TWI875930B - Resin composition, cured film, laminate, method for producing cured film, and semiconductor element - Google Patents

Abstract

The present invention aims to provide a resin composition capable of suppressing the generation of defects in a film composed of a resin composition even when another film composed of another composition is formed on the other film, a cured film formed by curing the resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate. The problem of the present invention can be solved by the following method, namely, a resin composition comprising at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor and a surfactant satisfying at least one of the following conditions 1 and 2, a cured film formed by curing the above resin composition, a laminate comprising the above cured film, a method for producing the above cured film, and a semiconductor element comprising the above cured film or the above laminate, wherein condition 1: the molecular weight is 500 or less; condition 2: it can be decomposed under heating at 250°C.

Description

Resin composition, cured film, laminate, method for producing cured film, and semiconductor element

The present invention relates to a resin composition, a hardened film, a laminate, a method for manufacturing the hardened film, and a semiconductor device.

Polyimide or polybenzoxazole has excellent heat resistance and insulation properties, and can be used for various purposes. The above-mentioned use is not particularly limited, but if the semiconductor element for actual mounting is taken as an example, it can be used as an insulating film, a material for a sealing material, or a protective film. In addition, it can also be used as a base film or a cover film of a flexible substrate.

For example, in the above-mentioned use, polyimide or polybenzoxazole is used in the form of a resin composition containing at least one resin selected from the group including polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor. For example, the resin composition is applied to a substrate by coating to form a resin film, and then exposure, development, heating, etc. are performed as needed to form a hardened resin on the substrate. The above-mentioned polyimide precursor and the above-mentioned polybenzoxazole precursor are cyclized by heating, for example, and become polyimide and polybenzoxazole respectively in the hardened film. The resin composition can be applied by a known coating method, and therefore, it can be said that the resin composition has excellent manufacturing adaptability, such as high degree of freedom in designing the shape, size, and application position when applied. In addition to the high performance of polyimide, polybenzoxazole, etc., from the perspective of such excellent manufacturing adaptability, the application of the above-mentioned resin composition in the industry is expected to expand.

For example, Patent Document 1 describes a resin composition characterized by comprising (a) 100 parts by mass of a polyimide precursor having a specific structure, (b) 0.001 to 5 parts by mass of a silicone-based surfactant, and (c) an organic solvent.

[Patent Document 1] Japanese Patent Application Publication No. 2019-090047

In the production of a laminate including a film composed of a resin composition, there is a case where another film composed of another composition is formed on the film composed of the resin composition.

An object of the present invention is to provide a resin composition that can suppress the generation of defects in another film even when another film composed of another composition is formed on a film composed of a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

Representative examples of the present invention are shown below. ＜1＞ A resin composition comprising: At least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor; and A surfactant that satisfies at least one of the following conditions 1 and 2: Condition 1: molecular weight is 500 or less; Condition 2: capable of decomposing under heating at 250°C. ＜2＞ The resin composition as described in ＜1＞, wherein The surfactant is a non-ionic surfactant. ＜3＞ The resin composition as described in ＜1＞ or ＜2＞, wherein The surfactant is a compound having fluorine atoms. <4> The resin composition as described in <1> or <2>, wherein the volatility of the above-mentioned surfactant alone is 1 μm/minute or more at 25°C and 1 atmosphere. <5> The resin composition as described in <1> or <2>, wherein the content of the above-mentioned surfactant relative to the total mass of all surfactants contained in the resin composition is 50% by mass or more. <6> The resin composition as described in <1> or <2>, which further contains a lactone solvent. <7> The resin composition as described in <1> or <2>, wherein at least two types of resins are contained as the above-mentioned resin. <8> The resin composition as described in <1> or <2>, which is used to form a film for development using a developer containing an organic solvent. <9> The resin composition as described in <1> or <2>, which is used to form a film, the film is composed of the resin composition of the present invention, and another film composed of another composition and in contact with the above film is formed on the above film. <10> The resin composition as described in <1> or <2>, which is used to form a film for use in a process including heating. <11> The resin composition as described in <1> or <2>, which is used to form an interlayer insulating film for a redistribution layer. <12> A cured film formed by curing the resin composition described in any one of <1> to <11>. <13> A laminate comprising two or more cured films described in <12>, wherein a metal layer is included between any of the cured films. <14> A method for producing a cured film, comprising a film forming process of applying the resin composition described in any one of <1> to <11> to a substrate to form a film. <15> The method for producing a cured film as described in <14>, comprising an exposure process of exposing the film and a development process of developing the film. <16> The method for producing a cured film as described in <14> or <15>, comprising a heating process of heating the film at 50 to 450°C. <17> A semiconductor device comprising the cured film described in <12> or the laminated body described in <13>. [Effect of the invention]

According to the present invention, there are provided a resin composition capable of suppressing the generation of defects in another film even when another film composed of another composition is formed on a film composed of a resin composition, a cured film formed by curing the resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate.

The main embodiments of the present invention are described below. However, the present invention is not limited to the embodiments indicated. In this specification, the numerical range indicated by the symbol "～" indicates a range including the numerical values before and after "～" as the lower limit and the upper limit, respectively. In this specification, the term "process" not only indicates an independent process, but also includes processes that cannot be clearly distinguished from other processes as long as the desired effect of the process can be achieved. Regarding the marking of groups (atomic groups) in this specification, the marking of unsubstituted and unsubstituted includes both groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes exposure using particle beams such as electron beams and ion beams, in addition to exposure using light, unless otherwise specified. In addition, as light used for exposure, there can be cited the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other actinic rays or radiation. In this specification, "(meth)acrylate" means both or either of "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either of "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either of "acryl" and "methacryl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content means the total mass of the components excluding the solvent from the total components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of the 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 permeation chromatography (GPC measurement) and are defined as polystyrene conversion values. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained, for example, by using HLC-8220GPC (manufactured by TOSOH CORPORATION) and using protective columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) as columns. Unless otherwise specified, the molecular weights are measured using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, the detection in the GPC measurement uses a UV (ultraviolet) wavelength 254nm detector. In this specification, when the positional relationship of each layer constituting the laminate is recorded as "up" or "down", it is sufficient that other layers exist on the upper side or lower side of the layer that serves as the reference among the multiple layers concerned. That is, a third layer or a third element may be further sandwiched between the layer that serves as the reference and the other layers mentioned above, and the layer that serves as the reference and the other layers mentioned above do not need to be in contact. In addition, unless otherwise specified, the direction of stacking layers on the substrate is called "up", or when there is a photosensitive layer, the direction from the substrate toward the photosensitive layer is called "up", and the opposite direction is called "down". In addition, the setting of these up and down directions is for the convenience of this specification. In actual forms, the "up" direction in this specification may also be different from the vertical up direction. In this specification, unless otherwise specified, as each component contained in the composition, the composition may contain two or more compounds that meet the requirements of the component. In addition, unless otherwise specified, the content of each component in the composition represents the total content of all compounds that meet the requirements of the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the best state is the best state.

(Resin composition) The resin composition of the present invention comprises at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor (hereinafter, also referred to as "specific resin") and a surfactant satisfying at least one of the following conditions 1 and 2 (hereinafter, also referred to as "specific surfactant"). Condition 1: Molecular weight is 500 or less. Condition 2: Able to decompose under heating at 250°C.

The resin composition of the present invention is preferably used to form a film for development, and is preferably used to form a film for development using a developer containing an organic solvent. As the above-mentioned developer and the above-mentioned developing method, for example, the developer and the developing method described in the developing process in the description of the method for producing a cured film described later can be used.

The resin composition of the present invention is preferably used to form a film composed of the resin composition of the present invention and formed on the above film, another film composed of another composition and in contact with the above film. The film composed of the above resin composition of the present invention may be in direct contact with at least a portion of the other film. That is, the resin composition of the present invention is preferably used to form a component layer first formed on a laminated body formed by two component layers in contact with each other by lamination. As a method for producing the above another film, for example, the method described in the lamination process in the description of the method for producing a cured film described later can be cited. Furthermore, the film composed of the resin composition of the present invention is preferably formed by a process including heating. Furthermore, the other composition may be the resin composition of the present invention or another composition. As the other composition, a composition containing at least a resin is preferred, and a composition containing a specific resin is more preferred. Furthermore, as the other composition, the resin composition of the present invention may be used.

The resin composition of the present invention is preferably used to form a film for use in a process including heating. As a process including heating, the heating process described in the method for producing a cured film described later can be cited.

The resin composition of the present invention can suppress the generation of defects in another film even when another film composed of another composition is formed on a film composed of the resin composition. The mechanism for achieving the above effect is not yet clear, but it can be inferred as follows.

For example, as described in Patent Document 1, when a resin composition containing a specific resin is used to form a film, the resin composition is made to contain a surfactant to improve the coating property. However, when a film is formed using a resin composition containing a surfactant, the surfactant is present on the surface of the formed film, and when another film composed of another composition such as the resin composition is formed on the above film, there is a situation in which defects are generated on the above another film due to a decrease in wettability when applying the other composition, for example, a decrease in coating property during coating. In the present invention, it is believed that by using a surfactant (specific surfactant) that satisfies at least one of the above conditions 1 and 2, the specific surfactant is unlikely to remain on the film surface during or after the film is formed due to volatilization, decomposition, etc., and even when a resin composition or other composition is further applied on the above film, the generation of defects can be suppressed. In addition, according to the resin composition of the present invention, in the obtained film, at least a part of the specific surfactant contained in the film is removed by the above volatilization, decomposition, etc., so it is estimated that the obtained film is also likely to have excellent adhesion to metal.

Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

<Specific surfactant> The resin composition of the present invention contains a specific surfactant. In the present invention, the surfactant refers to a component contained in the resin composition, which makes the surface tension of the resin composition lower than that of a composition not containing the component.

The specific surfactant may satisfy at least one of the above conditions 1 and 2, or both, but it is preferred to satisfy at least the above condition 1. When the specific surfactant satisfies only the above condition 2, the molecular weight of the specific surfactant is preferably 300 to 200,000, and more preferably 1,000 to 100,000, for example.

The molecular weight in the above condition 1 is not particularly limited, and can be measured, for example, by a known mass analysis method. In addition, when the specific surfactant has a molecular weight distribution, the above molecular weight represents the weight average molecular weight. The surfactant satisfying the above condition 1 is preferably a surfactant satisfying the following condition 1-1, more preferably a surfactant satisfying the following condition 1-2, and more preferably a surfactant satisfying the following condition 1-3. Condition 1-1: The molecular weight is 400 or less. Condition 1-2: The molecular weight is 350 or less. Condition 1-3: The molecular weight is 320 or less.

Whether the surfactant in the above condition 2 can be decomposed by heating at 250°C can be confirmed by the following method. The surfactant is heated to 250°C at 5°C/min in a pressure-resistant capsule, and the peak temperature of the lowest temperature heat peak is read. When the peak temperature is lower than temperature A, it can be determined that the surfactant can be decomposed by heating at temperature A. The surfactant that satisfies the above condition 2 is preferably the surfactant that satisfies the following condition 2-1, more preferably the surfactant that satisfies the following condition 2-2, and more preferably the surfactant that satisfies the following condition 2-3. Condition 2-1: Decomposition can be achieved by heating at 230°C. Condition 2-2: Decomposition can be achieved by heating at 200°C. Condition 2-3: Able to decompose under heating at 180°C.

As a specific surfactant, it can be a non-ionic surfactant or an ionic surfactant. From the perspective of suppressing defects on the above-mentioned other film, a non-ionic surfactant is preferred. In the present invention, a non-ionic surfactant refers to a compound that is not ionized in the resin composition. Among non-ionic surfactants, a compound having an alkyl group and an ester bond that can be substituted by a fluorine atom or a compound having an alkyl group and a siloxane bond that can be substituted by a fluorine atom is preferred, a compound having a fluorinated alkyl group and an ester bond or a compound having a fluorinated alkyl group and a siloxane bond is more preferred, and a compound having a fluorinated alkyl group and an ester bond is further preferred. As a preferred embodiment of the fluorinated alkyl group, a group represented by the formula (1-1) described later can be mentioned.

As the specific surfactant, a compound having a fluorine atom is preferred. The specific surfactant preferably has a fluorinated alkyl group as the group having a fluorine atom. The fluorinated alkyl group is not particularly limited, but a group represented by the following formula (1-1) is preferred. [Chemical Formula 1] In formula (1-1), n represents an integer greater than 1, and R represents a hydrogen atom, a fluorine atom, or a monovalent organic group. In formula (1-1), n preferably represents an integer of 1 to 10, and more preferably an integer of 1 to 4. In formula (1-1), R is preferably a hydrogen atom or a fluorine atom, and more preferably a hydrogen atom. The monovalent organic group in R is not particularly limited, and may be selected within the range in which the effect of the present invention can be obtained, and preferably includes an alkyl group, an aryl group, and the like.

In addition, as a specific surfactant, a compound having a polymerizable group can be used. As a polymerizable group, it is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. As specific examples of the polymerizable group, there can be cited a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxadiazole group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. As the group having ethylenic unsaturated bonds, vinyl, vinyl ether, vinyl phenyl, allyl, (meth)acryl, (meth)acrylamide, (meth)acryloxy, etc. can be cited, and (meth)acryloxy is preferred. In the present invention, the component that meets the requirements of the specific surfactant is set to be a component that does not meet the requirements of the crosslinking agent described later.

From the viewpoint of suppressing defects on the other film, as a specific surfactant, the volatility of the specific surfactant is preferably 1 μm/min or more at 25°C and 1 atmosphere. In the present invention, 1 atmosphere refers to 101,325 Pa. The lower limit of the above-mentioned volatility is preferably 2 μm/min or more, and 5 μm/min or more is more preferred. In addition, the upper limit is preferably 1000 μm/min or less. In the present invention, the above-mentioned volatility is not particularly limited, and can be measured, for example, by the following method. A specific surfactant is dripped on a flat support to prepare a circular droplet with a radius of about 2 mm when observed in the vertical direction of the support surface. The curvature radius (r1) when the droplet approximates a spherical cap is calculated based on the contact angle of the droplet and the radius of the droplet. After that, the droplet is left at 25°C and 1 atmosphere, and after a certain period of time, the contact angle and the radius of the droplet are calculated again, and the curvature radius (r2) is calculated. The volatility (μm/minute) is calculated by dividing the difference between the curvature radius (r1) and the curvature radius (r2) by the elapsed time. The contact angle is not particularly limited, and can be measured, for example, according to the measurement method described in JIS R 1703:2007. In addition, it can also be measured using a known contact angle measuring instrument.

As the specific surfactant, preferably, a compound represented by the following formula (1-2) can be cited. [Chemical Formula 2] In formula (1-2), ^A1 represents a polymerizable group, a and b each independently represent an integer greater than 1, ^L1 represents an a+b valent linking group, n represents an integer greater than 1, and R represents a hydrogen atom or a monovalent organic group.

In formula (1-2), ^A1 represents a polymerizable group. As the polymerizable group, the above-mentioned polymerizable groups can be cited, and (meth)acryloyloxy is preferred. In formula (1-2), a represents an integer greater than 1, preferably an integer from 1 to 4, more preferably an integer of 1 or 2, and further preferably 1. In formula (1-2), ^L1 represents an a+b valent linking group, preferably an a+b valent alkyl group, more preferably an a+b valent saturated aliphatic alkyl group, an a+b valent aromatic alkyl group, or a group represented by a combination thereof, and more preferably an a+b valent saturated aliphatic alkyl group. As the saturated aliphatic alkyl group, a saturated aliphatic alkyl group having 1 to 20 carbon atoms is preferred, a saturated aliphatic alkyl group having 1 to 10 carbon atoms is more preferred, a saturated aliphatic alkyl group having 1 to 4 carbon atoms is further preferred, and a saturated aliphatic alkyl group having 1 carbon atoms is particularly preferred. As the aromatic alkyl group, an aromatic alkyl group having 6 to 20 carbon atoms is preferred, an aromatic alkyl group having 6 to 10 carbon atoms is more preferred, and an aromatic alkyl group having 6 carbon atoms is further preferred. In formula (1-2), n and R have the same meanings as n and R in formula (1-1), and preferred embodiments are also the same. In formula (1-2), b represents an integer greater than or equal to 1, preferably an integer from 1 to 4, more preferably an integer of 1 or 2, and even more preferably 1. When b is an integer greater than or equal to 2, the b n and R may be the same or different. In the present invention, the embodiment in which both a and b are 1 is also one of the preferred embodiments.

Specific examples of the specific surfactant include Viscoat 8FM, 4F, and V8F (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), glyceryl stearate, MEGAFACE DS-21 (manufactured by DIC Corporation), and 1,1,1,3,5,5,5-heptamethyl-3-(3,3,3-trifluoropropyl) pentatrisiloxane, but are not limited thereto.

The content of the specific surfactant is not particularly limited. Relative to the total solid content of the resin composition, 0.1 to 10 mass % is preferred, 0.3 to 5 mass % is more preferred, and 0.7 to 2.5 mass % is further preferred. The resin composition of the present invention may contain one specific surfactant alone or two or more. When the resin composition of the present invention contains two or more specific surfactants, the total content of the specific surfactant is preferably within the above range.

In addition, the specific surfactant content relative to the total mass of all surfactants contained in the resin composition is preferably 50 mass% or more, 80 mass% or more is more preferably, and 90 mass% or more is further preferably. The upper limit of the above content is not particularly limited and can be 100 mass%. The above "total mass of all surfactants" refers to the sum of the content of the specific surfactant (the total amount of such when it contains more than two kinds) and the content of the components that meet the requirements of surfactants and do not meet any one of the above conditions 1 and 2 (the total amount of such when it contains more than two kinds). As the components that meet the requirements of surfactants and do not meet any one of the above conditions 1 and 2, other surfactants described later can be cited.

The water contact angle on the obtained pattern surface is preferably 0° to 110°, and more preferably 20° to 80°. The above contact angle is not particularly limited, and can be measured, for example, according to the measurement method described in JIS R 1703:2007. In addition, it can also be measured using a known contact angle measuring instrument.

<Specific resin> The resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor. As the specific resin, the resin composition of the present invention preferably contains polyimide or polyimide precursor, and more preferably contains polyimide precursor. In addition, the specific resin preferably has a free radical polymerizable group. When the specific resin has a radical polymerizable group, the resin composition preferably includes the photoradical polymerization initiator described below as a photosensitive agent, more preferably includes the photoradical polymerization initiator described below as a photosensitive agent and includes the radical crosslinking agent described below, and further preferably includes the photoradical polymerization initiator described below as a photosensitive agent, includes the radical crosslinking agent described below, and includes the sensitizer described below. For example, a negative photosensitive layer is formed by such a resin composition. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably includes the photoacid generator described below as a photosensitive agent. For example, a positive photosensitive layer or a negative photosensitive layer of a chemically amplified type is formed from the resin composition.

[Polyimide Precursor] The polyimide precursor used in the present invention is not particularly limited in type, but preferably comprises a repeating unit represented by the following formula (2). Formula (2) [Chemical Formula 3] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, preferably 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 these groups, and more preferably groups containing aromatic groups with 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with fluorine atoms, -O-, -CO-, -S-, -SO ₂ - or NHCO-, or a group consisting of 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 the diamine used in the preparation of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of aromatic groups include the following aromatic groups.

[Chemical formula 4] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, NHCO-, or a combination thereof; more preferably a single bond or a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, there can be mentioned 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 isophoronediamine; meta-phenylenediamine or para-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'-diaminodiphenylsulfone and 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2' -Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfonate, bis(4-amino-3-hydroxyphenyl)sulfonate, 4,4'-diaminoterphenyl, 4, 4'-Bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(2-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4' -Diaminodiphenylmethane, 4,4'-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)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)hexafluoropropane 1,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) At least one of the following diamines: 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 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’-hexafluorotoluidine and 4,4’-diaminoquaternaryl.

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

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

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or NHCO-, or a group consisting of a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or SO ₂ -. The aliphatic hydrocarbon group here is preferably an alkylene group.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 5] In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 6] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom or a trifluoromethyl group. Examples of the diamine compound that imparts the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more.

In addition, the following diamine can also be preferably used. [Chemical Formula 7]

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with other structures. [Chemical Formula 8] In formula (5), R ¹¹² preferably represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - and NHCO-, and a group selected from the combination thereof; more preferably, it represents a single bond or a group selected from an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and SO ₂ -; and even more preferably, it represents 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 includes a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 9] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ has the same meaning as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

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

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

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

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both contain a polymerizable group. The polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxycyclobutyl group, a benzoxazolyl group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. As the free radical polymerizable group possessed by a polyimide precursor, a group having an ethylenic unsaturated bond is preferred. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[Chemical formula 10]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a polyalkylene group. Preferred examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group. An ethylene group, a propylene group, a trimethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group are more preferred, and a polyalkylene group is further preferred. In the present invention, a polyalkoxyl group refers to an alkoxyl group directly bonded to two or more groups. The alkylene groups of the multiple alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains multiple alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 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 further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. Furthermore, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups is preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups, the ethyleneoxy and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of ethoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, there can be mentioned an aromatic group and an aralkyl group having an acid group bonded to one, two or three (preferably one) carbon atoms constituting the aromatic group. Specifically, there can be mentioned an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, there can be mentioned a phenyl group having an acid group and a benzyl group having an acid group. The acid group is preferably an OH group. It is also preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. As the monovalent organic group, a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferred, and an alkyl group substituted with an aromatic group is more preferred. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be any of a linear, branched, or cyclic group. As the linear or branched alkyl group, for example, there can be mentioned a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an isopropyl group, an isobutyl group, a dibutyl group, a tertiary butyl group, a 1-ethylpentyl group, a 2-ethylhexyl group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, a 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy group, and a 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy)ethoxy group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of high sensitivity. Furthermore, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group may be a substituted or unsubstituted benzene ring, a naphthyl ring, a pentylene ring, an indene ring, an azulene ring, a heptylene ring, an indenene ring, a perylene ring, a condensed pentaphenyl ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed tetraphenyl ring, a chrysene ring, a trisphenyl ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ... The ring may be a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a naphthidine ring, a quinazoline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthracene ring, a chromene ring, a phenanthroline ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring, a phenanthrene ring or a phenanthrene ring. The benzene ring is the most preferred.

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

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group. An acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, and the like are preferred. From the viewpoint of exposure sensitivity, an acetal group is more preferred. Specific examples of the acid-decomposable group include a tertiary butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tertiary butoxycarbonylmethyl group, and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferred.

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

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the exposure tolerance can be further expanded. Formula (2-A) [Chemical Formula 11] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are polymerizable groups.

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

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

As an embodiment of the polyimide precursor of the present invention, 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of the total repeating units are repeating units represented by formula (2).

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 further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly limited. For example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is further preferred, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is a value calculated by weight average molecular weight/number average molecular weight.

[Polyimide] The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer having an organic solvent as a main component. In this specification, an alkali-soluble polyimide means that in 100 g of a 2.38 mass % tetramethylammonium aqueous solution, 0.1 g or more of the polyimide is dissolved at 23°C. From the viewpoint of pattern formation, it is preferred to dissolve 0.5 g or more of the polyimide, and it is further preferred to dissolve 1.0 g or more of the polyimide. The upper limit of the above-mentioned dissolution amount is not particularly limited, and 100 g or less is preferred. In addition, from the perspective of the membrane strength and insulation of the obtained organic membrane, polyimide having multiple imide structures in the main chain is preferred. In this specification, "main chain" means the longest bond in the molecule of the polymer compound constituting the resin, and "side chain" means the other bonds.

-Fluorine atom- From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has fluorine atoms. The fluorine atom is preferably contained in ^R132 in the repeating unit represented by formula (4) described later or R131 in the repeating unit represented by formula (4) described later, and is more preferably contained in ^R132 in the repeating unit represented by formula (4) described later or ^R131 in the repeating unit represented by formula (4) described later as a ^fluorinated alkyl group. The amount of fluorine atoms relative to the total mass of the polyimide is preferably 1 to 50 mol/g, more preferably 5 to 30 mol/g.

-Silicon Atoms- From the viewpoint of the film strength of the obtained organic film, it is preferable that the polyimide has silicon atoms. The silicon atom is preferably contained in, for example, R ¹³¹ in the repeating unit represented by formula (4) described later, and it is more preferable that R ¹³¹ is contained in the repeating unit represented by formula (4) described later as an organic modified (poly)siloxane structure described later. In addition, the above silicon atom or the above organic modified (poly)siloxane structure may be contained in the side chain of the polyimide, but it is preferably contained in the main chain of the polyimide. The amount of silicon atoms relative to the total mass of the polyimide is preferably 0.01 to 5 mol/g, and more preferably 0.05 to 1 mol/g.

- Ethylenically unsaturated bonds - From the viewpoint of the membrane strength of the obtained organic membrane, it is preferable that the polyimide has ethylenically unsaturated bonds. The polyimide may have ethylenically unsaturated bonds at the ends of the main chain or in the side chains, preferably in the side chains. The above-mentioned ethylenically unsaturated bonds are preferably free radical polymerizable. ^R132 in the repeating unit represented by the formula (4) described later or R131 in the repeating unit represented by the formula (4) described later having an ethylenic unsaturated bond is preferred, and ^R132 in the repeating unit represented by the formula (4) described later or ^R131 in the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond is more preferred. Among them, ^R131 in the repeating unit represented by the formula (4) described later having an ethylenic unsaturated bond is preferred, and ^{R131 in} the repeating unit represented by the formula (4) described later as a group having an ethylenic unsaturated bond is more preferred. Examples of the group having an ethylenic unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloxy group, and a group represented by the following formula (IV).

[Chemical formula 12]

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

In formula (IV), R ²¹ represents an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH(OH)CH ₂ -, -C(=O)O-, -O(C=O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and particularly preferably 2 or 3 carbon atoms; the number of carbon atoms repeated is preferably 1 to 12, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), or a group consisting of two or more of the above groups.

Among them, ^R21 is preferably a group represented by any one of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1). [Chemical Formula 13] In formulas (R1) to (R3), L represents a single bond or an alkylene group having 2 to 12 carbon atoms, a (poly)alkoxyene group having 2 to 30 carbon atoms, or a group formed by bonding two or more of these groups, X represents an oxygen atom or a sulfur atom, * represents a bonding site to other structures, and ● represents a bonding site to the oxygen atom to which R ²⁰¹ in formula (III) is bonded. In formulas (R1) to (R3), preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in L are the same as preferred aspects of the alkylene group having 2 to 12 carbon atoms or the (poly)alkoxyene group having 2 to 30 carbon atoms in R ²¹ described above. In formula (R1), X is preferably an oxygen atom. In formulas (R1) to (R3), * has the same meaning as * in formula (IV), and preferred aspects are also the same. The structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenic unsaturated bond (e.g., 2-isocyanateethyl methacrylate, etc.). The structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenic unsaturated bond (e.g., 2-hydroxyethyl methacrylate, etc.). The structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenic unsaturated bond (e.g., glycidyl methacrylate, etc.). As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups are preferred, polyethyleneoxy or polypropoxy is more preferred, and polyethyleneoxy is further preferred. In the group in which a plurality of ethyleneoxy groups are bonded to a plurality of propoxy groups, the ethyleneoxy and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspect of the number of repetitions of the ethoxy group and the like in these groups is as described above.

In formula (IV), * represents a bonding site with other structures, preferably a bonding site with the main chain of polyimide.

The amount of ethylenic 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. In addition, from the perspective of production suitability, the amount of ethylenic unsaturated bonds relative to the total mass of polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.

-Crosslinking groups other than ethylenic unsaturated bonds- The polyimide may have crosslinking groups other than ethylenic unsaturated bonds. Examples of the crosslinking groups other than ethylenic unsaturated bonds include cyclic ether groups such as epoxy groups and cyclobutylene groups, alkoxymethyl groups such as methoxymethyl groups, and hydroxymethyl groups. The crosslinking groups other than ethylenic unsaturated bonds are preferably ^R131 contained in the repeating unit represented by formula (4) described later. The amount of crosslinking groups other than ethylenic unsaturated bonds relative to the total mass of the polyimide is preferably 0.05 to 10 mol/g, and more preferably 0.1 to 5 mol/g. Furthermore, from the viewpoint of production suitability, the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.

-Polarity Converting Group- The polyimide may have a polarity converting group such as an acid-decomposable group. The acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiments are also the same.

-Acid value- When polyimide is used for alkaline development, from the viewpoint of improving the developing property, the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more. In addition, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. In addition, when polyimide is used in development using a developer having an organic solvent as the main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH/g, more preferably 3 to 30 mgKOH/g, and even more preferably 5 to 20 mgKOH/g. The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992. In addition, as an acid group contained in the polyimide, from the viewpoint of both storage stability and developing properties, an acid group with a pKa of 0 to 10 is preferred, and an acid group with a pKa of 3 to 8 is more preferred. pKa is a dissociation reaction in which hydrogen ions are released from an acid and its equilibrium constant Ka is expressed by its negative common logarithm pKa. In this manual, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, the values described in "Revised 5th Edition Chemical Handbook Basics" compiled by the Chemical Society of Japan can be referred to. Furthermore, when the acid group is a polyacid such as phosphoric acid, the above pKa is the first dissociation constant. As such an acid group, the polyimide preferably contains at least one selected from the group including a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.

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

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably comprises a repeating unit represented by the following formula (4), and more preferably comprises a repeating unit represented by the formula (4) and has a polymerizable group. Formula (4) [Chemical Formula 14] In formula (4), R ¹³¹ represents a divalent organic group, and R ¹³² represents a tetravalent organic group. When there is a polymerizable group, the polymerizable group may be located on at least one of R ¹³¹ and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). Formula (4-1) [Chemical Formula 15] In formula (4-1), R ¹³³ is a polymerizable group, and the meanings of other groups are the same as those in formula (4). Formula (4-2) [Chemical formula 16] At least one of R ¹³⁴ and R ¹³⁵ is a polymerizable group, and if not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).

The meaning of the polymerizable group is the same as the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor, etc. R ¹³¹ represents a divalent organic group. As the divalent organic group, the same as R ¹¹¹ in formula (2) can be exemplified, and the preferred range is also the same. In addition, as R ¹³¹ , a diamine residue remaining after removing the amino group of a diamine can be cited. As the diamine, aliphatic, cycloaliphatic or aromatic diamine can be cited. As a specific example, the example of R ¹¹¹ in formula (2) of the polyimide precursor can be cited.

From the viewpoint of more effectively suppressing the generation of warp during firing, R ¹³¹ is preferably a diamine residue having at least two alkylene glycol units in the main chain. More preferably, it is a diamine containing two or more ethylene glycol chains or propylene glycol chains or both in total in one molecule, and further preferably, it is a diamine containing no aromatic ring.

Examples of the diamine containing two or more ethylene glycol chains or propylene glycol chains in total, or both, include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (these are trade names, manufactured by Huntsman Corporation), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, but are not limited thereto.

R ¹³² represents a tetravalent organic group. Examples of the tetravalent organic group include the same ones as those for R ¹¹⁵ in formula (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 bonded to the four -C(=O)- moieties in the above formula (4) to form a condensed ring.

^R132 may be a tetracarboxylic acid residue remaining after the anhydride group is removed from tetracarboxylic dianhydride. As a specific example, ^R115 in the formula (2) of the polyimide precursor may be cited. From the viewpoint of the strength of the organic film, ^R132 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 the above-mentioned (DA-1) to (DA-18) can be cited as preferred examples, and as R ¹³² , the above-mentioned (DAA-1) to (DAA-5) can be cited as more preferred examples.

Furthermore, the polyimide preferably has fluorine atoms in the structural unit. The content of fluorine atoms in the polyimide is preferably 10 mass % or more, and more preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. may be mentioned.

In order to improve the storage stability of the composition, the main chain ends of the polyimide are preferably sealed with a capping agent such as a monoamine, anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound. Among them, monoamines are more preferably used. Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Imidization rate (ring closure rate)- From the viewpoint of the film strength and insulation of the obtained organic film, the imidization rate (also called "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and more preferably 90% or more. The upper limit of the above-mentioned imidization rate is not particularly limited, and it can be 100% or less. For example, the above-mentioned imidization rate can be measured by the following method. Measure the infrared absorption spectrum of the polyimide, and determine the peak intensity P1 of the absorption peak originating from the imide structure, that is, near 1377cm ^-1 . Then, after the polyimide is heat-treated at 350°C for 1 hour, the infrared absorption spectrum is measured again to determine the peak intensity P2 near 1377cm ^-1 . The obtained peak intensities P1 and P2 can be used to calculate the imidization rate of the polyimide according to the following formula: Imidization rate (%) = (peak intensity P1/peak intensity P2) × 100

The polyimide may include repeating units of the above formula (4) each including one type of R ¹³¹ or R ¹³² , or may include repeating units of the above formula (4) including two or more different types of R ¹³¹ or R ^132. In addition to the repeating units of the above formula (4), the polyimide may also include other types of repeating units.

Polyimide can be prepared by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound (part of which is substituted with a monoamine, i.e., a capping agent) at low temperature, a method of reacting tetracarboxylic dianhydride (part of which is substituted with an acid anhydride, a monoacyl chloride compound, or a monoactive ester compound, i.e., a capping agent) with a diamine compound at low temperature, a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting the resulting diester in the presence of a diamine (part of which is substituted with a monoamine, i.e., a capping agent) and a condensing agent, a method of reacting tetracarboxylic dianhydride with ... After obtaining a diester from a dianhydride and an alcohol, the remaining dicarboxylic acid is chlorinated and reacted with a diamine (part of which is substituted with a monoamine, i.e., a capping agent) to obtain a polyimide precursor, which is synthesized by a known imidization reaction method and a method of complete imidization, a method of stopping the imidization reaction midway and introducing a part of the imide structure, and a method of introducing a part of the imide structure by mixing a completely imidized polymer and its polyimide precursor. Commercially available products of polyimide include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by Huntsman Corporation).

The weight average molecular weight (Mw) of the polyimide is preferably 4,000 to 100,000, more preferably 5,000 to 70,000, further preferably 8,000 to 50,000, and particularly preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In addition, when containing two or more polyimides, it is preferred that the weight average molecular weight of at least one polyimide is within the above range.

[Polybenzoxazole precursor] The polybenzoxazole precursor used in the present invention is not particularly limited in structure, but preferably comprises a repeating unit represented by the following formula (3). Formula (3) [Chemical Formula 17] In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ have the same meanings as R ¹¹³ in formula (2), and 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 contains at least one of an aliphatic group and an aromatic group. As an aliphatic group, a straight-chain aliphatic group is preferred. It is preferred that R ¹²¹ is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more may be used.

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred. As the dicarboxylic acid containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred, and dicarboxylic acids composed of linear or branched (preferably linear) aliphatic groups and 2 -COOH groups are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. As the dicarboxylic acid containing a straight chain aliphatic group, there can be mentioned malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylheptanecarboxylic 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 18] (In the formula, Z is a carbonyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

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

[Chemical formula 19] In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - and -C(CH ₃ ) ₂ -, and * represents a bonding site with other structures independently.

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

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2) above, and the preferred range is also the same. Preferably, the group ¹²² is derived from a diaminophenol derivative. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfonate, 4,4'-diamino-3,3'-dihydroxydiphenylsulfonate, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, and 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane. -(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. Such bisaminophenols can be used alone or in combination.

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

[Chemical formula 20] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, and * and # represent the bonding site with other structures, respectively. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. In addition, ^R122 is also preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded and two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or two * are bonding sites to the nitrogen atom to which R 122 in formula (3) is bonded and two # are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is more preferred that two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

[Chemical formula 21]

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

[Chemical formula 22] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is considered that the presence of a substituent at the adjacent position of the phenolic hydroxyl group, i.e., _R3 , is particularly preferred because the carbonyl carbon of the amide bond and the hydroxyl group are closer together and the effect of a high cyclization rate during curing at a low temperature is further improved.

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

In the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for _R1 include a linear or branched alkyl group having 1 to 8 carbon atoms, among which -CH2-, -CH(CH3)-, and -C( _{CH3 ) 2-} are more preferred from the viewpoint of obtaining a well-balanced polybenzoxazole precursor while maintaining high transparency to I-rays and high cyclization rate during curing at low temperature while having sufficient solubility in _the solvent.

As a method for producing the bisaminophenol derivative represented by the above formula (A-s), for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506 can be referred to, and the contents thereof are incorporated into the present specification.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include the contents described in paragraphs 0070 to 0080 of JP-A-2013-256506, which are incorporated into the present specification. Of course, the present invention is not limited to these.

In addition to the repeating units of the above formula (3), the polybenzoxazole precursor may also contain other types of repeating structural units. From the viewpoint of being able to suppress the warp associated with ring closure, it is preferred to contain a diamine residue represented by the following formula (SL) as the other type of repeating structural unit.

[Chemical formula 23] In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the remaining parts are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the molar % of the Z part, the molar % of the a structure is 5 to 95 molar %, the molar % of the b structure is 95 to 5 molar %, and the molar % of a+b is 100 molar %.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight to the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and the effect of suppressing warp and the effect of improving solvent solubility can be taken into account.

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

For example, when used in the composition described below, 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 further preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the above polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less.

[Polybenzoxazole] The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but a compound represented by the following formula (X) is preferred, and a compound represented by the following formula (X) and having a polymerizable group is more preferred. As the above-mentioned polymerizable group, a free radical polymerizable group is preferred. In addition, it may be a compound represented by the following formula (X) and having a polar conversion group such as an acid decomposable group. [Chemical Formula 24] In formula (X), R ¹³³ represents a divalent organic group, and R ¹³⁴ represents a tetravalent organic group. When there is a polar conversion group such as a polymerizable group or an acid-decomposable group, the polymerizable group or the polar conversion group such as an acid-decomposable group may be located on at least one of R ¹³³ and R ¹³⁴ , or may be located at the end of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2). Formula (X-1) [Chemical Formula 25] In formula (X-1), at least one of ^R135 and ^R136 is a polymerizable group or a polar conversion group such as an acid-decomposable group, and if not a polymerizable group or a polar conversion group such as an acid-decomposable group, it is an organic group, and the other groups have the same meanings as in formula (X). Formula (X-2) [Chemical Formula 26] In formula (X-2), R ¹³⁷ is a polar conversion group such as a polymerizable group or an acid-decomposable group, and the rest are substituents. The meanings of the other groups are the same as those in formula (X).

The meaning of the polymerizable group or the polarity converting group such as the acid-decomposable group is the same as the polymerizable group explained in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic group and an aromatic group. As a specific example, R ¹²¹ in the formula (3) of the polybenzoxazole precursor can be cited. The preferred examples have the same meaning as R ¹²¹ .

R ¹³⁴ represents a tetravalent organic group. As a tetravalent organic group, R ¹²² in the formula (3) of the polybenzoxazole precursor can be cited as an example. The meaning of the preferred example is the same as that of R ^122. For example, the four connecting bonds of the tetravalent organic group exemplified as R ¹²² are bonded to the nitrogen atom and the oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, the following structure is formed. [Chemical Formula 27]

The oxadiazole rate of polybenzoxazole is preferably 85% or more, and more preferably 90% or more. When the oxadiazole rate is 85% or more, the shrinkage of the film due to ring closure (occurring when oxadiazole is heated) is reduced, and the warping can be effectively suppressed.

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

For example, a diaminophenol derivative is reacted with a dicarboxylic acid containing R ¹³³ or a dicarboxylic acid dichloride and a dicarboxylic acid derivative selected from the above dicarboxylic acids to obtain a polybenzoxazole precursor, which is then oxazolidated by a known oxazolidation reaction method to obtain a polybenzoxazole. In addition, in the case of a dicarboxylic acid, an active ester type dicarboxylic acid derivative that has been reacted with 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield.

The weight average molecular weight (Mw) of the 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 more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties, a weight average molecular weight of 20,000 or more is particularly preferred. In addition, when containing two or more polybenzoxazoles, it is preferred that the weight average molecular weight of at least one polybenzoxazole is within the above range.

[Method for producing polyimide precursors, etc.] Polyimide precursors, etc. can be obtained by reacting dicarboxylic acid or dicarboxylic acid derivatives with diamines. It is preferably obtained by halogenating dicarboxylic acid or dicarboxylic acid derivatives with a halogenating agent and then reacting them with diamines. In the method for producing a polyimide precursor, it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one or more. As the organic solvent, it can be appropriately set according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone. Polyimide can be produced by cyclizing a polyimide precursor after synthesizing it by thermal imidization, chemical imidization (for example, by promoting the cyclization reaction by the action of a catalyst), or by directly synthesizing the polyimide precursor.

Furthermore, it is also preferable to use a non-halogen catalyst instead of the above-mentioned halogenating agent for synthesis. As the above-mentioned non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, for example, borane trimer compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, etc., and carbodiimide compounds can be cited. As the above-mentioned carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. can be cited.

-Capping agent- When manufacturing polyimide precursors, it is preferred to seal the ends of the polyimide precursors with a capping agent such as an acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound in order to further improve storage stability. As the end-capping agent, it is more preferable to use a monoamine. As preferred compounds of the monoamine, there can be cited aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 2-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

-Solid precipitation- When manufacturing a polyimide precursor, etc., a solid precipitation process may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor can be dissolved, thereby enabling solid precipitation. Thereafter, by drying the polyimide precursor, etc., a powdered polyimide precursor, etc. can be obtained.

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

Furthermore, the resin composition of the present invention preferably contains at least two kinds of resins. Specifically, the resin composition of the present invention may contain a total of two or more kinds of specific resins and other resins described below, or may contain two or more kinds of specific resins, preferably containing two or more kinds of specific resins. When the resin composition of the present invention contains two or more kinds of specific resins, for example, it is preferred to contain a polyimide precursor, and the polyimide precursor is derived from two or more kinds of polyimide precursors having different structures (R ¹¹⁵ represented by the above formula (2)) of dianhydride. It is speculated that since the resin composition of the present invention contains two or more specific resins, the compatibility between the specific surfactant and the resin is improved, and the specific surfactant is less likely to exist on the surface of the formed film. Therefore, even when another film composed of other compositions is formed, it is easy to suppress the generation of defects on the above-mentioned other film.

<Other resins> The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins" for short). As other resins, polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding a high polymerizable group valency acrylic resin having a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the polymerizable compound described below, the coating properties 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 is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 5% by mass or more, and more preferably 10% by mass or more relative to the total solid content of the composition. In addition, the content of the other resins in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, more preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less relative to the total solid content of the composition. Furthermore, as one of the preferred embodiments of the composition of the present invention, it is also possible to set the composition to have a low content of other resins. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, and 0% by mass or more is sufficient. The composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount is within the above range.

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

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

As the ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea 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, propylene glycol monopropyl ether acetate and the like are preferably mentioned.

As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosone, dihydrolevoglucosone and the like are preferably mentioned.

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

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

As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formyl propionamide, N-acetyl propionamide and the like are preferably mentioned.

As the urea, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferred.

As alcohols, there may be cited 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 the properties of the coated surface, it is better to mix two or more solvents.

In the present invention, one solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 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 mixed solvent consisting of two or more of them is preferred. It is particularly preferred to use dimethyl sulfoxide and γ-butyrolactone simultaneously. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, and cyclopentanone and γ-butyrolactone is also preferred.

Among them, the resin composition of the present invention preferably contains esters, and more preferably contains lactone solvents. Lactone solvents refer to solvents containing lactone structures, and examples thereof include γ-butyrolactone, ε-caprolactone, δ-valerolactone, etc. The content of lactone solvent relative to the total mass of the solvent is not particularly limited, and 30 to 100 mass % is preferred, 40 to 95 mass % is more preferred, and 50 to 90 mass % is further preferred.

Regarding the content of the solvent, from the viewpoint of coating properties, it is preferably set to an amount where the total solid content concentration of the resin composition of the present invention is 5 to 80 mass %, more preferably 5 to 75 mass %, more preferably 10 to 70 mass %, and even more preferably 40 to 70 mass %. The content of the solvent can be adjusted according to the required thickness of the coating film and the coating method.

The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount of the solvents is within the above range.

<Photosensitive agent> The composition of the present invention preferably contains a photosensitive agent. As the photosensitive agent, a photopolymerization initiator is preferred.

[Photopolymerization initiator] The composition of the present invention preferably contains a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can be an activator that reacts with a photoexcited sensitizer to generate active radicals. In addition, as the above-mentioned photoradical polymerization initiator, the oxime compound described later is preferred.

The photo-radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L/mol ^-1 /cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron aromatic complexes, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

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

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

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

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Application Publication No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF Corporation) can also be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF).

As the photo-radical polymerization initiator, an oxime compound is more preferred. By using an oxime compound, the exposure tolerance can be further effectively improved. Oxime compounds have a wider exposure tolerance (exposure margin) and also function as a photohardening accelerator, so they are particularly preferred.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures: 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the composition 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 linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 28]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02 (both manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, 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) can also be used. In addition, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can be used. In addition, an oxime compound having the following structure can be used. [Chemical Formula 29]

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Publication No. 2014-137466 and compounds described in Japanese Patent No. 06636081.

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

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

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

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

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

In addition, as the photoradical polymerization initiator, benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michler's ketone), aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-aminophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-amino-propanone-1, quinones formed by condensation of an aromatic ring with an alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin, benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, etc. can be used. In addition, compounds represented by the following formula (I) can also be used.

[Chemical formula 30]

In the formula (I), R ^I00 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, a phenyl group substituted by at least one of an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms and an alkyl group having 1 to 4 carbon atoms, or a biphenyl group, R ^I01 is a group represented by the formula (II) or is the same group as R ^I00 , and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

[Chemical formula 31]

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

Furthermore, the photoradical polymerization initiator may also include compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

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

[Photoacid generator] In addition, the composition of the present invention preferably contains a photoacid generator as a photosensitizer. By containing a photoacid generator, for example, acid is generated in the exposed part of the composition layer, and the solubility of the exposed part in the developer (for example, an alkaline aqueous solution) is increased, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, by containing a photoacid generator and a polymerizable compound other than a free radical polymerizable compound described later, for example, the following state can be set: the crosslinking reaction of the polymerizable compound is promoted by the acid generated in the exposed part, and the exposed part is less likely to be removed by the developer than the non-exposed part. According to this state, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinonediazide compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimidesulfonates, oximesulfonates, diazodisulfonates, disulfonates, and o-nitrobenzylsulfonates.

As the quinone diazide compound, there can be mentioned those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester, those in which the sulfonic acid of quinone diazide is bonded to a polyamine compound via a sulfonamide bond, those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamine compound via at least one of an ester bond and a sulfonamide bond, etc. In the present invention, for example, it is preferred that 50 mol% or more of the functional groups of the polyhydroxy compound and the polyamine compound are substituted with quinone diazide.

In the present invention, as quinone diazide, 5-naphthoquinone diazide sulfonyl and 4-naphthoquinone diazide sulfonyl can be preferably used. 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of mercury lamp, so it is suitable for i-ray exposure. 5-naphthoquinone diazide sulfonyl compound has absorption extending to the g-ray region of mercury lamp, so it is suitable for g-ray exposure. In the present invention, 4-naphthoquinone diazide sulfonyl compound and 5-naphthoquinone diazide sulfonyl compound are preferably selected according to the wavelength of exposure. Furthermore, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or it may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using the naphthoquinone diazide compound, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of the compounds, etc. can be cited.

Examples of the onium salt compound or the sulfonate salt compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

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

[Chemical formula 32]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are plural ^{X 3} groups, they may be the same or different. The alkyl group and alkoxy group in the above X ³ may have a substituent. As the alkyl group in the above X ³ group, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in the above X ³ group, a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above X ³ group, a chlorine atom or a fluorine atom is preferred. In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or 1. When m3 is 2 or 3, the plural X ³ groups may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or a benzamidic acid group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, 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, the substitution position of ^X3 is the ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl or p-tolyl.

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

[Chemical formula 33]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, when there are plural groups, R ^s2 each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, when there are plural groups, R ^s6 each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 may have a substituent T.

In formula (OS-103) to formula (OS-105), ^Rs2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and a hydrogen atom or an alkyl group is more preferred. When two or more ^Rs2 exist in the compound, one or two of them are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom, and one is an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by ^Rs2 may have a substituent T. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring system containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

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

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 34]

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

In formula (OS-106) to formula (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, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z) of the oxime may be any one or a mixture. As specific examples of the oxime sulfonate compound represented by the above-mentioned formula (OS-103) to formula (OS-105), 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 can be exemplified, and the contents thereof are incorporated into this specification.

As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

[Chemical formula 35]

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

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonic group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with a benzene ring. As R ^u1 to R ^u4, a hydrogen atom, a halogen atom or an alkyl group is preferred, and at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, the embodiment in which all of R ^u1 to R ^u4 are hydrogen atoms is preferred. The above substituents may further have substituents.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In addition, in the above oxime sulfonate compound, the stereostructures (E, Z, etc.) of the oxime and benzothiazole rings may be any one or a mixture. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification. Among the above compounds, b-9, b-16, b-31, and b-33 are preferred.

As the photoacid generator, a commercially available product may be used. Examples of the commercially available product include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

In addition, the compound represented by the following structural formula can also be cited as a preferred example. [Chemical Formula 36]

As photoacid generators, organic halogenated compounds can also be used. As organic halogenated compounds, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42,2924 (1969), U.S. 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, M.P. Hutt, "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, oxazole compounds substituted by trihalomethyl groups: S-trioxane compounds. Preferably, s-trioxane derivatives in which at least one monohalomethyl group, dihalomethyl group or trihalomethyl group is bonded to the s-trioxane ring, specifically, for example, 2,4,6-tris(monochloromethyl)-s-trioxane, 2,4,6-tris(dichloromethyl)-s-trioxane, 2,4,6-tris(trichloromethyl)-s-trioxane, 2-methyl-4,6-bis(trichloromethyl)-s-trioxane, 2-n-propyl-4,6-bis(trichloromethyl)-s-trioxane, -s-trioxanthate, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-trioxanthate, 2-phenyl-4,6-bis(trichloromethyl)-s-trioxanthate, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trioxanthate, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-trioxanthate, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-trioxanthate, 2-〔1-(p- methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trioxanyl, 2-phenylvinyl-4,6-bis(trichloromethyl)-s-trioxanyl, 2-(p-methoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trioxanyl, 2-(p-isopropoxyphenylvinyl)-4,6-bis(trichloromethyl)-s-trioxanyl, 2-(p-phenylmethyl)-4,6-bis(trichloromethyl)-s-trioxanyl, 2-(4-naphthalene)- 2-Benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.

As the photoacid generator, an organic borate compound can also be used. Examples of the organic borate compound include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., organic borate salts described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 Specific examples include organoboron phosphonium complexes, organoboron phosphonium complexes described in Japanese Patent Application Laid-Open No. 9-188710, and organoboron transition metal coordination complexes described in Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Application Laid-Open No. 7-128785, Japanese Patent Application Laid-Open No. 7-140589, Japanese Patent Application Laid-Open No. 7-306527, and Japanese Patent Application Laid-Open No. 7-292014.

As the photoacid generator, a disulfide compound can also be used. Examples of the disulfide compound include compounds described in Japanese Patent Application No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfide compounds.

As the above-mentioned onium salt compound, for example, there can be cited S.I.Schlesinger, Photogr.Sci.Eng., 18, 387 (1974), T.S.Bal et al. al, Polymer, 21, 423 (1980), ammonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and 4,069,056, European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, iodonium salts described in Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390,214 Copper salts described in the specifications of Patent No. 233,567, Patent No. 233,567, Patent No. 297,443, Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10 (6), 1307 (1977), selenonium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsonium salts, pyridinium salts and the like described in C.S.Wen et al, The, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and the like.

As the onium salt, onium salts represented by the following general formulas (RI-I) to (RI-III) can be cited. [Chemical Formula 37] In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carbonyloxy group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₁₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a sulfuric acid ion, or a sulfuric acid ion. In view of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carbonyloxy group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a sulfuric acid ion, or a sulfuric acid ion. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, or carboxylic acid ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms and which may have 1 to 6 substituents. In terms of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carbonyloxy group, a cyano group, a sulfonyl group, a sulfanyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₃₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a sulfuric acid ion, or a sulfuric acid ion. In view of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, and carboxylic acid ions are preferred.

As a specific example, the following can be cited. [Chemical formula 38]

[Chemical formula 39]

[Chemical formula 40]

[Chemical formula 41]

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

[Photobase generator] The resin composition of the present invention may contain a photobase generator as a photosensitive agent. It may also be configured as follows: the resin composition contains a photobase generator and a crosslinking agent described later, for example, by utilizing the effects of the base generated in the exposed part to promote the cyclization of a specific resin and the crosslinking reaction of the crosslinking agent, so that the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative relief pattern can be obtained.

As the photoalkali generator, there is no particular limitation as long as it generates alkali by exposure, and any known one can be used. For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadoka, 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) state that transition metal compound complexes, substances having structures such as ammonium salts, ionic compounds in which the alkaline components are neutralized by forming salts such as amidine moieties that are potentially oxidized by forming salts with carboxylic acids, and non-ionic compounds in which the alkaline components are potentially oxidized by carbamate bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds. In the present invention, more preferred examples of the photoalkali generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, and the like.

The alkaline substance generated from the photoalkali generator is not particularly limited, and compounds having an amino group, especially polyamines such as monoamines and diamines, and amidines, etc., can be cited. From the perspective of the imidization rate, the alkaline substance having a large pKa in DMSO (dimethyl sulfoxide) of the conjugated acid is preferred. The pKa is preferably 1 or more, and 3 or more is more preferred. The upper limit of the pKa is not particularly limited, and 20 or less is preferred. The above pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and can refer to the values described in Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; editor: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these references, the values calculated from the structural formula using the software ACD/pKa (manufactured by ACD/Labs) were used as pKa.

From the perspective of storage stability of the resin composition, it is preferable that the photoalkali generator does not contain salt in its structure, and it is preferable that the nitrogen atom of the alkali portion generated in the photoalkali generator has no charge. It is preferable that the generated alkali is potentially converted by covalent bonds, and it is preferable that the alkali generation mechanism is a mechanism in which the covalent bonds between the nitrogen atom of the generated alkali portion and the adjacent atom are cut to generate the alkali. If the photoalkali generator does not contain salt in its structure, the photoalkali generator can be made neutral, so that the solvent solubility is better and the shelf life is extended. For this reason, the amine generated from the photobase generator used in the present invention is preferably a primary amine or a secondary amine. In addition, from the perspective of the chemical resistance of the pattern, a photobase generator containing a salt in its structure is preferred.

Furthermore, considering the above reasons, as a photoalkali generator, as mentioned above, the generated base is preferably potentially transformed using a covalent bond, and the generated base is preferably potentially transformed using an amide bond, a carbamate bond, or an oxime bond. As the photobase generator of the present invention, for example, a photobase generator having a cinnamylamide structure as disclosed in Japanese Patent Application Publication No. 2009-080452 and International Publication No. 2009/123122, a photobase generator having a carbamate structure as disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747, a photobase generator having an oxime structure or an aminoformyl oxime structure as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581, etc. can be cited, but the present invention is not limited to these, and other known photobase generator structures can be used.

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

In addition, as the photoalkali generator, a commercial product can be used. Examples of the commercial product 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, and WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), and A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

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

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes 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 in the heating process described later, thereby further improving the solvent resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

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

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: by generating an acid by heating, the cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound is promoted.

The thermal decomposition start temperature of the thermal acid generator is preferably 50°C to 270°C, and more preferably 50°C to 250°C. In addition, if a substance that does not generate acid during drying (pre-baking: about 70 to 140°C) after the composition is applied to the substrate but generates acid during the final heating (hardening: about 100 to 400°C) after forming a pattern in the subsequent exposure and development is selected as the thermal acid generator, it is better to suppress the decrease in sensitivity during development. When the thermal acid generator is heated to 500°C at 5°C/min in a pressure-resistant capsule, the peak temperature of the lowest temperature heat peak is obtained as the thermal decomposition start temperature. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or halogenated alkylsulfonic acids such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, a substance that generates an alkylsulfonic acid having 1 to 4 carbon atoms or a halogenated alkylsulfonic acid having 1 to 4 carbon atoms is more preferred as a thermal acid generator, such as (4-hydroxyphenyl)dimethylcopperium methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium methanesulfonate, benzyl (4-hydroxyphenyl)methylcopperium methanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methylcopperium methanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium methanesulfonate, and (4-((methoxycarbonyl)oxy)phenyl)methyl)copperium trifluoromethanesulfonate. Preferred are (4-(((methoxycarbonyl)oxy)phenyl)dimethylcopperthionesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperthionesulfonate, benzyl(4-hydroxyphenyl)methylcopperthionesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperthionesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperthionesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, the compound described in 0059 of Japanese Patent Application Laid-Open No. 2013-167742 is also preferably used as the thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. In addition, from the viewpoint of the electrical insulation of the organic film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

<Onium salt> The resin composition of the present invention may further contain an onium salt. In particular, when the resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type of onium salt is not particularly limited, and ammonium salts, imide salts, cobalt salts, iodine salts, or phosphonium salts can be preferably mentioned. Among them, ammonium salts or imide salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodine salts, or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, the onium salt is a salt of a cation and anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt having cation molecules and anion molecules of different molecules bonded by ion, and the intermolecular salt is preferred. Furthermore, in the resin composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ion bonding or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a coronium cation, an iodine cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

The onium salt used in the present invention may also be a thermal alkali generator described later. The thermal alkali generator refers to a compound that generates an alkali by heating, and for example, a compound that generates an alkali when heated to 40°C or higher can be cited. As the onium salt, for example, the onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262 can be cited. In addition, onium salts that can be used in the field of polyimide precursors can also be used without particular limitation.

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

<Thermal alkali generator> The resin composition of the present invention may further contain a thermal alkali generator. In particular, when the resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal alkali generator. Other thermal alkali generators may be compounds that meet the above-mentioned onium salts, or thermal alkali generators other than the above-mentioned onium salts. As thermal alkali generators other than the above-mentioned onium salts, non-ionic thermal alkali generators can be cited. As non-ionic thermal alkali generators, compounds represented by formula (B1) or formula (B2) can be cited. [Chemical Formula 42]

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

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

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

As Rb ³ , there can be mentioned alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Aralkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or aralkyloxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aralkenyl, and aralkyloxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 43]

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

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

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

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 44]

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

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

As specific examples of the compound serving as a thermal alkali generator among the above-mentioned onium salts or specific examples of the thermal alkali generator other than the above-mentioned onium salts, the following compounds can be cited.

[Chemical formula 45]

[Chemical formula 46]

[Chemical formula 47]

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

<Crosslinking agent> The resin composition of the present invention preferably contains a crosslinking agent. As the crosslinking agent, free radical crosslinking agents or other crosslinking agents can be cited.

<Free radical crosslinking agent> The resin composition of the present invention preferably further contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the group containing the above-mentioned ethylenic unsaturated bond, there can be cited groups having ethylenic unsaturated bonds such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. Among them, as the group containing the above-mentioned ethylenic unsaturated bond, (meth)acryloyl is preferred, and from the viewpoint of reactivity, (meth)acryloyloxy is more preferred.

The radical crosslinking agent may be a compound having one or more ethylenic unsaturated bonds, and preferably a compound having two or more ethylenic unsaturated bonds. The compound having two ethylenic unsaturated bonds is preferably a compound having two groups containing the above ethylenic unsaturated bonds. In addition, from the perspective of the film strength of the obtained pattern (cured film), it is preferred that the resin composition of the present invention contains a compound having three or more ethylenic unsaturated bonds as a radical crosslinking agent. As the compound having more than 3 ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is preferred, a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenic unsaturated bonds is further preferred. In addition, the compound having more than 3 ethylenic unsaturated bonds is preferably a compound having more than 3 groups containing the above ethylenic unsaturated bonds, a compound having 3 to 15 is more preferred, a compound having 3 to 10 is further preferred, and a compound having 3 to 6 is particularly preferred. Furthermore, from the viewpoint of the film strength of the obtained pattern (cured film), it is also preferred that the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

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

As specific examples of free radical crosslinking agents, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides can be cited, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, thiohydrides, etc., and monofunctional or polyfunctional isocyanates or epoxides, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids can also be preferably used. Moreover, the addition reaction products of unsaturated carboxylic acid esters or amides with electrophilic substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and the substitution reaction products of unsaturated carboxylic acid esters or amides with dissociative substituents such as halogen groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Moreover, as another example, the above-mentioned unsaturated carboxylic acid can be replaced by a compound group substituted with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. As a specific example, the description of paragraphs 0113 to 0122 of Japanese Patent Publication No. 2016-027357 can be referred to, and the contents are incorporated into this specification.

In addition, the free radical crosslinking agent is preferably a compound having a boiling point of 100°C or more under normal pressure. Examples thereof include polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyletrol tri(meth)acrylate, neopentyletrol tetra(meth)acrylate, dipentyletrol penta(meth)acrylate, dipentyletrol hexa(meth)acrylate, hexylene glycol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, etc., which are obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth)acrylating the mixture. Acid-esterified compounds, (meth)acrylic acid urethanes described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, polyfunctional acrylates or methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth)acrylic acid; and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, polyfunctional (meth)acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate can also be mentioned.

Furthermore, as preferred radical crosslinking agents other than the above, compounds having a fluorene ring and two or more groups having ethylenically unsaturated bonds, and cardo resins described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, etc., can also be used.

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

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

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

Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as free radical crosslinking agents, and such contents are incorporated into this specification.

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

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc. as a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc. as a bifunctional methacrylate having four vinyloxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having six pentoxy chains, TPA-330 as a trifunctional acrylate having three isobutyloxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by NIPPON PAPER INDUSTRIES CO., LTD.), NK ESTER M-40G, NK ESTER 4G, NK ESTER M-9300, NK ESTER A-9300, 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.made), etc.

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

The free radical crosslinking agent may be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. Among the free radical crosslinking agents having an acid group, the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and the free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group is more preferred. Particularly preferred is a free radical crosslinking agent in which the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to give it an acid group, wherein the aliphatic polyhydroxy compound is a compound such as neopentyl triol or dipentyl triol. As commercially available products, for example, M-510, M-520, etc. can be cited as polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., Ltd.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and the particularly preferred acid value is 5 to 30 mgKOH/g. As long as the acid value of the free radical crosslinking agent is within the above range, the operability in manufacturing is excellent, and the developing property is excellent. In addition, the polymerizability is good. On the other hand, from the perspective of the developing speed during alkaline development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and the particularly preferred acid value is 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

Regarding the resin composition of the present invention, from the viewpoint of pattern resolution and film stretchability, it is also preferable to use a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A EO adduct dimethacrylate, methacrylate 2-hydroxy-3-acryloyloxypropyl, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds. Two or more of these may be used in combination as needed. Furthermore, from the viewpoint of suppressing warping caused by controlling the elastic modulus of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As the monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

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

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

<Other crosslinking agents> The resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents. It is preferred that the compound has multiple groups in the molecule that are promoted by the photosensitization of the above-mentioned photosensitive agent (forming covalent bonds with other compounds in the composition or their reaction products), and it is more preferred that the compound has multiple groups in the molecule that are promoted by the action of an acid or a base (forming covalent bonds with other compounds in the composition or their reaction products). The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator for the photosensitive agent in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group including hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which amino compounds such as melamine, acetylene urea, urea, alkyl urea, benzoguanamine, etc. are reacted with formaldehyde, or formaldehyde is reacted with alcohol and the hydrogen atom of the above amino group is replaced with a hydroxymethyl or alkoxymethyl group. The method for preparing these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds prepared by the above method. In addition, they may be oligomers formed by self-condensation of the hydroxymethyl groups of these compounds. As the above-mentioned amino-containing compound, a crosslinking agent using melamine is referred to as a melamine-based crosslinking agent, a crosslinking agent using acetylene urea, urea or alkyl urea is referred to as a urea-based crosslinking agent, a crosslinking agent using alkyl urea is referred to as an alkyl urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent. Among them, the resin composition of the present invention preferably contains at least one compound selected from the group including urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group including acetylene urea-based crosslinking agents and melamine-based crosslinking agents described later.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of the urea crosslinking agent include monohydroxymethylated acetylene urea, dihydroxymethylated acetylene urea, trihydroxymethylated acetylene urea, tetrahydroxymethylated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetramethoxymethylated acetylene urea, monomethoxymethylated acetylene urea, dimethoxymethylated acetylene urea, trimethoxymethylated acetylene urea, tetraethoxymethylated acetylene urea. , monopropoxymethylated acetylene urea, dipropoxymethylated acetylene urea, tripropoxymethylated acetylene urea, tetrapropoxymethylated acetylene urea, monobutoxymethylated acetylene urea, dibutoxymethylated acetylene urea, tributoxymethylated acetylene urea or tetrabutoxymethylated acetylene urea and other acetylene urea-based crosslinking agents; bismethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea and other urea-based crosslinking agents; monohydroxymethylated Ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethylated ethylene urea, monobutoxymethylated ethylene urea or dibutoxymethylated ethylene urea and other ethylene urea crosslinking agents, monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea and other propylene urea crosslinking agents, 1,3-bis(methoxymethyl)4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

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

In addition, as the compound having at least one group selected from the group including a hydroxymethyl group and an alkoxymethyl group, a compound in which at least one group selected from the group including a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include terephthalic acid, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylbenzene hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl)diphenyl ketone, methoxymethylbenzene methoxymethyl benzoate, 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-phenylenediol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

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

In addition, the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds and benzophenone compounds as other crosslinking agents.

[Epoxy compounds (compounds having epoxy groups)] As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C, and since dehydration reaction due to crosslinking does not occur, it is not easy to cause film shrinkage. Therefore, by containing epoxy compounds, low-temperature curing and warping of the resin composition can be effectively suppressed.

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

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy-containing silicones such as polymethyl (glycidoxypropyl) siloxane, etc., but are not limited to these. Specifically, the following can be cited: 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, EPICLON (registered trademark) EXA-485 0-150, EPICLONE (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 are product names, DIC Corporation), RIKARESIN (registered trademark) BEO-60E, RIKARESIN (registered trademark) HBE-100, RIKARESIN (registered trademark) DME-100, RIKARESIN (registered trademark) L-200 (trade names, New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, ADEKA CORPORATION), CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD GT400, Serviners B0134, B0177 (the above are trade names, DAICEL CORPORATION), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds having an oxycyclobutyl group)] Examples of the 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-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these may be used alone or in combination of two or more.

[Benzotriazole compounds (compounds having benzoxazolyl groups)] Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, thereby reducing thermal shrinkage and inhibiting the occurrence of warping.

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

The content of other crosslinking agents is preferably 0.1 to 30 mass % relative to the total solid content of the resin composition of the present invention, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass %. Other crosslinking agents may contain only one or more. When containing two or more other thermal crosslinking agents, their total content is preferably within the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure> From the perspective of improving the adhesion of the obtained pattern (cured film) to the substrate, it is preferred that the resin composition of the present invention further comprises at least one compound selected from the group consisting of compounds with sulfonamide structure and compounds with thiourea structure.

[Compounds having a sulfonamide structure] The sulfonamide structure is represented by the following formula (S-1). [Chemical formula 48] In formula (S-1), R represents a hydrogen atom or an organic group, and R may form a ring structure by bonding with other structures, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as ^R2 in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having one sulfonamide structure is preferred.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 49] In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. It is preferred that R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyrazole ring, an isoxadiazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a pyrimidine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring.

Among these, the compounds wherein R ¹ is an aryl group and R ² and R ³ are independently a hydrogen atom or an alkyl group 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-dimethylethylsulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethylsulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 50] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may bond to form a ring, ^R4 may bond to other structures bonded to * to form a ring structure, ^R5 may bond to other structures bonded to * to form a ring structure, and * each independently represents a bonding site to other structures.

^R4 and ^R5 are preferably independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group formed by combining two or more of these groups. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. As the above-mentioned cycloalkyl group, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl can be mentioned. As the above-mentioned alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 5 carbon atoms is more preferred. As the above-mentioned alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group can be mentioned. As the above-mentioned alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferred, and an alkoxysilyl group having 1 to 4 carbon atoms is more preferred. As the above-mentioned alkoxysilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group and a butoxysilyl group can be mentioned. As the above-mentioned aryl group, an aryl group having 6 to 20 carbon atoms is preferred, and an aryl group having 6 to 12 carbon atoms is more preferred. The above-mentioned aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include groups obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a pyrimidine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 51] In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 have the same meanings as ^R4 and ^R5 in formula (T-1), and preferred embodiments are also the same. In formula (T-2), ^R6 and ^R7 are preferably independently monovalent organic groups. In formula (T-2), preferred embodiments of monovalent organic groups in ^R6 and ^R7 are the same as preferred embodiments of monovalent organic groups in ^R4 and ^R5 in formula (T-1).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the resin composition of the present invention is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass %, and further preferably 0.2 to 3 mass %. The resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

<Migration inhibitor> The resin composition of the present invention preferably further comprises a migration inhibitor. By comprising the migration inhibitor, it is possible to effectively inhibit the migration of metal ions originating from the metal layer (metal wiring) into the resin composition layer.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, isothiazole ring, pyrazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, phenoxyl ring, 2H-pyran ring, 6H-pyran ring, trithiol ring), compounds having thiourea and thiohydrin, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

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

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

As specific examples of the migration inhibitor, the following compounds can be cited.

[Chemical formula 52]

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

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

<Polymerization inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, methoxyhydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl-o-catechol (tert-butyl-o-catechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N- Ethyl-N-sulfopropylamine)phenol, N-nitrosophenylhydroxylamine first barium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, 1,3,5-tri(4-tert-butyl-3-hydroxy- 2,6-dimethylbenzyl)-1,3,5-trioxan-2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl radical, phenathiophene, 1,1-diphenyl-2-picrylhydrazyl, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

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

[Chemical formula 53]

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

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

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

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 Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 54]

As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, 3-glycidoxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 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-butylenepropylmethyldimethoxysilane, 3-butylenepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding aid] As aluminum-based bonding aids, for example, tri(ethyl acetylacetate)aluminum, tri(acetylacetone)aluminum, diisopropylaluminum ethyl acetylacetate, etc. can be cited.

Furthermore, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is better that the total is within the above range.

<Metallic Adhesion Improver> The resin composition of the present invention preferably contains a metallic adhesion improver for improving adhesion to metal materials used in electrodes or wiring. As the metallic adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the heterocyclic polymer precursor. By setting it to be above the above lower limit, the adhesion between the cured film and the metal layer after the curing process becomes good, and by setting it to be below the above upper limit, the heat resistance and mechanical properties of the cured film after the curing process become good. The metal adhesion improver may be only one kind or may be two or more kinds. When two or more kinds are used, it is preferred that the total is within the above range.

<Other additives> The resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as sensitizers, chain transfer agents, surfactants other than specific surfactants, higher fatty acid derivatives, inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. When such additives are formulated, it is preferred that the total amount thereof be set to 3% by mass or less of the solid content of the resin composition.

[Sensitizer] The resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in an electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo chemical changes and decompose, and generate free radicals, acids, or bases. As the sensitizer, for example, michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone can be cited. , p-dimethylaminobenzylidene dihydroindanone, 2-(p-dimethylaminophenylbiphenyl)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl 3-Methoxycarbonyl-7-dimethylaminocoumarin, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin, N-Phenyl-N'-ethylethanolamine, N-Phenyldiethanolamine, N-p-Toluenediethanolamine, N-Phenylethanolamine, 4-Morpholinylbenzophenone, Isoamyl dimethylaminobenzoate, Diethylaminobenzene Isoamyl formate, 2-benzimidazole, 1-phenyl-5-benzyltetrazol, 2-benzylthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphthalene (1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As the sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

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

[Chain transfer agent] The resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by The Society of Polymer Science, Japan, 2005) pages 683-684. As chain transfer agents, for example, a group of compounds having SH, PH, SiH and GeH in the molecule is used. These generate free radicals by donating hydrogen to low-activity free radicals, or by deprotonating after oxidation. In particular, thiol compounds can be preferably used.

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

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

[Other surfactants except specific surfactants] From the viewpoint of further improving the coating properties, other surfactants except specific surfactants may be added to the resin composition of the present invention. As other surfactants, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content (molar %) of each repeating unit, and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 55] In addition, other surfactants may also include compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219.

Regarding the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. As specific examples, there can be cited compounds described in paragraphs 0050 to 0090 and paragraphs 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 the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of thickness of the coating film and liquid saving, and also has good solubility in the composition.

Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

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

Examples of the nonionic surfactant include glycerol, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (Boyd & Moore Executive Search.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), Pionin D-6112, D-6112-W, D-6315 (TAKEMOTO OIL & FAT CO., LTD.), Olfin E1010, Surfynol 104, 400, 440 (Nissin Chemical Industry Co., Ltd.) etc.

Specific examples of the cationic surfactant 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 Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

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

When the resin composition of the present invention contains other surfactants, the content of the other surfactants is preferably 0.001 to 2.0 mass % relative to the total solid content of the resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The other surfactants may be only one or more. When there are two or more other surfactants, the total amount thereof 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 behenic acid or behenic acid amide can be added to the resin composition of the present invention and are concentrated on the surface of the resin composition during the drying process after coating.

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

When the resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10 mass % relative to the total solid content of the resin composition of the present invention. The higher fatty acid derivative may be only one kind or may be two or more kinds. When there are two or more kinds of higher fatty acid derivatives, the total amount thereof is preferably within the above range.

[Thermal polymerization initiator] The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy and initiates or promotes 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, thereby further improving the solvent resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

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

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the 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 inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. Inorganic particles having a large amount of the above average particle size may deteriorate the mechanical properties of the cured film. In addition, if the average particle size of the inorganic particles is greater than 2.0 μm, the resolution may decrease due to scattering of the exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylic acid ester-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-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. 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, 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

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

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may contain an ultraviolet absorber or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, and more preferably 0.01 mass% or more and 0.1 mass% or less relative to the total solid content of the composition of the present invention.

[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer with excellent chemical resistance can be formed even when hardening at low temperatures.

As the organic titanium compound that can be used, there can be cited those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compound are shown in the following I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferred, considering that the storage stability of the negative photosensitive resin composition is excellent and a good curing pattern can be obtained. Specific examples include bis(triethanolamine)diisopropoxytitanium, di(n-butoxy)bis(2,4-pentanedioate)titanium, diisopropoxybis(2,4-pentanedioate)titanium, diisopropoxybis(tetramethylpimelate)titanium, diisopropoxybis(ethyl acetylacetate)titanium, etc. II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethoxypropoxytitanium, tetramethylphenoxytitanium, tetra(n-nonyloxy)titanium, tetra(n-propoxy)titanium, tetrastearyloxytitanium, tetra[bis{2,2-(allyloxymethyl)propoxy}]titanium, etc. III) Titanium cyclopentadiene compounds: for example, pentamethylcyclopentadiene trimethoxytitanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: for example, tri(dioctyl phosphate)isopropoxytitanium, tri(dodecyl benzenesulfonate)isopropoxytitanium, etc. V) Titanium oxide compounds: for example, bis(glutarate) titanium oxide, bis(tetramethylpimelate) titanium oxide, phthalocyanine titanium oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, diisopropoxybis(ethyl acetylacetate)titanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When the organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern shows good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. The antioxidant is contained as an additive to improve the ductility of the film after curing and the adhesion to the metal material. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to the phenolic hydroxyl group (adjacent position) are preferred. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, as for the antioxidant, a compound having a phenol group and a phosphite group in the same molecule is also preferred. Moreover, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tetaryldibenzo[d,f][1,3,2]dioxaphosphinocycloheptadien-2-yl)oxy]ethyl]amine, and bis(2,4-di-tetaryl-6-methylphenyl)ethyl phosphite. As commercially available antioxidants, 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, ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION) and the like can be cited. In addition, as antioxidants, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, there can be cited compounds in which the site that functions as an antioxidant is protected by a protecting group, and in which the protecting group is removed by heating at 100 to 250°C or by heating at 80 to 200°C in the presence of an acid/base catalyst, thereby functioning as an antioxidant. As potential antioxidants, there can be cited compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219. As commercially available products of potential antioxidants, there can be cited ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. As examples of preferred antioxidants, there can be cited 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and a compound represented by the following general formula (3).

[Chemical formula 56]

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

The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group and the phenolic hydroxyl group of the resin. In addition, it can inhibit the oxidation of the metal by its rust-proofing effect on the metal material.

In order to act on both the resin and the metal material, k is preferably an integer of 2 to 4. R ⁷ includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among them, from the viewpoint of solubility in a developer and metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion by metal complex formation, -NH- is more preferred.

The compounds represented by the following general formula (3) can be exemplified by the following compounds, but are not limited to the following structures.

[Chemical formula 57]

[Chemical formula 58]

[Chemical formula 59]

[Chemical formula 60]

The amount of antioxidant added is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, relative to the resin. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the ductility characteristics of the cured film and the effect of improving the adhesion to metal materials. When the amount added is more than 10 parts by weight, the sensitivity of the resin composition may decrease due to the interaction with the photosensitive agent. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, and even more preferably less than 0.6 mass%. As a method for maintaining the water content, the humidity under storage conditions and the reduction of the porosity of the storage container can be cited.

From the viewpoint of insulation, the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are included, the total of the metals is preferably within the above range.

Furthermore, as a method for reducing the metal impurities accidentally contained in the resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the resin composition of the present invention, filtering the raw material constituting the resin composition of the present invention through a filter, lining the inside of the device with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.

Considering the use as a semiconductor material and from the viewpoint of wiring corrosion, the content of halogen atoms in the resin composition of the present invention is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and further preferably less than 200 mass ppm. Among them, the content of halogen ions is preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and further preferably less than 0.5 mass ppm. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms or chlorine ions and bromine ions are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a container for the resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the resin composition, it is also preferable to use a multi-layer bottle having an inner wall of the container composed of six types of six layers of resin or a bottle having a seven-layer structure of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Application of resin composition> The resin composition of the present invention is preferably used to form an interlayer insulating film for a redistribution layer. In addition, it can also be used to form an insulating film for a semiconductor element or to form a stress buffer film, etc.

<Preparation of resin composition> The resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be performed by a conventionally known method.

Furthermore, for the purpose of removing foreign matter such as dust or particles in the resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, 0.5 μm or less is more preferred, and 0.1 μm or less is further preferred. On the other hand, from the perspective of productivity, 5 μm or less is more preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be used after being pre-cleaned with an organic solvent. In the filtering process of the filter, multiple filters can be used in parallel or in series. When using multiple filters, filters with different pore sizes or materials can be used in combination. In addition, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. In addition, filtering can be performed after pressurization. When filtering after pressurization, the pressure of pressurization is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is better, 0.03MPa or more and 0.9MPa or less is better, and 0.05MPa or more and 0.7MPa or less is even better. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filter filtering and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Resin film, cured film, laminate, semiconductor element, and method for manufacturing the same) Next, the resin film, cured film, laminate, semiconductor device, and method for manufacturing the same are described.

The cured film of the present invention is formed by curing the resin composition of the present invention or the resin film of the present invention. The film thickness of the cured film of the present invention can be set to 0.5 μm or more, and can be set to 1 μm or more. In addition, as an upper limit, it can be set to 100 μm or less, and can also be set to 30 μm or less.

The cured film of the present invention can be laminated in 2 or more layers, and further laminated in 3 to 7 layers to form a laminate. The laminate of the present invention includes 2 or more cured films, and preferably includes a metal layer between any of the above-mentioned cured films. For example, a laminate having a layered structure including at least three layers of a first cured film, a metal layer, and a second cured film laminated in sequence can be cited as a preferred one. The first cured film and the second cured film are both the cured films of the present invention. For example, the first cured film and the second cured film are both films formed by curing the resin composition of the present invention can be cited as a preferred one. The resin composition of the present invention used to form the first cured film and the resin composition of the present invention used to form the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a redistribution layer.

Examples of areas to which the cured film of the present invention can be applied include insulating films for semiconductor elements, interlayer insulating films for redistribution layers, and stress buffer films. In addition, examples include sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), and situations in which patterns are formed by etching insulating films for actual mounting purposes such as those described above. For such applications, for example, reference can be made to Science & Technology Co., Ltd., “Advanced Functionality and Application Technology of Polyimide”, April 2008, supervised by Masaaki Kakimoto, CMC Technical Library, “Fundamentals and Development of Polyimide Materials”, November 2011, and Japan Polyimide and Aromatic Polymer Research Society, “Latest Polyimide: Fundamentals and Applications”, NTS, August 2010.

Furthermore, the cured film of the present invention can also be used in the production of offset printing plates or screen printing plates, in the production of etching molded parts, and in the production of protective varnishes and dielectric layers in electronics, especially microelectronics.

The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming process of applying the resin composition of the present invention to a substrate to form a film (resin film). The method for producing a cured film of the present invention preferably includes the above-mentioned film forming process, an exposure process of exposing the above-mentioned film, and a development process of developing the above-mentioned film. Furthermore, the method for producing a cured film of the present invention includes the above-mentioned film forming process and the above-mentioned development process as needed, and more preferably includes a heating process of heating the above-mentioned film at 50 to 450°C. Specifically, it is also preferred to include the following processes (a) to (d). (a) A film forming process of applying a resin composition to a substrate to form a film (resin composition layer) (b) An exposure process of exposing the film after the film forming process (c) A developing process of developing the exposed film (d) A heating process of heating the developed film at 50 to 450°C By heating in the above heating process, the resin layer hardened by exposure can be further hardened. In the heating process, for example, the above-mentioned hot alkali generator is decomposed, and sufficient hardening can be obtained.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. After forming a cured film according to the above-mentioned method for manufacturing a laminated body of the present embodiment, the process (a) or the processes (a) to (c), or the processes (a) to (d) are performed again. In particular, it is preferred to perform the above-mentioned processes in sequence a plurality of times, for example 2 to 5 times (that is, a total of 3 to 6 times). By laminating the cured film in this way, a laminated body can be formed. In the present invention, it is preferred to provide a metal layer on a portion where a cured film is provided or between the cured films, or in both. Furthermore, in the manufacture of the laminate, it is not necessary to repeat all of the processes (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film-forming process (layer-forming process)> The manufacturing method of the preferred embodiment of the present invention includes a film-forming process (layer-forming process) of applying a resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately set according to the purpose, but there is no particular limitation. Examples include semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, evaporated 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 of plasma display panels (PDP). In addition, a bonding layer, an oxide layer, and the like can be provided on the surface of the substrates. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates, and casting substrates are more preferred. In addition, as a substrate, for example, a plate-shaped substrate (substrate) is used. In addition, a bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like may be provided on the surface of the substrate. The shape of the substrate is not particularly limited, and may be circular or rectangular, with the rectangular shape being preferred. As for the size of the substrate, if it is circular, the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

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

Specifically, applicable 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 the thickness uniformity of the resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By adjusting the appropriate solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc. are preferred, and for rectangular substrates, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, depending on the viscosity of the photosensitive resin composition or the set film thickness, it is also preferred to apply at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. In addition, in order to obtain a uniform film thickness, multiple rotation speeds can be combined for coating. Furthermore, a method of transferring a coating formed by pre-imparting the coating on a pseudo support by the above-mentioned imparting method to a substrate can also be applied. Regarding the transfer method, in the present invention, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used. Furthermore, a process of removing excess film at the end of the substrate can also be performed. Examples of such processes include edge bead removal (EBR), air knife, back rinsing, etc. Furthermore, the following pre-wetting process may be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process> The manufacturing method of the present invention may also include a drying process for removing the solvent after the film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. The drying time may be 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

<Exposure process> The manufacturing method of the present invention may include an exposure process for exposing the above-mentioned film (resin composition layer). The exposure amount is not particularly limited as long as it can cure the resin composition. For example, it is preferably 100 to 10,000 mJ/ ^cm2 , and more preferably 200 to 8,000 mJ/ ^cm2 , calculated as the exposure energy at a wavelength of 365 nm.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, with 240 to 550 nm being the best.

Regarding the exposure wavelength, if described in terms of its relationship with the light source, the following examples can be cited: (1) semiconductor lasers (wavelengths of 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), wide (3 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 light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic wave of YAG lasers at 532nm and the third harmonic wave at 355nm. The resin composition of the present invention is preferably exposed by a high-pressure mercury lamp, and preferably by i-rays, thereby achieving high exposure sensitivity.

<Developing process> The manufacturing method of the present invention may include a developing process for developing (developing) the exposed film (resin composition layer). By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as it can form the desired pattern. For example, it can be mentioned that the developer is sprayed from a nozzle, sprayed, and the substrate is immersed in the developer. The nozzle spraying can be preferably used. The developing process can adopt a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer using ultrasound, etc., and a process of combining these.

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

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula into ChemBioDraw.

When the developer contains an organic solvent, the organic solvent may be preferably esters such as 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 alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethyl 3-alkoxypropionate, etc.)), alkyl 3-alkoxypropionates (e.g. methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 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, etc.) ethyl ester)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea acetate, diethylene glycol dimethyl ether, Examples of the preferred organic solvents include propylene 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, propylene glycol monopropyl ether acetate, and the like; and examples of the preferred ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like; and examples of the preferred cyclic hydrocarbons include toluene, xylene, anisole, limonene, and the like; and examples of the preferred sulfoxides include dimethyl sulfoxide, and mixtures of the organic solvents may also be preferably mentioned.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are particularly preferred, and cyclopentanone is more preferred. When the developer contains an organic solvent, one organic solvent may be used or two or more organic solvents may be mixed and used.

When the developer contains an organic solvent, preferably 50% by mass or more of the developer is the organic solvent, more preferably 70% by mass or more of the developer is the organic solvent, and even more preferably 90% by mass or more of the developer is the organic solvent. In addition, 100% by mass of the developer may be the organic solvent.

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

The developer may further contain other components. As other components, for example, known surfactants, known defoaming agents, etc. can be cited.

[Developer supply method] As long as the desired pattern can be formed, there is no particular limitation on the developer supply method, including the following methods: a method of immersing the substrate in the developer, a method of supplying the developer to the substrate using a nozzle for liquid coating development, or a method of continuously supplying the developer. There is no particular limitation on the type of nozzle, and examples include direct current nozzles, shower nozzles, and mist nozzles. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, a method of supplying developer with a DC nozzle or a method of continuously supplying developer with a spray nozzle is preferred. From the perspective of developer permeability to the image portion, a method of supplying developer with a spray nozzle is preferred. In addition, the following process can be adopted: after continuously supplying developer with a DC nozzle, the substrate is rotated to remove the developer from the substrate, and after rotating and drying, the developer is continuously supplied with a DC nozzle again, and the substrate is rotated to remove the developer from the substrate. The process can also be repeated several times. In addition, as a method for supplying the developer in the developing process, a process of continuously supplying the developer on the substrate, a process of keeping the developer on the substrate in a substantially static state, a process of vibrating the developer on the substrate using ultrasound, etc., and a combination of these processes can be adopted.

The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing is not particularly limited, but can usually be carried out at 10 to 45°C (preferably 20 to 40°C).

After the treatment with the developer, rinsing can be performed. Alternatively, a method such as supplying a rinsing solution before the developer in contact with the pattern is completely dried can be adopted. It is preferred that the rinsing be performed with a solvent different from the developer. For example, a solvent contained in the resin composition can be used for rinsing. When the developer is a developer containing an organic solvent, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), etc. can be cited as the rinsing solution, and PGMEA is preferred. Furthermore, as a rinsing solution in development based on a developer containing an alkaline aqueous solution, water is preferred. Regarding the rinsing time, 20 seconds to 10 minutes is preferred, 10 seconds to 5 minutes is more preferred, and 5 seconds to 1 minute is further preferred. The temperature of the rinsing liquid during rinsing is not particularly limited, but it is preferably performed at 10 to 45°C (18 to 30°C is more preferred).

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as 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 alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, etc.)), alkyl 3-alkoxy propionates (e.g., 3- Alkoxy propionic acid methyl esters, 3-alkoxy propionic acid ethyl esters, etc. (for example, 3-methoxy propionic acid methyl ester, 3-methoxy propionic acid ethyl ester, 3-ethoxy propionic acid methyl ester, 3-ethoxy propionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example, 2-alkoxy propionic acid methyl ester, 2-alkoxy propionic acid ethyl ester, 2-alkoxy propionic acid propyl ester, etc. (for example, 2-methoxy propionic acid methyl ester, 2-methoxy propionic acid ethyl ester, 2-methoxy propionic acid propyl ester, 2-ethoxy propionic acid methyl ester, 2-ethoxy propionic acid ethyl ester)), 2-alkoxy-2-methyl propionic acid methyl ester and 2-alkoxy-2-methyl propionic acid ethyl ester (for example, 2-methoxy-2- As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, 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 Esters, etc., and ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and sulfoxides, for example, dimethyl sulfoxide, and alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, triethylene glycol, etc., and amides, for example, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

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

When the rinse liquid contains an organic solvent, preferably 50 mass % or more of the rinse liquid is the organic solvent, more preferably 70 mass % or more of the rinse liquid is the organic solvent, and even more preferably 90 mass % or more of the rinse liquid is the organic solvent. Alternatively, the rinse liquid may contain 100 mass % of the organic solvent.

The rinse solution may further contain other components. As other components, for example, known surfactants, known defoaming agents, etc. can be cited.

[Method for supplying the rinse liquid] As long as the desired pattern can be formed, there is no particular limitation on the method for supplying the rinse liquid. The following methods are available: a method of immersing the substrate in the rinse liquid, a method of developing the substrate with a liquid coating, a method of supplying the rinse liquid to the substrate with a shower head, a method of continuously supplying the rinse liquid to the substrate by a direct current nozzle, etc. From the perspective of the permeability of the rinse liquid, the removal of the non-image area, and the efficiency of manufacturing, it is better to supply the rinse liquid using a shower nozzle, a direct current nozzle, a spray nozzle, etc., and it is better to supply it continuously using a spray nozzle. From the perspective of the permeability of the rinse liquid to the image area, it is better to supply it using a spray nozzle. There is no particular limitation on the type of nozzle, and direct current nozzles, shower nozzles, spray nozzles, etc. can be cited. That is, the rinsing process is preferably a process in which a rinsing liquid is supplied or continuously supplied to the film after exposure using a direct current nozzle, and a process in which a rinsing liquid is supplied using a spray nozzle is more preferred. In addition, as a method for supplying the rinsing liquid in the rinsing process, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept substantially stationary on the substrate, a process in which the rinsing liquid is vibrated on the substrate using ultrasound or the like, and a process in which these are combined can be adopted.

<Heating process> The manufacturing method of the present invention preferably includes a process (heating process) of heating the developed film at 50 to 450°C. It is preferred to include a heating process after the film formation process (layer formation process), drying process and development process. In the heating process, for example, a base is generated by decomposing the above-mentioned hot alkali generator, and a cyclization reaction is carried out as a precursor of a specific resin. In addition, the resin composition of the present invention may contain a free radical polymerizable compound other than a precursor as a specific resin, and the curing of the free radical polymerizable compound other than a precursor as an unreacted specific resin may also be carried out in the process. As the heating temperature (maximum heating temperature) of the middle layer in the heating process, 50°C or higher is preferred, 80°C or higher is more preferred, 140°C or higher is further preferred, 150°C or higher is further preferred, 160°C or higher is further preferred, and 170°C or higher is further preferred. As the upper limit, 500°C or lower is preferred, 450°C or lower is more preferred, 350°C or lower is further preferred, 250°C or lower is further preferred, and 220°C or lower is further preferred.

Regarding heating, it is preferred that the heating rate be 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, it is possible to ensure productivity while preventing excessive volatile amines, and by setting the heating rate to 12°C/min or less, it is possible to alleviate the residual stress of the cured film. In addition, in the case of an oven capable of rapid heating, it is preferred that the heating rate be 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

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

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, when forming a multi-layer laminate, from the viewpoint of the adhesion between the layers of the cured film, heating is preferably performed at a heating temperature of 180°C to 320°C, and more preferably at 180°C to 260°C. The reason for this is not yet certain, but it is believed that this is because the acetylene groups of the specific resin between the layers undergo a cross-linking reaction.

Heating can be performed in stages. For example, the pre-treatment process can be performed by heating from 25°C to 180°C at 3°C/min and maintaining at 180°C for 60 minutes, and then heating from 180°C to 200°C at 2°C/min and maintaining at 200°C for 120 minutes. The heating temperature of the pre-treatment process is preferably 100-200°C, more preferably 110-190°C, and further preferably 120-185°C. In the pre-treatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. The properties of the membrane can be improved by such pre-treatment processes. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can be a process of two or more stages, for example, pretreatment process 1 can be carried out in the range of 100 to 150°C, and then pretreatment process 2 can be carried out in the range of 150 to 200°C.

Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5°C/minute.

Regarding the heating process, it is better to carry out the process in an atmosphere with low oxygen concentration by circulating inert gases such as nitrogen, helium, and argon to prevent the decomposition of specific resins. The oxygen concentration is preferably 50ppm (volume ratio) or less, and more preferably 20ppm (volume ratio) or less. There is no particular limitation on the heating method, and examples thereof include a heating plate, an infrared furnace, an electric oven, and a hot air oven.

<Metal layer forming process> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the film (resin composition layer) after development.

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

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be used. For example, photolithography, stripping, electrolytic plating, electroless plating, etching, printing, and a combination of these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest wall portion.

<Layering process> The manufacturing method of the present invention preferably further includes a layering process.

The lamination process includes a series of processes including (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process, which are performed again in sequence on the surface of the hardened film (resin layer) or metal layer. Among them, it can be a state where only the film formation process (a) is repeated. In addition, it can also be a state where the heating process (d) is performed at the end or in the middle of the lamination. That is, it can also be set as follows: the processes (a) to (c) are repeated a specified number of times, and then the heating (d) is performed, thereby hardening the resin composition layer to be laminated. Furthermore, the (c) developing process may include the (e) metal layer forming process, and the heating in (d) may be performed each time, or may be performed collectively after a predetermined number of layering processes. It is beyond doubt that the layering process may further appropriately include the above-mentioned drying process and heating process.

When a further layering process is performed after the layering process, a surface activation treatment process may be further performed after the heating process, after the exposure process, or after the metal layer forming process. As the surface activation treatment, plasma treatment may be exemplified.

The above-mentioned lamination process is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. In addition, each layer in the lamination process may be the same layer in composition, shape, film thickness, etc., or may be different layers.

For example, a structure such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, in which the number of resin layers is 2 or more and 20 or less is preferred, a structure of 3 or more and 7 or less is more preferred, and a structure of 3 or more and 5 or less is further preferred.

In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the resin composition in a manner covering the metal layer. Specifically, it is possible to cite an embodiment in which (a) a film forming process, (b) an exposure process, (c) a developing process, (e) a metal layer forming process, and (d) a heating process are sequentially repeated, or an embodiment in which (a) a film forming process, (b) an exposure process, (c) a developing process, and (e) a metal layer forming process are sequentially repeated, and (d) a heating process is provided at the end or in the middle. By alternately performing a lamination process of a resin composition layer (resin layer) and a metal layer forming process, it is possible to alternately laminarize a resin composition layer (resin layer) and a metal layer.

(Surface activation treatment process) The method for manufacturing a laminate of the present invention may include a surface activation treatment process for performing surface activation treatment on at least a portion of the above-mentioned metal layer and the photosensitive resin composition layer. The surface activation treatment process is usually performed after the metal layer forming process, but the metal layer forming process may be performed after the above-mentioned exposure and development process and after the photosensitive resin composition layer is subjected to the surface activation treatment process. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed photosensitive resin composition layer, or may be performed on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred that the surface activation treatment be performed on at least a portion of the metal layer, and it is preferred that the surface activation treatment be performed on a portion or the entirety of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. Thus, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. Furthermore, it is preferred that the surface activation treatment be performed on a portion or the entirety of the photosensitive resin composition layer (resin layer) after exposure. Thus, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or the resin layer disposed on the surface subjected to the surface activation treatment can be improved. Specifically, the surface activation treatment may be selected from plasma treatment using various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide film by immersion in aqueous hydrochloric acid solution and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 of Japanese Patent Publication No. 2016-027357 and FIG. 1, and such contents are incorporated into this specification. [Example]

The present invention is further described in detail below by way of examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

<Synthesis Example 1: Synthesis of polymer A-1> In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint with an internal thermometer, 9.49 g (32.25 mmol) of 4,4'-diphthalic acid dianhydride and 10.0 g (32.25 mmol) of oxydiphthalic acid dianhydride were suspended in 140 mL of diethylene glycol dimethyl ether while removing water. 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 0.05 g of pure water, and 10.7 g (135 mmol) of pyridine were added successively at 60°C for 18 hours. Then, after the mixture was cooled to -20°C, 16.1 g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridine hydrochloride was obtained. Then, the mixture was heated to room temperature and stirred for 2 hours, and then 9.7 g (123 mmol) of pyridine and 25 mL of N-methylpyrrolidone (NMP) were added to obtain a transparent solution. Then, 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of NMP was added dropwise over 1 hour to the obtained transparent solution. Then, 5.6 g (17.5 mmol) of methane and 0.05 g of 3,5-di-tert-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500 rpm for 15 minutes. The polyimide precursor resin was obtained by filtration, and was stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45° C. under reduced pressure for 3 days, thereby obtaining polymer A-1.

<Synthesis Example 2: Synthesis of polymer A-2> In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint with an internal thermometer, 65.56 g (179 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.48 g (10 mmol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were dissolved in 300 g of N-methylpyrrolidone (NMP) while removing water. Then, 62.04 g (200 mmol) of oxydiphthalic dianhydride 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, the temperature was raised to 180°C while nitrogen was circulated at a flow rate of 200 ml/min, and the mixture was stirred for 6 hours. After the reaction solution was cooled to 25°C, 0.005 g of p-methoxyphenol was added and dissolved. 24.82 g (160 mmol) of 2-isocyanatoethyl methacrylate was added dropwise to the solution, and the mixture was stirred at 25°C for 2 hours, and then stirred at 60°C for 3 hours. The mixture was 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, rinsed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again. The obtained polyimide was dried at 40° C. under reduced pressure for 1 day to obtain polymer A-2.

<Synthesis Example 3: Synthesis of polymer A-3> Into a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 27.55 g (0.160 mol) of 1,4-cyclohexanedicarboxylic acid (cis-trans mixture, manufactured by Tokyo Chemical Industry Co., Ltd.) and 64.28 g of N-methyl-2-pyrrolidone (NMP) were added, and 38.07 g (0.320 mol) of sulfinyl chloride was added dropwise at room temperature. After the addition was completed, the mixture was stirred at room temperature for 1 hour, and the excess sulfinyl chloride was distilled off under reduced pressure to obtain 1,4-cyclohexanedicarboxylic acid dichloride (cis-trans mixture) as a 30 mass% NMP solution. 73.25 g (0.200 mol) of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (Bis-AP-AF, manufactured by Central Glass Co., Ltd.), 31.64 g (0.400 mol) of pyridine and 293 g of NMP were added to a three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube. The mixture was stirred at room temperature and then cooled to -15°C in a dry ice/methanol bath. While maintaining the reaction temperature at -5°C to -15°C, 30.11 g (0.144 mol) of a 30% by mass NMP solution of 1,4-cyclohexanedicarboxylic acid dichloride, 3.83 g (0.016 mol) of butyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 96.25 g of a mixed solution of NMP were added dropwise to the solution. After the addition was completed, the obtained mixture was stirred at room temperature for 16 hours. Then, the reaction solution was cooled to below -5°C in an ice/methanol bath, and while maintaining the reaction temperature below -0°C, a mixed solution of 9.59 g (0.090 mol) of butyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.5 g of NMP was added dropwise. After the addition was completed, the mixture was stirred for 16 hours. The reaction solution was diluted with 550 g of NMP and added to a vigorously stirred 4 L deionized water/methanol (80/20 volume ratio) mixture. The precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was vacuum dried at 50°C for 2 days to obtain resin A-1a. 25.00 g of resin A-1a, 125 g of NMP and 125 g of methyl ethyl ketone were added to an eggplant-shaped flask and concentrated under reduced pressure at 60°C until the content became 160 g. 0.43 g (1.85 mmol) of camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd.) and 5.12 g (0.065 mol) of 2,3-dihydrofuran (FUJIFILM Wako Pure Chemical Corporation) were added thereto, and stirred at room temperature for 1.5 hours. 0.37 g of triethylamine and 150 g of NMP were added to the obtained solution, and the solution was diluted. The obtained solution was poured into a 2 L deionized water/methanol (80/20 volume ratio) mixture that was stirred vigorously, and the precipitated white powder was recovered by filtration and then washed with deionized water. The polymer was vacuum dried at 50°C for 2 days to obtain polymer A-3.

<Synthesis Example 4: Synthesis of Polymer A-4> In Synthesis Example 1, except that 6.82 g (58.7 mmol) of 1,6-diaminohexane was used instead of 11.8 g (58.7 mmol) of 4,4'-diaminodiphenyl ether, the same reaction method as described in Synthesis Example 1 was used to obtain Polymer A-4.

<Synthesis Example 5: Synthesis of Polymer A-5> 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140°C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diethylene glycol dimethyl ether (diethylene glycol dimethyl ether) were mixed and stirred at 60°C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10°C, and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while the temperature was maintained at -10±4°C. After dilution with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23°C over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 night. Next, 5 liters of water were added to precipitate the polyimide precursor, and the water-polyimide precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor was filtered, put into 4 liters of water and stirred for 30 minutes, and filtered again. The obtained polyimide precursor was then dried at 45° C. under reduced pressure for 3 days to obtain polymer A-5.

<Synthesis Example 6: Synthesis of Polymer A-6> In the synthesis of polymer A-1, 10.0 g (32.25 mmol) of oxydiphthalic acid dianhydride was replaced with 20.0 g (64.50 mmol) of oxydiphthalic acid dianhydride, and 4,4'-diphthalic acid dianhydride was not used. The same method as polymer A-1 was used to synthesize polymer A-1-1. In addition, 9.49 g (32.25 mmol) of 4,4'-diphthalic acid dianhydride was replaced with 18.98 g (64.50 mmol) of 4,4'-diphthalic acid dianhydride, and oxydiphthalic acid dianhydride was not used. The same method as polymer A-1 was used to synthesize polymer A-1-2. The obtained polymer A-1-1 and polymer A-1-2 were mixed at a ratio of 1:1 (mass ratio), thereby obtaining polymer A-6.

<Examples and Comparative Examples> In each example, the components listed in Tables 1 to 3 below were mixed to obtain each resin composition. In addition, in each comparative example, the components listed in Table 2 below were mixed to obtain each comparative composition. Specifically, the content of the components other than the solvents listed in Tables 1 to 3 is set to the amount (mass part) listed in each column of Tables 1 to 3. In addition, in each composition, the total content of the solvent is set to the solid content concentration (mass %) of the composition to be the value listed in Tables 1 to 3, and the content ratio of each solvent is set to be the mass ratio based on the values listed in each column of Tables 1 to 3. The obtained resin composition and the comparative composition were filtered under pressure through a polytetrafluoroethylene filter having a pore width of 0.8 μm. In Tables 1 to 3, the entry "-" indicates that the composition does not contain the component.

[Table 1] Embodiment 1 2 3 4 5 6 7 8 9 10 11 Composition Resin Type A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-2 Quality 80 80 80 80 80 80 80 80 80 80 54 Free Radical Crosslinking Agents Type B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-2 Quality 7 7 7 7 7 7 7 7 7 7 3 Type - - - - - - - - - - B-3 Quality - - - - - - - - - - 28 Acid crosslinking agent Type - - - - - - - - - - B-4 Quality - - - - - - - - - - 28 Photosensitizer Type C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-3 Quality 3 3 3 3 3 3 3 3 3 3 5 Silane coupling agent Type D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-3 Quality 1 1 1 1 1 1 1 1 1 1 1 Type D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 D-2 - Quality 1 1 1 1 1 1 1 1 1 1 - Polymerization inhibitor Type E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-1 E-3 Quality 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.02 Type E-5 E-5 E-5 E-5 E-5 E-5 E-5 E-5 E-5 E-5 - Quality 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 - Additives Type F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-1 F-4 Quality 2 2 2 2 2 2 2 2 2 2 1 Type F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 - Quality 5 5 5 5 5 5 5 5 5 5 - Thermal acid generator Type - - - - - - - - - - G-1 Quality - - - - - - - - - - 3 Thermoalkali generator Type - - - - - - - - - - - Quality - - - - - - - - - - - Surfactant Type I-1 I-2 I-3 I-4 I-5 I-6 I-1 I-1 I-1 I-1 I-1 Quality 1 1 1 1 1 1 0.5 2 3 0.5 1 Type - - - - - - I-7 - - - - Quality - - - - - - 0.5 - - - - Solvent Type S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 80 80 Type S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 Ratio in solvent 20 20 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 20 Pattern size (μm) 20 20 20 20 20 20 20 20 20 20 20 Developer S S S S S S S S S S A Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 Reviews Defects when stacking multiple layers A B A A A A B A B A B Metal adhesion A B A A A A B A A B A

[Table 2] Embodiment 12 13 14 15 16 17 18 19 20 twenty one twenty two Composition Resin Type A-3 A-1 A-4 A-5 A-5 A-5 A-5 A-5 A-5 A-5 A-5 Quality 100 80 80 32 32 32 32 32 32 32 32 Free Radical Crosslinking Agents Type - B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality - 7 7 6.88 6.88 6.88 6.88 6.88 6.88 6.88 6.88 Type - - - - - - - - - - - Quality - - - - - - - - - - - Acid crosslinking agent Type - - - - - - - - - - - Quality - - - - - - - - - - - Photosensitizer Type C-4 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 C-1 Quality 3 3 3 1.04 1.04 1.04 1.04 1.04 1.04 1.04 1.04 Silane coupling agent Type D-4 D-1 D-1 D-5 D-5 D-5 D-5 D-5 D-5 D-5 D-5 Quality 3 1 1 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Type - D-2 D-2 - - - - - - - - Quality - 1 1 - - - - - - - - Polymerization inhibitor Type - E-1 E-1 E-4 E-6 E-7 E-8 E-9 E-10 E-11 E-12 Quality - 0.2 0.2 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Type - E-5 E-5 - - - - - - - - Quality - 0.5 0.5 - - - - - - - - Additives Type - F-1 F-1 F-2 F-2 F-2 F-2 F-2 F-2 F-2 F-2 Quality - 2 2 1 1 1 1 1 1 1 1 Type - F-3 F-3 - - - - - - - - Quality - 5 5 - - - - - - - - Thermal acid generator Type - - - - - - - - - - - Quality - - - - - - - - - - - Thermoalkali generator Type - - - H-1 H-1 H-1 H-1 H-1 H-1 H-1 H-1 Quality - - - 1 1 1 1 1 1 1 1 Surfactant Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 Quality 1 1 1 1 1 1 1 1 1 1 1 Type - - - - - - - - - - - Quality - - - - - - - - - - - Solvent Type S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 80 80 Type S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 Ratio in solvent 20 20 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 30 20 20 20 20 20 20 20 20 20 Pattern size (μm) 20 20 20 20 20 20 20 20 20 20 20 Developer A S S S S S S S S S S Hardening temperature (℃) 230 230 230 230 230 230 230 230 230 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 120 Reviews Defects when stacking multiple layers B A A A A A A A A A A Metal adhesion A A B A A A A A A A A

[Table 3] Embodiment Comparison Example twenty three twenty four 25 26 27 28 29 30 1 2 Composition Resin Type A-5 A-6 A-1 A-1 A-1 A-1 A-1 A-1 A-1 A-1 Quality 32 80 80 80 80 80 80 80 80 80 Free radical crosslinking agent Type B-1 B-1 B-2 B-1 B-1 B-1 B-1 B-1 B-1 B-1 Quality 6.88 7 7 7 7 7 7 7 7 7 Type - - - - - - - - - - Quality - - - - - - - - - - Acid crosslinking agent Type - - - - - - - - - - Quality - - - - - - - - - - Photosensitizer Type C-1 C-1 C-1 C-2 C-1 C-1 C-1 C-1 C-1 C-1 Quality 1.04 3 3 3 3 3 3 3 3 3 Silane coupling agent Type D-5 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-1 Quality 0.7 1 1 1 2 1 1 1 1 1 Type - D-2 D-2 D-2 - D-2 D-2 D-2 D-2 D-2 Quality - 1 1 1 - 1 1 1 1 1 Polymerization inhibitor Type E-13 E-1 E-1 E-1 E-1 E-2 E-1 E-1 E-1 E-1 Quality 0.08 0.2 0.2 0.2 0.2 0.3 0.2 0.2 0.2 0.2 Type - E-5 E-5 E-5 E-5 - E-5 E-5 E-5 E-5 Quality - 0.5 0.5 0.5 0.5 - 0.5 0.5 0.5 0.5 Additives Type F-2 F-1 F-1 F-1 F-1 F-1 F-2 F-1 F-1 F-1 Quality 1 2 2 2 2 2 1 2 2 2 Type - F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 F-3 Quality - 5 5 5 5 5 5 5 5 5 Thermal acid generator Type - - - - - - - - - - Quality - - - - - - - - - - Thermoalkali generator Type H-1 - - - - - - - - - Quality 1 - - - - - - - - - Surfactant Type I-1 I-1 I-1 I-1 I-1 I-1 I-1 I-1 - I-7 Quality 1 1 1 1 1 1 1 1 - 1 Type - - - - - - - - - - Quality - - - - - - - - - - Solvent Type S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 S-1 Ratio in solvent 80 80 80 80 80 80 80 80 80 80 Type S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 S-2 Ratio in solvent 20 20 20 20 20 20 20 20 20 20 Solid content concentration 42 42 42 42 42 42 42 42 42 42 Process Film thickness (μm) 20 20 20 20 20 20 20 20 20 20 Pattern size (μm) 20 20 20 20 20 20 20 20 20 20 Developer S S S S S S S S S S Hardening temperature (℃) 230 230 230 230 230 230 230 190 230 230 Hardening time (min) 120 120 120 120 120 120 120 120 120 120 Reviews Defects when stacking multiple layers A A A A A A A A C C Metal adhesion A A A A A A A A C C

The details of each component listed in Tables 1 to 3 are as follows.

[Resin] ・A-1 to A-6: Polymers A-1 to A-6 synthesized in the above synthesis example

[Free Radical Crosslinking Agent] ・B-1: Tetraethylene glycol dimethacrylate ・B-2: Dipentatriol hexaacrylate ・B-3: LIGHT ESTER BP-6EM (manufactured by KYOEISHA CHEMICAL Co., LTD.)

[Acid crosslinking agent] ・B-4: NIKALAC MX-270 (manufactured by SANWA CHEMICAL CO., LTD.)

[Photosensitive compound] ・C-1: Irgacure 784 (manufactured by BASF) ・C-2: Irgacure OXE-01 (manufactured by BASF) ・C-3: ADEKA NCI-930 (manufactured by ADEKA CORPORATION) ・C-4: Photoacid generator represented by the following formula (C-4) (manufactured by BASF, PAG-103) [Chemical formula 61]

[Silane coupling agent] ・D-1: N-(3-(triethoxysilyl)propyl)-2-methylaminobenzoic acid ・D-2: Benzophenone-3,3'-bis(N-(3-triethoxysilyl)propylamide)-4,4'-dicarboxylic acid ・D-3: IM-1000 (manufactured by JX Nippon Mining & Metals Corporation) ・D-4: 3-Glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) ・D-5: N-[3-(triethoxysilyl)propyl]maleic acid monoamide

[Polymerization inhibitor] ・E-1: 2-Nitroso-1-naphthol ・E-2: 4-Methoxyphenol (MEHQ) ・E-3: 4-Methoxy-1-naphthol ・E-4: p-Benzoquinone ・E-5: Compound represented by the following formula (E-5) ・E-6: N,N'-diphenyl-p-phenylenediamine ・E-7: Phenothiazine ・E-8: 2,4-Di-tert-butylphenol ・E-9: Di-tert-butylhydroxytoluene ・E-10: Hydroquinone ・E-11: Methoxyhydroquinone ・E-12: 1,4-naphthoquinone ・E-13: Tert-butyl o-o-catechol [chemical formula 62]

[Additives] ・F-1: 7-(Diethylamino)coumarin-3-carboxylic acid ethyl ester ・F-2: 1H-tetrazolyl ・F-3: N-phenyldiethanolamine ・F-4: 1,3-dibutylthiourea

[Thermal acid generator] ・G-1: Isopropyl p-toluenesulfonate

[Thermoalkali generator] H-1: The compound represented by the following formula (H-1) [Chemical Formula 63]

[Surfactant] ・I-1: Viscoat 8FM (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) ・I-2: Glyceryl stearate ・I-3: Viscoat 4F (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) ・I-4: Viscoat 8F (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.) ・I-5: MEGAFACE DS-21 (manufactured by DIC Corporation) ・I-6: 1,1,1,3,5,5,5-heptamethyl-3-(3,3,3-trifluoropropyl) pentatrisiloxane ・I-7: PF-6520 (manufactured by KITAMURA CHEMICALS CO., LTD.) The above-mentioned I-7 is a surfactant that does not satisfy any one of the above-mentioned conditions 1 and 2.

[Solvent] ・S-1: γ-butyrolactone ・S-2: dimethyl sulfoxide In Tables 1 to 3, the column "Ratio in Solvent" indicates the content (mass %) of each solvent relative to the total mass of the solvent.

<Evaluation> [Evaluation of defects when forming multiple layers] The resin composition or comparative composition prepared in each embodiment and comparative example was applied in layers on a copper substrate by spin coating to form a resin layer 1. The copper substrate on which the resin layer 1 was formed was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer 1 or comparative composition layer 1 having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 on the copper substrate. In the case where a resin composition containing any one of C-1 to C-3 or a comparative composition was used as a photosensitive agent, resin composition layer 1 or comparative composition layer 1 was entirely exposed to i-rays at an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), thereby obtaining resin layer 1-2. In the case where a resin composition containing C-4 was used as a photosensitive agent, resin composition layer 1 was not entirely exposed and was directly used as resin layer 1-2. Furthermore, the resin layer 1-2 was heated at a heating rate of 10°C/min in a nitrogen atmosphere until it reached the temperature listed in the "hardening temperature (°C)" column of Tables 1 to 3, and then the temperature was maintained for the time listed in the "hardening time (min)" column of Tables 1 to 3, thereby obtaining a resin film. The resin layer 2 was formed by applying the same resin composition or comparative composition as that used to form the resin composition layer 1 or the comparative composition layer 1 in a layered manner on the resin film by spin coating. The copper substrate on which the obtained resin layer 2 was formed was dried on a hot plate at 100°C for 5 minutes, and a resin composition layer 2 or a comparative composition layer 2 having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 was formed on the resin composition layer 1 or the comparative composition layer 1. In the example where the resin composition or the comparative composition containing any one of C-1 to C-3 was used as a photosensitive agent, the resin composition layer 2 or the comparative composition layer ² was entirely exposed to i-rays at an exposure energy of 500mJ/cm2 using a stepper (Nikon NSR 2005 i9C), thereby obtaining a resin layer 2-2. In the example where the resin composition containing C-4 was used as the photosensitive agent, the resin composition layer 1 was not exposed as a whole, but was directly used as the resin layer 2-2. Furthermore, the resin layer 2-2 was heated at a heating rate of 10°C/min in a nitrogen atmosphere until it reached the temperature described in the "hardening temperature (°C)" column of Tables 1 to 3, and then the temperature was maintained for the time described in the "hardening time (min)" column of Tables 1 to 3, thereby obtaining a resin film 2. The generation of voids in the resin film 2 was confirmed using an optical microscope. The number of voids generated in an area of 1 ^mm2 was used as an index value, and the evaluation was performed according to the following evaluation criteria.

-Evaluation Criteria- A: The number of voids per 1 ^mm2 is 3 or less. B: The number of voids per 1 ^mm2 is more than 3 and less than 10. C: The number of voids per 1 ^mm2 is more than 10.

<Evaluation> [Evaluation of Metal Adhesion] The resin composition or comparative composition prepared in each embodiment and comparative example was applied in a layer on a copper substrate by spin coating to form a resin layer. The copper substrate on which the resin layer was formed was dried on a hot plate at 100°C for 5 minutes to form a resin composition layer or comparative composition layer having a thickness described in the "Film Thickness (μm)" column of Tables 1 to 3 on the copper substrate. In the case where a resin composition or a comparative composition containing any one of C-1 to C-3 was used as a photosensitive agent, a resin composition layer or a comparative composition layer on a copper substrate was exposed to i-rays at an exposure energy of 500 mJ/ ^cm2 using a mask having a square non-mask portion of 100 μm square using a stepper (Nikon NSR 2005 i9C). In the case where a resin composition containing C-4 was used as a photosensitive agent, a resin composition layer on a copper substrate was exposed to i-rays at an exposure energy of 150 mJ/ ^cm2 using a mask having a square mask portion of 100 μm square using a stepper (Nikon NSR 2005 i9C). After the above exposure, in the case where "S" is recorded in the "Developer" column of Tables 1 to 3, a resin layer having a square shape of 100 μm square was obtained by developing with cyclopentanone for 60 seconds. In addition, after the above exposure, in the case where "A" is recorded in the "Developer" column of Tables 1 to 3, a resin layer having a square shape of 100 μm square was obtained by developing with a 2.3 mass% tetramethylammonium hydroxide aqueous solution for 30 seconds. Furthermore, the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere until the temperature described in the "Curing Temperature (°C)" column of Tables 1 to 3 was reached, and the temperature was maintained for the time described in the "Curing Time (min)" column of Tables 1 to 3 to obtain a resin film 2. The shear force of the 100μm square resin film 2 on the copper substrate was measured using an adhesion tester (CondorSigma, manufactured by XYZTEC) in an environment of 25°C and 65% relative humidity (RH), and the evaluation was performed according to the following evaluation criteria. The evaluation results are described in the "Metal Adhesion" column of Tables 1 to 3. It can be said that the greater the shear force, the better the metal adhesion (copper adhesion) of the cured film.

-Evaluation criteria- A: Shear force exceeds 40gf. B: Shear force exceeds 30gf and is less than 40gf. C: Shear force is less than 30gf. In addition, 1gf is 0.00980665N.

From the above results, it can be seen that the resin composition of the present invention can obtain a cured film with excellent metal adhesion. The comparison composition of Comparative Example 1 does not contain a surfactant. It can be seen that the metal adhesion of this comparison composition is poor. In addition, the comparison composition of Comparative Example 2 only contains a surfactant that does not satisfy any one of the above conditions 1 and 2. It can be seen that the metal adhesion of this comparison composition is poor.

<Example 101> The resin composition used in Example 1 was applied to the copper thin layer surface of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 100°C for 4 minutes to form a resin composition layer with a film thickness of 20μm, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, heating was performed at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes and rinsing was performed with PGMEA for 30 seconds to obtain a layer pattern. Then, in a nitrogen atmosphere, the temperature was raised at a rate of 10°C/min to 230°C, and then maintained at 230°C for 120 minutes to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, the results of manufacturing semiconductor components using the interlayer insulating film for the redistribution layer confirmed normal operation.

without.

without.

Claims (18)

A resin composition comprising: a resin selected from polyimide, a polyimide precursor, a polybenzoic acid

Azoles and polybenzo

At least one resin in the group of azole promotors; and a surfactant that meets at least one of the following conditions 1 and 2, condition 1: molecular weight is 500 or less; condition 2: can be decomposed under heating at 250°C, the aforementioned surfactant is a non-ionic surfactant, and the content of the aforementioned surfactant is 0.1-10 mass % relative to the total solid content of the resin composition. A resin composition comprising: a resin selected from polyimide, a polyimide precursor, a polybenzoic acid

Azoles and polybenzo

At least one resin in the group of azole precursors; and a surfactant that satisfies at least one of the following conditions 1 and 2, condition 1: molecular weight is 500 or less; condition 2: can be decomposed under heating at 250°C, the aforementioned surfactant is a compound having a polymerizable group, and the aforementioned polymerizable group in the aforementioned surfactant is a free radical polymerizable group. The resin composition as described in claim 2, wherein the aforementioned surfactant is a non-ionic surfactant. A resin composition as described in any one of claim 1 to claim 3, wherein the surfactant is a compound having a fluorine atom. A resin composition as described in any one of claim 1 to claim 3, wherein the volatility of the aforementioned surfactant alone is 1 μm/minute or more at 25°C and 1 atmosphere. A resin composition as described in any one of claim 1 to claim 3, wherein the content of the aforementioned surfactant relative to the total mass of all surfactants contained in the resin composition is 50 mass % or more. The resin composition as described in any one of claim 1 to claim 3 further comprises a lactone solvent. A resin composition as described in any one of claim 1 to claim 3, wherein the resin comprises at least two types of resins. A resin composition as described in any one of claim 1 to claim 3, which is used to form a film for development using a developer containing an organic solvent. The resin composition as described in any one of claim 1 to claim 3 is used to form a film, which is composed of the resin composition of the present invention, and another film composed of other compositions and in contact with the aforementioned film is formed on the aforementioned film. A resin composition as described in any one of claims 1 to 3, which is used to form a film for use in a process involving heating. A resin composition as described in any one of claim 1 to claim 3, which is used to form an interlayer insulating film for a redistribution layer. A cured film, which is formed by curing the resin composition described in any one of claim 1 to claim 12. A laminate comprising two or more layers of the hardened films described in claim 13, and a metal layer between any of the hardened films. A method for manufacturing a hardened film, comprising a film forming process of applying the resin composition described in any one of claim 1 to claim 12 to a substrate to form a film. The method for manufacturing a hardened film as described in claim 15 includes an exposure process for exposing the aforementioned film and a development process for developing the aforementioned film. The method for manufacturing a hardened film as described in claim 15 or claim 16 includes a heating process of heating the aforementioned film at 50-450°C. A semiconductor device comprises the hardened film as claimed in claim 13 or the laminate as claimed in claim 14.