Photosensitive resin composition, cured product, and electronic component

Abstract

The purpose of the present invention is to provide a cured product which is provided in an electronic component and has excellent heat resistance, excellent adhesion to a metal material, particularly to copper, and excellent migration resistance, and a main object of the present invention is to provide a photosensitive resin composition which contains (A) a resin, (B) a sensitizing agent, (C) a compound that is represented by formula (1), and (D) a compound that is represented by formula (2).

Description

Photosensitive resin composition, cured product, and electronic component

[0001] The present invention relates to a photosensitive resin composition, a cured product, and an electronic component.

[0002] Traditionally, polyimide resins and polybenzoxazole resins, which offer excellent heat resistance and mechanical properties, have been widely used for surface protection films and interlayer insulating films for semiconductor elements in electronic devices. When polyimides or polybenzoxazoles are used as surface protection films or interlayer insulating films, etching using positive photoresists is one method for forming through-holes and other structures. However, this method requires the steps of applying and peeling the photoresist, which is cumbersome. Therefore, heat-resistant materials with photosensitivity have been developed to streamline the process (see, for example, Patent Documents 1 to 3). On the other hand, when heat-resistant resin compositions are used in semiconductor applications, the film remains permanently within the device after heat curing, making the physical properties of the cured film extremely important. Since reliable electrical insulation is also required, high migration resistance is also required. To ensure reliability in semiconductor packaging, adhesion to materials formed on the surface of semiconductor chips is important. In particular, when used as insulating films between wiring layers in wafer-level packaging, adhesion to metal materials used for electrodes and wiring is important. Heat-resistant resins are generally considered not to have high adhesive strength with metal materials due to their rigid main chain structure, and in particular, in the case of a cured resin film formed from a photosensitive resin composition, the adhesive strength is lower than that of a film that does not contain any additives, because the additives that make up the composition, such as the photosensitizer, sensitizer, acid generator, and dissolution adjuster, remain in the cured film even after heat curing.

[0003] Specific examples of methods for improving adhesion to metal materials include a positive-type photosensitive resin composition comprising an alkaline aqueous solution-soluble polymer, a photoacid generator, and a silane compound containing four or more specific functional groups directly bonded to aluminum atoms, titanium atoms, and silicon atoms (see Patent Document 4), and a heat-resistant resin precursor composition comprising a heat-resistant resin precursor such as a polyimide precursor and a specific amino compound or thiol derivative (see Patent Document 5).

[0004] Japanese Patent Laid-Open No. 49-115541 Japanese Patent Laid-Open No. 59-108031 Japanese Patent Laid-Open No. 59-219330 Japanese Patent Laid-Open No. 2008-276190 Japanese Patent Laid-Open No. 2007-39486

[0005] However, these resin compositions have had problems in providing a cured product that combines excellent heat resistance with adhesion to metal materials, particularly copper, and migration resistance. Therefore, further improvements in the properties of photosensitive compositions have been desired. An object of the present invention is to provide a cured product that can be used in electronic components and that has excellent heat resistance, excellent adhesion to metal materials, particularly copper, and excellent migration resistance.

[0006] In order to solve the above problems, the present invention relates to the following: [1] A photosensitive resin composition containing (A) a resin, (B) a photosensitizer, (C) a compound represented by formula (1), and (D) a compound represented by formula (2).

[0007]

[0008] (R １ ~R ３ are each independently a hydrogen atom, NR ４ R ５ , or L(R ６ ) ｓ L represents an n-valent organic group having 6 to 10 carbon atoms and an aromatic ring; ４ and R ５ are each independently a hydrogen atom, —CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ , or -CH ２ OCH (CH ３ ) ２ represents R ６ are each independently —CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３, or -CH ２ OCH (CH ３ ) ２ n represents an integer of 1 to 3, s represents an integer of 0 to 2, and n-s is 1.

[0009]

[0010] (R ７ represents an oxygen atom or a sulfur atom. ８ is a divalent organic group having 1 to 4 carbon atoms, R ９ represents a methyl group or an ethyl group. １０ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Here, the monovalent hydrocarbon group having 1 to 18 carbon atoms and the monovalent aromatic group having 6 to 12 carbon atoms may have a heteroatom.) [2] The photosensitive resin composition according to [1], wherein all or part of the (B) photosensitizer is (B1-1) an oxime ester compound. [3] The photosensitive resin composition according to [1] or [2], wherein the (C) compound represented by formula (1) is contained in an amount of 30 parts by mass or more and 1,200 parts by mass or less per 100 parts by mass of the (D) compound represented by formula (2). [4] The photosensitive resin composition according to any one of [1] to [3], wherein, when the content of the photosensitizer (B) contained in the photosensitive resin composition is α parts by mass, the content of the compound (C) represented by formula (1) is β parts by mass, and the content of the compound (D) represented by formula (2) is γ parts by mass, α > β ≧ γ is satisfied, 1.0 ≦ α / β ≦ 4.5 is satisfied, and 0.4 ≦ β / γ ≦ 5.0 is satisfied. [5] The photosensitive resin composition according to any one of [1] to [4], further containing either or both of a compound represented by formula (5) and a compound represented by formula (6).

[0011]

[0012] (In formula (5), R １５ , R １６ and R １７ are each independently an alkyl group having 1 to 6 carbon atoms. １８ and R １９ are each independently an alkyl group having 1 to 6 carbon atoms. ２０is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) [6] The photosensitive resin composition according to any one of [1] to [5], wherein all or part of the compound (D) represented by formula (2) is a compound having a structure of formula (4).

[0013]

[0014] (R １１ represents a methyl group or an ethyl group. １２ represents a divalent organic group having 1 to 4 carbon atoms.

[0015] R １３ ~R １４ each independently represents a carbon atom (i.e., a methine group) or a nitrogen atom.) [7] The photosensitive resin composition according to any one of [1] to [6], wherein all or part of the compound (C) represented by formula (1) is a compound having a structure of formula (3).

[0016]

[0017] (R ６０ ~R ６５ are each independently a hydrogen atom, —CH ３ , -CH ２ CH ２ CH ２ CH ３ , or -CH(CH ３ ) ２ (A-1) represents a repeating structural unit represented by formula (7).) [8] The photosensitive resin composition according to any one of [1] to [7], wherein all or a part of the resin (A) is one or more resins selected from the group consisting of (A-1) polyimide precursor, (A-2) polyimide, (A-3) polybenzoxazole precursor, (A-4) polybenzoxazole, and copolymers thereof. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the one or more resins selected from the group consisting of (A-1) polyimide precursor, (A-2) polyimide, (A-3) polybenzoxazole precursor, (A-4) polybenzoxazole, and copolymers thereof contain a phenolic hydroxyl group.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein all or a part of the resin (A) is a polyimide precursor or a copolymer thereof containing a repeating structural unit represented by formula (7):

[0018]

[0019] (X １ represents a tetravalent group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. １ represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ２１ and R ２２ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.)

[11] The photosensitive resin composition according to

[10] , wherein the esterification rate of the polyimide precursor is 40 mol % or more and 80 mol % or less.

[12] In the formula (7), X １

[11] The photosensitive resin composition according to

[10] , wherein all or part of the structure represented by the formula (10) is a structure represented by the formula (8).

[0020]

[0021] (In formula (8), * represents a bonding site that bonds to an amide structure, a carboxylic acid structure, or a carboxylic acid ester structure.)

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the content of halogen elements contained in the photosensitive resin composition is 50 ppm or less.

[14] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[13] .

[15] An electronic component comprising the cured product according to

[14] .

[16] The electronic component according to

[15] , which comprises a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and comprises the cured product on the substrate.

[0022] The photosensitive resin composition of the present invention can provide a cured product that has excellent adhesion to copper wiring and excellent heat resistance. In addition, the cured product can be provided as a cured product for use in electronic components that have excellent migration resistance. Furthermore, the electronic components of the present invention can provide electronic components that have excellent migration resistance.

[0023] The photosensitive composition according to the first aspect of the present invention will be described below. However, the present invention is not limited to the following embodiments, and various modifications are possible within the scope of the present invention, as long as the object of the invention can be achieved and the gist of the invention is not deviated from.

[0024] In the following description, the term "organic group" refers to a hydrocarbon group which may be substituted with a substituent such as a halogen, a cyano group, a nitro group, a carboxyl group, a hydroxyl group, an oxyalkyl group, or an oxyaryl group, and an atomic group in which such a hydrocarbon group is linked by a linking group such as an ether bond, a sulfide bond, a sulfone bond, or an ester bond.

[0025] <Photosensitive Resin Composition> The photosensitive resin composition of the first aspect of the present invention is a photosensitive resin composition containing (A) a resin (hereinafter, sometimes referred to as "component (A)"), (B) a photosensitizer (hereinafter, sometimes referred to as "component (B)"), (C) a compound represented by formula (1) (hereinafter, sometimes referred to as "component (C)"), and (D) a compound represented by formula (2) (hereinafter, sometimes referred to as "component (D)").

[0026]

[0027] (R １ ~R ３ are each independently a hydrogen atom, NR ４ R ５ , or L(R ６ ) ｓ L represents an n-valent organic group having 6 to 10 carbon atoms and an aromatic ring; ４ and R ５ are each independently a hydrogen atom, —CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ , -CH ２ OCH (CH ３ ) ２ represents R ６ When there are a plurality of groups, each group independently represents -CH ２ OH, -CH ２ OCH３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ , -CH ２ OCH (CH ３ ) ２ n represents an integer of 1 to 3, s represents an integer of 0 to 2, and n-s is 1.

[0028]

[0029] (R ７ represents an oxygen atom or a sulfur atom. ８ is a divalent organic group having 1 to 4 carbon atoms, R ９ represents a methyl group or an ethyl group. １０ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Here, the monovalent hydrocarbon group having 1 to 18 carbon atoms and the monovalent aromatic group having 6 to 12 carbon atoms may have a heteroatom.) By adopting the above-mentioned configuration, the photosensitive resin composition of the present invention can improve adhesion to metal materials, particularly copper, and can provide a cured product with excellent heat resistance due to the improved crosslink density of the resin.

[0030] Furthermore, the photosensitive resin composition of the present invention preferably satisfies α > β ≧ γ, 1.0 ≦ α / β ≦ 4.5, and 0.4 ≦ β / γ ≦ 5.0, where α parts by mass of component (B), β parts by mass of component (C), and γ parts by mass of component (D) relative to 100 parts by mass of component (A). Satisfying these conditions further improves adhesion to copper wiring, and also improves the crosslink density of the resin, making it possible to provide a cured product with excellent heat resistance.

[0031] The total amount of halogen elements (fluorine, chlorine, bromine, and iodine) contained in the photosensitive resin composition of the present invention is preferably 50 ppm or less. By keeping the content of halogen elements in the photosensitive resin composition at 50 ppm or less, it is possible to reduce the environmental load and improve migration resistance. The content of halogen elements contained in the photosensitive resin composition is measured by an analytical method in accordance with IEC 62321-3-2. As a pretreatment, a sample is combusted using a method in accordance with BS EN 14582, and the combustion gas containing halogen is absorbed in an absorption liquid, which is then measured by ion chromatography. Details are as described in the Examples section.

[0032] <(A) Resin (Component (A))> The (A) resin contained in the photosensitive resin composition of the present invention is a resin having heat resistance to such an extent that it does not disappear entirely even when the photosensitive resin composition is cured. The (A) resin is preferably a resin that cures by forming a crosslinked structure through a reaction. The curing reaction is not particularly limited, and may be one caused by heating, irradiation with energy rays, or the like, and may also be one in which a crosslinked structure is formed by a crosslinking agent (F) described below. The (A) resin is preferably a thermosetting resin.

[0033] Furthermore, the (A) resin is preferably an alkali-soluble resin or an organic solvent-soluble resin. The alkali-soluble resin refers to a resin that is soluble in an alkaline developer. The organic solvent-soluble resin refers to a resin that is soluble in an organic solvent developer. The alkali-soluble resin and organic solvent-soluble resin in the photosensitive composition of the present invention are preferably resins that are soluble enough to impart positive or negative photosensitivity to the composition by the (B) photosensitizer described below, and to form a positive or negative pattern by development with an alkaline developer or an organic solvent. The alkali-soluble group in the (A) resin is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a 1,1-bis(trifluoromethyl)methylol group, a mercapto group, a carboxy group, a carboxylic anhydride group, or a sulfonic acid group.

[0034] Furthermore, the resin (A) preferably has a radical polymerizable group. The radical polymerizable group is preferably a group having an ethylenically unsaturated double bond, and among these, an alkenyl group having 2 to 5 carbon atoms or an alkynyl group having 2 to 5 carbon atoms is more preferred, and a styryl group, a cinnamoyl group, a maleimide group, or a (meth)acryloyl group is also preferred, with a (meth)acryloyl group being more preferred from the viewpoints of improving sensitivity during exposure and promoting radical polymerization during heating at low temperatures. On the other hand, the alkenyl group having 2 to 5 carbon atoms or the alkynyl group having 2 to 5 carbon atoms is preferably a vinyl group, an allyl group, a 2-methyl-2-propenyl group, a crotonyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 2,3-dimethyl-2-butenyl group, an ethynyl group, or a 2-propargyl group, and with a vinyl group or an allyl group being more preferred from the viewpoints of improving sensitivity during exposure and promoting radical polymerization during heating at low temperatures.

[0035] From the viewpoint of improving heat resistance, it is preferable that all or a part of the component (A) is one or more resins selected from the group consisting of (A-1) polyimide precursor (hereinafter sometimes referred to as "component (A-1)"), (A-2) polyimide (hereinafter sometimes referred to as "component (A-2)"), (A-3) polybenzoxazole precursor (hereinafter sometimes referred to as "component (A-3)"), (A-4) polybenzoxazole (hereinafter sometimes referred to as "component (A-4)"), and copolymers thereof.

[0036] From the viewpoints of improving solubility, improving adhesion between the cured film and metal materials, particularly copper, after baking due to interaction with the component (C) described below, and improving heat resistance, it is preferred that one or more resins selected from the group consisting of the component (A-1), the component (A-2), the component (A-3), the component (A-4), and copolymers thereof contain a phenolic hydroxyl group.

[0037] <(A-1) Polyimide Precursor, (A-2) Polyimide> Examples of the component (A-1) include those obtained by reacting a tetracarboxylic acid or a derivative thereof, such as a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride, with a diamine or a derivative thereof, such as a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, and have a tetracarboxylic acid residue and a diamine residue. Examples of the component (A-1) include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.

[0038] Polyimide precursors are known as chemically curable or thermosetting resins, and are converted to polyimides by thermal curing at high temperatures and dehydration ring closure, forming highly heat-resistant imide bonds. Because polyimide precursors are resins whose heat resistance improves after dehydration ring closure, they are suitable for applications that require both the properties of the precursor structure before dehydration ring closure and the heat resistance of the cured film.

[0039] From the viewpoint of improving the heat resistance of the cured film, in the photosensitive resin composition of the present invention, all or a part of the component (A) is preferably a polyimide precursor having a repeating structural unit represented by formula (7) or a copolymer thereof.

[0040] When the photosensitive resin composition of the present invention uses the component (A-2) as the component (A), from the viewpoints of improving solubility in a developer, improving adhesion to metals, and improving migration resistance, it is preferable that all or a part of the component (A) be a polyimide resin containing a repeating structural unit represented by formula (11).

[0041]

[0042] In formula (7), X １ represents a tetravalent group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. １ represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ２１ and R ２２each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.

[0043] In formula (11), X ２ represents a tetravalent to decavalent group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ２ represents a divalent to decavalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ２３ and R ２４ each independently represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by formula (12) or formula (13). p represents an integer of 0 to 6. q represents an integer of 0 to 8.

[0044]

[0045] In formula (12) and formula (13), R ２５ ~R ２７ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Of these, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms is preferred. The above-mentioned alkyl group, acyl group, and aryl group may have a heteroatom, and the hydrogen atom in the group may be substituted with an alkyl group having 1 to 10 carbon atoms or a halogen atom.

[0046] When the sum of all polyamic acid repeating structural units and all polyamic acid ester repeating structural units in the component (A-1) is taken as 100 mol %, the proportion of all polyamic acid ester repeating structural units in the component (A-1) is defined as the esterification rate of the component (A-1).

[0047] The esterification rate can be easily determined by NMR measurement, etc. Specifically, a method can be used in which the peak intensity derived from all aromatic ring hydrogens in the polyimide precursor is compared with the peak intensity derived from hydrogens of hydrocarbons directly bonded to ester groups of all polyamic acid esters in all residues of tetracarboxylic acids and derivatives thereof, and all residues of dicarboxylic acids and derivatives thereof, or derived from monovalent organic groups having ethylenically unsaturated double bonds.

[0048] From the viewpoint of improving ion migration resistance, the esterification rate of the component (A-1) is preferably 40 mol % or more and 80 mol % or less.

[0049] X in formula (7) and formula (11) １ and X ２ represents a tetracarboxylic acid residue, Y １ and Y ２ represents a diamine residue.

[0050] Specific examples of the residue of a tetracarboxylic acid or a derivative thereof having an aliphatic structure include residues of butanetetracarboxylic acid, ethylene glycol bistrimellitic acid, 4,4'-ethylenebis(2,6-morpholinedione), meso-butane-1,2,3,4-tetracarboxylic acid, or their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid activated diesters. One or more of these residues may be contained in the molecular structure of component (A-1).

[0051] Specific examples of the residue of a tetracarboxylic acid or a derivative thereof having an alicyclic structure include butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid, dicyclohexyl-3,4,3',4'-tetracarboxylic acid, 4-(2,5-dioxotetrahydrofuran-3-yl)-tetralin-1,2-dicarboxylic acid, and octahydrobiphenylene-4a,8b : 4b,8a-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic acid, or residues of their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid activated diesters. One or more of these residues may be included in the molecular structure of component (A-1).

[0052] Specific examples of the residue of a tetracarboxylic acid or a derivative thereof having an aromatic structure include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenylethertetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2, Examples of such residues include residues of aromatic tetracarboxylic acids having the structures shown below, or residues of their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid activated diesters. One or more of these residues may be contained in the molecular structure of component (A-1).

[0053] Furthermore, the tetracarboxylic acid residue contained in the molecular structure of component (A-1) may be a residue containing an amide structure such as that shown in the following formula.

[0054]

[0055] In the formula, R ２８ is an oxygen atom, C(CF ３ ) ２ , or C(CH ３ ) ２ Represents R ２９ ~R ３２represents a hydrogen atom or a hydroxyl group. * represents a bond that bonds to an amide structure, a carboxylic acid structure, or a carboxylic acid ester structure.

[0056] Also R ２９ ~R ３２ is a hydroxyl group, and when these tetracarboxylic acid residues are introduced into formula (7), a polyimide precursor is obtained which can further provide benzoxazole groups by thermal curing.

[0057] From the viewpoint of improving heat resistance, X in the formula (7) １ It is preferable that all or part of the structure represented by formula (8) is a structure represented by formula (8).

[0058]

[0059] In formula (8), * represents a bond that binds to the amide structure, carboxylic acid structure, or carboxylic acid ester structure.

[0060] Specific examples of the residue of a diamine or derivative thereof having an aliphatic structure include residues of ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, or compounds in which the amine moiety of these isocyanated or trimethylsilylated. One or more of these residues may be contained in the molecular structure of component (A-1).

[0061] Specific examples of residues of diamines or derivatives thereof having an alicyclic structure include residues of bis(aminomethyl)norbornane, 4,4'-methylenebis(cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, or compounds in which the amine moiety of these isocyanated or trimethylsilylated. One or more of these residues may be contained in the molecular structure of component (A-1).

[0062] Specific examples of the residue of a diamine having an aromatic structure or a derivative thereof include bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 3-sulfonic acid-4,4'-diaminodiphenyl ether, dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 3-amino-4-hydroxy ... Aminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphen) phenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4 Examples of the amine moiety include residues of 2,4-tetramethyl-4,4'-diaminobiphenyl, 2,4-diamino-1,3,5-triazine (guanamine), 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine), 2,4-diamino-6-phenyl-1,3,5-triazine (benzoguanamine), 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane, or compounds in which the amine moiety thereof has been isocyanated or trimethylsilylated.One or more of these residues may be contained in the molecular structure of component (A-1).

[0063] Specific examples of the residue of a diamine having a phenolic hydroxyl group or a derivative thereof include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl) -3-amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3 Examples of such residues include, but are not limited to, residues of N,N'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 1,3-bis(4-amino-3-hydroxyphenoxy)benzene. These residues may be used alone or in combination of two or more types in component (A-1).

[0064] The diamine residue contained in the molecular structure of component (A-1) may also be a residue containing an amide structure such as that shown in the following formula.

[0065]

[0066] * represents the bond that connects to the amide structure.

[0067] In the formula, R ３３ ~R ４０ represents a hydrogen atom or a hydroxyl group.

[0068] Also in the formula, R ３３ ~R ４０ is a hydroxyl group, and when these diamine residues are introduced into formula (7), a polyimide precursor is obtained that can provide benzoxazole groups by thermal curing.

[0069] From the viewpoint of improving heat resistance and sensitivity, all or a part of the component (A) is a polyimide precursor or a copolymer thereof containing a repeating structural unit represented by formula (7), and when the amount of the repeating structural unit represented by formula (7) is taken as 100 mol %, Y １ It is preferable that the repeating structural unit having the structure represented by formula (14) accounts for 70 mol % or more and 100 mol % or less.

[0070]

[0071] In formula (14), * represents a bond that binds to the amide structure.

[0072] In addition, in the formula (7), R ２１ and R ２２ It is preferable that all or a part of the above be a monovalent organic group having an ethylenically unsaturated double bond represented by the following formula (15) or the following formula (16): By introducing an ethylenically unsaturated double bond, sensitivity can be improved.

[0073]

[0074] In formula (15), R ４１ represents a hydrogen atom or a methyl group. ４２ and R ４３each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.

[0075] In formula (16), R ４４ and R ４９ represents a hydrogen atom or a methyl group. ４５ ~R ４８ each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.

[0076] <(A-3) Polybenzoxazole Precursor, (A-4) Polybenzoxazole> Examples of the component (A-3) include those obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid activated diester with a diamine such as a bisaminophenol compound, and have a dicarboxylic acid residue and a bisaminophenol compound residue. Examples of the component (A-3) include poly-α-hydroxyamide.

[0077] Component (A-3) is a thermosetting resin that is thermally cured at high temperatures to undergo dehydration and ring closure to form a highly heat-resistant and rigid benzoxazole ring, thereby obtaining polybenzoxazole (A-4). Therefore, by incorporating component (A-3) into a photosensitive resin composition, the heat resistance of the resulting cured film can be significantly improved. This makes the composition suitable for applications requiring high heat resistance. Furthermore, because component (A-3) is a resin whose heat resistance improves after dehydration and ring closure, it is suitable for applications requiring both the properties of the precursor structure before dehydration and ring closure and the heat resistance of the cured film.

[0078] From the viewpoint of improving the heat resistance and i-line transmittance of the cured film, it is preferable that the component (A) contains a repeating structural unit represented by formula (17).

[0079] When the photosensitive resin composition of the present invention contains the component (A-4), from the viewpoints of improving solubility in a developer, improving adhesion to metals, and improving migration resistance, it is preferable that the component (A) contains a repeating structural unit represented by formula (18).

[0080]

[0081] In formula (17), X ３ represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ３ represents a tetravalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms.

[0082] R ５０ and R ５１ each independently represents a hydrogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.

[0083] In formula (18), X ４ represents a divalent to decavalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ４ represents a tetravalent to decavalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ５２ and R ５３ each independently represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above formula (12) or formula (13). f represents an integer of 0 to 8. g represents an integer of 0 to 6.

[0084] X in formula (17) and formula (18) ３ and X ４ represents a dicarboxylic acid residue, Y ３ and Y ４ represents a bisaminophenol residue. Examples of dicarboxylic acid derivatives that give dicarboxylic acid residues include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, and dicarboxylic acid activated esters.

[0085] Specific examples of dicarboxylic acids or derivatives thereof include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosane dioic acid, heneicosane dioic acid, docosane dioic acid, tricosane dioic acid, tetracosane dioic acid, pentacosane dioic acid, hexacosane dioic acid, heptacosane dioic acid, octacosane dioic acid, nonacosane dioic acid, and triacontanedioic acid. One or more of these residues may be contained in the molecular structure of the component (A-3).

[0086] From the viewpoint of improving heat resistance and sensitivity, the photosensitive resin composition of the present invention is preferably a compound represented by the formula (17) and the formula (18), wherein X ３ and X ４ It is preferable that all or part of the structure represented by formula (19) is a structure represented by formula (19).

[0087]

[0088] In formula (19), * represents a bond that binds to the amide structure.

[0089] Specific examples of the residue of a bisaminophenol compound or a derivative thereof include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-aminobenzamido)-3-amino-4-hydroxyphenyl]sulfone, and bis[N-(4-aminobenzamido)-3-amino-4-hydroxyphenyl]sulfone. 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 9,9-bis[N-(3-aminobenzoyl)-3 -amino-4-hydroxyphenyl]fluorene, 9,9-bis[N-(4-aminobenzoyl)-3-amino-4-hydroxyphenyl]fluorene, N,N'-bis(3-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-2,5-diamino-1,4-dihydroxybenzene, N,N'-bis(4-aminobenzoyl)-4,4'-diamino-3,3-dihydroxybiphenyl, N,N'-bis(3-aminobenzoyl)-3,3' Examples of such residues include, but are not limited to, residues of N,N'-diamino-4,4-dihydroxybiphenyl, N,N'-bis(4-aminobenzoyl)-3,3'-diamino-4,4-dihydroxybiphenyl, 3,3'-diamino-4,4'-biphenol, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 1,3-bis(4-amino-3-hydroxyphenoxy)benzene. These residues may be contained in component (A-3) either alone or in combination of two or more types.

[0090] In addition, in the formula (18), R ５０, R ５１ Preferably, the compound represented by formula (18) has an ethylenically unsaturated double bond represented by formula (20). By introducing an ethylenically unsaturated double bond into formula (18), sensitivity can be improved.

[0091]

[0092] In formula (20), R ５４ represents a hydrogen atom or a methyl group. ５５ and R ５６ each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.

[0093] <(B) Photosensitizer (Component (B))> The (B) photosensitizer used in the photosensitive resin composition of the present invention is a compound that undergoes bond cleavage, reaction, or structural change upon exposure to light to generate another compound, thereby imparting positive or negative photosensitivity to the resin composition or imparting positive or negative latent image formability to the resin composition.

[0094] The (B) photosensitizer is preferably one or more selected from the group consisting of (B1) a photopolymerization initiator, (B2) a naphthoquinone diazide compound, (B3) a photoacid generator, and (B4) a photobase generator. When negative photosensitivity is imparted to the composition, it is preferable to use (B1) a photopolymerization initiator, and more preferably one or more selected from the group consisting of (B2) a naphthoquinone diazide compound, (B3) a photoacid generator, and (B4) a photobase generator. When positive photosensitivity is imparted to the composition, it is preferable to use (B2) a naphthoquinone diazide compound, and more preferably one or more selected from the group consisting of (B1) a photopolymerization initiator, (B3) a photoacid generator, and (B4) a photobase generator.

[0095] In the photosensitive resin composition of the present invention, the content of component (B) is preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, relative to 100 parts by mass of component (A), from the viewpoint of improving sensitivity during exposure. On the other hand, the content of component (B) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to 100 parts by mass of component (A), from the viewpoint of suppressing residue after development.

[0096] <(B1) Photopolymerization Initiator> The (B1) photopolymerization initiator (hereinafter sometimes referred to as "component (B1)") refers to a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals. The inclusion of component (B1) is suitable for negative pattern formation, and significantly improves sensitivity during exposure. The component (B1) is preferably an α-hydroxyketone compound, an α-aminoketone compound, a biimidazole compound, an acylphosphine oxide compound, or an oxime ester compound. The preferred contents of these components (B) are the same as those described above.

[0097] From the viewpoint of improving sensitivity during exposure, all or part of the component (B) is preferably an oxime ester compound (B1-1) (hereinafter, sometimes referred to as "compound (B1-1)"). The oxime ester structure contained in compound (B1-1) undergoes bond cleavage and / or reaction upon exposure to generate radicals.

[0098] Examples of the (B1-1) compound include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[ 4-carboxyphenylthio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-(phenylthio)phenyl]-2-cyclopentylethane-1,2-dione-2-(O-acetyl)oxime, 1-[9,9-diethylfluoren-2-yl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9,9-di-n-propyl-7-(2-methylbenzoyl)-fluoren-2-yl]ethanone-1-(O-acetyl)oxime oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

[0099] From the viewpoint of photobleachability, the (B1-1) compound preferably has a fluorene structure, a benzofluorene structure, a dibenzofluorene structure, an indole structure, a benzoindole structure, a phenothiazine structure, a phenothiazine oxide structure, or a diphenyl sulfide structure. Even if the compound does not have these structures, it is also preferable for the compound to have a structure in which at least one oxime ester carbonyl structure is bonded to a fused polycyclic structure, a fused polycyclic heterocyclic structure, or a benzene structure. The photobleachability of the (B1-1) compound significantly improves sensitivity during exposure and pattern processability in thick films. Furthermore, it is believed that the reduction of low-molecular-weight components derived from the (B1-1) compound in the cured product suppresses ion migration and electromigration, improving migration resistance. The photobleachability refers to a decrease in absorbance at wavelengths in the ultraviolet region (e.g., 400 nm or less) and / or absorbance at wavelengths of visible light (380 to 780 nm) due to bond cleavage and / or reaction upon exposure to light.

[0100] From the viewpoint of improving sensitivity during exposure and pattern processability in thick films, it is particularly preferable that compound (B1-1) is a compound having a structure represented by formula (21). By having the structure represented by formula (21), the transmittance of i-line (wavelength 365 nm) does not decrease during photopolymerization, and undercut can be suppressed even in thick film processing.

[0101]

[0102] In formula (21), R ５７ and R ５８ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group; R ５９ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —OH, —COOH, —O(CH ２ )OH, —O(CH ２ ) ２ OH, -COO(CH ２ )OH or —COO(CH ２ ) ２ represents OH.

[0103] Examples of the compound (B1-1) having the structure represented by formula (21) include NCI-930 (trade name, manufactured by ADEKA Corporation) and some compounds described in WO 2015 / 036910.

[0104] From the viewpoint of improving sensitivity during exposure, all or part of the component (B) is preferably a phosphine oxide compound (B1-2) (hereinafter, sometimes referred to as "compound (B1-2)"). (B1-2) has a phosphine oxide structure in the molecule, and undergoes bond cleavage and / or reaction upon exposure to generate radicals. In addition, compound (B1-2) is preferably a compound having an acyl group in the molecule.

[0105] Examples of the (B1-2) compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0106] <(B2) Naphthoquinone Diazide Compound> The (B2) naphthoquinone diazide compound refers to a compound that undergoes a structural change upon exposure to generate an indene carboxylic acid or a sulfoindene carboxylic acid. The inclusion of a (B2) naphthoquinone diazide compound is suitable for forming a positive pattern. The (B2) naphthoquinone diazide compound used in the present invention is preferably a 5-naphthoquinone diazide sulfonic acid ester or a 4-naphthoquinone diazide sulfonic acid ester of a compound having a phenolic hydroxyl group. Either one or more (B2) naphthoquinone diazide compounds can be used.

[0107] <(B3) Photoacid Generator> The (B3) photoacid generator refers to a compound that generates an acid by bond cleavage and / or reaction upon exposure. The inclusion of a (B3) photoacid generator is suitable for negative pattern formation, from the viewpoint of promoting cationic polymerization, etc. On the other hand, when a resin or the like has an acidic group protected by an acid-dissociable group, it is suitable for positive pattern formation, from the viewpoint of liberating an alkali-soluble group upon exposure. Examples of the (B3) photoacid generator include ionic compounds and nonionic compounds. Triorganosulfonium salt compounds are preferred as ionic compounds. Preferred nonionic compounds include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, carboxylate ester compounds, sulfonimide compounds, phosphate ester compounds, and sulfonebenzotriazole compounds. The (B3) photoacid generator may be used alone or in combination.

[0108] <(B4) Photobase Generator> The (B4) photobase generator refers to a compound that generates a base by bond cleavage and / or reaction upon exposure. The inclusion of the (B4) photobase generator is suitable for negative-tone pattern formation from the viewpoint of promoting anionic polymerization, etc. On the other hand, when a resin or the like has a base-dissociable protected acidic group, it is suitable for positive-tone pattern formation from the viewpoint of liberating an alkali-soluble group upon exposure. Examples of the (B4) photobase generator include ionic compounds and nonionic compounds. Preferred ionic compounds include diazabicycloalkene salt compounds, triazabicycloalkene salt compounds, α-keto quaternary ammonium salt compounds, benzyl quaternary ammonium salt compounds, guanidine salt compounds, and biguanide salt compounds. The ionic compound preferably has a ketoprofen structure, an oxoxanthene structure, a benzofuran structure, or a naphthalene structure. The nonionic compound is preferably a nitrobenzyl carbamate compound, an anthracenyl carbamate compound, a benzoin-based carbamate compound, an anthraquinone-based carbamate compound, a hydroxycinnamamide-based compound, or a coumarinamide-based compound. One or more types of photobase generator (B4) can be used.

[0109] <(C) Compound Represented by Formula (1) (Component (C))> The photosensitive resin composition of the present invention contains the component (C).

[0110]

[0111] R １ ~R ３ are each independently a hydrogen atom, NR ４ R ５ , or L(R ６ ) ｓ L represents an n-valent organic group having 6 to 10 carbon atoms and an aromatic ring; ４ and R ５ are each independently a hydrogen atom, —CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ , -CH ２ OCH (CH ３ ) ２ represents R ６ are each independently —CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ , -CH ２ OCH (CH ３ ) ２ n represents an integer of 1 to 3, s represents an integer of 0 to 2, and n-s is 1.

[0112] The inclusion of component (C) significantly improves the adhesion of the cured film to metal materials, particularly copper, after baking. This is due to the interaction of the nitrogen moiety of the compound represented by formula (1) with the metal surface. This imparts photosensitivity to the resin composition, and even when additives are included, a cured resin film with excellent adhesion to metal materials can be obtained.

[0113] Examples of component (C) include, but are not limited to, compounds having the following structure:

[0114]

[0115] The content of the component (C) in the photosensitive resin composition of the present invention is preferably 30 parts by mass or more and 1,200 parts by mass or less per 100 parts by mass of the component (D) described below.

[0116] From the viewpoint of improving heat resistance and adhesion to copper substrates, it is preferred that all or part of component (C) is a compound having the structure of formula (3).

[0117] Examples of compounds having the structure of formula (3) include "NIKALAC" (registered trademark) MW-100LM and MW-390 (both manufactured by Sanwa Chemical Co., Ltd.).

[0118]

[0119] (R ６０ ~R ６５ are each independently a hydrogen atom, —CH ３ , -CH ２ CH ２ CH ２ CH ３ , or -CH(CH ３ ) ２ (D) Compound Represented by Formula (2) (Component (D)) The photosensitive resin composition of the present invention contains the component (D).

[0120]

[0121] R ７ represents an oxygen atom or a sulfur atom. ８ is a divalent organic group having 1 to 4 carbon atoms, R ９ represents a methyl group or an ethyl group. １０ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Here, the monovalent hydrocarbon group having 1 to 18 carbon atoms and the monovalent aromatic group having 6 to 12 carbon atoms may contain a heteroatom.

[0122] By including component (D), the adhesion between the cured film and metal materials, especially copper, after baking can be significantly improved. This is due to the nitrogen moiety of the compound represented by formula (2) interacting with the metal surface, and the urea structure having a three-dimensional structure that facilitates interaction with the metal surface. These effects impart photosensitivity to the resin composition, and even when additives are included, a cured resin film with excellent adhesion to metal materials can be obtained.

[0123] Examples of urea compounds having an alkoxysilyl group include, but are not limited to, the following structures:

[0124]

[0125]

[0126] The content of component (D) is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 5.0 parts by mass, per 100 parts by mass of component (A). If the content is less than 0.1 part by mass, it is difficult to obtain the effect of improving adhesion to metal materials. If the content is more than 5.0 parts by mass, the basicity of the component (D) may affect the photosensitizer, resulting in a decrease in the sensitivity of the resin composition. The content of component (D) is more preferably 0.2 parts by mass or more. Furthermore, the content is more preferably 3.0 parts by mass or less.

[0127] From the viewpoint of improving the adhesion between the cured film and the copper substrate after high-temperature heat treatment, it is preferable that all or part of component (D) is a compound having a structure represented by formula (4). Use of such a compound can significantly improve the adhesion between the cured film and metal materials, particularly copper, after firing.

[0128]

[0129] In formula (4), R １１ represents a methyl group or an ethyl group. １２ represents a divalent organic group having 1 to 4 carbon atoms. １３ ~R １４each independently represents a carbon atom (i.e., a methine group) or a nitrogen atom. In the photosensitive resin composition of the present invention, one or more types of component (D) may be used.

[0130] <Other Compounds That Can Be Preferably Used> The photosensitive resin composition of the present invention preferably contains either or both of a compound represented by formula (5) and a compound represented by formula (6), from the viewpoints of accelerating ring closure and curing of the component (A) and improving heat resistance.

[0131]

[0132] In formula (5), R １５ , R １６ and R １７ are each independently an alkyl group having 1 to 6 carbon atoms. １８ and R １９ are each independently an alkyl group having 1 to 6 carbon atoms. ２０ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0133] The β-alkoxypropionamide, which is the compound represented by formula (5), is preferably 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide, from the viewpoints of improving the solubility of component (A), promoting ring closure and curing of component (A), and improving heat resistance.

[0134] In the present invention, the content of the compound represented by formula (5) is preferably at least 0.1 parts by mass, and more preferably at least 1 part by mass, per 100 parts by mass of component (A) from the viewpoints of accelerating ring closure and curing of component (A) and improving heat resistance, while the content is preferably at most 15 parts by mass, and more preferably at most 7 parts by mass, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0135] The compound represented by formula (6) is preferably N,N-dimethylpropionamide or N,N-dimethylisobutyramide, from the viewpoint of accelerating the ring closure and curing of component (A) and improving the heat resistance of the cured film.

[0136] In the present invention, the content of the compound represented by formula (6) is preferably at least 0.1 parts by mass, and more preferably at least 1 part by mass, per 100 parts by mass of component (A) from the viewpoints of accelerating ring closure and curing of component (A) and improving heat resistance, while the content is preferably at most 15 parts by mass, and more preferably at most 7 parts by mass, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0137] <(E) Polymerizable Compound (Component (E))> The photosensitive composition of the present invention contains a (E) polymerizable compound (hereinafter sometimes referred to as "component (E)") and / or a (F) crosslinking agent. Component (E) refers to a compound having at least two radically polymerizable groups. The radically polymerizable groups are preferably ethylenically unsaturated double bond groups.

[0138] The photosensitive composition of the present invention preferably contains component (B) and further contains either or both of component (E) and (F) a crosslinking agent; from the viewpoint of accelerating the photoreaction, it is more preferable that it contains (B1) a photopolymerization initiator and further contains component (E). When the composition has negative photosensitivity, the inclusion of component (E) significantly improves the sensitivity during exposure. On the other hand, when the composition has positive photosensitivity, the inclusion of component (E) significantly improves the pattern shape control after thermal curing.

[0139] The radical polymerizable group of component (E) preferably has a (meth)acryloyl group from the viewpoint of improving sensitivity during exposure. The number of radical polymerizable groups of component (E) is preferably 3 or more, more preferably 4 or more, from the viewpoint of improving sensitivity during exposure. On the other hand, the number of radical polymerizable groups is preferably 12 or less, more preferably 10 or less, even more preferably 8 or less, and particularly preferably 6 or less, from the viewpoint of improving migration resistance.

[0140] Examples of the component (E) include polyethylene glycol dimethacrylate represented by formula (22) (E1) (hereinafter, sometimes referred to as "component (E1)") and polyethylene glycol dimethacrylate represented by formula (23) (E2) (hereinafter, sometimes referred to as "component (E2)"), which will be described later, as well as other compounds such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, pentyl glycol ... Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentaerythritol Examples of the acrylic acid-modified copolymer include pentaerythritol undeca(meth)acrylate, pentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, and acid-modified products thereof.

[0141] From the viewpoint of compatibility with the component (A), it is preferable to use a (meth)acrylate containing a structure represented by the following formula (24): In this specification, the term "(meth)acrylate" is used as a term that includes the meanings of both acrylic acid ester and methacrylic acid ester.

[0142]

[0143] In formula (24), * represents a bond to a structure derived from a (meth)acrylic acid ester, and n is an integer of 1 to 12.

[0144] From the viewpoint of preventing elution of exposed areas during development and further reducing a decrease in film thickness after development, it is preferable to use a polymerizable compound represented by the following formula (25).

[0145]

[0146] In formula (25), Me represents a methyl group, and Et represents an ethyl group.

[0147] When the photosensitive composition of the present invention contains the component (A) and the component (E), the content of the component (A) is preferably 25 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 45 parts by mass or more, based on 100 parts by mass of the total of the components (A) and (E). On the other hand, the content of the component (A) is preferably 85 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less, based on 100 parts by mass of the total of the components (A) and (E).

[0148] Furthermore, from the viewpoint of improving sensitivity during exposure, the content of component (E) is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 25 parts by mass or more, based on 100 parts by mass of the total of components (A) and (E). On the other hand, from the viewpoint of improving migration resistance, the content of component (E) is preferably 75 parts by mass or less, more preferably 65 parts by mass or less, and even more preferably 55 parts by mass or less, based on 100 parts by mass of the total of components (A) and (E).

[0149] <Component (E1) and Component (E2)> The photosensitive resin composition of the present invention further contains (E1) a polyethylene glycol dimethacrylate represented by formula (22) and (E2) a polyethylene glycol dimethacrylate represented by formula (23), and the component (E) preferably contains 4 to 20 parts by mass of component (E2) per 100 parts by mass of component (E1). This enables processing into a rectangular pattern shape with a low exposure dose even in thick film processing without reducing compatibility with component (A).

[0150]

[0151] In formula (22), a represents an integer of 4 to 9. In formula (23), b represents an integer of 1 to 3.

[0152] In formula (22), examples of the compound where a is an integer of 4 to 9 include polyethylene glycol #200 dimethacrylate and polyethylene glycol #400 dimethacrylate.

[0153] From the viewpoint of compatibility with component (A), polyethylene glycol #400 dimethacrylate is preferred.

[0154] In formula (23), examples of the compound where b is an integer of 1 to 3 include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. From the viewpoint of improving sensitivity, ethylene glycol dimethacrylate is preferred.

[0155] <(F) Crosslinking Agent (Component (F))> The (F) crosslinking agent (hereinafter sometimes referred to as "component (F)") used in the photosensitive composition of the present invention reacts with the (A) resin to form a crosslinked structure.

[0156] The photosensitive composition of the present invention preferably contains the above-mentioned (B) photosensitizer and further contains (F) crosslinking agent, and from the viewpoint of accelerating the photoreaction, it is more preferable to contain the above-mentioned (B3) photoacid generator or (B4) photobase generator and further contain (F) crosslinking agent. On the other hand, from the viewpoint of improving the degree of crosslinking of resins, etc., it is also preferable to contain the above-mentioned (B2) naphthoquinone diazide compound and further contain (F) crosslinking agent.

[0157] From the viewpoint of improving sensitivity during exposure, the (F) crosslinking agent is preferably a compound having at least two types of groups selected from the group consisting of alkoxyalkyl groups, hydroxyalkyl groups, epoxy groups, oxetanyl groups, vinyl groups, and allyl groups (hereinafter, these groups may be collectively referred to as "specific crosslinkable groups") (excluding the above-mentioned components (C) and (E)). The alkoxyalkyl groups are preferably alkoxymethyl groups, and more preferably methoxymethyl groups. The hydroxyalkyl groups are preferably methylol groups. From the viewpoint of improving sensitivity during exposure, the number of specific crosslinkable groups contained in one molecule of the (F) crosslinking agent is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 6 or more. On the other hand, from the viewpoint of improving mechanical properties during heating at low temperatures, the number of specific crosslinkable groups is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0158] The content of the (F) crosslinking agent, when the total of the (A) component and the (E) component is taken as 100 parts by mass (including the case where the (E) component is not included), is preferably 1.0 part by mass or more, more preferably 3.0 parts by mass or more, and even more preferably 5.0 parts by mass or more, from the viewpoint of improving sensitivity during exposure. On the other hand, the content of the (F) crosslinking agent, when the total of the (A) component and the (E) component is taken as 100 parts by mass (including the case where the (E) component is not included), is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of improving heat resistance. In the present invention, one type of (F) crosslinking agent or multiple types may be used.

[0159] <Component (F1) and Component (F2)> From the viewpoint of improving heat resistance and adhesion to metal wiring, it is preferable that the (F) crosslinking agent be, in whole or in part, either or both of the following component (F1) and component (F2).

[0160] Component (F1): A compound having at least two phenolic hydroxyl groups and at least two specific crosslinkable groups. Component (F2): A compound having a structure containing a heteroalicyclic structure and at least two specific crosslinkable groups.

[0161] Component (F1) is preferably a compound having at least two structures in which a phenolic hydroxyl group and a specific crosslinkable group are bonded to one aromatic ring, and more preferably a compound having at least two structures in which a phenolic hydroxyl group and at least two specific crosslinkable groups are bonded to one aromatic ring.

[0162] The heteroalicyclic structure in component (F2) is preferably a nitrogen-containing cyclic structure, more preferably a cyclic structure having at least two nitrogen atoms. The cyclic structure having at least two nitrogen atoms is preferably one or more selected from the group consisting of an isocyanuric acid structure, a triazine structure, a glycoluril structure, an imidazolidone structure, a pyrazole structure, an imidazole structure, a triazole structure, a tetrazole structure, and a purine structure, and more preferably contains an isocyanuric acid structure or a triazine structure. The number of nitrogen atoms in the heteroalicyclic structure in compound (F2) is preferably one or more, more preferably two or more, and even more preferably three or more. Meanwhile, the number of nitrogen atoms is preferably six or less, more preferably four or less.

[0163] <Other Additives> The photosensitive composition of the present invention preferably further contains one or more additives selected from the group consisting of a dissolution promoter, a sensitizer, a chain transfer agent, a polymerization inhibitor, a silane coupling agent, and a surfactant. Known additives may be used as these additives.

[0164] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

[0165] The content ratio of the solvent in the photosensitive resin composition of the present invention can be appropriately adjusted depending on the coating method, etc. For example, when a coating film is formed by spin coating, the content is generally 50 to 95 mass % of the entire photosensitive resin composition.

[0166] <Shape of the Photosensitive Resin Composition of the Present Invention> The photosensitive resin composition of the present invention is not limited in shape as long as it contains the components (A), (B), (C), and (D), and may be, for example, in the form of a paste or a sheet. The photosensitive sheet of the present invention refers to a photosensitive resin composition formed into a sheet before being irradiated with actinic rays, such as a sheet obtained by applying the photosensitive resin composition of the present invention to a support, drying it at a temperature and for a time within a range that allows the solvent to volatilize, and then leaving it in the form of an incompletely cured sheet that is soluble in an organic solvent or an alkaline aqueous solution.

[0167] The support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. The bonding surface between the support and the photosensitive resin composition may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and peelability. The thickness of the support is also not particularly limited, but from the viewpoint of workability, a thickness of 10 to 100 μm is preferred. Furthermore, to protect the surface of the photosensitive composition film obtained by coating, a protective film may be provided on the film surface. This protects the surface of the photosensitive resin composition from contaminants such as dust and dirt in the atmosphere.

[0168] Examples of methods for applying the photosensitive resin composition to a support include spin coating using a spinner, spray coating, roll coating, screen printing, and methods using a blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, slit die coater, etc. The coating film thickness varies depending on the coating technique, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying be 0.5 μm or more and 100 μm or less from the viewpoint of coating film uniformity, etc.

[0169] For drying, an oven, a hot plate, infrared rays, or the like can be used. The drying temperature and drying time may be within a range that allows the solvent to volatilize, and it is preferable to appropriately set a range that allows the photosensitive resin composition to be in an uncured or semi-cured state. Specifically, drying is preferably performed at a temperature in the range of 40°C to 150°C for 1 minute to several tens of minutes. Alternatively, the temperature may be increased stepwise using a combination of these temperatures; for example, heat treatment may be performed at 80°C and 90°C for 2 minutes each.

[0170] <Method for Producing Relief Pattern> A method for producing a relief pattern, which includes a step of applying the photosensitive resin composition of the present invention onto a substrate and drying it, a step of exposing the composition to light, a step of developing the composition using an alkaline developer, and a step of heat treatment, will be described below with specific examples.

[0171] The photosensitive resin composition of the present invention is applied to a substrate, or the photosensitive sheet is laminated to a substrate. Examples of substrates that can be used include, but are not limited to, copper-plated substrates, silicon wafers (silicon substrates), silicon carbide substrates, and gallium nitride substrates. Materials that can be used include ceramics and gallium arsenide. Application methods include spin coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the application technique, the solids concentration of the composition, and the viscosity, but the composition is typically applied so that the film thickness after drying is 0.1 to 150 μm.

[0172] To enhance the adhesion between the substrate and the photosensitive resin composition, the substrate can be pretreated with the aforementioned silane coupling agent. For example, the surface can be treated by spin coating, immersion, spray coating, steam treatment, or the like with a solution prepared by dissolving 0.5 to 20% by mass of the silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. In some cases, a subsequent heat treatment at 50°C to 300°C promotes the reaction between the substrate and the silane coupling agent.

[0173] Next, the substrate coated with the photosensitive resin composition or laminated with the photosensitive sheet is dried to obtain a photosensitive resin composition film. Drying is preferably carried out using an oven, a hot plate, infrared rays, or the like at a temperature in the range of 50°C to 150°C for 1 minute to several hours. In the case of a photosensitive sheet, the drying step is not necessarily required.

[0174] Next, the photosensitive resin composition film is exposed to actinic rays through a mask having a desired pattern. Actinic rays used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from a mercury lamp.

[0175] Next, a post-exposure bake treatment is carried out, with the temperature preferably being in the range of 50 to 180° C., and more preferably in the range of 60 to 150° C. The time is not particularly limited, but from the viewpoint of subsequent developability, a bake time of 10 seconds to several hours is preferred.

[0176] To form a resin pattern, after exposure, exposed or unexposed areas are removed using a developer. The developer used for development is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that dissolves in an alkaline aqueous solution, the developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. Examples of alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, may be added alone or in combination to these aqueous alkaline solutions.

[0177] After development, it is preferable to perform a rinsing treatment with water. When using water, the rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate to the water.

[0178] After development, a temperature of 150°C to 500°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to promote sufficient curing. The upper limit of the curing conditions is preferably 450°C or lower.

[0179] <Cured Product of the Photosensitive Resin Composition of the Present Invention> The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. Here, the term "cured product" refers to a product that has lost its film fluidity after being heat-treated at a temperature of 150°C to 500°C for 5 minutes to 5 hours. In other words, a product that does not lose its film fluidity even after being heat-treated at 500°C for 5 hours does not qualify as a cured product.

[0180] A cured product can be obtained by applying a photosensitive resin composition to a substrate and drying it to volatilize the solvent. Subsequently, exposure and post-exposure baking steps are performed as necessary, followed by curing at a temperature of 150°C to 400°C. This heat treatment is performed by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each. In the present invention, the lower limit of the curing conditions is preferably 170°C or higher, but more preferably 180°C or higher to ensure sufficient curing. The upper limit of the curing conditions is preferably 450°C or lower.

[0181] <Compounds in the Cured Product> The cured product of the present invention contains either or both of a compound having a structure represented by formula (9) and a compound having a structure represented by formula (10). These structures are contained in component (C) or component (D) in the photosensitive resin composition of the present invention. When the cured product contains these structures, the nitrogen moiety in the compound interacts with the metal surface, thereby obtaining a cured product having high adhesion to metal materials, particularly copper. When component (C) and / or component (D) in the resin composition of the present invention react or interact with component (A) during heat curing, the resulting bond will result in a structure represented by formula (9) or formula (10). Therefore, the cured product of the present invention may have only the structure represented by formula (9), only the structure represented by formula (10), or may simultaneously have the structure represented by formula (9) and the structure represented by formula (10). The compound having the structure represented by formula (9) and the compound having the structure represented by formula (10) are preferably contained in an amount of 0.01 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the cured film.

[0182] These structures in the cured product can be identified by nuclear magnetic resonance (NMR) analysis of the product obtained by hydrolyzing the cured product with alkali or the cured product itself. １ H-NMR, １３ The compound can be identified using 1C-NMR), infrared absorption spectroscopy (IR method), matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS), or the like.

[0183]

[0184] (In formulas (9) and (10), * represents a bond.)

[0185] <Electronic Component Comprising Cured Product> The electronic component of the present invention comprises the cured product of the present invention.

[0186] The cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or a protective film that constitutes an electronic component.

[0187] Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0188] Specific examples of the cured product in electronic components include passivation films for semiconductors, surface protective films for semiconductor elements, TFTs (Thin Film Transistors), and the like, interlayer insulating films such as interlayer insulating films between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers, insulating films and protective films for touch panel displays, and insulating layers for organic electroluminescent devices; however, the cured product is not limited to these and can have a variety of structures.

[0189] Furthermore, the electronic component of the present invention preferably comprises the cured product of the present invention on a substrate. The surface of the substrate on which the cured product is formed can be appropriately selected depending on the application and process. Examples of the substrate include a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, ceramics, gallium arsenide, metal, and epoxy resin. A silicon substrate, a silicon carbide substrate, or a gallium nitride substrate is preferred, and a silicon carbide substrate or a gallium nitride substrate is more preferred.

[0190] The present invention will be described below with reference to examples, but the present invention should not be construed as being limited by these examples. First, the evaluation methods used in each example and comparative example will be described. For the evaluation, a photosensitive resin composition before curing (hereinafter sometimes referred to as "varnish") that had been previously filtered through a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) with an average pore size of 1 μm was used.

[0191] (1) (A) Weight Average Molecular Weight of Resin The weight average molecular weight (Mw) of the resin or resin solution was measured in terms of polystyrene using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nippon Waters K.K.) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent.

[0192] (2) Esterification rate of polyamic acid Using a nuclear magnetic resonance (NMR) device (EX-270 manufactured by JEOL Ltd.), the esterification rate of a mixed solution of 10 mg of polyamic acid ester and 0.8 g of deuterated dimethyl sulfoxide (DMSO-d6) was measured. １ H-NMR was measured, and the integrated value of the peak derived from the aromatic protons of the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio of the peak derived from the methyl protons of the carboxylic acid ester and the ethylenically unsaturated double bond group. Since resins other than polyamic acid ester do not contain carboxylic acid esters, the esterification rate cannot be measured and is indicated by "-" in the table.

[0193] (3) Evaluation of the Content of the Compound Represented by Formula (5) and the Compound Represented by Formula (6) Relative to the (A) Resin 0.03 g of (A) resin, or 0.1 g of a resin solution containing 30 wt % of (A) resin, and 0.01 g of methyl 3-nitrobenzoate as an internal standard substance were dissolved in 0.7 g of deuterated dimethyl sulfoxide, and analyzed by NMR (GX-270, manufactured by JEOL Ltd.). Using the area of ​​the peak near 3.9 ppm derived from methyl 3-nitrobenzoate as a reference, the content [parts by mass] of the compound represented by formula (5) and the compound represented by formula (6) relative to the content of (A) resin was measured from the area of ​​each peak.

[0194] (4) Sensitivity The varnish was applied onto an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and prebaked at 100°C for 5 minutes to produce a prebaked film with a thickness of 15.0 μm in the case of a positive-type photosensitive resin composition. In the case of a negative-type photosensitive resin composition, a prebaked film with a thickness of 22.0 μm was produced. The film thickness was measured using a Lambda Ace STM-602 (manufactured by Dainippon Screen Mfg. Co., Ltd.) under a refractive index of 1.63. Thereafter, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the film was exposed to light at an exposure dose of 100 to 2000 mJ / cm through a mask having a 100 μm, 1:1 line and space pattern. ２ in the range of 50 mJ / cm ２Each exposure was performed. In the case of a negative photosensitive resin composition, after exposure, the composition was baked at 120°C for 1 minute after exposure. Thereafter, using the ACT-8 developing device, puddle development was performed for 120 seconds using a 2.38% by mass aqueous solution of tetramethylammonium (hereinafter referred to as "TMAH", manufactured by Tama Chemicals Co., Ltd.) as the developer, followed by rinsing with distilled water and shaking off to dry, thereby obtaining a pattern. The obtained pattern was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation). In the case of a positive photosensitive resin composition, the film thickness of the exposed area was measured, and the minimum exposure dose at which the film thickness of the exposed area was 5 nm or less (below the detection limit) and a line pattern with a mask size of 100 μm was determined, and this was taken as the sensitivity. In the case of a negative photosensitive resin composition, the film thickness of the exposed area was measured, and the minimum exposure dose at which the residual film ratio of the exposed area exceeded 80% and a line pattern with a mask size of 100 μm was determined, and this was taken as the sensitivity.

[0195] The sensitivity was judged as follows: ２ A, B, C, D and E are considered to be acceptable, and the sensitivity is less than 1000 mJ / cm ２ A: The minimum exposure dose for opening a 100 μm line pattern is 200 mJ / cm. ２ B: The minimum exposure dose for opening a 100 μm line pattern is 200 mJ / cm ２ or more and 400 mJ / cm ２ C: The minimum exposure dose for opening a 100 μm line pattern is 400 mJ / cm ２ or more and 600 mJ / cm ２ D: The minimum exposure dose for opening a 100 μm line pattern is 600 mJ / cm ２ or more and 800 mJ / cm ２ E: The minimum exposure dose for opening a 100 μm line pattern is 800 mJ / cm ２ or more and 1000 mJ / cm ２ F: The minimum exposure dose for opening a 100 μm line pattern is 1000 mJ / cm ２ That's all.

[0196] (5) Migration Resistance A varnish was applied to a migration evaluation substrate (WALTS-TEG ME0102JY; manufactured by Waltz Corporation) using a spin coater (MS-A100; manufactured by Mikasa Corporation), and then prebaked at 100°C for 5 minutes using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation). In the case of a positive-type photosensitive resin composition, a prebaked film with a film thickness of 15.0 μm was prepared. In the case of a negative-type photosensitive resin composition, a prebaked film with a film thickness of 18.0 μm was prepared. In the case of a negative-type photosensitive resin composition, a double-sided alignment single-sided exposure device (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) was used to measure migration resistance using the i-line (wavelength 365 nm) of an ultra-high pressure mercury lamp at 500 mJ / cm. ２ In the case of a negative photosensitive resin composition, after exposure, the composition was post-exposure baked at 120°C for 1 minute using the buzzer hot plate. The resulting film was thermally cured for 60 minutes at the temperature shown in Table 3 using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film with a thickness of approximately 10 µm.

[0197] Next, in the line-and-space pattern of the copper wiring of the comb teeth, a conductor was soldered to the measurement terminals with a line of 15 μm and a space of 10 μm to prepare an evaluation element. The prepared evaluation element was evaluated for insulation reliability under high temperature and high humidity using an insulation degradation characteristic evaluation system (ETAC SIR13; manufactured by Kusumoto Chemicals Co., Ltd.). The evaluation element was placed in a high-temperature, high-humidity chamber with test conditions set to a temperature of 85° C. and a humidity of 85% RH, and a voltage of 5.0 V was applied. The change in resistance value over time was measured at 5-minute intervals, and the resistance value was 1.0×10 ６The time (test time) until the resistance reached Ω or less was determined. This test time is an index of migration resistance. The determined test time was evaluated as follows: A+, A, B+, B, C+, and C, which are test times of 200 hours or more, were evaluated as pass; A+, A, B+, and B, which are test times of 400 hours or more, were evaluated as good; and A+ and A, which are test times of 800 hours or more, were evaluated as excellent. A+: Test time is 1,000 hours or more; A: Test time is 800 hours or more and less than 1,000 hours; B+: Test time is 600 hours or more and less than 800 hours; B: Test time is 400 hours or more and less than 600 hours; C+: Test time is 300 hours or more and less than 400 hours; C: Test time is 200 hours or more and less than 300 hours; D: Test time is 50 hours or more and less than 200 hours; E: Test time is less than 50 hours or cannot be measured.

[0198] (6) Adhesion Test An adhesion test to a metal material was carried out by the following method.

[0199] A substrate (copper-sputtered substrate) having a metal material layer formed on its surface by copper sputtering on a silicon wafer with a thickness of 200 nm was prepared. A varnish was applied to this substrate in the same manner as in (5), followed by exposure and heat treatment, to obtain a cured film with a thickness of approximately 10 μm.

[0200] Using a single-edged blade, 10 rows and 10 columns of grid-like cuts were made at 2 mm intervals on the heat-treated film. Next, a pressure cooker test (PCT) device (HAST CHAMBER EHS-211MD, manufactured by Tabai Spec Co., Ltd.) was used to perform a PCT treatment for 400 hours under saturated conditions of 121 ° C. and 2 atmospheres, and then the number of squares peeled out of 100 squares was counted by peeling with Cellotape (registered trademark), and the adhesion properties between the metal material and the cured resin film were evaluated. The results were judged as follows, with A, B, and C representing less than 40 peeled squares in the peel test being considered good, and D representing poor. A: 0 peeled squares; B: 1 to 10 peeled squares; C: 11 to 20 peeled squares; D: 21 or more peeled squares.

[0201] (7) Heat Resistance (5% Thermal Weight Loss Temperature Measurement) A varnish was applied to a silicon wafer in the same manner as in (5), followed by exposure and heat treatment, to obtain a cured film with a thickness of approximately 10 μm. The resulting cured film was peeled off from the silicon wafer to produce a single film (cured film). The 5% thermal weight loss temperature of the produced cured film was measured using a simultaneous differential thermal and thermogravimetric analyzer (Shimadzu Corporation, DTG-60A). This measurement was performed under the following conditions: test temperature: room temperature (25°C) to 550°C, heating rate: 10°C / min, measurement atmosphere: nitrogen, sample weight: 15 mg. The heat resistance in the examples and comparative examples was evaluated using the 5% thermal weight loss temperature [°C] of the single film (cured film) measured in this manner as an index of heat resistance, and was rated as follows: A was the best. A: 5% thermal weight loss temperature is 500°C or higher. B: 5% thermal weight loss temperature is 450°C or higher and lower than 500°C. C: 5% thermal weight loss temperature is 400°C or higher and lower than 450°C. D: 5% thermal weight loss temperature is 350°C or higher and lower than 400°C. E: 5% thermal weight loss temperature is lower than 350°C.

[0202] (8) Content of Halogen Element in Photosensitive Resin Composition (Halogen Content) Measured using a method in accordance with IEC 62321-3-2. As a pretreatment, a sample was combusted using a method in accordance with BS EN 14582, the combustion gas was absorbed in an absorption liquid, and the absorption liquid was measured using an ion chromatograph. Here, ppm is a unit of concentration based on weight, and is calculated as the weight of halogen (mg) per 1 kg of sample. <Combustion and Absorption Conditions> System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar / O ２ 200mL / min, O ２ 400 mL / min Absorption liquid: H ２ O ２ 0.1 mass% Absorption solution volume: 5 mL <Conditions for ion chromatography and anion analysis> System: ICS1600 (manufactured by DIONEX) Mobile phase: 2.7 mmol / L Na ２ CO ３ , 0.3 mmol / L NaHCO ３Flow rate: 1.50 mL / min Detector: electrical conductivity detector Injection volume: 100 μL Abbreviations of the compounds used in the synthesis examples and examples are listed below. BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd.) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane MAP: 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) NMP: N-methyl-2-pyrrolidone ODPA: 4,4'-oxydiphthalic anhydride DFA: dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd.) TDA-100: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dianhydride GBL: γ-butyrolactone OBBOC: 4,4'-oxybenzoyl chloride PBOM: compound of the structure shown below (1,1'-(4,4'-oxybis)benzoyldiimidazole)

[0203]

[0204] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane DAE: 4,4'-diaminodiphenyl ether NA: 5-norbornene-2,3-dicarboxylic anhydride XLN: 2,6-xylenol SAD: salicylaldehyde BAD: benzaldehyde HAD: formaldehyde HST: 4-hydroxystyrene STR: styrene MeTMS: methyltrimethoxysilane PhTMS: phenylmethoxysilane cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane TMOS: tetramethoxysilane HEMA: 2-hydroxyethyl methacrylate MPA: 3-methoxy-N,N-dimethylpropanamide (KJ Chemicals Co., Ltd.) DCC: dicyclohexylcarbodiimide DMIB: N,N-dimethylisobutyramide TrisP-HAP: Trade name, manufactured by Honshu Chemical Industry Co., Ltd. NAC-5: 5-naphthoquinone diazide sulfonyl chloride (manufactured by Toyo Gosei Co., Ltd.).

[0205] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (HA) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise to the solution. After the addition was completed, the mixture was stirred at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0206] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the autoclave using a balloon, and a reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After completion of the reaction, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HA) represented by the following formula:

[0207]

[0208] Synthesis Example 2: Synthesis of Polyimide (a-1) Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.2 g (0.005 mol) of SiDA, and 3.3 g (0.03 mol) of MAP as an end-capping agent were dissolved in 80 g of NMP. 31.2 g (0.1 mol) of ODPA was added to the solution together with 20 g of NMP, and the mixture was reacted at 60°C for 1 hour, followed by stirring at 180°C for 4 hours. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide (a-1).

[0209] Synthesis Example 3: Synthesis of Polyimide Precursor (a-2) Under a dry nitrogen stream, 51.4 g (0.085 mol) of the hydroxyl group-containing diamine (HA) obtained in Synthesis Example 1 and 1.2 g (0.005 mol) of SiDA were dissolved in 200 g of NMP. 31.0 g (0.100 mol) of ODPA was added thereto, and the mixture was stirred at 40°C for 2 hours. 2.2 g (0.02 mol) of MAP was then added as an end-capping agent along with 10 g of NMP, and the mixture was allowed to react at 40°C for 1 hour. Thereafter, a solution prepared by diluting 21.5 g (0.18 mol) of DFA with 10 g of NMP was added dropwise. After the dropwise addition, stirring was continued at 40°C for 2 hours. After stirring was completed, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The mixture was further washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyimide precursor (a-2).

[0210] Synthesis Example 4: Synthesis of Polyimide (a-3) Under a dry nitrogen stream, 30.03 g (0.100 mol) of TDA-100 and 100 g of GBL were added to a three-necked flask and dissolved with stirring at 60°C. Subsequently, 1.09 g (0.010 mol) of MAP and 32.96 g (0.090 mol) of BAHF were added and stirred at 60°C for 1 hour, and then the temperature was raised to 200°C and stirred for 4 hours. After stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide (a-3).

[0211] Synthesis Example 5: Synthesis of Polybenzoxazole Precursor (a-4) Under a dry nitrogen stream, 34.8 g (0.1 mol) of BAHF and 1.2 g (0.01 mol) of SiDA were dissolved in 200 g of NMP. Subsequently, while maintaining the temperature at 0 to 5°C, 23.6 g (0.08 mol) of 4,4'-oxybenzoyl chloride was added together with 50 g of NMP, and the mixture was allowed to react for 1 hour. The temperature was then returned to room temperature, and 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added together with 10 g of NMP, and the mixture was allowed to react for an additional 1 hour. After completion of the reaction, the solution was poured into 3.0 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days, yielding a powder of polybenzoxazole precursor (a-4).

[0212] Synthesis Example 6 Synthesis of Phenolic Resin (a-5) Phenolic resin (a-5) of Synthesis Example 6 was synthesized by the method described in Synthesis Example 5 in paragraph

[0120] of WO 2012 / 141165.

[0213] Synthesis Example 7 Synthesis of Polyhydroxystyrene (a-6) Polyhydroxystyrene (a-6) of Synthesis Example 7 was synthesized by the method described in Synthesis Example 23 in paragraph

[0742] of WO 2017 / 159876.

[0214] Synthesis Example 8 Synthesis of Polysiloxane (a-7) Polysiloxane (a-7) was synthesized by the method described in Synthesis Example 30 of paragraph

[0553] of WO 2017 / 057281.

[0215] Synthesis Example 9: Synthesis of Polyimide Precursor (a-8) 24.8 g (0.08 mol) of ODPA was placed in a 2-liter separable flask, and 21.9 g (0.17 mol) of HEMA and 310 g of MPA were added. 12.7 g (0.16 mol) of pyridine was added with stirring at room temperature to obtain a reaction mixture (ODPA-HEMA). After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then allowed to stand for a further 16 hours.

[0216] Next, under ice cooling, a solution of 28.9 g (0.14 mol) of dicyclohexylcarbodiimide (DCC) dissolved in 180 g of MPA was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 114.9 g (0.19 mol) of HA and 2.5 g (0.01 mol) of SiDA suspended in 230 g of MPA was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 31.0 g (0.16 mol) of ODPA was added, and stirring was continued at room temperature for 3 hours. Then, 4.3 g (0.04 mol) of MAP was added, and stirring was continued at room temperature for 1 hour. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0217] The reaction solution was poured into 3 L of water to obtain a white precipitate, which was collected by filtration, washed twice with water, washed once with isopropanol, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a polyimide precursor (a-8).

[0218] Synthesis Example 10: Synthesis of Polyimide Precursor (a-9) A polyimide precursor (a-9) was obtained in the same manner as in Synthesis Example 3, except that NMP was changed to MPA.

[0219] Synthesis Example 11 Synthesis of Polyimide Precursor (a-10) A polyimide precursor (a-10) was obtained in the same manner as in Synthesis Example 3, except that NMP was changed to DMIB.

[0220] Synthesis Example 12: Synthesis of Polyimide Precursor (a-11) A polyimide precursor (a-11) was obtained in the same manner as in Synthesis Example 3, except that the amount of DFA was changed from 21.5 g (0.18 mol) to 17.9 g (0.15 mol).

[0221] Synthesis Example 13: Synthesis of Polyimide Precursor (a-12) A polyimide precursor (a-12) was obtained in the same manner as in Synthesis Example 3, except that the amount of DFA was changed from 21.5 g (0.18 mol) to 23.8 g (0.20 mol).

[0222] Synthesis Example 14: Synthesis of quinone diazide compound (b-1) Under a dry nitrogen stream, 15.31 g (0.05 mol) of TrisP-HAP and 26.86 g (0.10 mol) of NAC-5 were dissolved in 450 g of 1,4-dioxane and the solution was allowed to warm to room temperature. A mixture of 50 g of 1,4-dioxane and 15.18 g of triethylamine was added dropwise to the solution, ensuring that the temperature in the reaction system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was removed by filtration, and the filtrate was poured into 3 L of water to obtain a precipitate. This precipitate was collected by filtration and washed with 1 L of 1 wt % hydrochloric acid. It was then washed twice with 2 L of water. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (b-1) represented by formula (4), in which an average of two Q groups per molecule were 5-naphthoquinone diazide sulfonate ester.

[0223]

[0224] Synthesis Example 15: Synthesis of Polyimide Precursor (a-13) Under a dry nitrogen stream, 22.0 g (0.085 mol) of BAP and 1.2 g (0.005 mol) of SiDA were dissolved in 200 g of NMP. 31.0 g (0.100 mol) of ODPA was added thereto, and the mixture was stirred at 40°C for 2 hours. 2.2 g (0.02 mol) of MAP was then added as an end-capping agent along with 10 g of NMP, and the mixture was allowed to react at 40°C for 1 hour. Thereafter, a solution prepared by diluting 23.8 g (0.2 mol) of DFA with 10 g of NMP was added dropwise. After the dropwise addition, stirring was continued for 2 hours at 40°C. After stirring was completed, the solution was poured into 2 L of water, and the precipitated polymer solid was collected by filtration. The mixture was further washed three times with 2 L of water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide precursor (a-13).

[0225] Synthesis Example 16: Synthesis of Polybenzoxazole Precursor (a-14) Under a dry nitrogen stream, 24.5 g (0.095 mol) of BAP and 1.2 g (0.005 mol) of SiDA were dissolved in 200 g of NMP. 28.7 g (0.08 mol) of PBOM was added together with 50 g of NMP, and the mixture was allowed to react at 85°C for 1 hour. Next, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added together with 10 g of NMP, and the mixture was allowed to react for an additional 1 hour. After completion of the reaction, the solution was poured into 3.0 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a forced-air dryer at 50°C for 3 days to obtain a powder of polybenzoxazole precursor (a-14).

[0226] Synthesis Example 17: Synthesis of Polyimide Precursor (a-15) A polyimide precursor (a-15) was obtained in the same manner as in Synthesis Example 9, except that HA was replaced with an equimolar amount of DAE.

[0227] Tables 1-1 and 1-2 show the measurement results of the constituent components (molar ratio), molecular weight (Mw), esterification rate [%], and content [parts by mass] of the compounds represented by formula (5) and formula (6) for Synthesis Examples 2 to 13, 15, and 16.

[0228]

[0229]

[0230] Examples and Comparative Examples The components were mixed as shown in Table 2 to obtain various resin compositions. The resin composition of Example 14 was prepared by adding 4.3 parts by mass of MPA to 100 parts by mass of resin (a-8) in Synthesis Example 9, while the resin composition of Example 15 was prepared by adding 4.0 parts by mass of MPA to 100 parts by mass of resin (a-9) in Synthesis Example 10, and the resin composition of Example 16 was prepared by adding 4.3 parts by mass of DMIB to 100 parts by mass of resin (a-10) in Synthesis Example 11. The values ​​in parentheses in Table 2 indicate the solids content [parts by mass] of each component. Using γ-butyrolactone as the solvent, the compositions were prepared so that the solids concentration was 45% by mass.

[0231]

[0232] The ingredients listed in Table 2 are as follows:

[0233] Component (A) (a-1), (a-3): The polyimide resin (a-1) and polyimide resin (a-3) described above, respectively. (a-2), (a-8) to (a-13), (a-15): The polyimide precursor resin (a-2), polyimide precursor resin (a-8) to polyimide precursor resin (a-13), polyimide precursor resin (a-15) described above, respectively. (a-4), (a-14): The polybenzoxazole precursor resin (a-4) and polybenzoxazole precursor resin (a-14) described above, respectively. (a-5): The phenolic resin (a-5) described above. (a-6): The polyhydroxystyrene resin (a-6) described above. (a-7): The polysiloxane resin (a-7) described above.

[0234] Component (B) (b-1): The above-mentioned quinone diazide compound (b-1) (b-2): CPI-310FG: a sulfonium salt containing a gallate ion (trade name, manufactured by San-Apro Co., Ltd.) (b-3): NCI-930 (manufactured by ADEKA Corporation).

[0235] Component (C) (c-1): MX-750LM (manufactured by Sanwa Chemical Co., Ltd.) (c-2): 1,3,5-triazine (manufactured by Tokyo Chemical Industry Co., Ltd.) (c-3): MW-390 (manufactured by Sanwa Chemical Co., Ltd.)

[0236]

[0237] Component (D) (d-1): X-12-1116 (manufactured by Shin-Etsu Chemical Co., Ltd.) (d-2): X-12-989MS (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0238]

[0239] Component (E) (e-1) NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) (e-2) NK Ester 1G (manufactured by Shin-Nakamura Chemical Co., Ltd.) Component (F) (f-1) HMOM-HAP (trade name: methoxymethyl crosslinker, manufactured by Honshu Chemical Industry Co., Ltd.) (f-2) YL980 (trade name: epoxy crosslinker, manufactured by Mitsubishi Chemical Corporation) (f-3) PG-100 (trade name: epoxy crosslinker, manufactured by Osaka Gas Chemicals) Other additives: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) Solvent: GBL (γ-butyrolactone, manufactured by Tokyo Chemical Industry Co., Ltd.) The properties of the obtained varnish were measured by the evaluation methods described above. Table 3 shows the heat curing temperature (represented as "heat treatment temperature" in the table) used in the evaluation of (5) migration resistance, the evaluation results of sensitivity and migration resistance, the evaluation results of the adhesion test, and the evaluation results of heat resistance.

[0240]

[0241] In Table 3, in the column "α>β≧γ", "○" indicates that "α>β≧γ" is true, "×" indicates that "α>β≧γ" is not true, and "-" indicates that the relationship was not determined. In addition, in the column "Halogen content", the elements detected are shown in parentheses for reference.

[0242] The above results show that the resin compositions of the Examples have excellent heat resistance, excellent adhesion to metal materials, particularly copper, and excellent migration resistance. In Comparative Examples 1 and 2, peeling of the cured film from the copper substrate was observed, and the insulation reliability was also low.

Claims

1. A photosensitive resin composition comprising (A) a resin, (B) a photosensitizer, (C) a compound represented by formula (1), and (D) a compound represented by formula (2). (R １ ~R ３ Each independently represents a hydrogen atom, NR ４ R ５ , or L(R ６ ) ｓ L represents an n-valent organic group having 6 to 10 carbon atoms and an aromatic ring; ４ and R ５ each independently represents a hydrogen atom, -CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ or -CH ２ OCH (CH ３ ) ２ represents R ６ Each independently represents -CH ２ OH, -CH ２ OCH ３ , -CH ２ OCH ２ CH ２ CH ２ CH ３ or -CH ２ OCH (CH ３ ) ２ n is an integer of 1 to 3, s is an integer of 0 to 2, and n-s is 1. (R ７ represents an oxygen atom or a sulfur atom. ８ is a divalent organic group having 1 to 4 carbon atoms; R ９ R represents a methyl group or an ethyl group. １０ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, or a monovalent aromatic group having 6 to 12 carbon atoms. Here, the monovalent hydrocarbon group having 1 to 18 carbon atoms and the monovalent aromatic group having 6 to 12 carbon atoms may have a heteroatom.

2. The photosensitive resin composition according to claim 1, wherein all or a part of the photosensitizer (B) is an oxime ester compound (B1-1).

3. A photosensitive resin composition according to claim 1 or 2, wherein the compound represented by formula (1) (C) is contained in an amount of 30 parts by mass or more and 1,200 parts by mass or less per 100 parts by mass of the compound represented by formula (2) (D).

4. The photosensitive resin composition according to claim 1 or 2, wherein, when the content of the photosensitizer (B) contained in the photosensitive resin composition is α parts by mass, the content of the compound (C) represented by formula (1) is β parts by mass, and the content of the compound (D) represented by formula (2) is γ parts by mass, α>β≧γ is satisfied, 1.0≦α / β≦4.5 is satisfied, and 0.4≦β / γ≦5.0 is satisfied.

5. The photosensitive resin composition according to claim 1 or 2, further comprising either or both of a compound represented by formula (5) and a compound represented by formula (6). (In formula (5), R １５ , R １６ and R １７ are each independently an alkyl group having 1 to 6 carbon atoms. １８ and R １９ are each independently an alkyl group having 1 to 6 carbon atoms. ２０ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

6. The photosensitive resin composition according to claim 1 or 2, wherein all or a part of the compound (D) represented by formula (2) is a compound having a structure represented by formula (4). (R １１ R represents a methyl group or an ethyl group. １２ R represents a divalent organic group having 1 to 4 carbon atoms. １３ ~R １４ each independently represents a carbon atom (i.e., a methine group) or a nitrogen atom.

7. The photosensitive resin composition according to claim 1 or 2, wherein all or a part of the compound (C) represented by formula (1) is a compound having a structure represented by formula (3). (R ６０ ~R ６５ each independently represents a hydrogen atom, -CH ３ , -CH ２ CH ２ CH ２ CH ３ or -CH(CH ３ ) ２ Represents.) 8. The photosensitive resin composition according to claim 1 or 2, wherein all or a part of the resin (A) is one or more resins selected from the group consisting of (A-1) a polyimide precursor, (A-2) a polyimide, (A-3) a polybenzoxazole precursor, (A-4) a polybenzoxazole, and copolymers thereof.

9. The photosensitive resin composition according to claim 8, wherein one or more resins selected from the group consisting of (A-1) a polyimide precursor, (A-2) a polyimide, (A-3) a polybenzoxazole precursor, (A-4) a polybenzoxazole, and copolymers thereof contain a phenolic hydroxyl group.

10. The photosensitive resin composition according to claim 8, wherein all or a part of the resin (A) is a polyimide precursor or a copolymer thereof containing a repeating structural unit represented by formula (7). (X １ represents a tetravalent group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. １ R represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. ２１ and R ２２ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.

11. The photosensitive resin composition according to claim 10, wherein the esterification rate of the polyimide precursor is 40 mol % or more and 80 mol % or less.

12. In the formula (7), X １ The photosensitive resin composition according to claim 10 , wherein all or a part of the structure represented by the formula (8) is a structure represented by the formula (8). (In formula (8), * represents a bond that bonds to an amide structure, a carboxylic acid structure, or a carboxylic acid ester structure.) 13. The photosensitive resin composition according to claim 1 or 2, wherein the amount of halogen elements contained in the photosensitive resin composition is 50 ppm or less.

14. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

15. An electronic part comprising the cured product according to claim 14.

16. The electronic component according to claim 15, comprising a silicon substrate, a silicon carbide substrate, or a gallium nitride substrate, and having the cured material on the substrate.

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