TW202409728A - Curable resin composition, resin cured film, printed circuit board, semiconductor package, and display device - Google Patents

Abstract

An object of the present invention is to provide a curable resin composition that suppresses pollutions caused by a polymerization initiator or decomposed products thereof and also ensures a bonding strength, a resin cured film, a printed circuit board, a semiconductor package, and a display device. The curable resin composition includes: (A) a specific unsaturated group-containing alkali-soluble resin having a fluorine skeleton, (B) a polymerizable compound having at least two unsaturated groups, (C) a specific photopolymerization initiator having a fluorine skeleton, and (D) a solvent. With respect to 100 parts by mass of the unsaturated group-containing alkali-soluble resin (A) and the polymerizable compound (B), the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less.

Description

Curable resin composition, cured resin film, printed circuit board, semiconductor package and display device

The present invention relates to a curable resin composition, a resin cured film, a printed circuit board, a semiconductor package and a display device.

When manufacturing printed circuit boards, semiconductor packages, display devices, etc., adhesives are used to bond various materials. For this kind of adhesive, in order to bond fine parts to each other, fine patterning is sometimes required. Therefore, a resin that can be developed by alkali, a polymerizable compound that imparts curability, and a polymerizable compound that imparts curability are sometimes used. A composition of a hardened polymerization initiator (Patent Document 1).

For example, Patent Document 1 describes an adhesive composition comprising an alkali-soluble polymer, a polymerizable compound, and a polymerization initiator. In Patent Document 1, Irgacure 907 is used as the polymerization initiator.

[Prior art documents] [Patent Document] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-176343

[Problem to be solved by the invention] Based on the research of the inventors and others, if one wants to use an adhesive as described in Patent Document 1 to bond various components, the bonded devices may be contaminated by the polymerization initiator or its decomposition products. On the other hand, if a polymerization initiator that is not easily contaminated by decomposition products is used, the bonding strength is not sufficient, and it is very difficult to balance the suppression of contamination by decomposition products and the assurance of bonding strength.

The present invention has been made in view of the above problems, and an object thereof is to provide a curable resin composition that can suppress contamination caused by a polymerization initiator or its decomposed products and ensure adhesive strength. A resin cured film obtained by curing, and a printed circuit board, a semiconductor package, and a display device using the curable resin composition as an adhesive. [Technical means to solve problems]

One embodiment of the present invention for solving the above problems relates to the curable resin compositions of the following [1] to [5]. [1] A curable resin composition containing: (A) an unsaturated group-containing alkali-soluble resin represented by the following general formula (1), (B) Polymeric compounds having at least two unsaturated groups, (C) A photopolymerization initiator represented by the following general formula (9), and (D) Solvent, The content of the (C) photopolymerization initiator is 1 part by mass or more and 15 parts by mass relative to a total of 100 parts by mass of the (A) unsaturated group-containing alkali-soluble resin and the (B) polymerizable compound. portion or less.

[Chemistry 1] ···General formula (1)

In formula (1), Ar ₁ is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms to which it is bonded may be substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group. R ₁ is independently an alkylene group having 2 to 4 carbon atoms, and l is independently a number of 0 to 3. G is independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3), and Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and one or more of them are substituents represented by the following general formula (4). n is a number whose average value is greater than or equal to 1 and less than or equal to 20.

[Chemicalization 2] ···General formula (2)

[Chemistry 3] ···General formula (3)

In formula (2) and formula (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or an alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number of 0 to 10. * represents a bonding site with the compound represented by general formula (1).

[Chemical 4] ···General formula (4)

In formula (4), W is a divalent or trivalent carboxylic acid residue, and m is 1 or 2. * represents a bonding site with the compound represented by general formula (1).

[Chemistry 5] ···General formula (9)

In the general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 10, Alkylcycloalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, cycloalkylalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, -N(R ₉ ) ₂ , -COR ₁₀ or -CO-CR ₆ R ₇ R ₈ represents the substituent. In addition, the methylene group (-CH ₂ -) of these substituents may be substituted by -O-, -N-, -S- or -C(=O)-. R ₅ independently represents a hydrogen atom, a halogen atom, a linear or optionally branched alkyl group with a carbon number of 1 to 20, a cycloalkylalkyl group with a carbon number of 3 to 20, or a cycloalkylalkyl group with a carbon number of 2 or more and Alkenyl group below 20. In addition, the methylene group (-CH ₂ -) of these functional groups may be substituted by -O-, -N-, -S- or -C(=O)-. In addition, two R ₅ may be bonded to each other to form a ring. R ₆ and R ₇ independently represent a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 20, or a cycloalkyl having a carbon number of 4 to 20. alkylalkyl group, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH ₂ -) of these functional groups may be substituted by -O-, -N-, -S- or -C(=O)-. R ₆ and R ₇ may bond with each other to form a ring. Alternatively, R ₆ may be a linear or optionally branched alkyl group having a carbon number of 1 to 20, or a linear or optionally branched alkenyl group having a carbon number of 2 to 20, And R ₇ is any one of the functional groups represented by the following general formula (10) to general formula (12).

[Chemical 6] ···General formula (10)

In the general formula (10), R ₁₃ represents a hydrogen atom, a linear or optionally branched alkyl group having a carbon number of 1 to 8, or a phenyl group, and R ₁₄ , R ₁₅ and R ₁₆ independently represent a hydrogen atom. , or a linear or optionally branched alkyl group having 1 to 4 carbon atoms. * indicates the bonding site with the compound represented by general formula (9).

[Chemistry 7] ···General formula (11)

In the general formula (11), s is a number of 0 or more and 4 or less. * represents a bonding site with the compound represented by the general formula (9).

[Chemistry 8] ···General formula (12)

In the general formula (12), Ar ₂ represents a phenyl group, a naphthyl group, a furyl group, a thienyl group or a pyridyl group which may be substituted. * represents a bonding site with the compound represented by the general formula (9).

R ₈ represents N-morpholinyl, N-piridyl, N-pyrrolyl or N-dialkyl. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted with a halogen atom or a hydroxyl group. R ₉ independently represents a linear or optionally branched alkyl group having a carbon number of 1 or more and 20 or less, a cycloalkyl group having a carbon number of 3 or more and 20 or less, a linear or optionally branched alkyl group having a carbon number of 2 or more and 20 or less. An alkenyl group having a branched chain, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH ₂ -) of these substituents may be substituted with -O-. In addition, two R _9s may be bonded to each other to form a ring. In this case, the ring may be a five-membered ring or a six-membered ring formed through -O-, -S-, or -NH-. R ₁₀ represents a linear or optionally branched alkyl group having a carbon number of 1 to 20, a cycloalkyl group having a carbon number of 3 to 20, an alkylcycloalkyl group having a carbon number of 4 to 10, a carbon A linear or optionally branched alkenyl group having a number of 2 or more and 20 or less, an aryl group having a carbon number of 6 or more and 20 or less, or an alkylaryl group having a carbon number of 7 or more and 20 or less. In addition, the methylene group (-CH ₂ -) of these functional groups may be substituted with -O- or -S-. One or more of the hydrogen atoms of these functional groups may be independently modified by a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a nitro group, a cyano group, -SR ₁₁ OR -OR ₁₂ replaced. R ₁₁ and R ₁₂ independently represent a hydrogen atom or a linear or optionally branched alkyl group having 1 to 20 carbon atoms.

[2] The curable resin composition according to [1], wherein the weight average molecular weight of the unsaturated group-containing alkali-soluble resin (A) is 1,000 to 40,000 and the acid value is 50 to 200 mgKOH/g. [3] The curable resin composition according to [1] or [2], comprising (E) a sensitizer. [4] The curable resin composition according to [3], wherein the (E) sensitizer comprises a benzophenone derivative or a thioxanthrone derivative. [5] The curable resin composition according to any one of [1] to [4], comprising (F) an epoxy compound having two or more epoxy groups.

One embodiment of the present invention for solving the above problems relates to the resin cured film of the following [6]. [6] A resin cured film obtained by curing the curable resin composition according to any one of [1] to [5].

One embodiment of the present invention for solving the above problems relates to the printed circuit board, semiconductor package, and display device of the following [7] to [9]. [7] A printed circuit board including the resin cured film according to [6] as an insulating film. [8] A semiconductor package including the resin cured film according to [6] as an insulating film. [9] A display device including the resin cured film according to [6] as an insulating film. [Effects of the invention]

According to the present invention, it is possible to provide a curable resin composition capable of both suppressing contamination caused by a polymerization initiator or its decomposed products and ensuring adhesive strength, and a resin cured film obtained by curing the curable resin composition. And printed circuit boards, semiconductor packages and display devices using the curable resin composition as an adhesive.

The following describes the embodiments of the present invention, but the present invention is not limited to the following embodiments. In addition, in the present invention, when the first decimal place is 0, the expression after the decimal point is sometimes omitted. In addition, as for the compounds, functional groups or structures exemplified below, only one of the exemplified ones may be used, or multiple ones may be used in combination unless otherwise specified.

1. Curable resin composition One embodiment of the present invention for solving the first problem relates to a curable resin composition, comprising: (A) an alkali-soluble resin containing an unsaturated group represented by general formula (1), (B) a polymerizable compound having at least two unsaturated groups, (C) a photopolymerization initiator represented by general formula (9), and (D) a solvent, wherein the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the total of the alkali-soluble resin containing an unsaturated group (A) and the polymerizable compound (B).

(A) 1-1. Unsaturated group-containing alkali-soluble resin represented by general formula (1) (A) The unsaturated group-containing alkali-soluble resin represented by the general formula (1) (hereinafter, also referred to as "(A) component") has a polymerizable unsaturated group in the molecule and is used to express alkali solubility. A compound that has an acidic group and hardens by polymerizing the polymerizable unsaturated group through stimulation by light or heat.

[Chemical 9] ···General formula (1)

In the general formula (1), Ar ₁ is independently an aromatic hydrocarbon group having a carbon number of 6 or more and 14 or less. A part of the hydrogen atoms constituting Ar ₁ may be an alkyl group having a carbon number of 1 or more and 10 or less, or an alkyl group having a carbon number of 6 or more and 14 or less. Substituted with an aryl group or arylalkyl group having 10 or less carbon atoms, a cycloalkyl group or cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number from 0 to 3. G is independently a (meth)acrylyl group or a substituent represented by the following general formula (2) or the following general formula (3). Y is a tetravalent carboxylic acid residue. Z is independently a hydrogen atom or a substituent represented by the following general formula (4), and at least one of Z is a substituent represented by the following general formula (4). n is a number whose average value is 1 or more and 20 or less.

In addition, "(meth)acrylyl" is the general term for acrylic and methacrylic groups, "(meth)acrylic acid" is the general term for acrylic acid and methacrylic acid, and (meth)acrylate is the general term for acrylic acid. The general terms of ester and methacrylate refer to one or both of these.

[Chemistry 10] ···General formula (2)

[Chemistry 11] ···General formula (3)

In general formula (2) and general formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is an alkylene group having 2 or more carbon atoms and 10 or less carbon atoms. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (1).

[Chemistry 12] ···General formula (4)

In the general formula (4), W is a divalent or trivalent carboxylic acid residue, and m is a number of 1 or 2. * indicates the bonding site with the compound represented by general formula (1).

The resin represented by the general formula (1) can be synthesized by the following method.

First, an epoxy compound (a-1) (hereinafter, also referred to as abbreviated as "Epoxy compound (a-1)") and (meth)acrylic acid, a (meth)acrylic acid derivative represented by the following general formula (6) and (methyl) represented by the following general formula (7) ) at least one reaction of an acrylic acid derivative to obtain a diol compound as (meth)acrylic acid epoxy ester. In addition, the bisaryl fluoride skeleton is preferably a bis-naphthol fluoride skeleton or a bisphenol fluoride skeleton.

[Chemistry 13] ···General formula (5)

In the general formula (5), Ar ₁ is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar ₁ may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number of 0 to 3.

[Chemical 14] ···General formula (6)

[Chemistry 15] ···General formula (7)

In the general formula (6) and the general formula (7), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having a carbon number of 2 or more and 10 or less, and R ₄ is an alkyl aryl group having a carbon number of 2 or more and 10 or less. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10.

The reaction of the epoxy compound (a-1) with (meth)acrylic acid or a derivative thereof can be carried out by a known method. For example, Japanese Patent Publication No. 4-355450 states that a diol compound containing a polymerizable unsaturated group can be obtained by using about 2 mol of (meth)acrylic acid per 1 mol of an epoxy compound having two epoxy groups. In the present embodiment, the compound obtained by the reaction is a diol (d) containing a polymerizable unsaturated group represented by the following general formula (8) (hereinafter also referred to as "diol (d)").

[Chemistry 16] ···General formula (8)

In the general formula (8), Ar ₁ is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms constituting Ar ₁ may be substituted by an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group or a halogen group having 1 to 5 carbon atoms. G is independently a (meth)acryloyl group, a substituent represented by the general formula (2) or the general formula (3), and R ₁ is independently an alkylene group having 2 to 4 carbon atoms. l is independently a number of 0 to 3.

[Chemistry 17] ···General formula (2)

[Chemical 18] ···General formula (3)

In general formula (2) and general formula (3), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group or alkyl aryl group having 2 or more carbon atoms and 10 or less carbon atoms, and R ₄ is an alkylene group having 2 or more carbon atoms and 10 or less carbon atoms. 20 or less saturated or unsaturated hydrocarbon groups, p is a number from 0 to 10. * indicates the bonding site with the compound represented by general formula (1).

Next, the obtained diol (d), dicarboxylic acid or tricarboxylic acid or its monoanhydride (b) and tetracarboxylic acid or its dianhydride (c) are reacted to obtain an unsaturated group-containing curable resin represented by the general formula (1) having a carboxyl group and a polymerizable unsaturated group in one molecule.

The acid component is a polyacid component that can react with the hydroxyl group in the diol (d) molecule. In order to obtain the resin represented by the general formula (1), it is necessary to use a dicarboxylic acid or a tricarboxylic acid or their acid monoanhydride (b) and a tetracarboxylic acid or its acid dianhydride (c). The carboxylic acid residue of the acid component can be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. In addition, these carboxylic acid residues can also contain bonds containing heterogeneous elements such as -O-, -S-, and carbonyl groups.

Examples of the dicarboxylic acid or tricarboxylic acid or their monoanhydrides (b) include chain hydrocarbon dicarboxylic acids or tricarboxylic acids, alicyclic hydrocarbon dicarboxylic acids or tricarboxylic acids, aromatic hydrocarbon dicarboxylic acids or tricarboxylic acids and their monoanhydrides.

Examples of the chain alkyl dicarboxylic acid or tricarboxylic acid include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid and diglycolic acid, as well as these dicarboxylic acids or tricarboxylic acids into which any substituents are introduced.

Examples of the alicyclic alkyl dicarboxylic acids or tricarboxylic acids include cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylendometriyltetrahydrophthalic acid, chlorendic acid, hexahydrotrimellitic acid and norbornanedicarboxylic acid, as well as these dicarboxylic acids or tricarboxylic acids into which any substituents are introduced.

Examples of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: phthalic acid, isophthalic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid and trimellitic acid etc., and these dicarboxylic acids or tricarboxylic acids introduced with optional substituents.

Among these, the dicarboxylic acid or tricarboxylic acid is preferably succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid, and more preferably amber acid, itaconic acid and tetrahydrophthalic acid.

The dicarboxylic acid or tricarboxylic acid is preferably its acid monoanhydride.

Examples of the tetracarboxylic acid or its acid dianhydride (c) include chain hydrocarbon tetracarboxylic acid, alicyclic hydrocarbon tetracarboxylic acid, aromatic hydrocarbon tetracarboxylic acid and their acid dianhydride, and the like.

Examples of the chain alkane tetracarboxylic acid include butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, and these chain alkane tetracarboxylic acids into which a substituent such as an alicyclic alkyl group and an unsaturated alkyl group is introduced.

Examples of the alicyclic hydrocarbon tetracarboxylic acid include: cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid and norbornane tetracarboxylic acid, and these alicyclic tetracarboxylic acids in which substituents such as chain hydrocarbon groups and unsaturated hydrocarbon groups are introduced.

Examples of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, diphenylsulfone tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, and naphthalene-2,3,6,7-tetracarboxylic acid.

Among these, the tetracarboxylic acid is preferably biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and diphenyl ether tetracarboxylic acid, and more preferably biphenyltetracarboxylic acid and diphenyl ether tetracarboxylic acid.

As the tetracarboxylic acid, its acid dianhydride is preferably used.

In addition, trimellitic anhydride aryl esters may be used instead of the tetracarboxylic acid or its acid dianhydride (c). The so-called trimellitic anhydride aryl esters are compounds produced by the method described in International Publication No. 2010/074065, for example, and are structurally aromatic diols (naphthalenediol, biphenol and terphenyldiol). It is an acid dianhydride in the form in which two hydroxyl groups of two molecules of trimellitic anhydride react with each other and form an ester bond with the carboxyl groups of two molecules of trimellitic anhydride.

The reaction method of diol (d) with acid component (b) and acid component (c) is not particularly limited, and a known method can be adopted. For example, Japanese Patent Laid-Open No. 9-325494 describes a method of reacting epoxy (meth)acrylate with tetracarboxylic dianhydride at a reaction temperature of 90° C. to 140° C.

At this time, in order to make the terminal of the compound a carboxyl group, it is preferred to react in a manner such that the molar ratio of (meth) acrylate epoxy ester (diol (d)), dicarboxylic acid or tricarboxylic acid or their acid monoanhydride (b) and tetracarboxylic dianhydride (c) becomes (d): (b): (c) = 1.0: 0.01 to 1.0: 0.2 to 1.0.

For example, when an acid monoanhydride (b) or an acid dianhydride (c) is used, it is preferred to react such that the molar ratio of the amount of the acid component [(b)/2+(c)] to the diol (d) [[(b)/2+(c)]/(d)] is greater than 0.5 and less than 1.0. If the molar ratio is less than 1.0, the terminal of the unsaturated group-containing curable resin represented by the general formula (1) will not become an acid anhydride, thereby suppressing the increase in the content of the unreacted acid dianhydride, thereby improving the temporal stability of each composition. In addition, if the molar ratio is greater than 0.5, the increase in the residual amount of the unreacted component in the diol (d) containing a polymerizable unsaturated group can be suppressed, thereby improving the temporal stability of each composition. In order to adjust the acid value and molecular weight of the unsaturated group-containing curable resin represented by the general formula (1), the molar ratio of the components (b), (c) and (d) can be arbitrarily changed within the above range.

The synthesis of the diol (d) and the subsequent reaction of the polycarboxylic acid or its anhydride are usually carried out in a solvent using a catalyst as necessary.

Examples of the solvent include solvent-based solvents such as ethyl solvent acetate and butyl solvent acetate, high-boiling-point ether-based or ester-based solvents such as diethylene glycol dimethyl ether, ethyl carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate, and ketone-based solvents such as cyclohexanone and diisobutyl ketone. In addition, there are no particular restrictions on the reaction conditions of the solvent, catalyst, etc. used, for example, it is preferred to use a solvent that does not have a hydroxyl group and has a boiling point higher than the reaction temperature as a reaction solvent.

The reaction of the epoxy group with the carboxyl group or the hydroxyl group is preferably carried out using a catalyst. As the catalyst, ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine are described in Japanese Patent Publication No. 9-325494.

The acid value of component (A) is preferably 50 mgKOH/g or more and 200 mgKOH/g or less, and more preferably 60 mgKOH/g or more and 150 mgKOH/g or less. If the acid value is 50 mgKOH/g or more, residue is less likely to remain during alkaline development, and if it is 200 mgKOH/g or less, the penetration of the alkaline developer does not become too fast, thereby suppressing peeling development. The acid value can be determined by titrating with a 1/10N-KOH aqueous solution using a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

The weight average molecular weight (Mw) of the component (A) in terms of polystyrene as measured by gel permeation chromatograph (GPC) (HLC-8220GPC, manufactured by Tosoh Corporation) is preferably 1,000 to 40,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 15,000. If the weight average molecular weight (Mw) is 1,000 or more, the adhesion between the support and the adherend can be improved. If the weight average molecular weight (Mw) is 40,000 or less, it is easy to adjust the solution viscosity of the composition suitable for coating, and coating on the surface of the support or the adherend does not require too much time, making it easier to improve the adhesion to the adherend. When emphasis is placed on adhesive strength, the weight average molecular weight (Mw) is preferably 1,000 or more and 5,000 or less.

(A) The component itself is not easily decomposed by heat, and is less likely to volatilize decomposed products compared to other resins. In addition, since component (A) has the same fluorine skeleton as component (C) described later, volatilization of component (C) or its decomposition products can be suppressed. In addition, the component (A) increases the glass transition temperature of the resin cured film obtained by curing the curable resin composition and suppresses a decrease in adhesiveness caused by heat.

The content of component (A) is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, relative to the total mass of the solid components. When the content of component (A) is 10% by mass or more, the volatility of component (C) or its decomposition product can be sufficiently suppressed, and a high-resolution pattern can be formed.

1-2. (B) Polymerizable compound having at least two unsaturated groups (B) A polymerizable compound having at least two unsaturated groups (hereinafter, also referred to as "(B) component") has two or more polymerizable unsaturated groups and causes a polymerization reaction by stimulation with light or heat. Compounds that do not have alkali-soluble groups.

The component (B) can improve the adhesion strength and solvent resistance of the cured film formed by curing the respective components to the adherend or substrate, and can also improve the sensitivity and developability during curing.

The component (B) only needs to have at least two polymerizable unsaturated groups that can react (polymerize) with the polymerizable unsaturated groups possessed by the component (A). The polymerizable unsaturated groups are preferably (meth)acryloyl groups. In addition, the component (B) may be a monomer, an oligomer, or a polymer.

Examples of the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tetramethylethylene glycol di(meth)acrylate, glycerol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol (Meth)acrylates such as glycerol tetra(meth)acrylate, glycerol tri(meth)acrylate, sorbitol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene epoxide-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and dendrimers having (meth)acrylic groups as compounds having ethylene double bonds. Only one of these polymerizable compounds may be used alone, or two or more may be used in combination. Component (B) may be used as long as it can crosslink the molecules of component (A). From the viewpoint of further fully exerting the above function, it is preferred to use a component having three or more unsaturated bonds. The acrylic acid group equivalent obtained by dividing the molecular weight of the polymerizable compound by the number of (meth)acrylic acid groups in one molecule is preferably 50 to 300, more preferably 80 to 200. Component (B) does not have a free carboxyl group.

In addition, the component (B) is preferably a modified alkylene oxide. The component (B) being a modified alkylene oxide can impart appropriate flexibility to the cured resin film, thereby further improving the adhesion to the adherend or the adhesion to the substrate when forming a pattern.

The mixing ratio of component (A) to component (B) is preferably 30/70 to 90/10, more preferably 40/60 to 80/20, in terms of the mass ratio (A)/(B). If the mixing ratio of component (A) to component (B) is 30/70 or more, it is less likely that component (C) or its decomposition product will volatilize when producing a resin cured film having the desired hardness, and the cured product will not become brittle after curing. In addition, the acid value of the coating film in the uncured part will not become low, so that the solubility in the alkaline developer can be suppressed. Therefore, it is less likely that the edge of the pattern will be burred or become unclear. In addition, if the mixing ratio of component (A) to component (B) is 90/10 or less, the proportion of the polymerizable functional group in the resin is sufficient, so that the desired cross-linked structure can be formed. In addition, since the acid value of the resin component is not too high, the solubility of the hardened portion in the alkaline developer is not likely to increase, thereby preventing the formed pattern from becoming thinner than the target line width or the pattern from being lost.

1-3. (C) Photopolymerization initiator represented by general formula (9) (C) The photopolymerization initiator represented by the general formula (9) (hereinafter also referred to as "component (C)") initiates polymerization of the component (A) and the component (B) when irradiated with light, thereby causing the The solubility of the hardened part is reduced and a desired fine pattern is formed.

[Chemical 19] ···General formula (9)

In the general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or optionally branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, Alkylcycloalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, cycloalkylalkyl group with 4 or more carbon atoms and 10 or less carbon atoms, -N(R ₉ ) ₂ , -COR ₁₀ or -CO-CR ₆ R ₇ R ₈ represents the substituent. In addition, the methylene group (-CH ₂ -) of these substituents may be substituted by -O-, -N-, -S- or -C(=O)-.

R ₅ independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkylalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. In addition, the methyl group (-CH ₂ -) possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-. In addition, two R ₅ groups may be bonded to each other to form a ring. Among these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferred.

_R6 and _R7 independently represent a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group ( _-CH2- ) possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-. _R6 and _R7 may be bonded to each other to form a ring.

Alternatively, R ₆ may be a linear or optionally branched alkyl group having a carbon number of 1 to 20, or a linear or optionally branched alkenyl group having a carbon number of 2 to 20, And R ₇ is any one of the functional groups represented by the following formula (10) to formula (12).

[Chemistry 20] ···General formula (10)

In the general formula (10), _R13 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group, and _R14 , _R15 , and _R16 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. * represents a bonding site to the compound represented by the general formula (9).

[Chemistry 21] ···General formula (11)

In general formula (11), s is a number from 0 to 4. * indicates the bonding site with the compound represented by general formula (9).

[Chemistry 22] ···General formula (12)

In the general formula (12), Ar ₂ represents phenyl, naphthyl, furyl, thienyl or pyridyl, which may be substituted. * indicates the bonding site with the compound represented by general formula (9).

R ₈ represents N-morpholinyl, N-piridyl, N-pyrrolyl or N-dialkyl. Among these, N-morpholinyl is preferred. In addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted with a halogen atom or a hydroxyl group.

R ₉ independently represents a linear or optionally branched alkyl group having a carbon number of 1 or more and 20 or less, a cycloalkyl group having a carbon number of 3 or more and 20 or less, a linear or optionally branched alkyl group having a carbon number of 2 or more and 20 or less. An alkenyl group having a branched chain, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, one or more of the hydrogen atoms of these functional groups may be independently substituted with a linear or branched alkyl group having a carbon number of 1 to 20, a halogen atom, a hydroxyl group, or a nitro group. In addition, the methylene group (-CH ₂ -) of these substituents may be substituted with -O-. In addition, two R _9s may be bonded to each other to form a ring. In this case, the ring may be a five-membered ring or a six-membered ring formed through -O-, -S-, or -NH-.

R ₁₀ represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. In addition, the methylene group (-CH ₂ -) possessed by these functional groups may be substituted by -O- or -S-. One or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, -SR ₁₁ , or -OR ₁₂ .

R ₁₁ and R ₁₂ independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms.

Specific examples of the component (C) include compounds described in Japanese Patent Application Publication No. 2020-507664.

Component (C) has a fluorene structure, so it itself is not easy to volatilize, and its decomposition products are also not easy to volatilize. In this embodiment, a resin having a fluorene structure is used as component (A), so the volatility of the decomposition products can be difficult to occur due to the affinity between component (A) and the decomposition products of component (C). Therefore, when component (C) is used in an adhesive in this embodiment, it is not easy to cause contamination of the adherend, etc. In addition, based on the research of the inventors and others, there is a photopolymerization initiator that is also not easy to volatilize in the initiator of oxime ester system, but the curability of this initiator is too high, so it will cause the curable resin composition to over-cure, and when used in an adhesive, the adhesion cannot be fully improved. In contrast, component (C) has moderate curability, so it can also fully improve the adhesion when used in an adhesive.

The content of component (C) is 1 to 15 parts by mass, preferably 2 to 10 parts by mass, based on 100 parts by mass of the total of components (A) and (B). If the content of component (C) is equal to or higher than the lower limit, a moderate photopolymerization speed is obtained, and therefore sufficient sensitivity can be ensured. In addition, when the content of component (C) is equal to or less than the upper limit, line widths faithful to the mask can be reproduced and pattern edges can be made clear.

1-4. (D) Solvent The (D) solvent (hereinafter, also referred to as "(D) component") dissolves or disperses each component contained in the curable resin composition and improves the coatability of each composition.

Examples of component (D) include: methanol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, propylene glycol, 3-methoxy-1-butanol, ethylene glycol monobutyl ether, 3-hydroxy- Alcohols such as 2-butanone and diacetone alcohol; terpenes such as α-terpineol or β-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone Class; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl Carbitol, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-3-butyl acetate, 3-methoxy-3- Methyl-1-butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, Esters such as butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, etc.

The content of the component (D) varies depending on the target viscosity, and is preferably 30% by mass or more and 90% by mass or less relative to the total mass of the curable resin composition. If the content of the component (D) is 30% by mass or more, a viscosity that allows the curable resin composition to be easily applied to a substrate can be formed, and if it is 90% by mass or less, the time required for drying the curable resin composition after it is applied to the substrate can be shortened.

1-5. (E) Sensitizer The curable resin composition may contain (E) sensitizer (hereinafter, also referred to as "(E) component").

The component (E) can cause the component (C) to cleave more efficiently and to efficiently carry out the polymerization reaction, thereby further improving the adhesion of the cured resin film to the substrate.

Examples of the component (E) include benzophenones such as triethanolamine, triisopropanolamine, benzophenone, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, and 4,4'-diethylaminobenzophenone; acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, and p-dimethylamine. Acetophenones such as acetophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, and dimethyl benzoate; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4- 2-Ethylhexyl dimethylaminobenzoate, 2,4-diisopropylthioxanthrone, 4-benzoyl-4'-methyl-diphenyl sulfide; benzophenone series such as acryloyl benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; thioxanthrone, 2-chlorothioxanthrone, 2-methylthioxanthrone, 2 - isopropylthioanthrone, 4-isopropylthioanthrone, 2,4-dimethylthioanthrone, 2,4-diethylthioanthrone, 2,4-dichlorothioanthrone, 1-chloro-4-propoxythioanthrone and other thioanthrone series; 4,4'-bisdiethylaminobenzophenone and other aminobenzophenone series; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like. In addition, these sensitizers may be used alone or in combination of two or more.

The component (E) preferably contains a benzophenone derivative or a thioxanthrone derivative. These sensitizers can make the component (C) cleave more efficiently, thereby significantly improving the adhesion of the cured resin film to the substrate.

When the total mass of component (C) is 100 parts by mass, the content of component (E) is preferably from 0.5 parts by mass to 400 parts by mass, more preferably from 1 part by mass to 300 parts by mass. If the content of the sensitizer is 0.5 parts by mass or more, the sensitivity of the photopolymerization initiator can be increased and the photopolymerization speed can be accelerated. In addition, if the content of the sensitizer is 400 parts by mass or less, an excessive increase in sensitivity can be suppressed, and when the composition is cured by irradiation with light, burning, peeling residue, etc. are less likely to occur.

1-6. (F) Epoxy compound having two or more epoxy groups The curable resin composition may also contain (F) an epoxy compound having two or more epoxy groups (hereinafter, also referred to as "(F) component").

The component (F) can impart appropriate flexibility to the resin cured film, further improving the adhesion to the adherend or the adhesion to the substrate when forming a pattern. In addition, the component (F) can also reduce the volatility of the component (C) or its decomposition products from the cured film.

Examples of the component (F) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, bisnaphthol fluorene type epoxy compounds, diphenyl fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, phenol aralkyl type epoxy compounds, phenol novolac compounds containing a naphthalene skeleton (for example, NC-7000L: manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compounds (for example, jER YX4000: manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the company), naphthol aralkyl type epoxy compounds, triphenol methane type epoxy compounds (for example, EPPN-501H: manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds, glycidyl ethers of polyols, glycidyl esters of polycarboxylic acids, copolymers of monomers having (meth) acrylic acid groups represented by copolymers of methacrylic acid and glycidyl methacrylate containing (meth) acrylic acid glycidyl ester as units, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celloxide 2021P: manufactured by Daicel Co., Ltd., "Celloxide" is a registered trademark of the company), butane oxadiazine tetracarboxylic acid tetra(3,4-epoxyepoxyhexylmethyl) modified ε-caprolactone (e.g., EPOLEAD GT401: manufactured by Daicel Co., Ltd., "EPOLEAD" is a registered trademark of the company), epoxy compounds having an epoxyepoxy group (e.g., HiREM-1: manufactured by Shikoku Chemical Industries, Ltd.), polyfunctional epoxy compounds having a dicyclopentadiene skeleton (e.g., HP7200 series: manufactured by DIC Corporation), 1,2-epoxy-4-(2-oxohexacyclopropyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150: manufactured by Daicel Co., Ltd.), epoxidized polybutadiene (e.g., NISSO-PB JP-100: manufactured by Nippon Soda Co., Ltd., "NISSO-PB" is a registered trademark of the company), epoxy compounds having a silicone skeleton, etc. In addition, only one of these compounds may be used, or two or more thereof may be used in combination.

Among these, preferred are bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol-type epoxy compounds, bis-naphthol-type epoxy compounds, phenol novolac-type epoxy compounds, and cresol novolac-type epoxy compounds. Varnish type epoxy compound, biphenyl type epoxy compound, more preferably biphenyl type epoxy compound. By using a biphenyl-type epoxy compound, it is possible to achieve both the mechanical strength and chemical resistance of a cured product that meets required characteristics and the patternability of the curable resin composition during curing, and the design of the curable resin composition can be increased. degree of freedom.

The epoxy equivalent of the component (F) is preferably from 100 g/eq to 300 g/eq, more preferably from 100 g/eq to 250 g/eq. In addition, the number average molecular weight (Mn) of component (F) is preferably from 100 to 5,000. If the epoxy equivalent is 100 g/eq or more and the number average molecular weight (Mn) of the epoxy compound is 100 or more, a cured film with good solvent resistance can be formed. If the epoxy equivalent is 300 g/eq. eq or less and the number average molecular weight (Mn) is 5000 or less, sufficient alkali resistance can be maintained even when an alkaline chemical solution is used in the subsequent step.

In addition, the epoxy equivalent of component (F) can be determined by titrating with a 1/10N-perchloric acid solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). In addition, the number average molecular weight (Mn) of the component (F) can be determined using, for example, the above-mentioned gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd.).

When using component (F), a hardener and a hardening accelerator may be used together.

Examples of the curing agent include amine compounds, polycarboxylic acid compounds, phenol resins, amino resins, dicyandiamide, and Lewis acid complex compounds.

Examples of the curing accelerator include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, borates, Lewis acids, organic metal compounds, and imidazoles that help accelerate the curing of epoxy resins. Examples of the thermal polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, and hindered phenol compounds. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silicon dioxide, mica, and aluminum oxide. Examples of the defoamer and leveling agent include silicone, fluorine, and acrylic compounds. Examples of the surfactant include fluorine surfactants and silicone surfactants. Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-ureidopropyltriethoxysilane.

The content of the component (F) is preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 25% by mass or less, relative to the total mass of the solid components. When the content of the component (F) is 1% by mass or more, the chemical resistance and moisture resistance of the cured resin film can be further improved. When the content of the component (F) is 30% by mass or less, the adhesion of the cured resin film to the substrate can be further improved.

1-7.Other ingredients The curable resin composition may contain an unsaturated group-containing alkali-soluble resin other than the compound represented by the general formula (1), a photopolymerization initiator and a thermal polymerization initiator other than the compound represented by the general formula (9), Polymerization inhibitors, antioxidants, chain transfer agents, plasticizers, fillers, leveling agents, pigments and dyes, defoaming agents, surfactants and coupling agents, etc.

Examples of the polymerization inhibitor and antioxidant include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine, hindered phenol compounds, and the like.

Examples of chain transfer agents include: 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, β-mercaptopropionic acid, 2-ethylhexyl-3-mercaptopropionate, n-Octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, stearyl-3-mercaptopropionate, trimethylolpropane tris(3-mercaptopropionate), Tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol Thiol compounds such as bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), 3,3'-thiodipropionic acid, dithiodipropionic acid, laurylthiopropionic acid, etc. wait.

Examples of plasticizers include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of fillers include: glass fiber, silica, mica, alumina, etc.

Examples of defoaming agents and leveling agents include silicone-based, fluorine-based, and acrylic-based compounds.

Examples of surfactants include fluorine-based surfactants, silicone-based surfactants, and the like.

Examples of the coupling agent include 3-(glycidyloxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, and the like.

1-8. Preparation of hardening resin composition The hardening resin composition can be obtained by mixing the above-mentioned components.

2. Applications The curable resin composition can be used for various applications including insulating materials, adhesives, and protective films that form a resin cured film by irradiation with radiation. In addition, since the curable resin composition contains an alkali-soluble resin, it can be developed after exposure or heating, and can therefore be suitably used for the purpose of forming a fine line pattern.

As an adhesive, it has high bonding strength especially after pattern formation, so it can be used to bond various components suitable for making microelectromechanical system (MEMS) packages or semiconductor packages such as LEDs.

As an insulating material, it has particularly high adhesion, moisture resistance, and acid resistance, so it can be suitably used to produce insulating films for printed wiring boards and semiconductor packages, such as solder resist layers and plating resists. layer, etching resist layer, buffer layer, rewiring layer, interlayer insulating layer, etc. In this application, the semiconductor package refers to a flip-chip package, a wafer-level package, etc., as well as a package formed by laminating a flip-chip package on an interposer. A package including a semiconductor chip that can be mounted on a printed circuit board. In addition, it can also be used to make top coats for paints or inks, hard coats for plastics, and anti-rust films for metals.

For example, when forming multi-layer printed wiring, a conductor wiring (first conductor wiring) is formed in advance by a method such as a dipping method, a spray method, a spin coating method, a roller coating method, a curtain coating method, or a screen printing method. A curable resin composition is applied to the surface of the substrate to form a wet coating film. Thereafter, component (D) (solvent) is volatilized at a temperature of about 60°C to 120°C to dry the wet coating film. Alternatively, the curable resin composition may be applied to the surface of a support such as polyester and dried to form a dry film, and the dried coating film may be transferred from the dry film to the substrate.

Thereafter, the coating is exposed through a negative mask to partially photoharden it. Exposure can be performed by irradiation with known radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray. Among these radiations, ultraviolet light is preferred. The wavelength of the irradiated radiation is preferably greater than 250 nm and less than 400 nm. The exposure amount of the radiation is preferably greater than 25 mJ/ ^cm2 and less than 3000 mJ/ ^cm2 . In addition, when using a dry film, the coating can also be exposed using the dry film before transfer.

Next, the coating is developed with alkaline to remove the unexposed portion. Examples of developing methods include shower developing, mist developing, dip developing, and puddle developing. In addition, examples of the developer used in the development include aqueous solutions of alkalis (alkaline compounds) such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene, etc. The developing conditions vary depending on the curable resin composition, but are preferably performed at a temperature of 20°C to 30°C for 10 seconds to 120 seconds. The development can be performed using a commercially available developer or ultrasonic cleaning machine or the like.

The exposure and development are performed in such a manner that the coating film is removed at the position where the through hole is to be formed in the multi-layer printed wiring.

Thereafter, the exposed part after development is heat-treated to cure the curable resin composition (post-baking). Post-baking can be performed by a known method (heating with an oven, hot air blower, heating plate, infrared heater, etc., vacuum drying, or a combination thereof). Regarding the heating conditions, there are no particular restrictions as long as the temperature for the resin cured film to be cured (post-baked) is achieved, but it is preferably performed at a temperature of 180°C to 250°C for 20 minutes to 120 minutes.

Thereafter, a conductor wiring (second conductor wiring) formed on the surface of the resin cured film and a via plating that covers the surface without through-holes and connects the first conductor wiring and the second conductor wiring can be produced by a known method such as an additive method, thereby obtaining a printed wiring board having a multi-layer printed wiring.

The above-described manufacturing method is merely an example of the use of the curable resin composition, and a single-layer printed wiring board instead of a multi-layer structure may be used.

In addition, when used for adhesive purposes, the entire coating can be exposed without a negative mask. In this case, alkaline development is not required. In addition, when it is used as an adhesive for semiconductor devices or different materials without patterning, the coating can be thermally cured by heating instead of photocuring by exposure.

In addition, the printed wiring substrate or semiconductor package can also be combined with other functional parts to form a semiconductor device or display device. [Example]

Hereinafter, the implementation mode of the present invention will be specifically described based on embodiments and comparative examples, but the present invention is not limited to these.

First, the synthesis examples of the unsaturated group-containing alkali-soluble resin as the component (A) will be described. However, unless otherwise specified, the evaluation of the resins in these synthesis examples was performed as follows.

In addition, when the same model is used for various measuring equipment, the equipment manufacturer name is omitted from the second place. In addition, in the embodiment, all glass substrates used in the production of the substrate with a cured film for measurement are subjected to the same treatment before use. In addition, when the first decimal place of the content of each component is 0, the expression after the decimal point may be omitted.

[Solid content concentration] The solid content concentration was calculated by using the following formula: 1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)] and the weight [W ₁ (g)] after heating at 160°C for 2 hours [W ₂ (g)]. Solid content concentration (weight %) = 100 × (W ₂ - _{W 0} ) / (W ₁ - W ₀ )

[Acid value] Dissolve the resin solution in dioxane and use a potentiometric titrator "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to titrate with a 1/10N-KOH aqueous solution to determine the acid value.

[Molecular weight] Measured using a gel permeation chromatograph (GPC) "HLC-8220GPC" (manufactured by Tosoh Co., Ltd., solvent: tetrahydrofuran, columns: TSKgelSuper H-2000 (2 columns) + TSKgelSuper H-3000 (1 column) + TSKgelSuper H-4000 (1 column) + TSKgelSuper H-5000 (1 column) (manufactured by Tosoh Co., Ltd.), temperature: 40°C, speed: 0.6 ml/min) and the weight average molecular weight (Mw) was calculated as a conversion value of standard polystyrene (manufactured by Tosoh Co., Ltd., PS-oligomer set).

The abbreviations described in the synthesis examples are as follows. BPFE: bisphenol-type epoxy resin (epoxy resin in which Ar ₁ is a benzene ring and l is 0 in the general formula (1), epoxy equivalent 256 g/eq) AA: acrylic acid (AA) TPP: tri Triphenyl phosphine (TPP) PGMEA: propylene glycol monomethyl ether acetate (PGMEA) BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (3,3 ',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) THPA: 1,2,3,6-tetrahydrophthalic anhydride (THPA) DCPMA: dimethacrylic acid Cyclopentyl ester (dicyclopentanyl methacrylate, DCPMA) GMA: glycidyl methacrylate (GMA) St: styrene (St) AIBN: azobisisobutyronitrile (AIBN) TDMAMP: tri -tris-dimethyl amino methyl phenol (TDMAMP) HQ: hydroquinone (HQ) SA: succinic anhydride (SA) TEA: triethyl amine (TEA) )

[Synthesis example 1] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product to adjust the solid content to 50 mass%.

Next, BPDA (14.37 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain an unsaturated group-containing alkali-soluble resin (A)-1. The obtained resin solution had a solid content concentration of 57.0 mass %, an acid value (solid content conversion) of 96 mgKOH/g, and a Mw of 3600 based on GPC analysis.

[Synthesis Example 2] BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler, and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product and adjusted to a solid content of 50% by mass.

Then, BPDA (10.06 g, 0.03 mol) and THPA (11.89 g, 0.08 mol) were added to the obtained reaction product, and stirred at 115°C to 120°C for 6 hours to obtain an unsaturated group-containing curable resin ( A)-2. The solid content concentration of the obtained resin solution was 57.0 mass%, the acid value (solid content conversion) was 98 mgKOH/g, and the Mw based on GPC analysis was 2300.

[Synthesis example 3] Put BPFE (50.00 g, 0.10 mol), AA (14.07 g, 0.20 mol), TPP (0.26 g) and PGMEA (40.00 g) into a 250 mL four-necked flask with a reflux cooler, and heat it at 100°C to 105 The mixture was stirred for 12 hours at ℃ to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product to adjust the solid content to 50 mass%.

Next, BPDA (19.25 g, 0.07 mol) and THPA (0.30 g, 0.002 mol) were added to the obtained reaction product, and the mixture was stirred at 115°C to 120°C for 6 hours to obtain a hardening resin (A)-3 containing an unsaturated group. The obtained resin solution had a solid content concentration of 56.3% by mass, an acid value (solid content conversion) of 97 mgKOH/g, and a Mw of 4700 based on GPC analysis.

[Synthesis Example 4] BPFE (50.00 g, 0.09 mol), AA (12.82 g, 0.20 mol), TPP (0.23 g) and PGMEA (40.00 g) were placed in a 250 mL four-necked flask equipped with a reflux cooler, and stirred at 100°C to 105°C for 12 hours to obtain a reaction product. Thereafter, PGMEA (25.00 g) was added to the reaction product and adjusted to a solid content of 50% by mass.

Then, 1,2,3,4-butanetetracarboxylic dianhydride (9.67 g, 0.05 mol) and THPA (7.43 g, 0.05 mol) were added to the obtained reaction product, and the mixture was heated at 115°C to 120°C. Stir for 6 hours to obtain unsaturated group-containing alkali-soluble resin (A)-4. The solid content concentration of the obtained resin solution was 56.0 mass%, the acid value (solid content conversion) was 106 mgKOH/g, and the Mw based on GPC analysis was 3300.

[Synthesis Example 5] PGMEA (300 g) was placed in a 1 L four-necked flask equipped with a reflux cooler, and the flask system was replaced with nitrogen, and the temperature was raised to 120°C. A mixture of AIBN (10 g) dissolved in a monomer mixture (DCPMA (77.1 g, 0.35 mol), GMA (49.8 g, 0.35 mol), St (31.2 g, 0.30 mol)) was added dropwise from a dropping funnel to the flask over 2 hours, and then stirred at 120°C for 2 hours to obtain a copolymer solution.

Then, after replacing the flask system with air, AA (24.0 g, 95% of glycidyl groups), TDMAMP (0.8 g), and HQ (0.15 g) were added to the obtained copolymer solution, and the mixture was stirred at 120°C. After 6 hours, a copolymer solution containing polymerizable unsaturated groups was obtained. Add SA (30.0 g, 90% of the molar number of AA added) and TEA (0.5 g) to the obtained copolymer solution containing polymerizable unsaturated groups, and react at 120°C for 4 hours to obtain polymerizable unsaturated group-containing copolymer solution. Saturated alkali-soluble copolymer resin solution (A)'-5. The solid content concentration of the resin solution is 46.0 mass%, the acid value (solid content conversion) is 76 mgKOH/g, and the Mw based on GPC analysis is 5300.

The curable resin compositions of Examples 1 to 10 and Comparative Examples 1 to 8 were prepared with the blending amounts (unit: mass %) listed in Tables 1 and 2. The blending components used in Table 1 are as follows.

(Alkaline-soluble resin containing unsaturated groups) (A)-1: Resin solution obtained in Synthesis Example 1 (solid content concentration 57.0 mass%) (A)-2: Resin solution obtained in Synthesis Example 2 (solid content concentration 57.0 mass%) (A)-3: Resin solution obtained in Synthesis Example 3 (solid content concentration 56.3 mass%) (A)-4: Resin solution obtained in Synthesis Example 4 (solid content concentration 56.0 mass%) (A)'-5: Resin solution obtained in Synthesis Example 5 (solid content concentration 46.0 mass%)

(Polymerizable compound) (B)-1: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) (B)-2: An ethylene oxide 6-mole adduct of trihydroxymethylpropane triacrylate (Aronix M-360, manufactured by Toagosei Co., Ltd.)

(Photopolymerization initiator) (C)-1: 1-(9,9-dibutyl-9H-fluoren-2-yl)-2-methyl-2-morpholin-4-yl-propane-1-one (manufactured by Tronly Corporation, "TR-NPI-20400" (a compound in which both _R5s in the general formula (9) are linear alkyl groups having 4 carbon atoms, _R6 and _R7 are both methyl groups, and _R8 is N-morpholinyl)) (C)'-2: 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (manufactured by IGM Resins BV, "Omnirad 907"("Omnirad" is a registered trademark of the aforementioned company)) (C)'-3: 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime) (manufactured by BASF, "Irgacure OXE-01" and "Irgacure" are registered trademarks of the aforementioned company) (C)'-4: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-oxazol-3-yl]-, 1-(O-acetyl oxime) (manufactured by BASF, Irgacure OXE-02) (C)'-5: 1-(biphenyl-4-yl)-2-methyl-2-oxolin-4-yl-propane-1-one (manufactured by YOUWEI, APi-307)

(solvent) (D): Propylene glycol monomethyl ether acetate (PGMEA)

(Sensitizer) (E)-1: Michler's ketone (E)-2: 2,4-diethylthioxanthrone (E)-3: 9,10-dibutoxyanthracene

(Epoxy compounds) (F)-1: Biphenyl type epoxy resin (jER YX4000, manufactured by Mitsubishi Chemical Co., Ltd., "jER" is a registered trademark of the company, epoxy equivalent 180 g/eq to 192 g/eq) (F)-2: Bisphenol A type epoxy resin (jER 828, manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent 120 g/eq to 150 g/eq)

[Table 1] Example Example Example Example Example Example Example Example Example Example 1 2 3 4 5 6 7 8 9 10 (A)-1 63.9 63.8 63.8 63.8 63.8 54.2 54.2 (A)-2 64.7 (A)-3 63.9 (A)-4 65.0 (A)'-5 (B)-1 12.1 12.1 12.1 12.1 12.1 12.1 12.1 10.3 10.3 (B)-2 12.1 (C)-1 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (C)'-2 (C)'-3 (C)'-4 (C)'-5 (D) 22.5 21.7 22.5 21.4 22.5 22.5 22.5 22.5 26.6 26.6 (E)-1 0.1 0.1 0.1 0.1 (E)-2 0.1 (E)-3 0.1 (F)-1 7.3 (F)-2 7.3

[Table 2] Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 (A)-1 63.9 63.9 63.9 63.9 54.2 54.2 54.2 (A)-2 (A)-3 (A)-4 (A)'-5 79.1 (B)-1 12.1 12.1 12.1 12.1 10.3 10.3 12.1 10.3 (B)-2 (C)-1 1.5 (C)'-2 1.5 1.5 (C)'-3 1.5 1.5 (C)'-4 1.5 (C)'-5 1.5 1.5 (D) 22.5 22.5 22.5 22.5 26.6 26.6 7.3 26.7 (E)-1 0.1 0.1 (E)-2 (E)-3 (F)-1 7.3 7.3 7.3 (F)-2

[Evaluation] The following evaluation was performed using a cured film formed by curing the curable resin composition.

[Evaluation of gas generation] (Preparation of resin film powder for evaluation of gas generation) The curable resin composition shown in Table 1 and Table 2 was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing was 20.0 μm, and pre-baked at 110°C for 5 minutes using a hot plate to prepare a dry film. Then, the dry film was irradiated with ultraviolet rays of 1000 mJ/ ^cm2 using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ ^cm2 to perform a photocuring reaction of the dry film.

Then, the exposed film was developed using 2.38% tetramethylammonium hydroxide (TMAH) developer at 23°C and a spray pressure of 1 kgf/cm ² for 60 seconds, and then The substrates with resin films of Examples 1 to 10 and Comparative Examples 1 to 8 were obtained by spray water washing at 5 kgf/cm ² . Thereafter, the obtained resin film was scraped off to obtain resin film powder for gas generation property evaluation.

(evaluation method) The powder of the obtained resin film was analyzed in the air using a thermogravimetry/differential thermal analysis (TG/DTA) device "TG/DTA6200" (manufactured by Seiko Instruments Co., Ltd.). The temperature was increased from 30°C to 120°C at a heating rate of 10°C/min, and after standing at 120°C for 5 minutes, the temperature was increased from 120°C to 230°C at a heating rate of 10°C/min. Then, after leaving it still at 230°C for 30 minutes, the temperature was raised from 230°C to 260°C at a temperature rising rate of 10°C/min, and finally, it was left still at 260°C for 3 minutes. The weight reduction rate of the resin film was measured along the temperature curve. In addition, △ or more was considered a pass.

(Evaluation criteria) ◎: Weight reduction rate is over 96% ○: Weight reduction rate is 94% or more and less than 96% △: Weight reduction rate is more than 92% and less than 94% ×: Weight reduction rate is less than 92%

[Evaluation of shear strength (adhesion strength)] (Preparation of a substrate with a resin cured film for evaluation of shear strength (adhesion strength)) Use a spin coater to apply the curable resins shown in Tables 1 and 2 The composition was applied on the glass substrate "#1737" so that the film thickness after heat-hardening treatment became 10.0 μm, and prebaked at 110°C for 5 minutes using a hot plate to produce a dry film. Then, the dry film was irradiated with ultraviolet light of 500 mJ/cm ² using an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm ² to perform a photohardening reaction on the photosensitive part of the dry film.

Next, the exposed film was developed for 60 seconds using a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C with a spray pressure of 1 kgf/ ^cm2 , and then washed with a spray of 5 kgf/ ^cm2 to remove the unexposed portion of the exposed film and form a 2 mm×2 mm pattern on the glass substrate. Next, a glass substrate "#1737" cut into 2 mm×2 mm was placed on the pattern, and temporarily bonded by heating on a heating plate at 110°C for 1 minute. After that, a hot air dryer was used to formally cure (post-bake) at 230°C for 30 minutes to obtain a substrate with a resin cured film for shear strength (adhesive strength) evaluation.

(evaluation method) The shear was measured using a chip shear tester (manufactured by Ark Tech) on a 2 mm × 2 mm glass substrate "#1737" bonded to the obtained resin cured film-attached substrate. Strength (bonding strength). In addition, △ or more was considered a pass.

(Evaluation criteria) ◎: Shear strength (adhesive strength) is 20 MPa or more ○: Shear strength (adhesive strength) is 18 MPa or more and less than 20 MPa △: Shear strength (adhesive strength) is 16 MPa or more and less than 18 MPa ×: Shear strength (adhesive strength) is less than 16 MPa

[Development Adhesion Evaluation] (Preparation of a substrate with a resin cured film for development adhesion evaluation) The curable resin composition shown in Table 1 and Table 2 was applied to a glass substrate "#1737" using a spin coater so that the film thickness after heat curing treatment was 10.0 μm, and a dry film was prepared by pre-baking at 110°C for 5 minutes using a hot plate. Then, the dry film was irradiated with ultraviolet rays of 500 mJ/ ^cm2 using an ultra-high pressure mercury lamp with an i-ray irradiance of 30 mW/ ^cm2 to perform a photocuring reaction of the dry film.

Then, the exposed film was developed using a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C and a spray pressure of 1 kgf/ ^cm for 60 seconds, and then 5 kgf/cm2 was developed. cm ² spray water washing to remove the unexposed parts and form a 10 μm dot pattern. Finally, the substrate was formally cured (post-baked) at 230° C. for 30 minutes using a hot air dryer to obtain a substrate with a resin cured film for development adhesion evaluation.

(evaluation method) The 10 μm dot pattern of the resin cured film of the obtained resin cured film-attached substrate was observed using an optical microscope, and the presence or absence of peeling in the pattern was determined. In addition, △ or more was considered a pass.

(Evaluation criteria) ◎: No pattern peeling was observed ○: A very small part of the pattern peeled off △: Half of the pattern peeled off ×: Most of the pattern peeled off

[Evaluation of Glass Transition Temperature] (Preparation of Resin Cured Film for Evaluation of Glass Transition Temperature) The curable resin composition shown in Table 1 and Table 2 was heated and cured using a spin coater so that the film thickness became 30.0 μm is applied to the release aluminum foil "Sepanium" (manufactured by Toyo Aluminum Co., Ltd.), and prebaked at 110°C for 5 minutes using a hot plate to produce a dry film. Then, the dry film was irradiated with ultraviolet light of 500 mJ/cm ² using an ultra-high-pressure mercury lamp with an i-ray illumination of 30 mW/cm ² to perform a photohardening reaction of the dry film.

Next, the exposed film was developed with a 2.38% TMAH (tetramethylammonium hydroxide) developer at 23°C at a spray pressure of 1 kgf/ ^cm2 for 60 seconds, and then washed with a spray of 5 kgf/ ^cm2 to remove the unexposed portion and form a 100 mm×5 mm pattern. Finally, a hot air dryer was used for formal curing (post-baking) at 230°C for 30 minutes, and the resin cured film was peeled off from the release aluminum foil to obtain a resin cured film for glass transition temperature evaluation.

(Evaluation method) Using a dynamic viscoelasticity (dynamic mechanical analysis (DMA)) measuring device (RSA-G2 manufactured by TA Instruments, Inc.), a 5 mm wide cured film was set so that the length between the chucks was 22 mm, and the glass transition temperature was measured in the temperature range of 30°C to 300°C. In addition, △ or above was regarded as passing.

(Evaluation criteria) ◎: Glass transition temperature is above 180℃ ○: Glass transition temperature is 160℃ or more and less than 180℃ △: Glass transition temperature is 140℃ or more and less than 160℃ ×: Glass transition temperature is less than 140℃

[table 3] Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment Embodiment 1 2 3 4 5 6 7 8 9 10 Gas generation △ △ △ △ △ △ △ △ ◎ ◎ Shear strength (adhesive strength) ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ◎ Development adhesion △ △ △ △ ◎ ◎ ○ ◎ ◎ ◎ Glass transition temperature ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ◎

[Table 4] Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example Comparative example 1 2 3 4 5 6 7 8 Gas generating property × △ 〇 × × × × ◎ Shear strength (bonding strength) 〇 × × 〇 ◎ ◎ 〇 × development adhesion △ ◎ ◎ × ◎ △ △ ◎ glass transition temperature ◎ ◎ ◎ ◎ ◎ ◎ △ ◎

As is clear from Tables 3 and 4, when (A) an unsaturated group-containing alkali-soluble resin represented by general formula (1) and (C) a photopolymerization initiator represented by general formula (9) are used, the gas generation of the resin cured film obtained by curing the curable resin composition is reduced, and the bonding strength to the adherend can be improved. In addition, when the photopolymerization initiator represented by general formula (9) is used, when an unsaturated group-containing alkali-soluble resin without a fluorene group is used as the (A) component, the decomposition product of the (A) component is also easy to volatilize and the (A) component cannot suppress the volatility of the decomposition product of the photopolymerization initiator represented by general formula (9), so the gas generation cannot be fully improved. [Industrial Applicability]

According to the present invention, contamination of an adherend caused by volatile matter from the resin cured film can be suppressed. Therefore, the present invention further expands the uses of curable adhesives and is expected to contribute to further development of the technical field.

Claims (9)

A curable resin composition comprises: (A) an alkali-soluble resin containing an unsaturated group, represented by the following general formula (1), (B) a polymerizable compound having at least two unsaturated groups, (C) a photopolymerization initiator, represented by the following general formula (9), and (D) a solvent, wherein the content of the photopolymerization initiator (C) is 1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the total of the (A) alkali-soluble resin containing an unsaturated group and the (B) polymerizable compound; ···General formula (1) In formula (1), Ar ₁ is independently an aromatic alkyl group having 6 to 14 carbon atoms, and a portion of the hydrogen atoms to which it is bonded may be substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group or an arylalkyl group having 6 to 10 carbon atoms, a cycloalkyl group or a cycloalkylalkyl group having 3 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen group; R ₁ is independently an alkylene group having 2 or more and 4 or less carbon atoms; l is independently a number of 0 or more and 3 or less; G is independently a (meth)acryloyl group, a substituent represented by the following general formula (2) or the following general formula (3); Y is a tetravalent carboxylic acid residue; Z is independently a hydrogen atom or a substituent represented by the following general formula (4); at least one of them is a substituent represented by the following general formula (4); n is a number having an average value of 1 or more and 20 or less; ···General formula (2) ···General formula (3) In formula (2) and formula (3), _R2 is a hydrogen atom or a methyl group, _R3 is a divalent alkylene group or alkylarylene group having 2 to 10 carbon atoms, _R4 is a divalent saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms, and p is a number from 0 to 10; * represents a bonding site with the compound represented by general formula (1), ···General formula (4) In formula (4), W is a divalent or trivalent carboxylic acid residue, m is 1 or 2; * represents the bonding site with the compound represented by general formula (1), ···General formula (9) In general formula (9), A is a hydrogen atom, a halogen atom, a nitro group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, a cycloalkylalkyl group having 4 to 10 carbon atoms, -N(R ₉ ) ₂ , -COR ₁₀ or -CO-CR ₆ R ₇ R ₈ ; in addition, -CH ₂ - in these substituents may be substituted by -O-, -N-, -S- or -C(=O)-; R _{R 5} independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms; in addition, the -CH ₂ - in these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-; in addition, two R ₅ may be bonded to each other to form a ring; R ₆ and R _R7 independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; one or more of the hydrogen atoms possessed by these functional groups may independently be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group; _-CH2- possessed by these functional groups may be substituted by -O-, -N-, -S-, or -C(=O)-; _R6 and _R7 may be bonded to each other to form a ring; or, R _R6 is a linear or branched alkyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 20 carbon atoms, and _R7 is any one of the functional groups represented by the following general formulae (10) to (12), ···General formula (10) In general formula (10), R ₁₃ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a phenyl group; R ₁₄ , R ₁₅ , and R ₁₆ independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms; * represents a bonding site with the compound represented by general formula (9); ···General formula (11) In the general formula (11), s is a number of 0 or more and 4 or less; * represents a bonding site with the compound represented by the general formula (9), ···General formula (12) In general formula (12), _Ar2 represents a phenyl group, a naphthyl group, a furyl group, a thienyl group or a pyridyl group which may be substituted; * represents the bonding site with the compound represented by general formula (9); _R8 represents an N-morpholinyl group, an N-piperidinyl group, an N-pyrrolyl group or an N-dialkyl group; in addition, one or more of the hydrogen atoms possessed by these functional groups may be independently substituted by a halogen atom or a hydroxyl group; R _{R 9} independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; one or more of the hydrogen atoms possessed by these functional groups may independently be substituted by a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group; -CH ₂ - possessed by these substituents may be substituted by -O-; two R ₉ may be bonded to each other to form a ring, in which case the ring may be a five-membered or six-membered ring formed via -O-, -S-, or -NH-; R _R10 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylcycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms; in addition, _-CH2- in these functional groups may be substituted with -O- or -S-; one or more of the hydrogen atoms in these functional groups may be independently substituted with a linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, _-SR11 , or _-OR12 ; _R11 and _R12 independently represent a hydrogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms. The curable resin composition as described in claim 1, wherein the weight average molecular weight of the unsaturated group-containing alkali-soluble resin (A) is 1000 or more and 40000 or less and the acid value is 50 mgKOH/g or more and 200 mgKOH/g or less. The hardening resin composition according to claim 1 or 2, further comprising (E) a sensitizer. The curable resin composition according to claim 3, wherein, The (E) sensitizer contains a benzophenone derivative or a thioxanthone derivative. The curable resin composition according to claim 1 or 2, which contains (F) an epoxy compound having two or more epoxy groups. A resin cured film obtained by curing the curable resin composition according to any one of claims 1 to 5. A printed circuit board including the resin cured film according to claim 6 as an insulating film. A semiconductor package comprises the resin hardening film as claimed in claim 6 as an insulating film. A display device including the resin cured film according to claim 6 as an insulating film.