Photosensitive resin composition, cured product, and semiconductor element

Abstract

A photosensitive resin composition according to the present disclosure comprises a maleimide compound, a crosslinking agent, a photopolymerization initiator, and a rust prevention agent. The maleimide compound is a reaction product of a tetracarboxylic dianhydride (a1), an amine (a2), and maleic anhydride (a3), and the rust prevention agent contains a compound represented by formula (I).　[Formula 1] [In formula (I), X represents a carbon atom or a nitrogen atom, and R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing group. However, when X represents a nitrogen atom, R1 and R2 do not simultaneously represent hydrogen atoms.]

Description

Photosensitive resin composition, cured product, and semiconductor device

[0001] The present disclosure relates to a photosensitive resin composition, a cured product, and a semiconductor device.

[0002] As semiconductor elements become more highly integrated, smaller, and more minute, insulating films used in surface protection layers, interlayer insulating layers, rewiring layers, and the like of semiconductor elements are required to have better electrical properties, heat resistance, mechanical properties, and the like. Development of photosensitive resin compositions for forming insulating films having all of these properties has been progressing (see, for example, Patent Documents 1, 2, and 3). These photosensitive resin compositions are applied to a substrate and dried to form a resin film, which is then exposed to light and developed to obtain a patterned resin film (a patterned resin film). The patterned resin film can then be heat-cured to form a patterned cured film (a patterned cured film), which can be used as an insulating film.

[0003] JP 2008-309885 A JP 2007-057595 A International Publication No. 2010 / 073948 JP 9-12712 A

[0004] Metal wiring containing copper or the like is formed in the rewiring layer of a semiconductor element. From the viewpoint of preventing corrosion of the metal wiring, the use of a photosensitive resin composition containing a rust inhibitor has been considered. However, when a photosensitive resin composition containing a rust inhibitor is used, the metal wiring may be prone to discoloration. The present disclosure aims to provide a photosensitive resin composition, a cured product, and a semiconductor element that can prevent discoloration of the metal wiring.

[0005] One aspect of the present disclosure relates to the following photosensitive resin composition, a cured product of the photosensitive resin composition, and a semiconductor device. [1] The photosensitive resin composition according to one aspect of the present disclosure contains a maleimide compound, a crosslinking agent, a photopolymerization initiator, and a rust inhibitor, wherein the maleimide compound is a reaction product of a tetracarboxylic dianhydride (a1), an amine (a2), and maleic anhydride (a3), and the rust inhibitor includes a compound represented by formula (I) described below. [2] In the above [1], the amine (a2) may include a dimer diamine and a second amine other than the dimer diamine. [3] In the above [1] or [2], at least one of the tetracarboxylic dianhydride (a1) and the amine (a2) may include a compound having a fluorene skeleton. [4] In any of the above [1] to [3], the tetracarboxylic dianhydride (a1) may include at least one of 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride. [5] In any of the above [2] to [4], the second amine may include at least one of norbornanediamine and 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene. [6] A cured product according to one embodiment of the present disclosure is a cured product of the photosensitive resin composition according to any of the above [1] to [5]. [7] A semiconductor element according to one embodiment of the present disclosure has a rewiring layer including a cured product of the photosensitive resin composition according to any one of [1] to [5] above.

[0006] According to the present disclosure, it is possible to provide a photosensitive resin composition, a cured product, and a semiconductor element that can prevent discoloration of metal wiring.

[0007] Preferred embodiments of the present disclosure will be described in detail below. However, the present invention is not limited to the following embodiments and can be practiced in various modifications within the scope of the present disclosure.

[0008] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this specification, the upper or lower limit of a numerical range in a certain stage can be arbitrarily combined with the upper or lower limit of a numerical range in another stage. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in the examples. "A or B" may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. When multiple substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.

[0009] In this specification, the terms "layer" and "film" include not only structures with shapes formed over the entire surface when observed in a plan view, but also structures with shapes formed on a portion of the surface. The term "process" includes not only an independent process, but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0010] In this specification, "(meth)acryloyl" means at least one of "acryloyl" and its corresponding "methacryloyl," and the same applies to other similar expressions such as (meth)acrylic acid, (meth)acrylate, etc. In this specification, "solid content" refers to the non-volatile content excluding volatile substances (water, solvent, etc.) contained in the photosensitive resin composition, and also includes components that are liquid, syrup-like, or wax-like at room temperature (around 25°C).

[0011] [Photosensitive Resin Composition] The photosensitive resin composition according to this embodiment contains a maleimide compound, a crosslinking agent, a photopolymerization initiator, and a rust inhibitor. The photosensitive resin composition according to this embodiment is a negative photosensitive resin composition, and a cured product of the photosensitive resin composition can be suitably used as an insulating film for a rewiring layer. Hereinafter, each component used in the photosensitive resin composition according to this embodiment will be described in more detail.

[0012] (Maleimide Compound) The maleimide compound according to this embodiment (hereinafter also referred to as "component (A)") can be obtained by reacting a tetracarboxylic dianhydride (a1) (hereinafter also referred to as "component (a1)"), an amine (a2) (hereinafter also referred to as "component (a2)"), and maleic anhydride (a3) ​​(hereinafter also referred to as "component (a3)"). That is, the component (A) is a maleimide compound obtained by reacting the components (a1), (a2), and (a3). The component (A) may have multiple maleimide groups in the molecule. The component (A) may be a bismaleimide compound. The component (A) may be used alone or in combination of two or more types.

[0013] The tetracarboxylic dianhydride of component (a1) may be any known polyimide raw material. Examples of component (a1) include pyromellitic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 3, 3',4,4'-Benzophenonetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene- 2,3,5,6-tetracarboxylic dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(ethyne-1,2-diyl)diphthalic anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyl-3,4,3',4'-tetracarbo diphthalic anhydride, 3,4'-oxydiphthalic anhydride, 3,4'-biphthalic anhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride, 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic-5,5',6,6'-dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride.

[0014] From the viewpoint of low dielectric properties or high Tg, the component (a1) may be selected from the group consisting of 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5,5'-diphenyl-2,3-dione ... -(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride, 3,4'-biphthalic anhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)-2,4-dicarboxylic acid]anhydride. )phenyl]fluorene dianhydride, and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, and 9,9-bis[4- and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride.

[0015] The component (a2) may contain a dimer diamine (first amine) and a second amine other than a dimer diamine.

[0016] Dimer diamine is a compound derived from a dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, as described in, for example, JP-A-9-12712. By using dimer diamine as component (a2), the dielectric properties of the cured product can be reduced. In this embodiment, any known dimer diamine can be used without particular limitation. The dimer diamine may include, for example, at least one of a compound represented by the following formula (1) and a compound represented by the following formula (2):

[0017]

[0018]

[0019] In formulas (1) and (2), m, n, p, and q each represent an integer of 1 or greater selected so that m+n=6 to 17 and p+q=8 to 19, and the bond shown by a dashed line represents a carbon-carbon single bond or a carbon-carbon double bond. However, when the bond shown by a dashed line is a carbon-carbon double bond, formulas (1) and (2) have a structure in which the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond is reduced by one from the number shown in formulas (1) and (2).

[0020] As the dimer diamine, from the viewpoints of solubility in organic solvents, heat resistance, heat-resistant adhesion, low viscosity, etc., a compound represented by the above formula (2) may be used, and in particular a compound represented by the following formula (3) may be used.

[0021]

[0022] Commercially available dimer diamine products include, for example, PRIAMINE 1075 and PRIAMINE 1074 (both manufactured by Croda Japan Co., Ltd.).

[0023] The second amine is an amine that does not fall under the category of the above-mentioned dimer diamine. The second amine may be a diamine or a triamine. From the viewpoint of low dielectric constant, an alicyclic diamine may be used as the second amine. From the viewpoint of improving the elastic modulus and Tg of the cured product, an aromatic diamine may be used as the second amine.

[0024] When the second amine is a diamine, examples of the diamine include 1,3-diaminopropane, norbornanediamine, 4,4-methylenedianiline, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis[3-fluoro-4-aminophenyl]fluorene, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, 4,4'-(hexafluoroisopropylidene)dianiline, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 ２，６] decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), 1,1-bis(4-aminophenyl)cyclohexane, 2,7-diaminofluorene, 4,4'-ethylenedianiline, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylene Bis(2-ethyl-6-methylaniline), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]methane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ketone, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethylbiphenyl-4,4'-diamine, (4,4'-diamino)diphenyl ether, (3,3'-diamino)diphenyl ether, para-phenylenediamine, o-phenylenediamine, meta-phenylenediamine, bis[4-(3-aminophenoxy)phenyl]sulfone, meta-xylylenediamine, 4,4'-diamino-2,2'-diethylbiphenyl, 4,4'-diamino-3 ,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-diethylbiphenyl, 4,4'-diamino-3,3',5,5'-tetramethylbiphenyl, 4,4'-diamino-3,3',5,5'-tetraethylbiphenyl, 4,4'-diamino-2,2'-dimethoxybiphenyl, 4,4'-diamino-3,3'-dimethoxybiphenyl, and bis[4-(4-aminophenoxy)phenyl]sulfone.

[0025] When the second amine is a triamine, examples of the triamine include tris(2-aminomethyl)amine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, 2-(aminomethyl)-2-methyl-1,3-propanediamine, trimer triamine, 3,4,4'-triaminodiphenyl ether, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene, 1,2,3-triaminobenzene, 1,3,5-triazine-2,4,6-triamine, 2,4,6-triaminopyrimidine, 1,3,5-tris(4-aminophenyl)benzene, and 1,3,5-tris(4-aminophenoxy)benzene. From the viewpoint of the solubility of the synthesized component (A) in organic solvents, an aliphatic triamine may be used as the triamine. From the viewpoint of achieving a high Tg, tris(2-aminomethyl)amine and tris(2-aminoethyl)amine, which have a small number of carbon atoms, may be used.

[0026] From the viewpoint of high Tg and high modulus of elasticity, the second amine may include at least one of norbornanediamine and 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene.

[0027] In component (a2), the molar ratio of the second amine to the total amount of amines (moles of second amine / (moles of dimer diamine+moles of second amine)) may be 70 mol% or less, or may be 50 mol% or less, from the viewpoint of low dielectric properties of the cured product. When the second amine includes a diamine, the molar ratio of the diamine in the second amine to the total amount of diamines in component (a2) (moles of diamine in second amine / (moles of dimer diamine+moles of diamine in second amine)) may be 70 mol% or less, or may be 50 mol% or less, from the viewpoint of low dielectric properties of the cured product.

[0028] The use of dimer diamine as component (a2) can lower the dielectric properties of the cured product, while the use of a second amine in combination with dimer diamine can improve the modulus of elasticity and Tg while maintaining the dielectric properties of the cured product.

[0029] From the viewpoint of achieving a low dielectric constant, a low dielectric loss tangent, a high modulus of elasticity, and a high Tg, at least one of the above-mentioned component (a1) and component (a2) may contain a compound having a fluorene skeleton, or both of the above-mentioned component (a1) and component (a2) may contain a compound having a fluorene skeleton.

[0030] Component (A) can be produced by various known methods. For example, components (a1) and (a2) are first subjected to a polyaddition reaction at a temperature of 60 to 120°C or 70 to 90°C for 0.1 to 2 hours or 0.1 to 1.0 hour. The resulting polyaddition product is then subjected to an imidization reaction, i.e., a dehydration ring-closing reaction, at a temperature of 80 to 250°C or 100 to 200°C for 0.5 to 30 hours or 0.5 to 10 hours. The product resulting from the dehydration ring-closing reaction is then subjected to a maleimidization reaction, i.e., a dehydration ring-closing reaction, with component (a3) ​​at a temperature of 60 to 250°C or 80 to 200°C for 0.5 to 30 hours or 0.5 to 10 hours, thereby obtaining the desired component (A).

[0031] In the imidization reaction or maleimidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents can be used.

[0032] Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as pyridine, picoline, isoquinoline, and organic acids such as methanesulfonic acid, paratoluenesulfonic acid monohydrate, etc. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides such as benzoic anhydride.

[0033] Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and pseudocumene; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; ketone-based solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclopentanone, cyclohexanone, isophorone, and acetophenone; cellosolves such as methyl cellosolve and ethyl cellosolve, ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, and γ-butyrolactone; and ethylene glycol mononitrile. glycol ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether, and tetraethylene glycol mono-n-butyl ether; and nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. The organic solvents can be used alone or in combination of two or more.

[0034] Component (A) can be purified by various known methods to increase its purity. For example, first, component (A) dissolved in an organic solvent and pure water are placed in a separatory funnel. The separatory funnel is then shaken and allowed to stand. Subsequently, the aqueous layer and the organic layer are separated, and only the organic layer is recovered, thereby purifying component (A).

[0035] The assumed structure of the component (A) produced by the above method is shown in formula (4) below.

[0036]

[0037] In formula (4), each X independently represents a tetravalent organic group, each Y independently represents a divalent organic group, and a represents an integer of 1 or greater. Y represents a divalent organic group derived from component (a2). When the above-mentioned dimer diamine and a diamine that is a second amine other than dimer diamine are used as component (a2), at least one of the multiple Ys represents a divalent organic group derived from the above-mentioned dimer diamine, and at least one of the multiple Ys represents a divalent organic group derived from the above-mentioned second amine. Furthermore, X and Y may be organic groups having an aliphatic group, an alicyclic structure, or an aromatic ring, and may contain heteroatoms.

[0038] The molecular weight of component (A) can be controlled by the number of moles of component (a1) and component (a2), and the smaller the number of moles of component (a1) is relative to the number of moles of component (a2), the smaller the molecular weight can be. The number of moles of component (a1) per mole of component (a2), i.e., [number of moles of component (a1)] / [number of moles of component (a2)], may be 0.30 to 0.98, 0.30 to 0.90, 0.50 to 0.90, 0.60 to 0.90, or 0.60 to 0.80.

[0039] From the viewpoints of solubility in solvents and heat resistance, the weight average molecular weight (Mw) of the component (A) may be 3,000 to 40,000, 4,000 to 30,000, 5,000 to 28,000, or 7,000 to 27,000. Mw can be measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.

[0040] The content of the (A) component may be 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, or 80 parts by mass or more, when the total amount of the (A) component and the (B) component described below is 100 parts by mass.

[0041] (Crosslinking Agent) The crosslinking agent (hereinafter also referred to as "component (B)") may be a polymerizable crosslinking agent. The polymerizable group may be a photopolymerizable group or a thermally polymerizable group. Examples of the polymerizable group include a (meth)acryloyl group, an allyl group, and a vinyl group. The component (B) may be a polyfunctional compound having two or more polymerizable groups. The component (B) can crosslink not only with each other but also with the component (A), for example, during exposure of the photosensitive layer. The component (B) can crosslink with each other, for example, during heating of the resin film after pattern formation. The component (B) can be used alone or in combination of two or more.

[0042] From the viewpoint of dielectric properties, the component (B) may contain a polymerizable crosslinking agent having a (meth)acryloyl group. The polymerizable crosslinking agent having a (meth)acryloyl group can crosslink not only with itself but also with the component (A) during exposure of the photosensitive layer. The polymerizable crosslinking agent having a (meth)acryloyl group may be an acrylate compound or a methacrylate compound. From the viewpoint of dielectric properties, the component (B) may contain a methacrylate compound.

[0043] Examples of polymerizable crosslinking agents having a (meth)acryloyl group include tricyclodecane dimethanol di(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, dioxane glycol di(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkoxylated pentaerythritol tetra(meth)acrylate, and 1,6-hexane. Examples of the diol di(meth)acrylate include diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A (meth)acrylate, dipentaerythritol poly(meth)acrylate, alkoxylated dipentaerythritol poly(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate.

[0044] The polymerizable crosslinking agent having a (meth)acryloyl group may contain at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, and dioxane glycol di(meth)acrylate, from the viewpoints of heat resistance, dielectric properties, and microprocessability, and may contain tris-(2-(meth)acryloyloxyethyl)isocyanurate from the viewpoints of heat resistance and dielectric properties.

[0045] From the viewpoint of dielectric properties and heat resistance, component (B) may contain a polymerizable crosslinking agent having an allyl group or a vinyl group, which can crosslink with other polymerizable crosslinking agents when the resin film is heated after pattern formation.

[0046] Examples of polymerizable crosslinking agents having an allyl group include 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl monoglycidyl isocyanurate, diallyl monomethyl isocyanurate, diallyl isocyanurate, triallyl trimellitate, and triallyl orthoformate.

[0047] Examples of the polymerizable crosslinking agent having a vinyl group include a polyvinylbenzyl compound and a polyvinylbenzyl ether compound.

[0048] The polymerizable crosslinking agent having an allyl group or a vinyl group may contain at least one selected from the group consisting of 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl isocyanurate, and a polyvinyl benzyl ether compound from the viewpoint of dielectric properties and microprocessability, and may contain triallyl isocyanurate from the viewpoint of dielectric properties.

[0049] From the viewpoint of improving the balance between low dielectric properties and fine processability, the content of component (B) may be 1 to 45 parts by mass, 5 to 40 parts by mass, 8 to 30 parts by mass, or 10 to 20 parts by mass, relative to 100 parts by mass of the total amount of component (A) and component (B).

[0050] (Photopolymerization initiator) The photopolymerization initiator (hereinafter also referred to as "component (C)") is not particularly limited as long as it is a compound that initiates polymerization upon irradiation with actinic rays (ultraviolet rays, etc.), and examples thereof include alkylphenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction photopolymerization initiators, and oxime ester-based photopolymerization initiators.

[0051] Alkylphenone-based photopolymerization initiators are commercially available, for example, from IGM Resins B.V. as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 379EG, etc. Acylphosphine oxide-based photopolymerization initiators are commercially available, for example, from IGM Resins B.V. as Omnirad 819, Omnirad TPO H, etc. Intramolecular hydrogen abstraction photopolymerization initiators are commercially available, for example, from IGM Resins B.V. Omnirad MBF, Omnirad 754, etc. manufactured by BASF Japan Ltd. Oxime ester photopolymerization initiators are commercially available, for example, as Irgacure OXE01, Irgacure OXE02, etc. manufactured by BASF Japan Ltd. In order to promote the photoreaction, a titanocene photopolymerization initiator (for example, Irgacure 784 manufactured by BASF Japan Ltd.) may be used in combination.

[0052] From the viewpoint of easily obtaining excellent micro-processability, the content of the component (C) may be 0.1 to 10 parts by mass, 0.5 to 8 parts by mass, or 1 to 5 parts by mass relative to 100 parts by mass of the total amount of the component (A) and the component (B).

[0053] (Rust inhibitor) The rust inhibitor (hereinafter also referred to as "component (D)") contains a compound represented by the following formula (I). The photosensitive resin composition according to this embodiment can prevent discoloration of metal wiring by using the specific compound as the rust inhibitor. The component (D) can be used alone or in combination of two or more types.

[0054]

[0055] In formula (I), X represents a carbon atom or a nitrogen atom, and R １ and R ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing group, provided that when X represents a nitrogen atom, R １ and R ２ and R cannot be simultaneously a hydrogen atom. From the viewpoint of preventing discoloration, in formula (I), X may represent a nitrogen atom, and R１ may represent a hydrogen atom, and R ２ may represent a nitrogen-containing group.

[0056] The number of carbon atoms in the alkyl group may be 1 to 6, 1 to 4, or 1 to 3. The alkyl group may be linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

[0057] The number of carbon atoms in the aryl group may be 6 to 10 or 6 to 8. Examples of the aryl group include a phenyl group and a benzyl group.

[0058] Examples of the nitrogen-containing group include a group represented by the following formula (I-1) and an amino group (NH ２ From the viewpoint of preventing discoloration, the nitrogen-containing group may be an amino group.

[0059]

[0060] In formula (I-1), R ３ represents an alkylene group, and R ４ and R ５ R each independently represents an alkyl group. ３ The number of carbon atoms in the alkylene group represented by may be 1 to 3 or 1 to 2. ４ and R ５ The number of carbon atoms in the alkyl group represented by R may be 1 to 15, 3 to 12, or 5 to 10. ４ and R ５ The alkyl group represented by may be linear or branched. ４ and R ５ may be the same or different. From the viewpoint of preventing discoloration, R ４ and R ５ The group represented by formula (I-1) may be, for example, —CH ２ -N(C ８ H １７ ) ２ Examples include:

[0061] When X is a carbon atom, in order to prevent discoloration, in formula (I), R １ may be a group represented by formula (I-1), and R２ When X is a nitrogen atom, in order to prevent discoloration, R １ may be a hydrogen atom, and R ２ may be an amino group.

[0062] Component (D) may be a commercially available product, such as HAT (product name: 5-amino-1H-tetrazole, manufactured by Toyobo MC Co., Ltd.) or TA-LX (product name: 1-bis(2-ethylhexyl)aminomethyl-1,2,4-triazole, manufactured by Johoku Chemical Industry Co., Ltd.).

[0063] The content of component (D) may be 0.01 mass% or more, 0.10 mass% or more, 0.50 mass% or more, or 1.0 mass% or more, and may be 10.0 mass% or less, 8.0 mass% or less, 6.0 mass% or less, or 5.0 mass% or less, based on the mass of all components excluding the solvent in the photosensitive resin composition (total mass of solids). The content of component (D) may be 0.01 mmol / g or more, 0.05 mmol / g or more, 0.10 mmol / g or more, 0.12 mmol / g or more, 0.16 mmol / g or more, or 0.18 mmol / g or more, and may be 3.0 mmol / g or less, 1.0 mmol / g or less, or 0.5 mmol / g or less, based on the total mass of solids in the photosensitive resin composition.

[0064] The photosensitive resin composition according to this embodiment may further contain a coupling agent, a polymerization inhibitor, a thermal polymerization initiator, and the like, as needed.

[0065] (Coupling Agent) The photosensitive resin composition according to this embodiment may further contain a coupling agent (hereinafter also referred to as "component (E)") from the viewpoint of improving the adhesion of a cured product of the photosensitive resin composition. The coupling agent may be a silane coupling agent. The silane coupling agent may have, for example, a vinyl group, an epoxy group, a styryl group, an acryloyl group, a methacryloyl group, an amino group, a ureido group, an isocyanate group, an isocyanurate group, a mercapto group, or the like.

[0066] Examples of silane coupling agents having a vinyl group include KBM-1003 and KBE-1003 (product names manufactured by Shin-Etsu Chemical Co., Ltd.; the same applies hereinafter). Examples of silane coupling agents having an epoxy group include KBM-303, 402, 403, KBE-402, 403, X-12-981S, and X-12-984S. Examples of silane coupling agents having a styryl group include KBM-1403. Examples of silane coupling agents having a methacryloyl group include KBM-502, 503, KBE-502, and 503. Examples of silane coupling agents having an acryloyl group include KBM-5103, X-12-1048, and X-12-1050. Examples of silane coupling agents having an amino group include KBM-602, 603, 903, 573, 575, KBE-903, 9103P, and X-12-972F. Examples of silane coupling agents having a ureido group include KBE-585. Examples of silane coupling agents having an isocyanate group include KBE-9007 and X-12-1159L. Examples of silane coupling agents having an isocyanurate group include KBM-9659. Examples of silane coupling agents having a mercapto group include KBM-802, 803, X-12-1154, and X-12-1156. The silane coupling agent may be a silane coupling agent having a methacryloyl group. The silane coupling agents may be used alone or in combination of two or more.

[0067] The content of the silane coupling agent may be 0.01 to 10 parts by mass, 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

[0068] (Polymerization Inhibitor) From the viewpoint of storage stability, the photosensitive resin composition according to this embodiment may further contain a polymerization inhibitor (hereinafter also referred to as "component (F)"). Examples of polymerization inhibitors include 4-tert-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy radical, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, and nitrosamines. One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.

[0069] The content of the polymerization inhibitor may be 0.01 to 10 parts by mass, 0.05 to 5 parts by mass, or 0.10 to 2 parts by mass, relative to 100 parts by mass of the total amount of the components (A) and (B).

[0070] (Thermal Polymerization Initiator) The photosensitive resin composition according to this embodiment may further contain a thermal polymerization initiator in order to promote the polymerization reaction of the thermally polymerizable crosslinking agent. The thermal polymerization initiator may be a compound that decomposes upon heating during curing to generate radicals and promote the polymerization reaction of component (A) and component (B). Examples of the thermal polymerization initiator include organic peroxides.

[0071] Examples of organic peroxides include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxy)cyclohexane, t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3,-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxy Examples of peroxybenzoates include tert-butylperoxymethyl ...

[0072] The content of the thermal polymerization initiator is not particularly limited, but may be 0.1 to 10.0 parts by mass, 0.5 to 5.0 parts by mass, or 0.7 to 3.0 parts by mass relative to 100 parts by mass of the total amount of the components (A) and (B).

[0073] (Sensitizer) The photosensitive resin composition according to the present embodiment may further contain a sensitizer from the viewpoint of maintaining both a good resolution and a good film remaining rate over a wide range of exposure doses. The sensitizer may be used alone or in combination of two or more.

[0074] Examples of sensitizers include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetylbenzyl, benzil dimethyl ketal, and benzil. diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutylate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis(p-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethylaminobenzylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compounds, biscoumarin compounds, N-phenylglycine, N-phenyldiethanolamine, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone.

[0075] When the photosensitive resin composition contains a sensitizer, the content thereof may be 0.1 to 2.0 parts by mass, or 0.2 to 1.5 parts by mass, per 100 parts by mass of the component (A).

[0076] (Solvent) The photosensitive resin composition according to this embodiment contains a solvent for dissolving and dispersing each component, which makes it easy to apply the composition to a substrate and allows a coating film of uniform thickness to be formed. The solvent may be used alone or in combination of two or more.

[0077] Examples of the solvent include ketones such as methyl ethyl ketone, cyclohexanone, and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, pseudocumene, and mesitylene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, and γ-butyrolactone; and nitrogen-containing compounds such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

[0078] The amount of the solvent to be added is not particularly limited, but may be an amount such that the solid content in the photosensitive resin composition is 5 to 60 mass %, 10 to 50 mass %, or 15 to 40 mass %.

[0079] The preparation method, conditions, etc. of the photosensitive resin composition are not particularly limited. For example, a method may be used in which predetermined amounts of each main component are thoroughly and uniformly stirred and mixed using a mixer or the like, and then kneaded using a mixing roll, an extruder, a kneader, a roll, an extruder, etc. The kneading method is not particularly limited.

[0080] The photosensitive resin composition according to this embodiment can prevent discoloration of metal wiring. By using the photosensitive resin composition according to this embodiment, a semiconductor element having an interlayer insulating layer formed from a cured product of the photosensitive resin composition, and an electronic device including the semiconductor element can be produced. The semiconductor element may have a rewiring layer including a cured product of the photosensitive resin composition according to this embodiment. The semiconductor element may be, for example, a memory, a package, or the like having a multilayer wiring structure, a rewiring structure, or the like. Examples of electronic devices include mobile phones, smartphones, tablet terminals, personal computers, and hard disk suspensions.

[0081] The present disclosure will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0082] [Synthesis of Maleimide Compound] (Synthesis Example 1) Into a 1 L flask equipped with a condenser, a nitrogen inlet tube, a thermocouple, a stirrer, and a vacuum pump, 96.28 parts by mass of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (manufactured by JFE Chemical Corporation, trade name "BPAF"), 385.55 parts by mass of pseudocumene (manufactured by Toyo Gosei Co., Ltd.), 86.50 parts by mass of Solmix A-11 (trade name, manufactured by Japan Alcohol Sales Co., Ltd., an alcohol-based solvent mainly composed of ethanol), and 90.50 parts by mass of γ-butyrolactone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. After addition, the temperature was raised to 80°C and maintained at that temperature for 0.5 hours, and 90.21 parts by mass of dimer diamine (DDA) (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise. After the dropwise addition, 17.28 parts by mass of norbornanediamine (NBDA) (manufactured by Mitsui Fine Chemicals, Inc.) was added dropwise. The mixture was then kept at 80°C for approximately 0.25 hours. After keeping the temperature, 3.79 parts by mass of an aqueous methanesulfonic acid solution (manufactured by BASF under the trade name "Lutropur MSA") was added. The temperature was then raised to 160°C. After the temperature was raised, the pressure was reduced from atmospheric pressure to a reduced pressure of 0.03 MPa, and a dehydration ring-closing reaction was carried out at 160°C under reduced pressure for 2 hours. Water and alcohol in the reaction solution were removed, and an intermediate polyimide resin was obtained (imidization step). Subsequently, the pressure inside the reaction vessel was returned to atmospheric pressure, and the obtained polyimide resin was cooled to 130°C. 20.59 parts by mass of maleic anhydride (manufactured by Fuso Chemical Co., Ltd.) was added, and the temperature was raised to 160°C. A dehydration ring-closing reaction was carried out at 160°C for 4 hours under a reduced pressure of 0.03 MPa from atmospheric pressure, and water was removed from the reaction solution to obtain a maleimide compound (maleimidization step).

[0083] The resulting maleimide compound was placed in a separatory funnel, and 500 parts by mass of pure water was added. The separatory funnel was shaken and allowed to stand. After standing, the aqueous and organic layers separated, and only the organic layer was recovered. The recovered organic layer was placed in a 0.3 L glass vessel equipped with a cooler, a nitrogen inlet tube, a thermocouple, a stirrer, and a vacuum pump, heated to 88-93°C, and water was removed. The temperature was then raised to 100°C, and the solvent was partially removed for 0.5 hours under a reduced pressure of 0.1 MPa from atmospheric pressure, yielding a solution of maleimide compound (A-1) (non-volatile content 40% by mass), which is component (A). The Mw of maleimide compound (A-1) was 9,000.

[0084] Synthesis Example 2 A 0.3 L flask equipped with a condenser, a nitrogen inlet tube, a thermocouple, a stirrer, and a vacuum pump was charged with 18.48 parts by mass of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride (manufactured by JFE Chemical Corporation, trade name "BPAF"), 8.80 parts by mass of pyromellitic dianhydride (manufactured by Daicel Corporation), 125.9 parts by mass of pseudocumene (manufactured by Toyo Gosei Co., Ltd.), 33.6 parts by mass of Solmix A-11 (trade name, manufactured by Japan Alcohol Sales Co., Ltd., an alcohol-based solvent containing ethanol as the main component), and 33.25 parts by mass of γ-butyrolactone (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.). After the addition, the temperature was raised to 80°C and maintained at that temperature for 0.5 hours, and 27.57 parts by mass of dimer diamine (DDA) (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.), 10.85 parts by mass of 2,2'-dimethylbiphenyl-4,4'-diamine (trade name "m-TB-HG", manufactured by Wakayama Seika Kogyo Co., Ltd.), and 0.52 parts by mass of tris(2-aminoethyl)amine (Tokyo Chemical Industry Co., Ltd.) were added. Thereafter, the temperature was maintained at 80°C for approximately 0.25 hours. After maintaining the temperature, 2.70 parts by mass of an aqueous methanesulfonic acid solution (trade name "Lutropur MSA", manufactured by BASF) was added. Thereafter, the temperature was raised to 160°C. After the temperature increase, the pressure was reduced from atmospheric pressure to a state reduced by 0.03 MPa, and a dehydration ring-closing reaction was carried out under reduced pressure at 160°C for 3 hours, and water and alcohol were removed from the reaction solution to obtain an intermediate polyimide resin (imidization step). Subsequently, the pressure inside the reaction vessel was returned to atmospheric pressure, and the obtained polyimide resin was cooled to 130°C, and 7.93 parts by mass of maleic anhydride (manufactured by Fuso Chemical Co., Ltd.) was added, and the temperature was increased to 160°C. A dehydration ring-closing reaction was carried out under reduced pressure of 0.03 MPa from atmospheric pressure at 160°C for 4 hours, and water was removed from the reaction solution to obtain a maleimide compound (maleimide step).

[0085] The resulting maleimide compound was placed in a separatory funnel, and 500 parts by mass of pure water was added. The separatory funnel was shaken and allowed to stand. After standing, the aqueous and organic layers separated, and only the organic layer was recovered. The recovered organic layer was placed in a 0.3 L glass vessel equipped with a cooler, a nitrogen inlet tube, a thermocouple, a stirrer, and a vacuum pump, heated to 88-93°C, and water was removed. The temperature was then raised to 100°C, and the solvent was partially removed for 0.5 hours under a reduced pressure of 0.1 MPa from atmospheric pressure, yielding a solution of maleimide compound (A-2) (non-volatile content 44.4% by mass), which is component (A). The Mw of maleimide compound (A-2) was 12,000.

[0086] (Nonvolatile Content) 0.75 g±0.25 g of the maleimide compound solution was weighed out using a precision balance and placed in a metal Petri dish, and then dried in a hot air dryer at 150°C for 0.5 hours. The nonvolatile content (NV) was calculated using the following formula: NV (mass%)={(W3-W1) / W2}×100, where W1 is the mass (g) of the empty metal Petri dish, W2 is the mass (g) of the maleimide compound solution before drying, and W3 is the mass (g) of the metal Petri dish + maleimide compound after drying.

[0087] (Weight-average molecular weight) The Mw of the maleimide compound was measured by GPC (gel permeation chromatography). A sample prepared by dissolving the maleimide compound in tetrahydrofuran (THF) to a concentration of 3% by mass was injected in an amount of 50 μL into a column (GL-R420 x 1, GL-R430 x 1, GL-R440 x 1 (all manufactured by Hitachi High-Tech Fielding Corporation)) heated to 30°C, and measurement was carried out using THF as the developing solvent at a flow rate of 1.6 mL / min. The detector used was an L-3350 RI detector (manufactured by Hitachi, Ltd.), and the Mw was calculated from the elution time using a molecular weight / elution time curve prepared using standard polystyrene (manufactured by Tosoh Corporation).

[0088] [Photosensitive Resin Composition] Photosensitive resin compositions were prepared by mixing each component in the amounts (parts by mass, solid content) shown in Table 1 with a solvent (mesitylene, 210 parts by mass), stirring at 25°C for 30 minutes or more, and then filtering through a filter with a mesh size of 0.5 µm. The amounts of component (D) and component (D)' shown in Table 1 are in mmoles per gram of the total mass of the solid content of the photosensitive resin composition.

[0089] Details of each component in Table 1 are as follows: A-1: ​​Maleimide compound (A-1) synthesized in Synthesis Example 1 A-2: Maleimide compound (A-2) synthesized in Synthesis Example 2 A-9300: Tris-(2-acryloyloxyethyl)isocyanurate (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) TAIC: Triallyl isocyanurate (product name, manufactured by Mitsubishi Chemical Corporation) A-DOG: Dioxane glycol diacrylate (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.) OXE01: Oxime ester photopolymerization initiator (product name: Irgacure OXE01, manufactured by BASF Japan Ltd.) OXE02: Oxime ester photopolymerization initiator (product name: Irgacure OXE02, manufactured by BASF Japan Ltd.) HAT: 5-amino-1H-tetrazole (product name, manufactured by Toyobo MC Co., Ltd.) TA-LX: 1-bis(2-ethylhexyl)aminomethyl-1,2,4-triazole (product name, manufactured by Johoku Chemical Industry Co., Ltd.) BT-120SG: 1,2,3-benzotriazole (product name, manufactured by Johoku Chemical Industry Co., Ltd.) BT-LX: 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole (product name, manufactured by Johoku Chemical Industry Co., Ltd.) KBM-503: 3-methacryloxypropyltrimethoxysilane (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyradical (product name, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0090] [Evaluation] A photosensitive resin composition was spin-coated onto a silicon wafer A with a Cu sputtered film, and the resulting film was dried by heating at 70°C for 3 minutes using a hot plate to form a resin film with a thickness of 7 µm. The film was then exposed to light at an exposure dose of 1000 mJ / cm using a mask aligner exposure machine (MA-20 manufactured by Mikasa Co., Ltd.) and a 365 nm bandpass filter for mercury emission lines (100 mm x 100 mm, 2.2 mm thick manufactured by Asahi Spectroscopy Co., Ltd.). ２The wafer was subjected to pattern exposure under the conditions of (a) to obtain a 1 mm wide resin film, and then heated on a hot plate for 1 minute at 100° C. The exposed resin film was immersed twice in a developer (a mixed liquid of cyclopentanone and propylene glycol monomethyl ether acetate) at 25° C. for 15 seconds, and then washed with propylene glycol monomethyl ether acetate and cured for 2 hours at 200° C. in a nitrogen atmosphere to obtain a silicon wafer B with a Cu sputtered film on which a patterned cured film (insulating film) was formed.

[0091] Using a digital microscope VHX-6000 (manufactured by Keyence, illumination: coaxial incident light, lens: ZS20, magnification: 20x), the Cu sputtered film side of silicon wafer B (the area where copper was exposed by development) was observed, and an image of Cu not covered by an insulating film was obtained. Next, the "eyedropper function" (shutter speed: auto 70) of Microsoft PowerPoint (Powerpoint 2016) was used to obtain the RGB values ​​of the obtained Cu image (hereinafter also referred to as "RGB values ​​of Cu after treatment"). The RGB values ​​of Cu after treatment and the RGB values ​​of Cu formed on silicon wafer A (hereinafter also referred to as "RGB values ​​of Cu before treatment") were captured as three-dimensional coordinates, and the distance d between them was calculated using the following formula 1. The smaller the value of d, the better the color fastness. d = {(R ｓ -R ｃｕ ) ２ + (G ｓ -G ｃｕ ) ２ + (B ｓ -B ｃｕ ) ２} １／２ (Formula 1) In Formula 1, R ｓ , G ｓ and B ｓ indicates the RGB value of Cu after treatment, and R ｃｕ , G ｃｕ and B ｃｕ indicates the RGB values ​​of Cu before treatment, and R ｃｕ is 227, and G ｃｕ 186, B ｃｕ was 160.

[0092]

Claims

1. A photosensitive resin composition comprising a maleimide compound, a crosslinking agent, a photopolymerization initiator, and a rust inhibitor, wherein the maleimide compound is a reaction product of a tetracarboxylic dianhydride (a1), an amine (a2), and maleic anhydride (a3), and the rust inhibitor comprises a compound represented by the following formula (I): [In formula (I), X represents a carbon atom or a nitrogen atom, and R １ and R ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a nitrogen-containing group; provided that when X represents a nitrogen atom, R １ and R ２ does not simultaneously represent a hydrogen atom.

2. The photosensitive resin composition according to claim 1, wherein the amine (a2) comprises a dimer diamine and a second amine other than the dimer diamine.

3. The photosensitive resin composition according to claim 1, wherein at least one of the tetracarboxylic dianhydride (a1) and the amine (a2) contains a compound having a fluorene skeleton.

4. The photosensitive resin composition according to claim 1, wherein the tetracarboxylic dianhydride (a1) comprises at least one of 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride.

5. The photosensitive resin composition according to claim 2, wherein the second amine comprises at least one of norbornane diamine and 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene.

6. A cured product of the photosensitive resin composition according to any one of claims 1 to 5.

7. A semiconductor device having a rewiring layer comprising a cured product of the photosensitive resin composition according to any one of claims 1 to 5.