japanese Patent Application Publication Nos. 6-175554 and 6-175553. Organoboron-iodine complexes, organoboron-phosphorus complexes disclosed in Japanese Patent Application Publication No. 9-188710, and organoboron transition metal coordination complexes disclosed in Japanese Patent Application Publication Nos. 6-348011, 7-128785, 7-140589, 7-306527, and 7-292014 are examples of such organoboron transition metal coordination complexes.

As a photoacid generator, disulfide compounds can also be used. Examples of disulfide compounds include those described in Japanese Patent Application Publication No. 61-166544 and Japanese Patent Application No. 2001-132318, as well as diazonium compounds.

Examples of such onmium salt compounds include, for instance, S.I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), and T.S. Bal et al. Diazo salts as described in al, Polymer, 21,423 (1980); ammonium salts as described in U.S. Patent No. 4,069,055; Japanese Patent Application Publication No. 4-365049; phosphonium salts as described in the specifications of U.S. Patent Nos. 4,069,055 and 4,069,056; European Patent Nos. 104,143, 339,049, and 410,201; tin salts as described in Japanese Patent Application Publication Nos. 2-150848 and 2-296514; and European Patent Nos. 370,693 and 390,2... 14, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, US Patent No. 4,933,377, US Patent No. 161,811, US Patent No. 410,201, US Patent No. 339,049, US Patent No. 4,760,013, US Patent No. 4,734,444, US Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, and the strontium salt described in the specifications of each of these patents, J.V. Crivello. Selenium salts described in J.V. Crivello et al., Macromolecules, 10(6), 1307(1977), and thallium salts such as pyridinium salts and pyridinium salts described in C.S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988).

Examples of onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited. [Chemical Formula 39] In formula (RI-I), Ar ₁₁ represents an aryl group having 1 to 6 substituents and having 20 or fewer carbon atoms. Examples of preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamide or arylamide groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₁₁ ^- indicates a monovalent anion, including halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. From a stability perspective, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, and sulfinate ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ represent aryl groups with 20 or fewer carbon atoms that can each independently have 1 to 6 substituents. Examples of preferred substituents include alkyl groups with 1 to 12 carbon atoms, alkenyl groups with 1 to 12 carbon atoms, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, aryloxy groups with 1 to 12 carbon atoms, halogen atoms, alkylamino groups with 1 to 12 carbon atoms, dialkylamino groups with 1 to 12 carbon atoms, alkylamide or arylamide groups with 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups with 1 to 12 carbon atoms, and thioaryl groups with 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, such as halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, or sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ represent aryl, alkyl, alkenyl, or alkynyl groups with 1 to 6 substituents and fewer than 20 carbon atoms, which can each independently have 1 to 6 substituents. Considering reactivity and stability, aryl groups are preferred. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamide or arylamide groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z ₃₁ ^- indicates a monovalent anion, including halogen ions, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, thiosulfate ions, and sulfate ions. Considering stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonate ions, sulfinate ions, and carboxylate ions are preferred.

As a specific example, the following example can be given. [Chemical Formula 40] [Chemical Formula 41] [Chemical Formula 42] [Chemical Formula 43]

When the photosensitive acid generator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, and even more preferably 2-15% by mass. The photosensitive acid generator may contain only one type or may contain two or more types. When two or more photosensitive acid generators are included, their total content within the above range is preferred.

[Photoalkali generator] The photosensitive resin composition of this invention may include a photoalkali generator as a photosensitizer. Alternatively, it can be configured such that, by containing a photoalkali generator and a crosslinking agent (described later) in the photosensitive resin composition, for example, by utilizing the alkali generated in the exposed area to promote the cyclization of a specific resin and the crosslinking reaction of the crosslinking agent, the exposed area is less susceptible to removal by the developing solution than the unexposed area. According to this configuration, a negative relief pattern can be obtained.

As a photoalkali generator, there are no particular restrictions as long as alkali is produced through exposure; it can be used by any known party. For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kakuoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol., 9, 13 (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006) describe examples of ionic compounds in which the base component is neutralized by salt formation, such as transition metal complexes, substances with structures like ammonium salts, and compounds whose base component is potentially neutralized by salt formation with carboxylic acids, as well as nonionic compounds such as carbamate derivatives, oxime derivatives, and acetylated compounds whose base component is potentially neutralized by carbamate or oxime bonds. In this invention, carbamate derivatives, amide derivatives, amide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, etc., can be cited as preferred examples as photoalkali generators.

The alkaline substance produced from the photoalkali generator is not particularly limited; examples include compounds with amine groups, especially polyamines such as monoamines and diamines, as well as amidines. From the perspective of acetylation rate, a higher pKa is preferred for the aforementioned alkaline substance, specifically DMSO (dimethyl sulfoxide) containing conjugated acids. A pKa of 1 or higher is preferred, and 3 or higher is even better. There is no particular upper limit to the pKa, but 20 or lower is preferred. Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can be found in *Determination of Organic Structures by Physical Methods* (authors: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; edited by Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) and *Data for Biochemical Research* (authors: Dawson, R.M.C. et al.; Oxford, Clarendon Press, 1959). For compounds not described in these publications, the pKa will be calculated using ACD/pKa software (made by ACD/Labs) and derived from the structural formula.

From the perspective of the storage stability of photosensitive resin components, it is preferable to use a photoalkali generator that does not contain salt in its structure, and preferably, the nitrogen atom of the alkali portion produced in the photoalkali generator should not have an electric charge. As a photoalkali generator, it is preferable that the produced alkali is latent through covalent bonding, and the alkali generation mechanism should ideally involve the cleavage of the covalent bonds between the nitrogen atom of the alkali portion and its neighboring atoms. If the photoalkali generator does not contain salt in its structure, it can be made neutral, thus resulting in better solvent solubility and an extended shelf life. For this reason, it is preferable that the amine produced by the photoalkali generator used in this invention is a primary or secondary amine. Furthermore, from the viewpoint of the resistance of the pattern to chemicals, it is preferable that the photoalkali generator contains a salt in its structure.

Furthermore, considering the above reasons, as a photoalkali generator, it is preferable that the generated alkali is potentially converted into a covalent bond, and it is preferable that the generated alkali is potentially converted into a amide bond, carbamate bond, or oxime bond. Examples of photoalkali generators of the present invention include, for example, those with a cinnamylamine structure disclosed in Japanese Patent Application Publication No. 2009-080452 and International Patent Application Publication No. 2009/123122; those with a carbamate structure disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747; and those with an oxime structure or an aminomethyloxime structure disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581. However, the invention is not limited to these examples. In addition, known photoalkali generator structures can be used.

In addition, as photoalkali generators, examples include compounds described in paragraphs 0185-0188, 0199-0200 and 0202 of Japanese Patent Application Publication No. 2012-093746, compounds described in paragraphs 0022-0069 of Japanese Patent Application Publication No. 2013-194205, compounds described in paragraphs 0026-0074 of Japanese Patent Application Publication No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631.

In addition, commercially available products can be used as photoalkali generators. Examples of commercially available products include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photoalkali generator is included, its content relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 2 to 15% by mass. The photoalkali generator may contain only one type or two or more types. When two or more photoalkali generators are included, their total content within the above range is preferred.

<Thermal Polymerization Initiator> The composition of this invention may include a thermal polymerization initiator, and more particularly, a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the resin and crosslinking agent can also undergo polymerization reactions during the heating process described later, thus further improving solvent resistance.

As a thermal free radical polymerization initiator, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as examples.

When a thermal polymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 5 to 15% by mass. The thermal polymerization initiator may contain only one type or may contain two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

<Thermal Acid Generator> The composition of this invention may include a thermal acid generator. The thermal acid generator has the following effect: by generating acid upon heating, it promotes cross-linking reactions of at least one compound selected from compounds having hydroxymethyl, alkoxymethyl, or acetomethyl groups, epoxides, oxocyclobutanes, and benzo[a] compounds.

The thermal decomposition initiation temperature of the thermal acid generator is preferably 50℃～270℃, and more preferably 50℃～250℃. Furthermore, if a substance that does not generate acid during drying (pre-baking: approximately 70～140℃) after the composition is applied to the substrate but generates acid during the final heating (curing: approximately 100～400℃) after pattern formation during subsequent exposure and development is selected as the thermal acid generator, the decrease in sensitivity during development can be suppressed, which is therefore preferable. The thermal decomposition initiation temperature is determined by heating the thermal acid generator in a pressure-resistant capsule at 5℃/min to 500℃, and identifying the temperature at which the lowest heating peak occurs. As a machine used to measure the temperature at which thermal decomposition begins, examples include the Q2000 (manufactured by TA Instruments Inc.).

The acid produced from the hot acid generator is preferably a strong acid, such as aryl sulfonic acids like p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids like methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or halogenated alkyl sulfonic acids like trifluoromethanesulfonic acid. As an example of such a hot acid generator, paragraph 0055 of Japanese Patent Application Publication No. 2013-072935 can be cited.

Among these, considering the minimal residue in organic membranes and the minimal reduction in the properties of the organic membrane, substances that produce alkyl sulfonic acids with 1 to 4 carbon atoms or halogenated alkyl sulfonic acids with 1 to 4 carbon atoms are preferred as hot acid generators. Examples include methanesulfonic acid (4-hydroxyphenyl)dimethyl strontium, methanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethyl strontium, methanesulfonic acid benzyl(4-hydroxyphenyl)methyl strontium, methanesulfonic acid benzyl(4-((methoxycarbonyl)oxy)phenyl)methyl strontium, methanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium, and trifluoromethanesulfonic acid (4-... Hydroxyphenyl)dimethyl strontium, trifluoromethanesulfonic acid (4-((methoxycarbonyl)oxy)phenyl)dimethyl strontium, trifluoromethanesulfonic acid benzyl(4-hydroxyphenyl)methyl strontium, trifluoromethanesulfonic acid benzyl(4-((methoxycarbonyl)oxy)phenyl)methyl strontium, trifluoromethanesulfonic acid (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)strontium, 3-(5-(((propylsulfony)oxy)imino)thiophene-2(5H)-yenyl)-2-(ortho-tolyl)propionitrile, 2,2-bis(3-(methanesulfonamide)-4-hydroxyphenyl)hexafluoropropane are preferred.

Furthermore, the compound described in Japanese Patent Application Publication No. 2013-167742, 0059, is also preferred as a thermal acid generator.

The content of the hot acid generator is preferably 0.01 parts by weight or more relative to 100 parts by weight of a specific resin, and more preferably 0.1 parts by weight or more. By containing more than 0.01 parts by weight, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic membrane. Furthermore, from the viewpoint of the electrical insulation of the organic membrane, 20 parts by weight or less is preferred, 15 parts by weight or less is even better, and 10 parts by weight or less is even more preferred.

<Onium Salts> The photosensitive resin composition of the present invention may further include onium salts. In particular, when the photosensitive resin composition of the present invention includes a polyimide precursor or a polybenzoxazole precursor as a specific resin, the inclusion of onium salts is preferred. The type of onium salt is not particularly limited, and ammonium salts, imine salts, strontium salts, zirconia salts, or phosphonium salts are preferred. Of these, ammonium salts or imine salts are preferred from the viewpoint of high thermal stability, and strontium salts, zirconia salts, or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, onmium salts are salts containing both cations and anions with an onmium structure. These cations and anions may or may not be covalently bonded. That is, onmium salts can be intramolecular salts containing both cation and anion portions within the same molecular structure, or they can be intermolecular salts consisting of ionicly bonded cation and anion molecules of different molecular weights, but intermolecular salts are preferred. Moreover, in the photosensitive resin composition of this invention, the aforementioned cation portions or cation molecules and the aforementioned anion portions or anion molecules can be bonded by ionic bonds or can be dissociated. As a cation in the onium salt, ammonium cation, pyridinium cation, strontium cation, zeolite cation, or phosphonium cation is preferred, and it is even more preferred to select at least one cation from the group consisting of tetraalkylammonium cation, strontium cation, and zeolite cation.

The onium salt used in this invention can also be a thermal alkali generator, as described later. A thermal alkali generator refers to a compound that produces alkali upon heating; for example, compounds that produce alkali when heated to above 40°C. As an onium salt, examples include those described in paragraphs 0122 to 0138 of International Publication No. 2018/043262. Furthermore, onium salts that can be used in the field of polyimide precursors can also be used without particular restriction.

When the photosensitive resin composition of the present invention contains a cyclonite, the content of the cyclonite relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1% to 50% by mass. The lower limit is preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, further preferably 20% by mass or less, and even more preferably 10% by mass or less, and can be 5% by mass or less, or even 4% by mass or less. One or more cyclonite salts can be used. When two or more are used, the total amount within the above range is preferred.

<Thermal Alkali Generator> The photosensitive resin composition of the present invention may further include a thermal alkali generator. In particular, it is preferable to include a thermal alkali generator when the photosensitive resin composition of the present invention includes a polyimide precursor or a polybenzoxazole precursor as a specific resin. The thermal alkali generator may be a compound conforming to the above-mentioned onium salt, or it may be a thermal alkali generator other than the above-mentioned onium salt. As a thermal alkali generator other than the above-mentioned onium salt, nonionic thermal alkali generators can be cited. As a nonionic thermal alkali generator, compounds represented by formula (B1) or formula (B2) can be cited. [Chemical Formula 44]

In formulas (B1) and (B2), ^Rb1 , ^Rb2 , and ^Rb3 are independently organic groups, halogen atoms, or hydrogen atoms that do not possess a tertiary amine structure. ^Rb1 and ^Rb2 cannot simultaneously be hydrogen atoms. Furthermore, ^Rb1 , ^Rb2 , and ^Rb3 do not possess a carboxyl group. In addition, in this specification, a tertiary amine structure refers to a structure where all three bonds of the trivalent nitrogen atom are covalently bonded to hydrocarbon carbon atoms. Therefore, this is not a limitation when the bonded carbon atoms are carbon atoms forming a carbonyl group, i.e., when they form an amide group together with the nitrogen atom.

In formulas (B1) and (B2), it is preferable that at least one of ^Rb1 , ^Rb2, and ^Rb3 contains a cyclic structure, and it is even more preferable that at least two contain a cyclic structure. The cyclic structure can be either a monocyclic ring or a condensed ring, preferably a monocyclic ring or a condensed ring formed by the condensation of two monocyclic rings. A 5-membered or 6-membered ring is preferred, with a 6-membered ring being more preferred. A cyclohexane ring or a benzene ring is preferred, with a cyclohexane ring being more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably with 1-24 carbon atoms, more preferably with 2-18 carbon atoms, and even more preferably with 3-12 carbon atoms), alkenyl groups (preferably with 2-24 carbon atoms, more preferably with 2-18 carbon atoms, and even more preferably with 3-12 carbon atoms), aryl groups (preferably with 6-22 carbon atoms, more preferably with 6-18 carbon atoms, and even more preferably with 6-10 carbon atoms), or aralkyl groups (preferably with 7-25 carbon atoms, more preferably with 7-19 carbon atoms, and even more preferably with 7-12 carbon atoms). These groups may have substituents within the scope of achieving the effects of the present invention. ^Rb1 and ^Rb2 may bond to each other to form a ring. A nitrogen-containing heterocycle with 4-7 members is preferred as the formed ring. In particular, Rb ¹ and Rb ² are preferably straight-chain, branched or cyclic alkyl groups with substituents (preferably 1 to 24 carbons, more preferably 2 to 18 carbons, and even more preferably 3 to 12 carbons), preferably cyclic alkyl groups with substituents (preferably 3 to 24 carbons, more preferably 3 to 18 carbons, and even more preferably 3 to 12 carbons), and preferably cyclohexyl groups with substituents.

Examples of Rb ³ include alkyl groups (preferably with 1-24 carbons, more preferably with 2-18 carbons, and even more preferably with 3-12 carbons), aryl groups (preferably with 6-22 carbons, more preferably with 6-18 carbons, and even more preferably with 6-10 carbons), alkenyl groups (preferably with 2-24 carbons, more preferably with 2-12 carbons, and even more preferably with 2-6 carbons), aralkyl groups (preferably with 7-23 carbons, more preferably with 7-19 carbons, and even more preferably with 7-12 carbons), and aromatic groups. The preferred substituents are alkenyl (preferably 8-24 carbons, more preferably 8-20, and even more preferably 8-16 carbons), alkoxy (preferably 1-24 carbons, more preferably 2-18, and even more preferably 3-12 carbons), aryloxy (preferably 6-22 carbons, more preferably 6-18, and even more preferably 6-12 carbons), or arylalkoxy (preferably 7-23 carbons, more preferably 7-19, and even more preferably 7-12 carbons). Cycloalkyl (preferably 3-24 carbons, more preferably 3-18, and even more preferably 3-12 carbons), arylalkenyl, and arylalkoxy are preferred. ^Rb3 may further have substituents within the scope of the invention's effects.

The compound represented by formula (B1) is preferably represented by either formula (B1-1) or formula (B1-2) below. [Chemical Formula 45]

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² have the same meanings as Rb ¹ and Rb ² in formula (B1), respectively. Rb ¹³ is an alkyl group (preferably with 1 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons), an alkenyl group (preferably with 2 to 24 carbons, more preferably with 2 to 18 carbons, and even more preferably with 3 to 12 carbons), an aryl group (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 12 carbons), or an aralkyl group (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 12 carbons), and may have substituents within the scope of achieving the effects of the present invention. Among them, it is preferred that Rb ¹³ is an aralkyl group.

Rb ³³ and Rb ³⁴ are respectively independently hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 8 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 8 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), and hydrogen atoms are preferred.

Rb ³⁵ series alkyl (1-24 carbons are preferred, 1-12 are more preferred, 3-8 are even more preferred), alkenyl (2-12 carbons are preferred, 2-10 are more preferred, 3-8 are even more preferred), aryl (6-22 carbons are preferred, 6-18 are more preferred, 6-12 are even more preferred), aralkyl (7-23 carbons are preferred, 7-19 are more preferred, 7-12 are even more preferred), aryl is preferred.

The compound represented by formula (B1-1) is preferred over the compound represented by formula (B1-1a). [Chemical Formula 46]

The meanings of Rb ¹¹ and Rb ¹² are the same as those of Rb ¹¹ and Rb ¹² in formula (B1-1). Rb ¹⁵ and Rb ¹⁶ are preferably hydrogen atoms, alkyl groups (preferably with 1 to 12 carbons, more preferably with 1 to 6 carbons, and even more preferably with 1 to 3 carbons), alkenyl groups (preferably with 2 to 12 carbons, more preferably with 2 to 6 carbons, and even more preferably with 2 to 3 carbons), aryl groups (preferably with 6 to 22 carbons, more preferably with 6 to 18 carbons, and even more preferably with 6 to 10 carbons), aralkyl groups (preferably with 7 to 23 carbons, more preferably with 7 to 19 carbons, and even more preferably with 7 to 11 carbons), hydrogen atoms, or methyl groups. Rb ¹⁷ series alkyl (preferably 1-24 carbons, more preferably 1-12, and even more preferably 3-8 carbons), alkenyl (preferably 2-12 carbons, more preferably 2-10, and even more preferably 3-8 carbons), aryl (preferably 6-22 carbons, more preferably 6-18, and even more preferably 6-12 carbons), aralkyl (preferably 7-23 carbons, more preferably 7-19, and even more preferably 7-12 carbons), wherein aryl is preferred.

For nonionic thermal alkali generators, a molecular weight of 800 or less is preferred, 600 or less is even better, and 500 or less is still preferred. As a lower limit, a molecular weight of 100 or more is preferred, 200 or more is even better, and 300 or more is still even better.

The following compounds can be cited as specific examples of compounds that are thermal alkali generators among the above-mentioned onium salts, or as specific examples of thermal alkali generators other than the above-mentioned onium salts.

[Chemical Formula 47]

[Chemical Formula 48]

[Chemical Formula 49]

The content of other alkali-generating agents relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1% to 50% by mass. The lower limit is preferably 0.5% by mass or more, and 1% by mass or more is further preferred. The upper limit is preferably 30% by mass or less, and 20% by mass or less is further preferred. One or more alkali-generating agents can be used. When two or more are used, the total amount is preferably within the above range.

<Crosslinking Agent> It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent. Examples of crosslinking agents include free radical crosslinkers or other crosslinking agents.

<Free Radical Crosslinker> It is preferable that the photosensitive resin composition of the present invention further includes a free radical crosslinker. The free radical crosslinker is a compound having a free radical polymerizable group. As a free radical polymerizable group, a group containing an ethylene unsaturated bond is preferred. Examples of groups containing ethylene unsaturated bonds include vinyl, allyl, vinylphenyl, and (meth)acrylonitrile groups. Among these, (meth)acrylonitrile is preferred as a group containing the aforementioned ethylene unsaturated bonds, and from a reactivity point of view, (meth)acrylonitrileoxy is more preferred.

The free radical crosslinker is a compound having one or more ethylene unsaturated bonds, and preferably a compound having two or more ethylene unsaturated bonds. A compound having two ethylene unsaturated bonds is preferably a compound having two groups containing the aforementioned ethylene unsaturated bonds. Furthermore, from the viewpoint of the film strength of the obtained pattern, it is preferable that the photosensitive resin composition of the present invention includes a compound having three or more ethylene unsaturated bonds as a free radical crosslinker. As compounds having three or more of the aforementioned ethylene unsaturated bonds, compounds having 3 to 15 ethylene unsaturated bonds are preferred, compounds having 3 to 10 ethylene unsaturated bonds are even more preferred, and compounds having 3 to 6 ethylene unsaturated bonds are further preferred. Furthermore, compounds having three or more of the aforementioned ethylene unsaturated bonds are preferably compounds having three or more groups containing the aforementioned ethylene unsaturated bonds, compounds having 3 to 15 are more preferred, compounds having 3 to 10 are further preferred, and compounds having 3 to 6 are particularly preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern, it is also preferable that the photosensitive resin composition of the present invention contains compounds having two ethylene unsaturated bonds and compounds having three or more of the above-mentioned ethylene unsaturated bonds.

The molecular weight of the free radical crosslinker is preferably below 2,000, even better below 1,500, and further preferably below 900. The lower limit of the molecular weight of the free radical crosslinker is preferably above 100.

Specific examples of free radical crosslinkers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyols, and amides of unsaturated carboxylic acids and polyamines. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides with nucleophilic substituents such as hydroxyl, amino, or hydrogen thio groups with monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reactions with monofunctional or polyfunctional carboxylic acids, are also preferred. Furthermore, addition reactions of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are preferred, as are substitution reactions of unsaturated carboxylic acid esters or amides having deionizing substituents such as halogen groups or toluenesulfonoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols. As another example, compounds substituted with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc., can also be used to replace the aforementioned unsaturated carboxylic acids. For specific examples, please refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

Furthermore, free radical crosslinkers are preferably compounds with a boiling point above 100°C at normal pressure. Examples include polyethylene glycol di(meth)acrylate, trihydroxymethyl ethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl tetramethyl acrylate, neopentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, dinepentyl tetramethyl acrylate, hexanediol (meth)acrylate, trihydroxymethyl propane tri(acryloyloxypropyl) ether, tri(acryloyloxyethyl) trimerocyanate, glycerol, or trihydroxymethyl ethane, which are added to polyfunctional alcohols to form ethylene oxide or propylene oxide, followed by (meth)acrylate addition. Esterified compounds, such as (meth)acrylate aminocarbamates disclosed in Japanese Patent Application Publications Nos. 48-041708, 50-006034, and 51-037193, polyester acrylates disclosed in Japanese Patent Application Publications Nos. 48-064183, 49-043191, and 52-030490, multifunctional acrylates or methacrylates that are products of the reaction between epoxy resin and (meth)acrylic acid; and mixtures thereof. Furthermore, compounds disclosed in paragraphs 0254 to 0257 of Japanese Patent Application Publication No. 2008-292970 are also preferred. Furthermore, examples include polyfunctional (meth)acrylates obtained by reacting polyfunctional carboxylic acids with compounds such as (meth)acrylate glycidyl esters, which have cyclic ether groups and vinyl unsaturated bonds.

Furthermore, as a better free radical crosslinking agent besides the above, compounds having a ring and having two or more ethylene-unsaturated groups, as described in Japanese Patent Application Publication No. 2010-160418, Japanese Patent Application Publication No. 2010-129825, and Japanese Patent No. 4364216, as well as cardo resin, can also be used.

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

In addition to the above, compounds described in paragraphs 0048 to 0051 of Japanese Patent Application Publication No. 2015-034964 and compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference, may also be used more readily.

Furthermore, the following compounds, which are described together with specific examples of formulas (1) and (2) in Japanese Patent Application Publication No. 10-062986, can also be used as free radical crosslinking agents: compounds obtained by esterification of (meth)acrylate after the addition of ethylene oxide or propylene oxide to a polyfunctional alcohol.

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

As free radical crosslinking agents, dinepentylenetetraacrylate (commercially available product, manufactured by KAYARAD D-330; Nippon Kayaku Co., Ltd.), dinepentylenetetraacrylate (commercially available product, manufactured by KAYARAD D-320; Nippon Kayaku Co., Ltd., and A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dinepentylenetetraacrylate penta(meth)acrylate (commercially available product, manufactured by KAYARAD D-310; Nippon Kayaku Co., Ltd.), and dinepentylenetetraacrylate hexa(meth)acrylate (commercially available product, manufactured by KAYARAD DPHA; Nippon Kayaku Co., Ltd., and A-DPH: Shin-Nakamura Chemical Co., Ltd.) are used. (Made by Co., Ltd.) and the structure in which the (meth)acrylic acid groups are bonded by ethylene glycol residues or propylene glycol residues is preferred. These oligomer types can also be used.

Commercially available free radical crosslinking agents include, for example, SR-494 (a tetrafunctional acrylate with four ethoxy groups) manufactured by Sartomer Company, Inc.; SR-209, 231, and 239 (a difunctional methacrylate with four ethoxy groups) manufactured by Sartomer Company, Inc.; DPCA-60 (a hexafunctional acrylate with six pentyloyl groups) manufactured by Nippon Kayaku Co., Ltd.; TPA-330 (a trifunctional acrylate with three isopyloyl groups); carbamate oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO.,LTD.); NK ESTER M-40G; NK ESTER 4G; NK ESTER M-9300; and NK ESTER... A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION.) etc.

As free radical crosslinking agents, urethane ester acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, Japanese Patent Publication No. 02-016765, and urethane ester compounds with an ethylene oxide backbone 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 are also preferred. Furthermore, as a free radical crosslinking agent, compounds having an amino group structure or a sulfide structure within the molecule as described in Japanese Patent Application Publication No. 63-277653, Japanese Patent Application Publication No. 63-260909, and Japanese Patent Application Publication No. 01-105238 can also be used.

Free radical crosslinkers can be free radical crosslinkers containing acid groups such as carboxyl groups and phosphate groups. Among free radical crosslinkers containing acid groups, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, and free radical crosslinkers that react the unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to form acid groups are even more preferred. Particularly preferred are free radical crosslinkers that react the unreacted hydroxyl groups of aliphatic polyhydroxy compounds with non-aromatic carboxylic anhydrides to form acid groups, wherein the aliphatic polyhydroxy compound is a neopentyl tetrol or dinepentyl tetrol. Commercially available examples include M-510 and M-520, which are used by TOAGOSEI CO., Ltd. to manufacture polybasic acid-modified acrylic oligomers.

The preferred acid value of a free radical crosslinker containing an acid group is 0.1–40 mg KOH/g, and particularly preferably 5–30 mg KOH/g. When the acid value of the free radical crosslinker is within the above range, it exhibits excellent manufacturability and consequently excellent developing properties. Furthermore, it demonstrates good polymerizability. On the other hand, from the viewpoint of developing speed during alkaline developing, the preferred acid value of a free radical crosslinker containing an acid group is 0.1–300 mg KOH/g, and particularly preferably 1–100 mg KOH/g. The above acid values were determined according to JIS K 0070:1992.

From the perspectives of pattern resolution and film stretchability, it is preferable to use difunctional methacrylates or acrylates in the photosensitive resin composition of this invention. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, and 1,6-hexanediol are also acceptable. Dimethacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, EO adduct dimethacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloxypropyl methacrylate, EO-modified dimethacrylate of isocyanuric acid, EO-modified dimethacrylate of isocyanuric acid, other difunctional acrylates having ethyl carbamate bonds, and difunctional methacrylates having ethyl carbamate bonds. Two or more of these can be used in combination as needed. Furthermore, from the perspective of suppressing warping caused by the elastic modulus control of the accompanying pattern, monofunctional free radical crosslinkers can be better used as free radical crosslinkers. As a monofunctional free radical crosslinking agent, the following are preferred: n-butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, butoxyethyl methacrylate, carbitol methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, N-hydroxymethyl methacrylamide, glycidyl methacrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate and other methacrylic acid derivatives, N-vinylpyrrolidone, N-vinylcaprolactone and other N-vinyl compounds, allyl glycidyl ether, diallyl phthalate, trimellitic acid triallyl and other allyl compounds. As a monofunctional free radical crosslinker, compounds with a boiling point above 100°C at normal pressure are preferred in order to suppress volatilization before exposure.

When free radical crosslinkers are present, it is preferable that their content, relative to the total solid content of the photosensitive resin composition of the present invention, is more than 0% by mass and less than 60% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and less than 30% by mass or less is even more preferred.

Free radical crosslinkers can be used alone or in combination of two or more. When using two or more at the same time, it is better to keep their total amount within the range mentioned above.

<Other Crosslinking Agents> Preferably, the photosensitive resin composition of this invention includes other crosslinking agents different from the aforementioned free radical crosslinking agents. In this invention, "other crosslinking agents" refers to crosslinking agents other than the aforementioned free radical crosslinking agents. Preferably, these are compounds having a plurality of groups within the molecule that react with the photosensitivity of the aforementioned photosensitizer (forming covalent bonds with other compounds in the composition or their reaction products). More preferably, these are compounds having a plurality of groups within the molecule that react with the action of an acid or alkali (forming covalent bonds with other compounds in the composition or their reaction products). Preferably, the aforementioned acid or alkali is an acid or alkali generated from a photoacid generator or photoalkali generator used as a photosensitizer in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups are preferred, and compounds having a structure in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups is directly bonded to a nitrogen atom are even more preferred. As other crosslinking agents, examples include compounds having the following structure: reacting amine-containing compounds such as melamine, acetylenurea, urea, alkyl urea, and benzoguanidine with formaldehyde, or reacting formaldehyde with an alcohol and replacing the hydrogen atom of the aforementioned amine group with a hydroxymethyl or alkoxymethyl group. The method of manufacturing these compounds is not particularly limited, as long as the compound has the same structure as the compound manufactured by the above method. Furthermore, oligomers formed by the self-condensation of the hydroxymethyl groups of these compounds can also be used. As for the aforementioned amine-containing compounds, crosslinkers using melamine are referred to as melamine-based crosslinkers, crosslinkers using acetylene urea, urea, or alkylene urea are referred to as urea-based crosslinkers, crosslinkers using alkylene urea are referred to as alkylene urea-based crosslinkers, and crosslinkers using benzoguanidine are referred to as benzoguanidine-based crosslinkers. Among these, it is preferable that the photosensitive resin composition of the present invention comprises at least one compound selected from the group consisting of urea-based crosslinkers and melamine-based crosslinkers, and it is even more preferable that it comprises at least one compound selected from the group consisting of acetylene urea-based crosslinkers and melamine-based crosslinkers described below.

Specific examples of melamine-based crosslinking agents include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine.

Specific examples of urea crosslinkers include, for instance, monohydroxymethylated ethynylurea, dihydroxymethylated ethynylurea, trihydroxymethylated ethynylurea, tetrahydroxymethylated ethynylurea, monomethoxymethylated ethynylurea, dimethoxymethylated ethynylurea, trimethoxymethylated ethynylurea, tetramethoxymethylated ethynylurea, monoethoxymethylated ethynylurea, diethoxymethylated ethynylurea, triethoxymethylated ethynylurea, and tetraethoxymethylated ethynylurea. Acetylene urea crosslinking agents including monopropoxymethylated acetylenoid, dipropoxymethylated acetylenoid, tripropoxymethylated acetylenoid, tetrapropoxymethylated acetylenoid, monobutoxymethylated acetylenoid, dibutoxymethylated acetylenoid, tributoxymethylated acetylenoid, or tetrabutoxymethylated acetylenoid; Urea crosslinking agents including dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea; Monohexylmethylated acetylenoid. Vinylurea crosslinking agents such as dihydroxymethylated vinylurea, monomethoxymethylated vinylurea, dimethoxymethylated vinylurea, monoethoxymethylated vinylurea, diethoxymethylated vinylurea, monopropoxymethylated vinylurea, dipropoxymethylated vinylurea, monobutoxymethylated vinylurea, or dibutoxymethylated vinylurea; Acrylamide crosslinking agents such as monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monoethoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea; 1,3-Di(methoxymethyl)4,5-dihydroxy-2-imidazolidineone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone, etc.

Specific examples of benzoguanidine crosslinking agents include, for example, monohydroxymethylated benzoguanidine, dihydroxymethylated benzoguanidine, trihydroxymethylated benzoguanidine, tetrahydroxymethylated benzoguanidine, monomethoxymethylated benzoguanidine, dimethoxymethylated benzoguanidine, trimethoxymethylated benzoguanidine, tetramethoxymethylated benzoguanidine, monoethoxymethylated benzoguanidine, diethoxymethylated benzoguanidine, triethoxymethylated benzoguanidine, tetraethoxymethylated benzoguanidine, monopropoxymethylated benzoguanidine, dipropoxymethylated benzoguanidine, tripropoxymethylated benzoguanidine, tetrapropoxymethylated benzoguanidine, monobutoxymethylated benzoguanidine, dibutoxymethylated benzoguanidine, tributoxymethylated benzoguanidine, and tetrabutoxymethylated benzoguanidine.

Furthermore, as a compound having at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups, it is also preferable to use a compound in which at least one group selected from the group consisting of hydroxymethyl and alkoxymethyl groups is directly bonded to an aromatic ring (preferably a benzene ring). Specific examples of such compounds include benzenediethanol, 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, and bis(methoxymethyl)diphenylbenzene. Ketones, methoxymethylbenzoic acid, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4’,4’’-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5’-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3’,5,5’-tetra(methoxymethyl)-1,1’-biphenyl-4,4’-diol, etc.

As other crosslinking agents, commercially available products can be used. Among the better commercially available products are 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, and 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, same below) MX-290, NIKALACMX-280, NIKALACMX-270, NIKALACMX-279, NIKALACMW-100LM, NIKALACMX-750LM (all manufactured by SANWA CHEMICAL CO.,LTD), etc.

Furthermore, it is preferable that the photosensitive resin composition of the present invention includes at least one compound selected from the group consisting of epoxides, oxocyclobutanes and benzo[a] compounds as other crosslinking agents.

[Epoxy Compounds (Compounds Containing Epoxy Groups)] Epoxy compounds are preferably compounds with two or more epoxy groups per molecule. Epoxy groups undergo cross-linking reactions below 200°C without dehydration due to cross-linking, thus minimizing the risk of membrane shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of photosensitive resin components can be effectively suppressed.

The presence of polyethylene oxide in the epoxy compound is preferred. This further reduces the elastic modulus and suppresses warping. Polyethylene oxide refers to ethylene oxide with 2 or more repeating units, with 2 to 15 repeating units being preferred.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diepoxypropyl ether, neopentyl glycol diepoxypropyl ether, ethylene glycol diepoxypropyl ether, butanediol diepoxypropyl ether, hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, etc., alkyl glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polyalkyl glycol type epoxy resins such as polypropylene glycol diepoxypropyl ether; epoxy-containing silicones such as polymethyl (epoxypropoxypropyl)siloxane, etc., but are not limited to these. Specifically, examples include 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) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, and EPICLON (registered trademark) EXA-48. 50-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (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, RIKARESIN (registered trademark) BEO-20E (the above product names, DIC) (Manufactured by Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above trade names, manufactured by 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, EP PN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above trade names, Nippon Made by Kayaku Co., Ltd.) etc.

[Oxycyclobutane compounds (compounds containing oxycyclobutyl groups)] Examples of oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenediacarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl] ester, etc. As a specific example, the ARON OXETANE series (e.g., OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO.,LTD. can be used alone or in combination of two or more.

[Benzozoline compounds (compounds containing benzoxazole groups)] Because the ring-opening addition reaction causes crosslinking, benzozoline compounds do not undergo degassing during hardening, thereby reducing thermal shrinkage and inhibiting warping, and are therefore preferred.

Preferred examples of benzo[a] compounds include B-a type benzo[a], B-m type benzo[a], P-d type benzo[a], F-a type benzo[a] (trade names, manufactured by Shikoku Chemicals Corporation), benzo[a] adducts of polyhydroxystyrene resins, and phenolic varnish-type dihydrobenzo[a] compounds. These can be used alone or in combination of two or more.

The content of other crosslinking agents relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1-30% by mass, more preferably 0.1-20% by mass, further preferably 0.5-15% by mass, and especially preferably 1.0-10% by mass. The other crosslinking agents may be contained in only one type or in two or more types. When two or more other thermal crosslinking agents are contained, it is preferable that their total content falls within the above range.

<Compounds having a sulfonamide structure, compounds having a thiourea structure> From the viewpoint of improving the adhesion of the obtained pattern to the substrate, the photosensitive resin composition of the present invention further includes at least one compound selected from the group consisting of compounds having a sulfonamide structure and compounds having a thiourea structure.

[Compounds possessing a sulfonamide structure] The sulfonamide structure is represented by the following formula (S-1). [Chemical Formula 50] In formula (S-1), R represents a hydrogen atom or an organic group. R can bond with other structures to form a ring structure, and * represents the bonding site with other structures independently. It is preferable that the above R is the same group as ^R2 in formula (S-2) below. The compound having a sulfonamide structure can be a compound having two or more sulfonamide structures, and a compound having one sulfonamide structure is preferred.

Compounds with a sulfonamide structure, preferably those represented by the following formula (S-2), are preferred. [Chemical Formula 51] In formula (S-2), ^R1 , ^R2 , and ^R3 each independently represent a hydrogen atom or a monovalent organic group, and two or more of ^R1 , ^R2, and ^R3 can bond together to form a ring structure. It is preferable that ^R1 , ^R2 , and ^R3 each independently represent a monovalent organic group. Examples of ^R1 , ^R2 , and ^R3 include hydrogen atoms, 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, or groups formed by combining two or more of these. Among the aforementioned alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred, and alkyl groups having 1 to 6 carbon atoms are even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of alkoxy groups include alkoxy groups with 1 to 10 carbon atoms, and more preferably alkoxy groups with 1 to 5 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of alkoxysilyl groups include alkoxysilyl groups with 1 to 10 carbon atoms, and more preferably alkoxysilyl groups with 1 to 4 carbon atoms. Examples of alkoxysilyl groups include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of aryl groups include those with 6 to 20 carbon atoms, and those with 6 to 12 carbon atoms. The aryl groups may have substituents such as alkyl groups. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl. Examples of heterocyclic groups include those formed by removing one hydrogen atom from heterocyclic structures such as triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, succinazole ring, thiazole ring, pyrazole ring, isosuccinazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridyl ring, pyridine ring, piperidine ring, piperidine ring, oxymethylene ring, dihydropiperanium ring, tetrahydropiperanium ring, and trihydropiperanium ring.

Among these, compounds in which ^R1 is aryl and ^R2 and ^R3 are independently hydrogen atoms or alkyl groups are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanylsulfonamide, and 2-aminoethanesulfonamide.

[Compounds with a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical Formula 52] In equation (T-1), ^R4 and ^R5 independently represent hydrogen atoms or monovalent organic groups, ^R4 and ^R5 can bond to form a ring, ^R4 can bond with other structures bonded to form a ring structure, ^R5 can bond with other structures bonded to form a ring structure, and * independently represent the bonding sites with other structures.

It is preferable that ^R4 and ^R5 are each an independent hydrogen atom. Examples of ^R4 and ^R5 include hydrogen atoms or groups consisting of alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, or combinations of two or more of these. Among the alkyl groups, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are even more preferred. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Among the cycloalkyl groups, those having 5 to 10 carbon atoms are preferred, and those having 6 to 10 carbon atoms are even more preferred. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of alkoxy groups include those with 1 to 10 carbon atoms, and those with 1 to 5 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, and pentoxy. Examples of alkoxysilyl groups include those with 1 to 10 carbon atoms, and those with 1 to 4 carbon atoms. Examples of alkoxysilyl groups include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of aryl groups include those with 6 to 20 carbon atoms, and those with 6 to 12 carbon atoms. The aryl groups may have substituents such as alkyl groups. Examples of aryl groups include phenyl, tolyl, xylyl, and naphthyl. Examples of heterocyclic groups include groups formed by removing one hydrogen atom from heterocyclic structures such as triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, acetazole ring, thiazole ring, pyrazole ring, isoacetazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridyl ring, pyridine ring, piperidine ring, piperidine ring, oxomorphine ring, dihydropiperanium ring, tetrahydropiperanium ring, and trihydropiperanium ring. Compounds with a thiourea structure can be compounds with two or more thiourea structures, but compounds with one thiourea structure are preferred.

Compounds with a thiourea structure, preferably those represented by the following formula (T-2), are preferred. [Chemical Formula 53] In equation (T-2), ^R4 to ^R7 represent hydrogen atoms or monovalent organic groups independently, and at least two of ^R4 to ^R7 can bond with each other to form a ring structure.

In equation (T-2), the meanings of ^R4 and ^R5 are the same as those ⁱⁿ equation (T-1), and the preferred states are also the same. In equation (T-2), it is preferable that ^R6 and ^R7 are each independently monovalent organic groups. In equation (T-2), the preferred states of the ^monovalent organic groups in ^R6 and ^R7 are the same as the preferred states of the monovalent organic groups in ^R4 and ^R5 in equation (T-1).

Examples of compounds having a thiourea structure include N-acetylacetonide, N-allyl thiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-dalcanyl thiourea, N-benzoyl thiourea, N,N'-diphenyl thiourea, 1-benzyl-phenylthiourea, 1,3-dibutyl thiourea, 1,3-diisopropyl thiourea, 1,3-dicyclohexyl thiourea, 1-(3-(trimethoxysilyl)propyl)-3-methyl thiourea, trimethyl thiourea, tetramethyl thiourea, N,N-diphenyl thiourea, ethylene thiourea (2-imidazoline thione), carbimazole, and 1,3-dimethyl-2-thioethenurea.

[Content] The total content of the sulfonamide-based compound and the thiourea-based compound relative to the total mass of the photosensitive resin composition of the present invention is preferably 0.05-10% by mass, more preferably 0.1-5% by mass, and even more preferably 0.2-3% by mass. The photosensitive resin composition of the present invention may contain only one compound selected from the group consisting of compounds having a sulfonamide-based compound and compounds having a thiourea-based compound, or it may contain two or more compounds. When only one compound is contained, the content of that compound is within the above range; when two or more compounds are contained, the total content is preferably within the above range.

<Migration Inhibitor> It is preferable that the photosensitive resin composition of the present invention further includes a migration inhibitor. By including a migration inhibitor, the transfer of metal ions originating from the metal layer (metal wiring) into the photosensitive film can be effectively inhibited.

There are no particular limitations on its role as a migration inhibitor. Examples of such inhibitors include compounds with heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, acetazole ring, thiazole ring, pyrazole ring, isoacetazole ring, isothiazole ring, tetrazolium ring, pyridine ring, pyridoxine ring, pyridine ring, piperidine ring, piperidine ring, oxyphenoxine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds with thiourea and hydrogen sulfide groups, hindered phenolic compounds, salicylic acid derivative compounds, and acehydrazine derivative compounds. In particular, it is possible to use triazole compounds such as 1,2,4-triazole and benzotriazole, as well as tetraazole compounds such as 1H-tetrazole and 5-phenyltetrazole more effectively.

Alternatively, ion trapping agents that capture anions such as halogen ions can be used.

As other migration inhibitors, the following can be used: rust inhibitors described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701; compounds described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711; compounds described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656; compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520; and compounds described in paragraph 0166 of International Publication No. 2015/199219.

The following compounds can be cited as examples of migration inhibitors.

[Chemical Formula 54]

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

There may be only one migration inhibitor or two or more. When there are two or more migration inhibitors, it is preferable that their total number is within the above range.

<Polymerization Inhibitor> It is preferable that the photosensitive resin composition of the present invention contains a polymerization inhibitor.

As polymerization inhibitors, hydroquinone, ortho-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallnut phenol, tert-Butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), and 2,2'-methylene can be preferably used, for example. Bis(4-methyl-6-tertiary butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenanthrene, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylene glycol etherdiaminetetraacetic acid, 2,6-di-tertiary butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1- Naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitrosophenylhydroxyamine monocyanate, N-nitroso-N-(1-naphthyl)hydroxyamine ammonium salt, bis(4-hydroxy-3,5-trimethylbutyl)phenylmethane, 1,3,5-tris(4-trimethylbutyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H) The following compounds can be used: (3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical, 1,1-diphenyl-2-picrylhydrazyl, copper(II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxyamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tertiary butylphenol, di-tertiary butylhydroxytoluene, 1,4-naphthoquinone, etc. Furthermore, polymerization inhibitors described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

Furthermore, the following compounds can be used (Me is methyl).

[Chemical Formula 55]

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor relative to the total solid content of the photosensitive resin composition of the present invention can be 0.01 to 20.0% by mass, 0.01 to 5% by mass is preferred, 0.02 to 3% by mass is more preferred, and 0.05 to 2.5% by mass is even more preferred.

The polymerization inhibitor may be a single agent or two or more agents. When there are two or more polymerization inhibitors, it is preferable that their total amount is within the above range.

<Metal Adhesion Modifier> The photosensitive resin composition of this invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion modifiers include silane coupling agents, aluminum-based adhesives, titanium-based adhesives, compounds having a sulfonylurea structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-keto ester compounds, and amino compounds.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358, it is preferable to use two or more different silane coupling agents. Also, it is preferable to use the following compounds as silane coupling agents. In the following formula, Et represents ethyl.

[Chemical Formula 56] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureapropyltrialkoxysilane, 3-piperylpropylmethyldimethoxysilane, 3-piperylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding aids] Examples of aluminum-based bonding aids include tri(ethyl acetate)aluminum, tri(acetone)aluminum, and diisopropylaluminum ethyl acetate.

As a metal adhesion modifier, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 can also be used.

The content of the metal adhesion modifier relative to 100 parts by weight of a specific resin is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it above the lower limit above, the adhesion between the pattern and the metal layer becomes better; by setting it below the upper limit above, the heat resistance and mechanical properties of the pattern become better. The metal adhesion modifier may be a single type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

<Metal Adhesion Modifier> The photosensitive resin composition of this invention preferably includes a metal adhesion modifier for improving adhesion to metal materials used in electrodes or wiring. As a metal adhesion modifier, compounds described in paragraphs 0046 to 0049 of Japanese Patent Application Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Application Publication No. 2013-072935 may also be used.

The content of the metal adhesion modifier relative to 100 parts by weight of the heterocyclic polymer precursor is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 15 parts by weight, and even more preferably 0.5 to 5 parts by weight. By setting it above the lower limit above, the adhesion between the pattern and the metal layer after the heat treatment process is improved; by setting it below the upper limit above, the heat resistance and mechanical properties of the hardened product after the heat treatment process are improved. The metal adhesion modifier may be a single type or two or more types. When using two or more types, it is preferable that their total content is within the above range.

<Other Additives> Within the range of achieving the effects of this invention, the photosensitive resin composition can be formulated with various additives as needed, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, UV absorbers, aggregation inhibitors, etc. When incorporating these additives, it is preferable that their total amount is 3% by mass or less of the solid content of the photosensitive resin composition.

[Sensitizer] The photosensitive resin composition of this invention may contain sensitizers different from the specific sensitizers mentioned above (also referred to as "other sensitizers"). The sensitizer absorbs specific active radiation to become electronically excited. The electronically excited sensitizer comes into contact with thermosetting accelerators, thermal free radical polymerization initiators, photofree radical polymerization initiators, etc., resulting in electron transfer, energy transfer, and heating. Thereby, the thermosetting accelerator, thermal free radical polymerization initiator, and photofree radical polymerization initiator undergo chemical changes and decompose, generating free radicals, acids, or alkalis. As other sensitizers, milchlerone can be cited as an example. ketone), 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzyl)cyclopentane, 2,6-bis(4'-diethylaminobenzyl)cyclohexanone, 2,6-bis(4'-diethylaminobenzyl)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminobenzylpropenedihydroindene, 1,3-bis(4'-dimethylaminobenzyl)propene Ketones, 1,3-bis(4'-diethylaminobenzyl)acetone, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-toluenediethanolamine, N-phenylethanolamine, 4-methylphenidylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 1-phenyl-5-tertetrazol, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetylamine, benzoaniline, N-methylacetylaniline, 3',4'-dimethylacetylaniline, etc. Sensitizing dyes can also be used as sensitizers. For details regarding the sensitizing pigment, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated herein by reference.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and even more preferably 0.5 to 10% by weight. The sensitizer can be used alone or two or more at the same time.

[Chain Transfer Agent] The photosensitive resin composition of this invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the 3rd edition of the Polymer Dictionary (edited by the Society of Polymer Science, Japan, 2005), pages 683-684. As chain transfer agents, for example, compounds containing SH, PH, SiH, and GeH within the molecule are used. These generate free radicals by donating hydrogen to less reactive free radicals, or by deprotonation after oxidation. In particular, thiols are preferred.

Furthermore, the chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent relative to 100 parts by weight of the total solid content of the photosensitive resin composition of the present invention is preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight, and even more preferably 1 to 5 parts by weight. The chain transfer agent may be only one type or may be two or more types. When there are two or more chain transfer agents, it is preferable that their total amount is within the above range.

[Surfactant] From the viewpoint of further improving coatability, a surfactant can be added to the photosensitive resin composition of the present invention. Various surfactants, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants, can be used as surfactants. Furthermore, the following surfactant is also preferred. In the following formula, the parentheses representing the repeating unit of the main chain indicate the content (mol%) of each repeating unit, and the parentheses representing the repeating unit of the side chain indicate the number of repetitions of each repeating unit. [Chemical Formula 57] Furthermore, compounds described in paragraphs 0159 to 0165 of International Patent Application Publication No. 2015/199219 can also be used as surfactants. Regarding fluorinated surfactants, fluoropolymers having vinyl unsaturated groups on their side chains can also be used as fluorinated surfactants. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.

The fluorine content in fluorinated surfactants is preferably 3-40% by mass, more preferably 5-30% by mass, and even more preferably 7-25% by mass. Fluorinated surfactants with fluorine content within this range are effective in terms of uniformity of coating thickness, liquid saving, and 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, Toray Silicone SH8400 (manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, and BYK330 (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 nonionic surfactants include glycerol, trihydroxymethylpropane, trihydroxymethylethane, and their ethoxylated and propoxylated derivatives (e.g., glycerol propoxylated, glycerol ethoxylated, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearate ether, polyoxyethylene oil-based ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), and SOLSPERSE 20000 (Boyd & Moore Executive). Search.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), Pionin D-6112, D-6112-W, D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD), Olfin E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

As cationic surfactants, examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers POLYFLOW No.75, No.77, No.90, No.95 (manufactured by Kyoisha chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

As anionic surfactants, examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by SANYO KASEI Co., Ltd.).

When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one type, or it may be two or more types. When there are two or more surfactants, their total content is preferably within the above range.

[Higher Fatty Acid Derivatives] In order to prevent polymerization hindrance caused by oxygen, higher fatty acid derivatives such as docosanoic acid or docosanoic acid amide can be added to the photosensitive resin composition of the present invention so that they are concentrated on the surface of the photosensitive resin composition during the drying process after coating.

Furthermore, higher fatty acid derivatives can also use the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the photosensitive resin composition of the present invention contains higher fatty acid derivatives, the content of higher fatty acid derivatives relative to the total solid content of the photosensitive resin composition of the present invention is preferably 0.1% to 10% by mass. There may be only one type of higher fatty acid derivative, or there may be two or more types. When there are two or more types of higher fatty acid derivatives, their total content is preferably within the above range.

[Thermal Polymerization Initiator] The resin composition of this invention may contain a thermal polymerization initiator, and more particularly, a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals through thermal energy, thereby initiating or promoting the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can also proceed, thus further improving solvent resistance.

As a thermal free radical polymerization initiator, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554 can be cited as examples.

When a thermal polymerization initiator is included, its content relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass. The thermal polymerization initiator may contain only one type or two or more types. When two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[Inorganic Particles] The resin composition of this invention may contain inorganic particles. Specifically, these inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the aforementioned inorganic particles is preferably 0.01–2.0 μm, more preferably 0.02–1.5 μm, even more preferably 0.03–1.0 μm, and particularly preferably 0.04–0.5 μm. If the average particle size of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may sometimes deteriorate. Furthermore, if the average particle size of the inorganic particles is greater than 2.0 μm, the resolution may sometimes decrease due to the scattering of the exposed light.

[Ultraviolet Absorber] The composition of this invention may include an ultraviolet absorber. As an ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-butylphenyl salicylate. Examples of benzophenone-based ultraviolet 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. Furthermore, examples of benzotriazole-based ultraviolet 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'-isobutyl) 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 acrylonitrile-based UV absorbers that can replace cyano-3,3-diphenylacrylate include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Furthermore, examples of triterpenoid-based UV absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triterpenoid and 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -Bis(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, etc.; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(hydroxyphenyl) compounds, 2,4-Bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-tris(2,4-bis(2-hydroxy-4-)) Tris(hydroxyphenyl)tris(2,4-dibutoxyphenyl)-1,3,5-tris(2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-tris(2,4,6-tris(2-hydroxyphenyl)tris(2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(2,4,6-tris(2-hydroxyphenyl) ...-hydroxyphenyl)tri

In this invention, the aforementioned ultraviolet absorbers can be used individually or in combination of two or more. The composition of this invention may or may not contain ultraviolet absorbers, but when contained, the content of the ultraviolet absorber relative to the total solid content of the composition of this invention is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organic Titanium Compounds] The resin composition of this embodiment may contain organic titanium compounds. By containing organic titanium compounds, a resin layer with excellent chemical resistance can be formed even when hardened at low temperatures.

As usable organic titanium compounds, those in which the organic groups are bonded to titanium atoms via covalent or ionic bonds can be cited. Specific examples of organic titanium compounds are shown in I) to VII) below: I) Chelated titanium compounds: Among these, titanium chelates having two or more alkoxy groups are preferred, considering excellent preservation stability of negative photosensitive resin compositions and the ability to obtain good curing patterns. Specific examples include titanium bis(triethanolamine) diisopropoxy titanium, bis(n-butoxy)bis(2,4-glutarate) titanium, diisopropoxybis(2,4-glutarate) titanium, diisopropoxybis(tetramethylheptanediate) titanium, and diisopropoxybis(ethyl acetoacetate) titanium. II) Tetraalkoxytitanium compounds: Examples include tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearoxytitanium, tetra[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-pyrrolo-1-yl)phenyl)titanium. IV) Monoalkoxytitanium compounds: Examples include tris(dioctyl phosphate)isopropoxytitanium and tris(dodecyl benzenesulfonate)isopropoxytitanium. V) Titanium oxide compounds: Examples include bis(glutarate)titanium oxide, bis(tetramethylheptane)titanium oxide, and phthalocyanine titanium oxide. VI) Tetraacetone titanium compounds: Examples include tetraacetone titanium. VII) Titanium ester coupling agents: such as isopropyltridodecylbenzenesulfonyl titanium ester, etc.

Among these, from the viewpoint of exhibiting better drug resistance, it is preferable to select at least one compound from the group consisting of I) chelated titanium compounds, II) tetraalkoxy titanium compounds and III) dicene titanium compounds. In particular, diisopropoxybis(acetyl ethyl acetate)titanium, tetra(n-butoxy)titanium and bis(n5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrolo-1-yl)phenyl)titanium are preferred.

When incorporating organotitanium compounds, the amount incorporating is preferably 0.05 to 10 parts by weight relative to 100 parts by weight of the cyclized resin precursor, and more preferably 0.1 to 2 parts by weight. When the amount incorporating is 0.05 parts by weight or more, the resulting curing pattern exhibits good heat resistance and chemical resistance; on the other hand, when the amount incorporating is 10 parts by weight or less, the composition exhibits excellent storage stability.

[Antioxidant] The composition of this invention may include an antioxidant. By including an antioxidant as an additive, the stretchability and adhesion to metal materials of the cured film can be improved. Examples of antioxidants include phenolic compounds, phosphite compounds, and thioether compounds. As a phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferred phenolic compound, hindered phenolic compounds can be mentioned. Compounds having a substituent at the site (orthoside) adjacent to the phenolic hydroxyl group are preferred. As the aforementioned substituent, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, regarding antioxidants, compounds having both a phenolic group and a phosphite group within the same molecule are also preferred. Furthermore, phosphorus-based antioxidants can be used more effectively as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxanephosphonium-heptadecadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f][1,3,2]dioxanephosphonium-heptadecadien-2-yl)oxy]ethyl]amine, and bis(2,4-di-tertiary butyl-6-methylphenyl) ethyl phosphite. Commercially available antioxidants include, for example, 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, the antioxidants can also be compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. Additionally, the composition of this invention may contain potential antioxidants as needed. As potential antioxidants, examples include compounds whose antioxidant activity is achieved by protecting groups at the site of their action. In these compounds, the protecting groups are removed by heating at 100–250°C or heating at 80–200°C in the presence of an acid/base catalyst, thereby enabling them to function as antioxidants. Examples of potential antioxidants include compounds described in International Publication Nos. 2014/021023, 2017/030005, and Japanese Patent Application Publication No. 2017-008219. Commercially available examples of potential antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of better antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-bis-tert-butylphenol and compounds represented by general formula (3).

[Chemical Formula 58]

In general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and ^R6 represents an alkyl group having 2 or more carbon atoms. ^R7 represents an alkyl group having 2 or more carbon atoms, and includes a 1- to 4-valent organic group selected from at least one of the O and N atoms. k represents an integer from 1 to 4.

Compounds represented by general formula (3) inhibit the oxidative degradation of aliphatic and phenolic hydroxyl groups in resins. Furthermore, by preventing rust on metallic materials, they can inhibit metal oxidation.

To ensure simultaneous action on both resins and metal materials, an integer from 2 to 4 in the k series is preferred. Examples of ^R7 include alkyl, cycloalkyl, alkoxy, alkyl ether, alkylsilyl, alkoxysilyl, aryl, aryl ether, carboxyl, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH-, and combinations thereof, which may further have substituents. Among these, alkyl ethers and -NH- are preferred from the viewpoint of solubility in the developing solution and metal adhesion; -NH- is more preferred from the viewpoint of interaction with resins and metal adhesion based on the formation of metal complexes.

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

[Chemical Formula 59]

[Chemical Formula 60]

[Chemical Formula 61]

[Chemical Formula 62]

The preferred amount of antioxidant relative to the resin is 0.1 to 10 parts by weight, with 0.5 to 5 parts by weight being even better. Adding less than 0.1 parts by weight makes it difficult to obtain the effect of improving the ductility and adhesion to metal materials after curing. Furthermore, adding more than 10 parts by weight may lead to a decrease in the sensitivity of the resin composition due to interaction with the photosensitizer. Only one type of antioxidant may be used, or two or more types may be used. When using two or more types, the total amount within the above-mentioned range is preferred.

<Regarding limitations on other contained substances> From the viewpoint of coating properties, it is preferable that the water content of the photosensitive resin composition of the present invention is less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass. Methods for maintaining water content include adjusting the humidity under storage conditions and reducing the porosity of the container.

From an insulation perspective, it is preferable that the metal content of the photosensitive resin composition of the present invention is 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, chromium, and nickel. When multiple metals are included, it is preferable that the total amount of these metals is within the above-mentioned range.

Furthermore, as a method to reduce metal impurities accidentally included in the photosensitive resin composition of the present invention, the following methods can be cited: selecting raw materials with lower metal content as raw materials for constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive resin composition of the present invention using a filter, lining the device with polytetrafluoroethylene or the like, and performing distillation under conditions that suppress contamination as much as possible.

Considering its application as a semiconductor material and from the viewpoint of wiring corrosion, the halogen atom content in the photosensitive resin composition of this invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass. Of these, the content of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine and bromine atoms. It is preferable that the total number of chlorine and bromine atoms, or chlorine and bromine ions, falls within the above-mentioned ranges. As a method for adjusting the halogen atom content, ion exchange treatment is a preferred example.

As a container for the photosensitive resin composition of the present invention, conventionally known containers can be used. Furthermore, as a container, to prevent impurities from contaminating the raw materials and the photosensitive resin composition, it is preferable to use a multi-layered bottle with an inner wall composed of six layers of six different resins, or a bottle with a seven-layered structure of the six resins. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

<Applications of the Photosensitive Resin Composition> The photosensitive resin composition of this invention is preferably used for forming interlayer insulating films for redistribution layers. Furthermore, it can also be used to form insulating films for semiconductor devices or stress-absorbing films, etc.

<Preparation of Photosensitive Resin Composition> The photosensitive 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 carried out by conventionally known methods.

Furthermore, filtration using a filter is preferable for removing foreign matter such as dust or particulate matter from photosensitive resin compositions. A filter pore size of 1 μm or less is preferred, 0.5 μm or less is even better, and 0.1 μm or less is still preferable. From a production standpoint, 5 μm or less is preferred, 3 μm or less is even better, and 1 μm or less is still even better. Filter materials such as polytetrafluoroethylene, polyethylene, or nylon are preferred. Filters can be pre-cleaned with an organic solvent. Multiple filters can be used in parallel or in series during the filtration process. When using multiple filters, filters with different pore sizes or materials can be combined. Furthermore, various materials can be filtered multiple times. Multiple filtrations can constitute cyclic filtration. Filtration can also be performed after pressurization. When filtration is performed after pressurization, a pressure of 0.05 MPa or higher and 0.3 MPa or lower is preferred. However, from a production perspective, a pressure of 0.01 MPa or higher and 1.0 MPa or lower is preferred, 0.03 MPa or higher and 0.9 MPa or lower is even better, and 0.05 MPa or higher and 0.7 MPa or lower is further preferred. In addition to filtration using a filter, impurity removal using adsorption materials can also be performed. A combination of filter filtration and impurity removal using adsorption materials can also be used. As an adsorbent, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silicone and zeolite, and organic adsorbent materials such as activated carbon can be used.

(Photosensitive film, curing material, laminate, element and manufacturing method thereof) Next, the manufacturing methods of photosensitive film, curing material, laminate, element and the like shall be explained.

The photosensitive film of this invention is a film formed from the photosensitive resin composition of this invention. The photosensitive film of this invention is formed, for example, by applying the photosensitive resin composition of this invention onto a substrate. The application method and the type of substrate are not particularly limited; preferred examples are those used in the film formation process described later. The film thickness of the photosensitive film can be set to a thickness within the range described later for the cured material. For example, the film thickness of the photosensitive film can be determined considering shrinkage caused by curing during the formation of the cured material.

The cured product of this invention is a cured product of the photosensitive resin composition of this invention or a cured product of the photosensitive film of this invention. Preferably, the pattern obtained by the pattern forming method of this invention described later is used in the cured product. The cured product of this invention is obtained by curing the photosensitive resin composition of this invention or the photosensitive film of this invention. The thickness of the cured film of this invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Furthermore, as an upper limit, it can be 100 μm or less, and can also be 30 μm or less. The cured product of this invention is preferably used as an interlayer insulating film for redistribution layers.

A laminate consisting of two or more layers, or even three to seven layers, of the hardened material of the present invention can be configured as a laminate. The laminate of the present invention comprises two or more layers composed of hardened material, and it is preferable that any of the layers composed of the hardened material includes a metal layer between them. For example, a laminate consisting of at least three layers sequentially stacked: a layer composed of a first hardened material, a metal layer, and a layer composed of a second hardened material is preferred. Both the layer composed of the first curing agent and the layer composed of the second curing agent described above are layers composed of the curing agents of the present invention. For example, it is preferable that both the layer composed of the first curing agent and the layer composed of the second curing agent are films formed by curing the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention used to form the layer composed of the first curing agent and the photosensitive resin composition of the present invention used to form the layer composed of the second curing agent can be composed of the same composition or can be composed of different compositions. The metal layer in the laminate of the present invention can preferably be used as a rewiring layer or other metal wiring.

Examples of materials for which the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, and stress-relief films. Other examples include sealing films, substrate materials (base films, cover films, and interlayer insulating films for flexible printed circuit boards), or patterns formed by etching insulating films used for practical installation purposes as described above. Regarding these applications, for example, one can refer to Science & Technology Co., Ltd. "High Functionalization and Application Technology of Polyimide" April 2008, Masaaki Kakimoto/supervisor, CMC Technical Library "Basic and Development of Polyimide Materials" November 2011, Japan Polyimide and Aromatic Polymer Research Association/ed. "Latest Polyimide Basics and Applications" NTS August 2010, etc.

Furthermore, the hardened material of this invention can also be used in the manufacture of offset printing plates or screen printing plates, in the etching and molding of parts, and in the manufacture of protective coatings and dielectric layers in electronics, especially microelectronics.

The method for manufacturing the pattern of the present invention (hereinafter also referred to as "the method for manufacturing the present invention") preferably includes a film forming process in which the photosensitive resin composition of the present invention is applied to a substrate to form a film (photosensitive film). The method for manufacturing the pattern of the present invention preferably includes the above-described film forming process, an exposure process for exposing the above-described film, and a development process for developing the above-described exposed film to obtain the pattern. Furthermore, the method for manufacturing the pattern of the present invention includes the above-described film forming process and the above-described development process as needed, and more preferably includes a heating process for curing the pattern obtained by the above-described development process by heating. Specifically, processes including (a) to (c) are preferred, and processes including (a) to (d) are even more preferred. (a) A film forming process in which a photosensitive resin composition is applied to a substrate to form a film (photosensitive film) (b) An exposure process in which the above-mentioned film is exposed (c) A developing process in which the above-exposed film is developed to obtain a pattern (d) A heating process in which the pattern obtained by the above-mentioned developing process is heated to harden the pattern By heating in the above-mentioned heating process, the photosensitive film can be further hardened.

The preferred embodiment of the method for manufacturing a laminated body includes the method for manufacturing the pattern of the present invention. In the method for manufacturing a laminated body according to the above-described method, after forming the pattern, the process of (a) or processes (a) to (c), or processes (a) to (d) are performed again. In particular, it is preferable to perform each of the above processes multiple times, for example, 2 to 5 times (i.e., a total of 3 to 6 times). A laminated body can be formed by such a patterned design. In the present invention, it is particularly preferable to provide a metal layer on the portion where the pattern is provided, between the patterns, or both. Furthermore, in the manufacturing of the laminate, it is not necessary to repeat all of the processes (a) to (d). As mentioned above, a laminate with a pattern can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) multiple times.

<Film Formation Process (Layer Formation Process)> The preferred embodiment of the present invention includes a film formation step (layer formation step) of applying a photosensitive resin composition onto a substrate to form a film (layer).

The type of substrate can be appropriately set according to the application, but there are no particular limitations. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon; quartz; glass; optical films; ceramic materials; vapor-deposited films; magnetic films; reflective films; metal substrates such as Ni, Cu, Cr, and Fe; paper; SOG (Spin-On Glass); TFT (Thin Film Transistor) array substrates; and electrode plates for plasma display panels (PDPs). Furthermore, bonding layers, oxide layers, etc., can be formed on the surface of these substrates. In this invention, semiconductor substrates are particularly preferred, with silicon substrates, Cu substrates, and casting substrates being even more preferred. Furthermore, a close-bonding layer or oxide layer formed of hexamethyldisilazane (HMDS) or similar material can be provided on the surface of such substrates. Also, a plate-shaped substrate (substrate) can be used as the substrate. The shape of the substrate is not particularly limited; it can be circular or rectangular, with a rectangular shape being preferred. Regarding the dimensions of the substrate, if it is circular, the diameter is, for example, 100–450 mm, preferably 200–450 mm. If it is rectangular, for example, the length of the shorter side is 100–1000 mm, preferably 200–700 mm.

Furthermore, when a photosensitive film is formed on the surface of the resin layer (a layer composed of a hardened material) and the surface of the metal layer, the resin layer and the metal layer become the substrate.

As a method for applying photosensitive resin components to a substrate, coating is preferred.

Specifically, examples of application methods include dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the perspective of uniformity of photosensitive film thickness, spin coating, slit coating, spray coating, and inkjet coating are preferred. By appropriately adjusting the solid content and coating conditions according to the method, a resin layer of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected based on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, or inkjet coating are preferred. For rectangular substrates, slit coating, spray coating, or inkjet coating are preferred. In the case of spin coating, for example, a rotation speed of 500–2000 rpm can be applied for approximately 10 seconds to 1 minute. Also, depending on the viscosity of the photosensitive resin composition or the intended film thickness, a rotation speed of 300–3500 rpm for 10–180 seconds is also preferable. Furthermore, to obtain a uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method for transferring a coating pre-applied to a pseudo-support using the aforementioned coating method onto a substrate can also be applied. Regarding the transfer method, the present invention preferably utilizes the manufacturing methods described in Japanese Patent Application Publication No. 2006-023696, paragraphs 0023, 0036-0051, and Japanese Patent Application Publication No. 2006-047592, paragraphs 0096-0108. Furthermore, a process for removing excess film at the ends of the substrate can also be performed. Examples of such processes include edge bead removal (EBR), air knife, and backwashing. Alternatively, the following pre-wetting process can be used: before applying the resin composition to the substrate, apply various solvents to the substrate to improve the wettability of the substrate, and then apply the resin composition.

<Drying Process> The manufacturing method of this invention can also include a drying process to remove solvent after the film formation process (layer formation process). A preferred drying temperature is 50–150°C, more preferably 70–130°C, and further preferably 90–110°C. As for the drying time, examples include 30 seconds to 20 minutes, 1 minute to 10 minutes are preferred, and 3 minutes to 7 minutes are even better.

<Exposure Process> The manufacturing method of this invention may include an exposure process of exposing the above-mentioned film (photosensitive film). The exposure amount is not particularly limited as long as it is sufficient to harden the photosensitive resin composition. For example, it is preferable to irradiate with an exposure energy of 100 to 10,000 mJ/ ^cm² at a wavelength of 365 nm, and even more preferable to irradiate with an exposure energy of 200 to 8,000 mJ/ ^cm² .

The exposure light used in the above exposure process preferably includes light with a wavelength of 150 to 1,000 nm, more preferably includes light with a wavelength of 150 to 450 nm, and even more preferably includes light with a wavelength of 240 to 550 nm.

Regarding the exposure wavelength, if we explain it in relation to the light source, we can cite (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), broadband (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), _F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet; EUV (wavelength 13.6nm), (6) electron beams, (7) the second harmonic of YAG lasers at 532nm and the third harmonic at 355nm, etc. Regarding the photosensitive resin composition of this invention, exposure to a high-pressure mercury lamp is particularly preferred, especially exposure to i-rays. This allows for particularly high exposure sensitivity. Furthermore, from an operability and production perspective, a broadband (three wavelengths of g, h, and i-rays) light source from a high-pressure mercury lamp or a 405nm semiconductor laser is also preferred.

<Developing Process> The manufacturing method of this invention may include a developing process of developing an exposed film (photosensitive film). By developing, the unexposed portions (non-exposed areas) are removed. There are no particular limitations on the developing method as long as the desired pattern can be formed; examples include spraying developer from a nozzle, spraying, and immersing the substrate in developer. Spraying from a nozzle is preferred. The developing process may employ a process of continuously supplying developer to the substrate, a process of holding the developer on the substrate in a substantially static state, a process of vibrating the developer using ultrasound, or a combination of these methods.

Development is performed using a developer. Regarding the developer, it can be used without particular restrictions as long as it can remove the unexposed areas (non-exposed portions). As a developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

In this invention, it is preferable that the developing solution contains an organic solvent with a ClogP value of -1 to 5, and even more preferable that it contains an organic solvent with a ClogP value of 0 to 3. The ClogP value can be calculated by inputting the structural formula in ChemBioDraw.

When the developing solution contains organic solvents, the organic solvents, preferably esters, include 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, and alkyl alkoxyacetic acids (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate; e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, etc.). Alkyl esters of 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc., such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), and alkyl esters of 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc., such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.). ethyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celecoxetate, ethyl celecoxetate, diethylene glycol dimethyl ether, diethylene glycol mono ... Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and as ketones, such as preferably methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as cyclic hydrocarbons, such as preferably toluene, xylene, anisole, limonene, etc., and as ionides, preferably dimethyl ionides, and mixtures of these organic solvents are also preferred examples.

When the developing solution contains an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferred in this invention, with cyclopentanone being even more preferred. Furthermore, when the developing solution contains an organic solvent, one type of organic solvent or a mixture of two or more types can be used.

When the developing solution contains organic solvents, it is preferable that 50% or more of the developing solution is an organic solvent, even better that 70% or more is an organic solvent, and even more preferably that 90% or more is an organic solvent. Furthermore, 100% of the developing solution can be an organic solvent.

The developing solution may further contain other ingredients. Other ingredients include, for example, known surfactants and known defoamers.

When the developing solution is an alkaline aqueous solution, examples of alkaline compounds that can be contained in the alkaline aqueous solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, with TMAH being preferred. For example, when using TMAH, the content of the alkaline compound in the total amount of the developing solution is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass.

[Developer Supply Method] As long as the desired pattern can be formed, there are no particular limitations on the developer supply method. Methods include immersing the substrate in the developer, applying the developer to the substrate using a nozzle (coating development), or continuous supply. There are no particular limitations on the type of nozzle; examples include direct-flow nozzles, spray nozzles, and mist nozzles. From the perspectives of developer penetration, non-image area removal, and manufacturing efficiency, a direct-flow nozzle or a continuous mist nozzle method is preferable. From the perspective of developer penetration into the image area, a mist nozzle method is even better. Furthermore, the following process can be adopted: after continuously supplying developer solution with a DC nozzle, rotating the substrate to remove the developer solution from the substrate, rotating to dry, and then continuously supplying it with a DC nozzle again, rotating the substrate to remove the developer solution from the substrate; this process can also be repeated several times. Furthermore, as a method for supplying developer solution in the developing process, processes such as continuously supplying developer solution to the substrate, maintaining the developer solution in a substantially static state on the substrate, using ultrasound or the like to vibrate the developer solution on the substrate, and combinations thereof can be adopted.

For development time, 5 seconds to 10 minutes is preferred, and 10 seconds to 5 minutes is even better. There is no particular limitation on the temperature of the developing solution during development, which is usually 10 to 45°C, but preferably 20 to 40°C.

After treatment with the developer, further rinsing can be performed. Alternatively, a rinsing solution can be supplied before the developer in contact with the pattern is completely dry. It is preferable to use a solvent different from the developer for rinsing. For example, a solvent contained in the photosensitive resin composition can be used for rinsing. When the developer contains an organic solvent, examples of rinsing solutions include PGMEA (propylene glycol monoethyl ether acetate) and IPA (isopropanol), with PGMEA being preferred. Furthermore, water is preferred as a rinsing solution in developing with a developer containing an alkaline aqueous solution. The rinsing time is preferably 10 seconds to 10 minutes, even better is 20 seconds to 5 minutes, and even better is 5 seconds to 1 minute. There is no particular limitation on the temperature of the rinsing solution, but it is preferably 10 to 45°C, and even better is 18°C to 30°C.

When the rinsing solution contains organic solvents, the organic solvents, preferably esters, include, 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 alkoxyacetic acid esters (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), and alkyl 3-alkoxypropionic acid esters (e.g., 3-alkyl...). Methyl hydroxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., 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 (e.g., 2-methoxy-2-methylpropionate) Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, preferably diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl celusone acetate, ethyl celusone 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, as ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, such as toluene, xylene, anisole, limonene, etc., and as iones, such as dimethyl iones, and as alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl methanol, triethylene glycol, etc., and as amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

When the rinsing solution contains organic solvents, one type of organic solvent or a mixture of two or more types can be used. In this invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are even more preferred, and cyclohexanone and PGMEA are even more preferred.

When the rinsing solution contains organic solvents, it is preferable that 50% or more of the rinsing solution is an organic solvent, more preferably 70% or more, and even more preferably 90% or more. Furthermore, 100% of the rinsing solution may be an organic solvent.

Rinsing solutions may further contain other ingredients. Other ingredients include, for example, known surfactants and known defoamers.

[Rinsing Solution Supply Method] There are no particular restrictions on the rinsing solution supply method as long as the desired pattern can be formed. Methods include: immersing the substrate in the rinsing solution; forming a liquid film of the rinsing solution on the substrate; supplying the rinsing solution to the substrate using a spray head; and continuously supplying the rinsing solution to the substrate using a direct-flow nozzle, etc. Considering the penetrability of the rinsing fluid, its ability to remove non-image areas, and manufacturing efficiency, various methods of supplying the rinsing fluid can be used, including spray nozzles, direct-flow nozzles, and mist nozzles. Continuous supply via a mist nozzle is preferable, and from the perspective of the rinsing fluid's penetrability to the image area, a mist nozzle is even better. There are no particular limitations on the type of nozzle; examples include direct-flow nozzles, spray nozzles, and mist nozzles. That is, it is preferable to use a direct current nozzle to supply or continuously supply the rinsing solution to the exposed film during the rinsing process, and even better to use a spray nozzle. Furthermore, as a method for supplying the rinsing solution in the rinsing process, processes that continuously supply the rinsing solution to the substrate, processes that hold the rinsing solution on the substrate in a substantially static state, processes that use ultrasound or the like to vibrate the rinsing solution on the substrate, and processes combining these methods are all possible.

<Heating Process> The manufacturing method of this invention preferably includes a process of heating the developed film at 50–450°C (heating process). It is preferable to include the heating process after the film formation process (layer formation process), drying process, and developing process. In the heating process, for example, alkali is generated by the decomposition of the aforementioned thermal alkali generator, and a cyclization reaction, serving as a precursor for a specific resin, is carried out. Furthermore, the photosensitive resin composition of this invention may contain a free radical crosslinker other than the precursor, serving as a specific resin, and the curing of the unreacted free radical crosslinker other than the precursor, etc., can also be carried out during this process. For the heating temperature (maximum heating temperature) in the middle layer of the heating process, 50°C or above is preferred, 80°C or above is better, 140°C or above is even better, 150°C or above is still better, 160°C or above is still better, and 170°C or above is still better. As for the upper limit, 500°C or below is preferred, 450°C or below is better, 350°C or below is better, 250°C or below is still better, and 220°C or below is still better.

Regarding heating, a heating rate of 1–12 °C/min from the initial heating temperature to the maximum heating temperature is preferred, 2–10 °C/min is even better, and 3–10 °C/min is further preferred. Setting the heating rate to 1 °C/min or higher ensures productivity while preventing excessive amine volatilization, while setting it to 12 °C/min or lower mitigates residual stress in the pattern. Furthermore, in the case of ovens capable of rapid heating, a heating rate of 1–8 °C/sec from the initial heating temperature to the maximum heating temperature is preferred, 2–7 °C/sec is even better, and 3–6 °C/sec is further preferred.

The initial heating temperature is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The initial heating temperature refers to the temperature at which the process begins and heats to the maximum heating temperature. For example, it is the temperature of the dried film (layer) after the photosensitive resin composition has been applied to a substrate and dried. It is preferable to start at a temperature 30°C to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition and gradually increase the temperature.

The heating time (heating time at the highest heating temperature) is preferably 10–360 minutes, more preferably 20–300 minutes, and even more preferably 30–240 minutes. Furthermore, by using the photosensitive resin composition of this invention, the above heating time can also be set to 15 minutes or less.

Especially when forming multilayered bodies, from the perspective of interlayer adhesion, heating at a temperature of 180℃ to 320℃ is preferred, and heating at 180℃ to 260℃ is even better. The reason for this is not yet determined, but it is believed that by setting this temperature, the acetylene groups of specific resins between the layers undergo cross-linking reactions.

Heating can be performed in stages. For example, a pretreatment process can be performed as follows: increasing the temperature from 25°C to 180°C at a rate of 3°C/min, holding at 180°C for 60 minutes, then increasing the temperature from 180°C to 200°C at a rate of 2°C/min, and holding at 200°C for 120 minutes. The heating temperature for this pretreatment process is preferably 100–200°C, more preferably 110–190°C, and even more preferably 120–185°C. In this pretreatment process, as described in U.S. Patent No. 9159547, simultaneous ultraviolet irradiation is also preferable. This pretreatment process can improve the properties of the film. Pretreatment processes can be performed in a short time of about 10 seconds to 2 hours, with 15 seconds to 30 minutes being even better. Pretreatment can be a two-stage or more process. For example, pretreatment process 1 can be performed in the range of 100 to 150°C, followed by pretreatment process 2 in the range of 150 to 200°C.

Furthermore, cooling can be performed after heating, and a cooling rate of 1–5°C/min is preferable in this case.

Regarding the heating process, to prevent the decomposition of certain resins, it is preferable to conduct the process in a low-oxygen atmosphere by circulating inert gases such as nitrogen, helium, or argon. An oxygen concentration of 50 ppm (by volume) or lower is preferred, and 20 ppm (by volume) or lower is even better. As for the heating method, there are no particular limitations; examples include heating plates, infrared furnaces, electric ovens, and hot air ovens.

<Metal Layer Formation Process> The manufacturing method of this invention includes a metal layer formation process in which a metal layer is formed on the surface of the film (photosensitive film) after development.

As a metal layer, there are no particular limitations; existing metal types can be used, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are preferred, with copper being even more preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be used. For example, methods described in Japanese Patent Application Publication Nos. 2007-157879, 2001-521288, 2004-214501, and 2004-101850 can be used. For example, photolithography, peeling, electrolytic plating, electroless plating, etching, printing, and combinations thereof can be considered. More specifically, patterning methods combining sputtering, photolithography, and etching, and patterning methods combining photolithography and electrolytic plating can be cited.

Regarding the thickness of the metal layer, 0.01–100 μm is preferred for the thickest part, 0.1–50 μm is even better, and 1–10 μm is even better.

<Lamination Process> The manufacturing method of this invention further includes a lamination process, which is preferred.

The lamination process includes a series of processes performed sequentially on the surface of a pattern (a layer composed of a hardened material) or a metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process. This can be a case where only the film formation process (a) is repeated. Alternatively, the heating process (d) can be performed at the end or in the middle of the lamination process. That is, it can also be a case where processes (a) to (c) are repeated a predetermined number of times, followed by heating (d), thereby curing the laminated photosensitive film. Furthermore, (c) the developing process may include (e) the metal layer formation process, in which the heating in (d) may be performed each time, or the heating in (d) may be performed collectively after a specified number of laminations. It is beyond doubt that the lamination process may further appropriately include the aforementioned drying process and heating process.

When performing a further deposition process after the deposition process, a surface activation treatment process can be performed after the heating process, the exposure process, or the metal layer formation process described above. Plasma treatment can be cited as an example of a surface activation treatment.

The above-mentioned lamination process is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even better if performed 3 to 5 times. Furthermore, the layers in the lamination process can be layers with the same composition, shape, and film thickness, or they can be different layers.

For example, it is better to have a structure with 2 or more but less than 20 resin layers, more than 3 but less than 7 layers, and more than 3 but less than 5 layers.

In this invention, it is particularly preferable to further form the pattern (resin layer) of the photosensitive resin composition by covering the metal layer after setting the metal layer. Specifically, examples include repeating (a) the film formation process, (b) the exposure process, (c) the development process, (e) the metal layer formation process, and (d) the heating process in sequence, or repeating (a) the film formation process, (b) the exposure process, (c) the development process, and (e) the metal layer formation process in sequence and setting (d) the heating process at the end or in the middle. By alternately performing the deposition process of the photosensitive film and the metal layer formation process, the hardened material (pattern) and the metal layer can be deposited alternately.

(Surface Activation Process) The method for manufacturing the laminate of the present invention may include a surface activation process for surface-activating at least a portion of the aforementioned metal layer and photosensitive resin composition layer. The surface activation process is typically performed after the metal layer formation process, but it can also be performed after the aforementioned exposure and development process, followed by the surface activation process on the photosensitive resin composition layer and then the metal layer formation process. The surface activation process may be performed on only at least a portion of the metal layer, or only on at least a portion of the exposed photosensitive resin composition layer, or on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferable to perform surface activation treatment on at least a portion of the metal layer, and preferably on a portion or all of the area on the metal layer where the photosensitive resin composition layer is formed. As described above, by performing surface activation treatment on the surface of the metal layer, the adhesion to the resin layer disposed on its surface can be improved. Furthermore, it is preferable to perform surface activation treatment on a portion or all of the exposed photosensitive resin composition layer (resin layer). As described above, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion to the metal layer and resin layer disposed on the surface-activated surface can be improved. As a surface activation treatment, specifically, plasma treatment, corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 /O2, _etc. , can be selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixture, argon/oxygen mixture, etc.), surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide coating by immersion in hydrochloric acid aqueous solution and then immersion in organic surface treatment agent containing at least one of amine and thiol groups, and mechanical roughening treatment using a brush are preferred. Plasma treatment is preferred, especially oxygen plasma treatment with oxygen as the raw material gas. In the case of corona discharge treatment, an energy level of 500–200,000 J/ ^m² is preferred, 1,000–100,000 J/ ^m² is even better, and 10,000–50,000 J/ ^m² is optimal.

This invention also discloses an element (e.g., a semiconductor device) comprising a cured material or laminate of this invention. As a specific example of using the photosensitive resin composition of this invention to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213-0218 of Japanese Patent Application Publication No. 2016-027357 and the description in Figure 1, and these contents are incorporated herein by reference. [Example]

The following embodiments provide a further detailed description of the present invention. The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart 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 "%" refer to the mass measure.

<Synthetic Example 1: Synthesis of Polymer A-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diethylene glycol dimethyl ether were mixed and stirred at 60°C for 18 hours to prepare a diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and while maintaining the temperature at -10 ± 4°C, 16.12 g (135.5 mmol) of _SOCl₂ was added over 10 minutes. The viscosity increased during the addition of _SOCl₂ . After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture over 20 minutes at -5 to 0 °C. Next, the reaction mixture was allowed to react at 0 °C for 1 hour, followed by the addition of 70 g of ethanol and stirring overnight at room temperature. Then, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. A polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes, and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45°C for 3 days to obtain polymer A-1. The weight-average molecular weight of polymer A-1 is 19,000. It is presumed that polymer A-1 contains repeating units represented by the following formula (A-1). [Chemical Formula 63]

<Synthetic Example 2: Synthesis of Polymer A-2> In Synthetic Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 °C for 12 hours) was replaced with 20.0 g (64.5 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride (dried at 140 °C for 12 hours), and polymer A-2 was obtained by the same method as in Synthetic Example 1. The weight-average molecular weight of polymer A-2 is 22,000. It is presumed that the obtained polymer A-2 contains a repeating unit represented by the following formula (A-2). In the repeating unit represented by formula (A-2), there are cases where the single bond contained in the biphenyl structure of 3,3',4,4'-biphenyltetracarboxylic anhydride and the ester structure formed by 3,3',4,4'-biphenyltetracarboxylic anhydride and 2-hydroxyethyl methacrylate are present at the meta position on the benzene ring, and cases where they are present at the para position (e.g., the repeating unit represented by formula (A-2-2) below), and it is considered that these structures coexist in polyimide precursor A-2. Similarly, in the following, the chemical formulas of the repeating units in the polyimide precursors produced when 3,3',4,4'-biphenyltetracarboxylic anhydride or 4,4'-oxophthalic anhydride are used as acid dianhydrides in the synthetic examples, will be used to indicate that the positional relationships of the single bonds in the biphenyl structure of 3,3',4,4'-biphenyltetracarboxylic anhydride or the ether bonds in 4,4'-oxophthalic anhydride with the ester bonds and amide bonds bonded to the benzene ring in each repeating unit on the benzene ring are not limited to the structures shown in the chemical formulas, and are assumed to be a mixture of different positional relationships. [Chemical Formula 64]

<Synthetic Example 3: Synthesis of Polymer A-3> In Synthetic Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) was replaced with 20.0 g (64.5 mmol) of 4,4'-oxophthalic anhydride (dried at 140°C for 12 hours), and polymer A-3 was obtained by the same method as in Synthetic Example 1. The weight-average molecular weight of polymer A-3 is 19,300. It is presumed that the obtained polymer A-3 contains a repeating unit represented by the following formula (A-3). [Chemical Formula 65]

<Synthetic Example 4: Synthesis of Polymer A-4> In Synthetic Example 1, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) was replaced with 9.49 g (32.25 mmol) of 4,4'-biphenyltetracarboxylic dianhydride and 10.0 g (32.25 mmol) of oxadiopteric dianhydride (both dried at 140°C for 12 hours). Otherwise, the synthesis was carried out in the same manner as in Synthetic Example 1, thereby obtaining polymer A-4. The weight-average molecular weight of polymer A-4 is 18,000. It is presumed that the obtained polymer A-4 contains two repeating units represented by the following formula (A-4). [Formula 66]

<Synthetic Example 5: Synthesis of Polymer A-5> Solution A was prepared by dissolving 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in 200 g of N-methylpyrrolidone. Next, 12.1 g (153 mmol) of pyridine was added to solution A, and while maintaining the temperature at -10 to 0 °C for 1 hour, a solution containing 1.38 g (70.1 mmol) of heptadiene chloride in 75 g of N-methylpyrrolidone was added dropwise. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was stirred further for 60 minutes. After cooling the reaction solution to 25 °C, 0.005 g of p-methoxyphenol was added and dissolved. 16.75 g (160 mmol) of methacryl chloride was added dropwise to the solution, and the mixture was stirred at 25 °C for 2 hours, followed by further stirring at 60 °C for 3 hours. Next, the polybenzo[a]azole precursor resin was precipitated in 6 liters of water, and the water-polybenzo[a]azole precursor resin mixture was stirred at 500 rpm for 15 minutes. The polybenzo[a]azole precursor resin was collected by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. The obtained polybenzo[a]azole precursor resin was then dried under reduced pressure at 45 °C for 3 days to obtain polymer A-5. The obtained polymer A-5 has a weight-average molecular weight of 20,000. It is presumed that the obtained polymer A-5 contains repeating units represented by the following formula (A-5). [Formula 67]

<Synthetic Example 6: Synthesis of Polymer A-6> While removing moisture in a dry reactor equipped with a stirrer, condenser, and a flat-bottomed connector containing an internal thermometer, 43.25 g (200 mmol) of 2-hydroxy-4,4'-diaminodiphenyl ether was dissolved in 300 g of N-methylpyrrolidone (NMP). Next, 88.85 g (200 mmol) of 4,4'-(hexafluoroisopropyl)diphthalic anhydride was added, and the mixture was stirred at 40 °C for 2 hours. Then, 50 mL of toluene and 2.18 g (10 mmol) of 3-aminophenol were added, and the mixture was stirred at 40 °C for 2 hours. After stirring, nitrogen was flowed through the reactor at a flow rate of 200 mL/min, and the temperature was raised to 180 °C and stirred for 6 hours. After cooling the above reaction solution to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 16.75 g (160 mmol) of methacryl chloride was added dropwise to the solution, and the mixture was stirred at 25°C for 2 hours, followed by further stirring at 60°C for 3 hours. The solution was then cooled to 25°C, 10 g of acetic acid was added, and the mixture was stirred at 25°C for 1 hour. After stirring, the mixture was precipitated in 2 liters of water/methanol (75/25, volume ratio) and stirred at 2,000 rpm for 30 minutes. The precipitated polyimide resin was collected by filtration, washed with 1.5 liters of water, and the filtrate was mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried at 40°C for 1 day under reduced pressure to obtain polymer A-6. The weight-average molecular weight of polymer A-6 is 18,500. It is presumed that polymer A-6 contains repeating units represented by the following formula (A-6). [Chemical Formula 68]

<Synthetic Example 7: Synthesis of Polymer A-7> Solution A was prepared by dissolving 28.0 g (76.4 mmol) of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane in 200 g of N-methylpyrrolidone. Next, 12.1 g (153 mmol) of pyridine was added to solution A. While maintaining the temperature at -10 to 0 °C for 1 hour, a solution containing 1.38 g (70.1 mmol, synthesized product) of 2,5-dihydroxy-p-dicarboxylic acid dichloride dissolved in 75 g of N-methylpyrrolidone was added dropwise. After stirring for 30 minutes, 1.00 g (12.7 mmol) of acetyl chloride was added, and the mixture was stirred further for 60 minutes. After stirring, nitrogen was flowed through the solution at a flow rate of 200 ml/min while the temperature was raised to 180°C and stirred for 6 hours. The reaction solution was then cooled to 25°C, and 0.005 g of p-methoxyphenol was added and dissolved. 16.75 g (160 mmol) of methacrylic acid chloride was added dropwise to the solution, and the mixture was stirred at 25°C for 2 hours, followed by further stirring at 60°C for 3 hours. Next, the polybenzoxazole resin was precipitated in 6 liters of water, and the water-polybenzoxazole resin mixture was stirred at 500 rpm for 15 minutes. The polybenzoxazole resin was collected by filtration, stirred again in 6 liters of water for 30 minutes, and filtered again. Next, the obtained polybenzoxazole resin was dried under reduced pressure at 45°C for 3 days to obtain polymer A-7. The weight-average molecular weight of the obtained polymer A-7 was 19,200. It is presumed that the obtained polymer A-7 contains repeating units represented by the following formula (A-7). [Chemical Formula 69]

<Synthetic Example 8: Synthesis of Polymer A’-1> 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 °C for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol), and 200 g of γ-butyrolactone were mixed and stirred at room temperature for 36 hours to prepare a diester of pyromellitic dianhydride and 2-hydroxyethyl methacrylate. Next, while stirring, a solution containing 26.6 g of dicyclohexanediimide (DCC) dissolved in 25 g of γ-butyrolactone was added dropwise under ice-cold conditions. Next, while stirring, 12.0 g of 4,4'-diaminodiphenyl ether suspended in 45 ml of γ-butyrolactone was added after 60 minutes. After further stirring at room temperature for 2 hours, 30 ml of ethanol was added and stirred for 1 hour, followed by the addition of 100 ml of γ-butyrolactone. The precipitate formed in the reaction mixture was removed by filtration, thereby obtaining the reaction solution. Then, the polyimide precursor was precipitated in 3 liters of water, and the water-polyimide precursor mixture was stirred at 5,000 rpm (revolutions per minute) for 15 minutes. The polyimide precursor was obtained by filtration, dissolved in 300 mL of tetrahydrofuran, and then the polyimide precursor was obtained again as a precipitate in 2 liters of water. The obtained polyimide precursor was dried at 45°C under reduced pressure for 3 days to obtain polymer A’-1. The weight average molecular weight of polymer A’-1 is 21,000. It is presumed that the obtained polymer A’-1 contains repeating units represented by the above formula (A-1).

<Synthetic Example 9: Synthesis of Polymer A’-2> In Synthetic Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) was replaced with 20.0 g (64.5 mmol) of 3,3’,4,4’-biphenyltetracarboxylic anhydride (dried at 140°C for 12 hours). Otherwise, the synthesis was carried out in the same manner as in Synthetic Example 8, thereby obtaining polymer A’-2. The weight-average molecular weight of polymer A’-2 is 22,500. It is presumed that the obtained polymer A’-2 contains a repeating unit represented by the above formula (A-2).

<Synthetic Example 10: Synthesis of Polymer A’-3> In Synthetic Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) was replaced with 20.0 g (64.5 mmol) of 4,4’-oxophthalic anhydride (dried at 140°C for 12 hours), and polymer A’-3 was obtained by the same method as in Synthetic Example 8. The weight-average molecular weight of polymer A’-3 is 21,200. It is presumed that the obtained polymer A’-3 contains a repeating unit represented by the above formula (A-3).

<Synthetic Example 11: Synthesis of Polymer A’-4> In Synthetic Example 8, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140°C for 12 hours) was replaced with 9.49 g (32.25 mmol) of 4,4’-biphenyltetracarboxylic dianhydride and 10.0 g (32.25 mmol) of oxadiopteric dianhydride (both dried at 140°C for 12 hours). Otherwise, the synthesis was carried out in the same manner as in Synthetic Example 8, thereby obtaining polymer A’-4. The weight-average molecular weight of polymer A’-4 is 21,000. It is presumed that the obtained polymer A’-4 contains two repeating units represented by the above formula (A-4).

<Examples and Comparative Examples> In each embodiment, the components listed in Tables 1 to 4 below were mixed to obtain various photosensitive resin compositions. Furthermore, in each comparative example, the components listed in Table 4 below were mixed to obtain various comparative compositions. Specifically, the content of each component listed in Tables 1 to 4 was set as the amount (parts by mass) recorded in each column of Tables 1 to 4. The obtained photosensitive resin compositions and comparative compositions were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8 μm at a pressure of 0.3 MPa. Furthermore, in Tables 1 to 4, a "-" indicates that the composition does not contain that component.

[Table 1] Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples 1 2 3 4 5 6 7 8 9 Composition Resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 36.393 36.393 36.393 36.393 36.393 36.393 36.393 36.393 36.393 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitive agent B-1 1.283 - 0.5415 6.415 - - - - - B-2 - - - - - - - - - B-3 - 1.283 - - - - - - - B-4 - - - - 1.283 - - - - B-5 - - - - - 1.283 - - - B-6 - - - - - - 1.283 - - B-7 - - - - - - - 1.283 - B-8 - - - - - - - - 1.283 B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - Cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 - - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 C-6 - - - - - - - - - Photoradical polymerization initiator F-1 - - - - - - - - - Polymerization inhibitors G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - Migration inhibitors H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal adhesion modifier I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A B B A A A A A Exposure sensitivity A A B B A A A A A Drug resistance A B A A A A A A A Resolution (direct exposure) A A A A A A A A A

[Table 2] Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples 10 11 12 13 14 15 16 17 18 Composition Resin A-1 - - - - - - 36.393 - - A-2 - - - - - - - 36.393 18.1965 A-3 36.393 36.393 36.393 36.393 36.393 36.393 - - 18.1965 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitive agent B-1 - - - - 0.6415 0.6415 1.283 1.283 1.283 B-2 - - - - - 0.6415 - - - B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - 0.6415 - - - - B-9 1.283 - - - - - - - - B-10 - 1.283 - - - - - - - B-11 - - 1.283 - - - - - - B-12 - - - 1.283 - - - - - Cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 - - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 C-6 - - - - - - - - - Photoradical polymerization initiator F-1 - - - - - - - - - Polymerization inhibitors G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - Migration inhibitors H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal adhesion modifier I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A A A A Exposure sensitivity A A A A A A A A A Drug resistance A A A A A A A A A Resolution (direct exposure) A A A A A A A A A

[Table 3] Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples 19 20 twenty one twenty two twenty three twenty four 25 26 27 Composition Resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 - - - - 36.393 35.11 35.11 35.11 35.11 A-4 36.393 - - - - - - - - A-5 - 36.393 - - - - - - - A-6 - - 36.393 - - - - - - A-7 - - - 36.393 - - - - - Sensitive agent B-1 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 1.283 B-2 - - - - - - - - - B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - - - - - - B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - Cross-linking agent E-1 5.501 5.501 5.501 5.501 - 5.501 5.501 5.501 5.501 E-2 - - - - 5.501 - - - - Organometallic complexes C-1 - - - - - 1.283 - - - C-2 - - - - - - 1.283 - - C-3 - - - - - - - 1.283 - C-4 - - - - - - - - 1.283 C-5 1.283 1.283 1.283 1.283 1.283 - - - - C-6 - - - - - - - - - Photoradical polymerization initiator F-1 - - - - - 1.283 1.283 1.283 1.283 Polymerization inhibitors G-1 - - - - - - - - - G-2 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 0.073 G-3 - - - - - - - - - Migration inhibitors H-1 - - - - - - - - - H-2 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 0.121 Metal adhesion modifier I-1 - - - - - - - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A A A A Exposure sensitivity A A A A A A A A A Drug resistance A A A A A B B A A Resolution (direct exposure) A A A A A A A A A

[Table 4] Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Implementation Examples Comparative example 28 29 30 31 32 33 1 2 3 Composition Resin A-1 - - - - - - - - - A-2 - - - - - - - - - A-3 35.11 35.11 36.393 36.393 36.393 36.393 36.393 36.393 36.393 A-4 - - - - - - - - - A-5 - - - - - - - - - A-6 - - - - - - - - - A-7 - - - - - - - - - Sensitive agent B-1 1.283 1.283 1.283 1.283 1.283 1.283 - 1.283 - B-2 - - - - - - - - 1.283 B-3 - - - - - - - - - B-4 - - - - - - - - - B-5 - - - - - - - - - B-6 - - - - - - - - - B-7 - - - - - - - - - B-8 - - - - - - - - - B-9 - - - - - - - - - B-10 - - - - - - - - - B-11 - - - - - - - - - B-12 - - - - - - - - - Cross-linking agent E-1 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 5.501 E-2 - - - - - - - - - Organometallic complexes C-1 0.6415 - - - - - - - - C-2 - - - - - - - - - C-3 - - - - - - - - - C-4 - - - - - - - - - C-5 0.6415 - 1.283 1.283 1.283 1.283 1.283 - 1.283 C-6 - 1.283 - - - - - - - Photoradical polymerization initiator F-1 1.283 1.283 - - - - - 1.283 - Polymerization inhibitors G-1 - - 0.073 - - - - - - G-2 0.073 0.073 - - - 0.073 0.073 0.073 0.073 G-3 - - - 0.073 - - - - - Migration inhibitors H-1 - - - - 0.073 - - - - H-2 0.121 0.121 0.121 0.121 0.121 - 0.121 0.121 0.121 Metal adhesion modifier I-1 - - - - - 0.121 - - - I-2 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 0.733 solvent J-1 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 43.69 J-2 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 10.923 Evaluation Resolution A A A A A A C C A Exposure sensitivity A A A A A A C C A Drug resistance A A A A A A A A C Resolution (direct exposure) A A A A A A C A A

The detailed information of each component recorded in Tables 1 to 4 is as follows.

[Resin] ・A-1～A-7: The above-mentioned polymers A-1～A-7

[Sensitizers] • B-1: 2,4-Dimethylthiatonone • B-2: N-Phenylenediethanolamine • B-3: Ethyl 7-(diethylamino)coumarin-3-carboxylate • B-4: 2,4-Dimethylthiatonone • B-5: 2-Chlorothiatonone • B-6: 2,4-Diisopropylthiatonone • B-7: Acridinone • B-8: N-Methylacridinone • B-9: N-Butylacridinone • B-10: N-Butyl-2-chloroacridinone • B-11: 9-Phenylecridinone • B-12: 1,7-Bis(9-acridin)heptane The above B-2 is a sensitizer without a condensed ring structure.

[Organometallic Complexes] • C-1: Tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co., Ltd.) • C-2: Diisopropoxybis(acetylacetone)titanium (manufactured by Matsumoto Fine Chemical Co., Ltd.) • C-3 to C-6: Compounds with the following structures, where C-5 is also a compound capable of initiating free radical polymerization. [Chemical Formula 70] In the above formula, Me represents a methyl group.

[Crosslinking Agent] • E-1: SR-209 (Tetraethylene glycol dimethacrylate, manufactured by Sartomer Company, Inc.) • E-2: A-DPH (Dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Photoradical polymerization initiator] • F-1: IRGACURE OXE 01 (manufactured by BASF)

[Polymerization Inhibitors] • G-1: 2,6-Di-tertiary-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) • G-2: p-Benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) • G-3: 2-Nitrosamino-1-naphthol

[Migration Inhibitor] • H-1: Compounds with the following structure, manufactured by Tokyo Chemical Industry Co., Ltd. • H-2: Compounds with the following structure, manufactured by Tokyo Chemical Industry Co., Ltd. [Chemical Formula 71]

[Metal Adhesion Modifier] • I-1: Compounds with the following structure, manufactured by Sigma-Aldrich Co. LLC • I-2: Compounds with the following structure, manufactured by Sigma-Aldrich Co. LLC [Chemical Formula 72] In the above formula, Et represents ethyl.

[Solubilizer] • J-1: γ-Butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) • J-2: Dimethyl monoxide (manufactured by FUJIFILM Wako Pure Chemical Corporation)

<Evaluation> [Evaluation of Resolution] The photosensitive resin composition prepared in each embodiment or the comparative composition prepared in each comparative example was spin-coated onto a silicon wafer. The spin-coated silicon wafer was dried on a heated plate at 100°C for 5 minutes, thereby forming a photosensitive film with a uniform thickness of 10 μm on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed using i-rays at a wavelength of 365 nm, with exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/ ^cm² . A photomask with 1 μm graduations from 5 μm to 25 μm was used to obtain the resin layer. The resin layer was developed with cyclopentanone for 60 seconds. The minimum linewidth among the exposures with the widest linewidth within the 200–800 mJ/ ^cm² range was used as the index value, and evaluation was performed according to the following evaluation criteria. The evaluation results are recorded in the "Resolution" column of the table. A smaller index value indicates a greater difference in solubility between the illuminated and unilluminated areas in the developing solution, resulting in a better outcome. Furthermore, if the linewidth change is small relative to the change in exposure energy, it indicates excellent resolution and is considered a better result. The measurement limit is 5μm. -Evaluation Criteria- A: The above indicator value is 5μm or higher and less than 10μm. B: The above indicator value is 10μm or higher and less than 20μm. C: The above indicator value is 20μm or higher, or no line and spatial pattern is formed.

[Evaluation of Exposure Sensitivity] A resin layer with line and spatial patterns was formed on a silicon wafer using the same method as described in the resolution evaluation above. While cooling the line and spatial patterns with liquid nitrogen, each silicon wafer was diced, and the cross-section of the line and spatial patterns was vapor-deposited using a scanning electron microscope sample coating apparatus (ion sputtering apparatus E-1030, manufactured by HITACHI). After the vapor-deposit process, scanning electron microscopy was performed from the cross-sectional side to measure the angle between the side of the line and spatial pattern with the smallest linewidth and the silicon wafer surface, and the angle was calculated. The evaluation was then performed according to the following evaluation criteria. Generally speaking, the closer the angle is to 90°, the better the exposure sensitivity of the photosensitive resin composition. -Evaluation Criteria- A: A pattern was formed at an angle greater than 75° and less than 90°. B: No pattern was formed, but the angle was less than 75° or greater than 90°. C: Pattern formation could not be confirmed.

[Evaluation of Drug Resistance] The photosensitive resin composition prepared in each embodiment or the comparative composition prepared in each comparative example was spin-coated onto a silicon wafer. The spin-coated silicon wafer was dried on a heated plate at 100°C for 5 minutes, thereby forming a photosensitive film with a uniform thickness of 10 μm on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). Exposure was performed using i-rays at a wavelength of 365 nm with exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/ ^cm² , using a photomask with lines and spatial patterns ranging from 5 μm to 25 μm in 1 μm increments to obtain a resin layer. For the sake of simplicity, development was not performed in the evaluation of chemical resistance. The exposed resin layer and silicon wafer were heated to 230 °C at a rate of 10 °C/min under a nitrogen atmosphere and maintained at that temperature for 180 minutes to obtain a hardened film. The obtained hardened film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated. Drug: A mixture of dimethyl sulfoxide (DMSO) and 25% by mass of tetramethylammonium hydroxide (TMAH) aqueous solution in a 90:10 ratio. Evaluation conditions: The hardened film was immersed in the drug at 75°C for 15 minutes, and the film thickness before and after immersion was compared to calculate the dissolution rate (nm/min). The obtained dissolution rate values were evaluated according to the following evaluation criteria, and the evaluation results were recorded in the "Drug Resistance" column of Tables 1 to 4. Generally speaking, the slower the dissolution rate, the better the drug resistance. -Evaluation Criteria- A: Dissolution rate less than 250 nm/min. B: Dissolution rate greater than 250 nm/min but less than 500 nm/min. C: Dissolution rate greater than 500 nm/min.

[Evaluation of Resolution (Direct Exposure)] The photosensitive resin composition of each embodiment or comparative example was spin-coated onto a silicon wafer. The silicon wafer was dried on a heated plate at 100°C for 5 minutes, thereby forming a photosensitive film with a uniform thickness of 10 μm on the silicon wafer. The photosensitive film on the silicon wafer was exposed using a direct exposure apparatus (AdTech DE-6UH III). Regarding the exposure, laser direct imaging exposure was performed at a wavelength of 405 nm with exposure energies of 200, 300, 400, 500, 600, 700, and 800 mJ/ ^cm² , thereby obtaining a resin layer such as lines on a 1 μm scale from 5 μm to 25 μm. The resin layer was developed with cyclopentanone for 60 seconds. The minimum linewidth among the exposures with the widest linewidth within the range of 200–800 mJ/ ^cm² was used as the index value, and the evaluation was conducted according to the following evaluation criteria. The evaluation results are recorded in the "Resolution (Direct Exposure)" column of the table. The smaller the index value, the greater the difference in solubility between the illuminated and unilluminated areas in the developing solution, resulting in a better result. The measurement limit is 5 μm. -Evaluation Criteria- A: The index value is 5 μm or more and less than 10 μm. B: The index value is 10 μm or more and less than 20 μm. C: The index value is 20 μm or more or no line and spatial pattern is formed.

Furthermore, in the embodiments where polymers A-1, A-2, A-3, and A-4 are used as resins, polymer A-1 is replaced with an equal mass of polymer A’-1, polymer A-2 is replaced with an equal mass of polymer A’-2, polymer A-3 is replaced with an equal mass of polymer A’-3, and polymer A-4 is replaced with an equal mass of polymer A’-4. The results of the evaluation of resolution, exposure sensitivity, chemical resistance, and resolution (direct exposure) are performed in the same manner. The evaluation results of each evaluation item in each embodiment are the same as the evaluation results before the change.

The results above show that the photosensitive resin composition of this invention can produce patterns with excellent resolution and drug resistance. The comparative composition of Comparative Example 1 does not contain the specific sensitizer. Therefore, the resolution of this comparative composition is poor. Furthermore, the comparative composition of Comparative Example 2 does not contain organometallic complexes. Therefore, the resolution of this comparative composition is poor. The comparative composition of Comparative Example 3 contains only a sensitizer different from the specific sensitizer. Therefore, when using this comparative composition, the drug resistance of the pattern is poor.

<Example 101> The photosensitive resin composition used in Example 1 was applied layerwise to the surface of a copper thin layer on a resin substrate with a copper thin layer formed thereon using a spin coating method. After drying at 100°C for 4 minutes, a photosensitive film with a thickness of 20 μm was formed. Exposure was then performed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-space pattern and a linewidth of 10 μm). After exposure, it was heated at 100°C for 4 minutes. Following the heating, it was developed with cyclohexanone for 2 minutes and washed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C/min until it reached 230°C, and then maintained at 230°C for 120 minutes, thereby forming an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer exhibits excellent insulation properties. Furthermore, semiconductor devices were fabricated using these interlayer insulating films for the redistribution layer, and normal operation was confirmed.

Claims (16)

A photosensitive resin composition comprising: a resin, which is a polyimide precursor; an organometallic complex; and a sensitizer having a condensed ring structure, wherein the aforementioned polyimide precursor comprises a repeating unit represented by the following formula (A-4); A photosensitive resin composition comprising: selected from polyimide precursors, polybenzo[a]pyrene, and other pigments. azole precursors, polyimides and polybenzo[a]azoles At least one resin in the group of azoles; an organometallic complex; and a sensitizer having a condensed ring structure, wherein the sensitizer comprises ethyl 7-(diethylamino)coumarin-3-carboxylate. The photosensitive resin composition as described in claim 1, wherein the aforementioned sensitizer comprises at least one atom selected from the group consisting of nitrogen and sulfur atoms as a ring member in the condensed ring structure. The photosensitive resin composition as described in claim 1, wherein the aforementioned sensitizer comprises at least one structure selected from the group consisting of acridinone, thiotonone, and acridinium structures as a condensed ring structure. The photosensitive resin composition as described in claim 1 or claim 2, wherein the content of the aforementioned sensitizer is 0.5 to 5.0 parts by weight relative to 1 part by weight of the aforementioned organometallic complex. The photosensitive resin composition as described in claim 1 or claim 2, wherein the aforementioned organometallic complex is a metallocene compound. The photosensitive resin composition as described in claim 1 or claim 2, wherein the metal contained in the aforementioned organometallic complex is selected from at least one metal selected from the group consisting of titanium, zirconium, and iron. The photosensitive resin composition as described in claim 1 or claim 2, wherein the aforementioned organometallic complex has photoradical polymerization initiation capability. A method for manufacturing a pattern includes: a film forming process, applying a photosensitive resin composition according to any one of claims 1 to 8 onto a substrate to form a photosensitive film; an exposure process, exposing the photosensitive film; and a developing process, developing the exposed photosensitive film to obtain the pattern. The method for manufacturing the pattern as described in claim 9, wherein the exposure light used in the aforementioned exposure process includes light with a wavelength of 150-450 nm. The method for manufacturing the pattern as described in claim 9 further includes: a heating process, wherein the pattern obtained by the aforementioned developing process is heated to harden the pattern. A photosensitive film formed from a photosensitive resin composition as described in any one of claims 1 to 8. A cured material, which is a cured version of the photosensitive film described in claim 12. The cured material as described in claim 13 is used as an interlayer insulating film for a redistribution layer. A laminate comprising two or more layers made of the hardened material described in claim 13 or claim 14, wherein any layer made of the aforementioned hardened material includes a metal layer between them. An element comprising the hardened material described in claim 13 or claim 14.