Photosensitive resin composition, cured product, and semiconductor element

Abstract

The present invention relates to a photosensitive resin composition containing a base resin containing a maleic imide compound, a crosslinking agent, and a photopolymerization initiator, the maleic imide compound being a reactant of a tetracarboxylic dianhydride, a diamine, and a maleic anhydride, the diamine includes a dimer diamine and a second diamine other than the dimer diamine.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product and a semiconductor element. Background Art

[0002] With the high integration, miniaturization and micronization of semiconductor elements, the insulating films used for the surface protection layer, interlayer insulating layer and redistribution layer of semiconductor elements are required to have better electrical properties, heat resistance, mechanical properties, etc. As a material for forming an insulating film having such properties, a photosensitive resin composition containing an alkali-soluble resin has been developed (for example, refer to patent documents 1, 2 and 3). These photosensitive resin compositions are applied and dried on a substrate to form a resin film, and a patterned resin film (a resin film having a pattern) is obtained by exposing and developing the resin film. Then, a patterned cured film (a cured film having a pattern) can be formed by heat curing the above-mentioned patterned resin film, and the patterned cured film can be used as an insulating film.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2008-309885

[0006] Patent Document 2: Japanese Patent Application Publication No. 2007-057595

[0007] Patent Document 3: International Publication No. 2010 / 073948 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] A photosensitive resin composition for forming an insulating film of a redistribution layer is required to form an insulating film having excellent photosensitivity and low dielectric properties. Therefore, an object of the present invention is to provide a photosensitive resin composition capable of forming an insulating film having excellent photosensitivity and low dielectric properties.

[0010] One embodiment of the present invention relates to the following photosensitive resin composition, cured product, and semiconductor element.

[0011] [1] A photosensitive resin composition comprising a base resin containing a maleimide compound, a crosslinking agent, and a photopolymerization initiator, wherein:

[0012] The maleimide compound is a reaction product of tetracarboxylic dianhydride, diamine, and maleic anhydride, and the diamine includes a dimer diamine and a second diamine other than the dimer diamine.

[0013] [2] The photosensitive resin composition according to [1] above, wherein

[0014] The tetracarboxylic dianhydride includes at least one selected from the group consisting of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, 4,4′-oxydiphthalic anhydride, and 1,2,3,4-butanetetracarboxylic dianhydride.

[0015] [3] The photosensitive resin composition according to [1] above, wherein

[0016] The tetracarboxylic dianhydride includes 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione.

[0017] [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein

[0018] The second diamine includes at least one selected from the group consisting of meta-xylylenediamine, 4,4′-diaminodiphenylmethane, 1,3-diaminopropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0019] [5] The photosensitive resin composition according to any one of [1] to [3] above, wherein

[0020] The second diamine includes norbornanediamine.

[0021] [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein

[0022] The crosslinking agent includes a polymerizable crosslinking agent having a (meth)acryloyl group.

[0023] [7] The photosensitive resin composition according to [6] above, wherein

[0024] The polymerizable crosslinking agent having a (meth)acryloyl group includes at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, tri-(2-(meth)acryloyloxyethyl)isocyanurate, and dioxane glycol di(meth)acrylate.

[0025] [8] The photosensitive resin composition according to any one of [1] to [6] above, wherein

[0026] The cross-linking agent includes a polymerizable cross-linking agent having an allyl group or a vinyl group.

[0027] [9] The photosensitive resin composition according to [8] above, wherein

[0028] The polymerizable crosslinking agent having an allyl group or a vinyl group includes at least one selected from the group consisting of 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl isocyanurate, and polyvinyl benzyl ether compounds.

[0029]

[10] The photosensitive resin composition according to any one of [1] to [9], further comprising a thermal polymerization initiator.

[0030]

[11] A cured product, which is a cured product of the photosensitive resin composition according to any one of [1] to

[10] above.

[0031]

[12] A semiconductor element having a redistribution layer formed from a cured product of the photosensitive resin composition according to any one of [1] to

[10] above.

[0032] Effects of the Invention

[0033] According to the present invention, there can be provided a photosensitive resin composition capable of forming an insulating film having excellent photosensitivity and low dielectric properties, a cured product of the photosensitive resin composition having low dielectric properties, and a semiconductor element having a redistribution layer including the cured product. DETAILED DESCRIPTION

[0034] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made without departing from the gist of the present invention.

[0035] In this specification, the numerical range represented by "~" represents the range in which the numerical values ​​recorded before and after "~" are included as the minimum and maximum values, respectively. In the numerical range recorded in stages in this specification, the upper limit or lower limit of the numerical range of a certain stage can be arbitrarily combined with the upper limit or lower limit of the numerical range of another stage. In the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. "A or B" can include any one of A and B, or both. Unless otherwise specified, the materials exemplified in this specification can be used alone or in combination of two or more. The content of each component in the composition, when there are multiple substances equivalent to each component in the composition, represents the total amount of the multiple substances present in the composition unless otherwise specified.

[0036] In this specification, "layer" and "film" include structures formed on a part of a surface in addition to structures formed on the entire surface when viewed from a top view. The term "process" includes not only independent processes, but also processes that achieve the desired purpose of the process even if they cannot be clearly distinguished from other processes.

[0037] In this specification, the so-called "(meth)acrylate" refers to at least one of "acrylate" and its corresponding "methacrylate", and the same applies to other similar expressions such as (meth)acrylic acid, (meth)acryloyl, etc. In this specification, "solid content" refers to non-volatile components other than volatile substances (water, solvent, etc.) contained in the photosensitive resin composition, and also includes components that are liquid, syrupy, or waxy at room temperature (about 25°C).

[0038] [Photosensitive resin composition]

[0039] The photosensitive resin composition of the present embodiment contains a base resin containing a maleimide compound, a crosslinking agent and a photopolymerization initiator as essential components. The photosensitive resin composition of the present embodiment may further contain a thermal polymerization initiator, a coupling agent, a rust inhibitor, a polymerization inhibitor, etc. as needed. The photosensitive resin composition of the present embodiment is a negative photosensitive resin composition, and the cured product of the photosensitive resin composition can be appropriately used as an insulating film for a redistribution layer. Below, each component used in the photosensitive resin composition of the present embodiment is described in more detail.

[0040] (Base resin)

[0041] The base resin contains a maleic imide compound (hereinafter also referred to as "(A) component".). The maleic imide compound of the present embodiment is a reaction product of tetracarboxylic dianhydride, diamine and maleic anhydride. (A) component is a compound formed by reacting tetracarboxylic dianhydride (a1) (hereinafter also referred to as "(a1) component".), diamine (a2) (hereinafter also referred to as "(a2) component".), and maleic anhydride (a3) ​​(hereinafter also referred to as "(a3) component".).

[0042] Examples of the component (a1) include pyromelitic dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonic acid tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-(4,4'-isopropylidene)diphenoxy ) diphthalic anhydride, 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho[1,2-C]furan-1,3-dione, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutane tetracarboxylic dianhydride, bicyclo[2.2.2]octane-7-ene-2,3,5,6-tetracarboxylic dianhydride, 4,4'-(acetylene-1,2-diyl)diphthalic anhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 3,4'-oxydiphthalic anhydride, 3,4'-biphenyltetracarboxylic dianhydride, 9,9-diphthalic anhydride (3,4-dicarboxyphenyl)fluorene dianhydride, 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 dianhydride, and 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride. The component (a1) may be used alone or in combination of two or more.

[0043] From the viewpoint of low dielectric properties, component (a1) may include at least one selected from the group consisting of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride (BPADA), 4,4'-oxydiphthalic anhydride (ODPA) and 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (TDA). From the viewpoint of dielectric properties, photosensitivity and heat resistance, component (a1) preferably includes TDA.

[0044] (a2) component includes a dimer diamine (the first diamine) and a second diamine other than the dimer diamine. Using dimer diamine as a diamine, a cured product with excellent dielectric properties can be obtained. On the other hand, when only dimer diamine is used as a diamine, the elastic modulus and Tg of the cured product will decrease. In contrast, by using the second diamine and dimer diamine in combination, the elastic modulus and Tg of the cured product can be increased.

[0045] For example, as described in Japanese Patent Application Laid-Open No. 9-12712, dimer diamine is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid. In this embodiment, known dimer diamines can be used without particular limitation. The dimer diamine may be a branched aliphatic diamine.

[0046] As the dimer diamine, a diamine represented by the following formula (1) can be used.

[0047]

[0048] In formula (1), R 2 and R 3 Each independently represents an alkylene group having 4 to 50 carbon atoms, and R 4 represents an alkyl group having 4 to 50 carbon atoms, R 5 It represents an alkyl group having 2 to 50 carbon atoms.

[0049] From the perspective of further improving flexibility and ease of synthesis, R 2 and R 3 Each of them independently is preferably an alkylene group having 5 to 25 carbon atoms, more preferably an alkylene group having 6 to 10 carbon atoms, and still more preferably an alkylene group having 7 to 10 carbon atoms. 4 It is preferably an alkyl group having 5 to 25 carbon atoms, more preferably an alkyl group having 6 to 10 carbon atoms, and still more preferably an alkyl group having 7 to 10 carbon atoms. 5 An alkyl group having 3 to 25 carbon atoms is preferred, an alkyl group having 4 to 10 carbon atoms is more preferred, and an alkyl group having 5 to 8 carbon atoms is further preferred.

[0050] As a commercial item of dimer diamine, PRIAMINE 1075, PRIAMINE 1074 (both manufactured by Croda Japan KK) etc. are mentioned, for example.

[0051] The second diamine is a diamine that does not conform to the above-mentioned dimer diamine. The second diamine may be a linear diamine. The second diamine may be used alone or in combination of two or more.

[0052] Examples of the second diamine include 1,3-diaminopropane, norbornanediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(aminomethyl)norbornane, m-xylenediamine, 4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 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, 4,4'-(hexafluoroisopropylidene)diphenylamine, 3( 4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, isophoronediamine, 4,4'-methylenebis(cyclohexylamino), 4,4'-methylenebis(2-methylcyclohexylamino), 1,1-bis(4-aminophenyl)cyclohexane, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl Phenyl ether, 1,3-bis(4-aminophenoxy)benzene, 1,3'-bis(3-aminophenoxy)benzene, 1,4'-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ketone, p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, bis[4-(3-aminophenoxy)phenyl]sulfonic acid, bis[4-(4-aminophenoxy)phenyl]sulfonic acid, 9,9-bis(4-aminophenyl)fluorene, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 2,7-diamino Fluorene, 2,2'-dimethylbenzidine (4,4'-diamino-2,2'-dimethylbiphenyl), 4,4'-diamino-2,2'-diethylbiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 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 and 4,4'-diamino-3,3'-dimethoxybiphenyl.

[0053] From the viewpoint of increasing the glass transition temperature (Tg) of the cured product, the second diamine may include at least one selected from the group consisting of norbornanediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. From the viewpoint of dielectric properties, photosensitivity and heat resistance, the second diamine preferably includes norbornanediamine.

[0054] In the component (a2), the molar ratio of the second diamine (the number of moles of the second diamine / (the number of moles of the dimer diamine+the number of moles of the second diamine)) can be 5 to 90 mol%, 10 to 85 mol%, 20 to 80 mol%, 25 to 75 mol%, 30 to 70 mol%, or 30 to 50 mol%. If the ratio is 5 mol% or more, it becomes easy to increase the elastic modulus and Tg of the cured product, and if the ratio is 90 mol% or less, a cured product having lower low dielectric properties can be formed.

[0055] The method for producing component (A) is not limited. Component (A) can be produced, for example, by reacting components (a1) and (a2) to synthesize an amine-terminated compound, and then reacting the amine-terminated compound with an excess of component (a3).

[0056] (A) component can be produced by various known methods. For example, first, (a1) component and (a2) component are subjected to addition polymerization reaction at a temperature of about 60 to 120° C., preferably at a temperature of 70 to 90° C., usually for about 0.1 to 2 hours, preferably for 0.1 to 1.0 hours. Then, the obtained addition polymer is further subjected to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of about 80 to 250° C., preferably at a temperature of 100 to 200° C., for about 0.5 to 30 hours, preferably for 0.5 to 10 hours. Then, the substance obtained by the dehydration ring-closure reaction and (a3) ​​component are subjected to a maleimide reaction, i.e., a dehydration ring-closure reaction, at a temperature of about 60 to 250° C., preferably at a temperature of 80 to 200° C., for about 0.5 to 30 hours, preferably for 0.5 to 10 hours, thereby obtaining the target (A) component.

[0057] (A) component may be a compound obtained by reacting (a1) component, (a2) component, triamine and (a3) ​​component. Examples of the triamine include tris(2-aminomethyl)amine, tris(2-aminoethyl)amine, tris(2-aminopropyl)amine, 2-(aminomethyl)-2-methyl-1,3-propylenediamine, trimerized 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.

[0058] In the imidization reaction or the maleimide reaction, various known reaction catalysts, dehydrating agents and organic solvents can be used.

[0059] As the reaction catalyst, for example, 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 and p-toluenesulfonic acid monohydrate can be cited. The reaction catalyst can be used alone or in combination of two or more. As the dehydrating agent, for example, aliphatic anhydrides such as acetic anhydride and aromatic anhydrides such as benzoic anhydride can be cited.

[0060] Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; alcohol solvents such as methanol, ethanol, isopropanol, butanol, pentanol, hexanol, propylene glycol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclopentanone, cyclohexanone, isophorone, and acetophenone; cellulose such as methyl cellulose and ethyl cellulose; esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, and γ-butyrolactone. Solvents; glycol ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-isobutyl 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-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide. The organic solvent can be used alone or in combination of two or more.

[0061] The (A) component can be purified by various known methods to improve the purity. For example, first, the (A) component dissolved in the organic solvent and pure water are placed in a separatory funnel. Then, the separatory funnel is shaken and left to stand. Then, after the aqueous layer and the organic layer are separated, only the organic layer is recovered, thereby purifying the (A) component.

[0062] The molecular weight of component (A) can be controlled by the molar number of component (a1) and component (a2). The smaller the molar number of component (a1) is than the molar number of component (a2), the lower the molecular weight can be. In order to easily achieve the effect of the present invention, usually, [the molar number of component (a1)] / [the molar number of component (a2)] is about 0.30 to 0.85, preferably in the range of 0.50 to 0.80.

[0063] The molecular weight of the component (A) may be 3000 to 100000, 4000 to 80000, 5000 to 60000, 6000 to 40000, or 7000 to 20000 in terms of weight average molecular weight (Mw) from the viewpoint of solubility in solvents and heat resistance. Mw can be measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.

[0064] (Crosslinking agent)

[0065] As a cross-linking agent (hereinafter also referred to as "component (B)"), a polyfunctional compound having two or more polymerizable groups can be used. Regarding the cross-linking agent, for example, when the photosensitive layer is exposed, not only can the cross-linking agents be cross-linked with each other, but also with component (A). And regarding the cross-linking agent, for example, when the resin film after pattern formation is heated, the polymerizable cross-linking agents can be cross-linked with each other. Component (B) can be a polymerizable cross-linking agent. The polymerizable group can be a photopolymerizable group or a thermal polymerizable group. As the polymerizable group, for example, (meth)acryloyl, allyl and vinyl can be mentioned. The cross-linking agent can be used alone or in combination of two or more.

[0066] From the viewpoint of excellent dielectric properties, the resin composition of the present embodiment may contain a polymerizable crosslinking agent having a (meth)acryloyl group as a crosslinking agent. Regarding the polymerizable crosslinking agent having a (meth)acryloyl group, when the photosensitive layer is exposed, not only the crosslinking agents are crosslinked with each other, but also with the (A) component. The polymerizable crosslinking agent having a (meth)acryloyl group may be an acrylate compound or a methacrylate compound. From the viewpoint of excellent dielectric properties, the (B) component may contain a methacrylate compound.

[0067] Examples of the polymerizable crosslinking agent having a (meth)acryloyl group include tricyclodecane dimethanol di(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, dioxane glycol di(meth)acrylate, alkoxylated glycerol 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, 1, 6-hexanediol 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, dipentatriol poly(meth)acrylate, alkoxylated dipentatriol poly(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, polyethylene glycol di(meth)acrylate and polypropylene glycol di(meth)acrylate.

[0068] From the viewpoint of excellent heat resistance, dielectric properties and photosensitivity, the polymerizable crosslinking agent having a (meth)acryloyl group may include 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, and from the viewpoint of excellent compatibility with the (A) component, tricyclodecane dimethanol di(meth)acrylate may be contained.

[0069] From the viewpoint of dielectric properties and heat resistance, the resin composition of the present embodiment may contain a polymerizable crosslinking agent having an allyl group or a vinyl group as a crosslinking agent. The polymerizable crosslinking agent having an allyl group or a vinyl group can crosslink the polymerizable crosslinking agents when the patterned resin film is heated.

[0070] Examples of the polymerizable crosslinking agent 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.

[0071] Examples of the polymerizable crosslinking agent having a vinyl group include polyvinyl benzyl compounds and polyvinyl benzyl ether compounds.

[0072] From the viewpoint of dielectric properties and photosensitivity, the polymerizable crosslinking agent having an allyl group or a vinyl group may include at least one selected from the group consisting of 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl isocyanurate and polyvinyl benzyl ether compounds.

[0073] From the viewpoint of further improving the balance between low dielectric properties and photosensitivity, the content of component (B) is preferably less than 50 parts by mass when the total amount of components (A) and (B) is 100 parts by mass, and can 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.

[0074] (Photopolymerization Initiator)

[0075] The photopolymerization initiator (hereinafter also referred to as "component (C)") is not particularly limited as long as it is a compound that starts polymerization by irradiation with active light (ultraviolet rays, etc.), and examples thereof include alkyl phenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction-type photopolymerization initiators, and oxime ester-based photopolymerization initiators.

[0076] Regarding the alkylphenone-based photopolymerization initiator, for example, it can be purchased as Omnirad 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 379EG, etc. manufactured by IGM Resins BV. Regarding the acylphosphine oxide-based photopolymerization initiator, for example, it can be purchased as Omnirad 819, Omnirad TPO H, etc. manufactured by IGM Resins B.V. Regarding the intramolecular hydrogen abstraction type photopolymerization initiator, for example, it can be purchased as Omnirad MBF, Omnirad 754, etc. manufactured by IGM Resins BV. Regarding the oxime ester-based photopolymerization initiator, for example, it can be purchased as Irgacure OXE01, Irgacure OXE02, etc. manufactured by BASF Japan Ltd. In order to promote the photoreaction, a titanocene-based photopolymerization initiator (for example, Irgacure 784 manufactured by BASF Japan Ltd.) may be used in combination.

[0077] From the viewpoint of easily obtaining excellent analytical properties, 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 based on 100 parts by mass of the total amount of the components (A) and (B).

[0078] (Thermal polymerization initiator)

[0079] From the viewpoint of promoting the polymerization reaction of the thermally polymerizable crosslinking agent, the photosensitive resin composition of the present embodiment may further contain a thermal polymerization initiator as component (D). As component (D), it is preferred that the compound decomposes by heating during curing to generate free radicals and promote the polymerization reaction of components (A) and (B). As component (D), for example, an organic peroxide can be cited.

[0080] Examples of the organic peroxide include methyl ethyl ketone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, n-butyl-4,4-bis(tert-butylperoxy)valerate, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, tert-butyl hydroperoxide, and p-butyl hydroperoxide. Menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-hexyl hydroperoxide, diisopropylbenzene peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, α,α'-bis(tert-butylperoxy)diisopropylbenzene, tert-butylisopropylbenzene peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-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-tert-butylcyclohexyl) peroxydicarbonate Ester, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, α,α'-bis(neodecanoyl peroxy)diisopropylbenzene, isopropylbenzene peroxyneodecanoate, 1,1,3,3,-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-butyl peroxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1-cyclohexyl Hexyl-1-methylethyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxymaleic acid, tert-butyl peroxylaurate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxyacetate, tert-hexyl peroxybenzoate, tert-butyl peroxy-m-toluoyl benzoate, tert-butyl peroxybenzoate, bis(tert-butylperoxy)isophthalate, tert-butyl peroxyallyl monocarbonate and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone.These can be used individually by 1 type or in combination of 2 or more types.

[0081] The content of the component (D) 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 based on 100 parts by mass of the total amount of the components (A) and (B).

[0082] (Coupling agent)

[0083] From the viewpoint of improving the adhesion of the cured product of the photosensitive resin composition, the photosensitive resin composition of the present embodiment may further contain a coupling agent. 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 acryl group, a methacryl group, an amino group, an ureide group, an isocyanate group, an isocyanurate group, a mercapto group, and the like.

[0084] As silane coupling agents having a vinyl group, KBM-1003, KBE-1003 (product names manufactured by Shin-Etsu Chemical Co., Ltd.. The same applies hereinafter.) and the like can be cited. As silane coupling agents having an epoxy group, KBM-303, 402, 403, KBE-402, 403, X-12-981S, X-12-984S and the like can be cited. As silane coupling agents having a styrene group, KBM-1403 and the like can be cited. As silane coupling agents having a methacryloyl group, KBM-502, 503, KBE-502, 503 and the like can be cited. As silane coupling agents having an acryl group, KBM-5103, X-12-1048, X-12-1050 and the like can be cited. As silane coupling agents having amino groups, KBM-602, 603, 903, 573, 575, KBE-903, 9103P, X-12-972F, etc. can be cited. As silane coupling agents having ureide groups, KBE-585, etc. can be cited. As silane coupling agents having isocyanate groups, KBE-9007, X-12-1159L, etc. can be cited. As silane coupling agents having isocyanurate groups, KBM-9659, etc. can be cited. As silane coupling agents having mercapto groups, KBM-802, 803, X-12-1154, X-12-1156, etc. can be cited. The silane coupling agent can be a silane coupling agent having a methacryloyl group. The silane coupling agent can be used alone or in combination of two or more.

[0085] 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 based on 100 parts by mass of the total amount of the components (A) and (B).

[0086] (Rust Inhibitor)

[0087] From the viewpoint of inhibiting the corrosion of copper wiring or preventing the discoloration of copper wiring, the photosensitive resin composition of the present embodiment may further contain a rust inhibitor. As the rust inhibitor, for example, triazole derivatives such as benzotriazole, tetrazole derivatives, etc. can be cited. The rust inhibitor can be used alone or in combination of two or more.

[0088] The content of the rust inhibitor may be 0.01 to 10 parts by mass, 0.1 to 5 parts by mass, or 0.5 to 3 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B).

[0089] (Polymerization Inhibitor)

[0090] The photosensitive resin composition of this embodiment may further contain a polymerization inhibitor. By using a polymerization inhibitor, the storage stability of the photosensitive resin composition can be ensured.

[0091] Examples of the polymerization inhibitor include 4-tert-butylcatechol, 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical, p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, gallol, phenothiazine, resorcinol, o-dinitrobenzene, p-dinitrobenzene, m-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferroline, 2,5-methoxyquinone, tannic acid, p-benzylaminophenol, tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid, and nitrosamines. The polymerization inhibitor may be used alone or in combination of two or more.

[0092] 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 based on 100 parts by mass of the total amount of the components (A) and (B).

[0093] (Sensitizer)

[0094] From the viewpoint of achieving both maintenance of the residual film rate in a wide range of exposure amounts and good resolution, the photosensitive resin composition may further contain a sensitizer.

[0095] Examples of the sensitizer include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-tert-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-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholine-1-propanone, diacetylbenzyl, benzyl dimethyl ketal, benzyl ketal, 1,2-diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, 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, aminophenyl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N-phenyldiethanolamine and 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone. The sensitizer may be used alone or in combination of two or more.

[0096] When the photosensitive resin composition contains a sensitizer, the content thereof is preferably 0.1 to 2.0 parts by mass, more preferably 0.2 to 1.5 parts by mass, based on 100 parts by mass of the component (A).

[0097] (Solvent)

[0098] The photosensitive resin composition of the present embodiment contains a solvent for dissolving / dispersing each component, and can be easily applied on a substrate to form a coating film with uniform thickness. The solvent may be used alone or in combination of two or more.

[0099] As the solvent, for example, ketones such as methyl ethyl ketone, cyclohexanone, and cyclopentanone; aromatic hydrocarbons such as toluene, xylene, mesitylene, and tetramethylbenzene; glycol ethers such as methyl cellulose, butyl cellulose, 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, ethyl cellulose 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-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

[0100] The amount of the solvent added is not particularly limited, and may be an amount such that the solid content in the photosensitive resin composition becomes 5 to 60% by mass, 10 to 50% by mass, or 15 to 40% by mass.

[0101] The preparation means and conditions of the photosensitive resin composition are not particularly limited. For example, a method in which each main component in a predetermined amount is sufficiently stirred and mixed with a stirrer or the like and then kneaded using a mixing roll, an extruder, a kneader, a roll, an extruder, etc. is cited. The kneading method is not particularly limited.

[0102] The relative dielectric constant of the cured product of the photosensitive resin composition of the present embodiment at 10 GHz may be 2.80 or less, 2.70 or less, 2.65 or less, or 2.60 or less. The dielectric loss tangent of the cured product of the photosensitive resin composition at 10 GHz may be 0.0050 or less, 0.0045 or less, 0.004 or less, or 0.0030 or less. The relative dielectric constant and dielectric loss tangent may be measured using a cured film of the photosensitive resin composition by the method described in the Examples.

[0103] The photosensitive resin composition of the present embodiment can form a fine pattern. The photosensitive resin composition of the present embodiment can form an insulating film showing low dielectric properties and excellent insulation reliability. A semiconductor element having an interlayer insulating layer formed by a cured product of the above-mentioned photosensitive resin composition and an electronic device comprising the semiconductor element can be produced. The semiconductor element can improve high-frequency characteristics by having a redistribution layer comprising a cured product of the photosensitive resin composition of the present embodiment. The semiconductor element can be, for example, a memory, a package, etc. having a multi-layer wiring structure, a redistribution structure, etc. As an electronic device, for example, a mobile phone, a smart phone, a tablet terminal, a personal computer, and a hard disk suspension can be cited. By having a patterned cured film formed by the photosensitive resin composition of the present embodiment, a semiconductor element and an electronic device with excellent reliability can be provided.

[0104] Example

[0105] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0106] [Synthesis of Maleimide Compounds]

[0107] In order to synthesize the maleimide compound, the following components (a1) to (a3), an acid catalyst, and a solvent were prepared.

[0108] ((a1) ingredient)

[0109] TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd., product name "TDA-100")

[0110] BPAF: 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (manufactured by JFE Chemical Corporation, product name "BPAF")

[0111] PMDA: Pyromelitic acid dianhydride (manufactured by Daicel Corporation)

[0112] BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by JFE Chemical Corporation, product name "BPDA")

[0113] (Component (a2))

[0114] DDA: Dimer diamine (manufactured by Croda Japan KK, product name "PRIAMINE1075")

[0115] NBDA: Norbornanediamine (manufactured by MITSUI FINE CHEMICALS, INC Co., Ltd.)

[0116] mTBHG: 4,4'-diamino-2,2'-dimethylbiphenyl (manufactured by SEIKA CORPORATION, product name "m-TB-HG")

[0117] BPF-AN: 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (manufactured by JFE Chemical Corporation, product name "BPF-AN")

[0118] (Component (a3))

[0119] Maleic anhydride (manufactured by Fuso Chemical Co., Ltd.)

[0120] (Acid Catalyst)

[0121] Methanesulfonic acid aqueous solution (manufactured by BASF, product name "Lutropur MSA")

[0122] (Solvent)

[0123] T-SOL 100 (manufactured by ENEOS Corporation, aromatic high boiling point solvent)

[0124] Solmix A-11 (manufactured by Japan Alcohol Trading CO., LTD, alcohol solvent)

[0125] Toluene (manufactured by Yamaichi Chemical Industries Co., Ltd.)

[0126] Trimethylol (manufactured by Toyo Gosei Co., Ltd., aromatic high boiling point solvent)

[0127] γ-Butyrolactone (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0128] (Synthesis example A1)

[0129] In a 1L flask container equipped with a cooler, a nitrogen inlet tube, a thermocouple, and a stirrer, 24.35 parts by mass of 1,3,3a,4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho[1,2-C]furan-1,3-dione (TDA-100), 132.69 parts by mass of T-SOL 100 (aromatic high boiling point solvent), and 29.33 parts by mass of solmix A-11 (alcohol solvent) were added. After the addition, the temperature was raised to 80°C, the temperature was kept for 0.5 hours, and 40.68 parts by mass of dimer diamine (DDA) was added dropwise. After the addition, 5.01 parts by mass of norbornane diamine (NBDA) was added. After the addition, 2.08 parts by mass of a methanesulfonic acid aqueous solution was added, and the temperature was raised to 160°C. After the temperature was raised, 40.00 parts by mass of toluene was added, and a dehydration ring-closure reaction was carried out at 160° C. for 1 hour to remove water and alcohol in the reaction solution, thereby obtaining an intermediate polyimide. Subsequently, the obtained polyimide was cooled to 130° C., 7.96 parts by mass of maleic anhydride was added, the temperature was raised to 160° C., and a dehydration ring-closure reaction was carried out at 160° C. for 4 hours to remove water in the reaction solution, thereby obtaining a maleimide compound.

[0130] The obtained maleic imide compound was placed in a separatory funnel, 500 parts by mass of pure water was added, and the separatory funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer were separated, and only the organic layer was recovered. The recovered organic layer was placed in a 1L glass container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, a stirrer and a vacuum pump, and the temperature was raised to 88-93°C. After removing water, the temperature was raised to 100°C, and the solvent was removed for 0.5 hours under a state of reducing the pressure by 0.1 MPa from the atmospheric pressure, thereby obtaining the maleic imide compound (A-1) of component (A).

[0131] The molecular weight of the maleic imide compound (A-1) was measured by GPC. The maleic imide compound was dissolved in tetrahydrofuran (THF) to a sample with a concentration of 3% by mass, and 50 μL was injected into a column (GL-R420 (manufactured by Hitachi High-Tech Corporation) × 1 root, GL-R430 (manufactured by Hitachi High-Tech Corporation) × 1 root, GL-R440 (manufactured by Hitachi High-Tech Corporation) × 1 root) heated to 30°C, and THF was used as a developing solvent, and the flow rate was 1.6 mL / min. The detector used an L-3350RI detector (manufactured by Hitachi, Ltd.), and the weight average molecular weight (Mw) was converted from the molecular weight / dissolution time curve made using standard polystyrene (manufactured by TOSOH CORPORATION) from the dissolution time. The Mw of (A-1) is 10900.

[0132] (Synthesis Example A2)

[0133] In a 0.3L flask container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, and a stirrer, 29.22 parts by mass of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 125.71 parts by mass of trimethylol, 126.95 parts by mass of solmix A-11, and 29.00 parts by mass of γ-butyrolactone were added. After the addition, the temperature was raised to 80°C, kept warm for 0.5 hours, 31.95 parts by mass of dimer diamine (DDA) was added dropwise, and then 5.41 parts by mass of 4,4'-diamino-2,2'-dimethylbiphenyl (mTBHG) was added. After the addition, 1.63 parts by mass of an aqueous solution of methanesulfonic acid was added, and the temperature was raised to 160°C. After the temperature was raised, 40.00 parts by mass of toluene was added, and a dehydration ring-closure reaction was carried out at 160°C for 1 hour to remove water and alcohol from the reaction solution, thereby obtaining an intermediate polyimide resin. Next, the polyimide resin was cooled to 130° C., 6.25 parts by mass of maleic anhydride was added, the temperature was raised to 160° C., and a dehydration ring-closure reaction was performed at 160° C. for 4 hours to remove water in the reaction solution, thereby obtaining a maleimide compound.

[0134] The obtained maleic imide compound was placed in a separatory funnel, 500 parts by mass of pure water was added, and the separatory funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer were separated, and only the organic layer was recovered. The recovered organic layer was placed in a 1L glass container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, a stirrer, and a vacuum pump, and the temperature was raised to 88-93°C. After removing water, the temperature was raised to 100°C, and a portion of the solvent was removed over 0.5 hours under a state of reducing the pressure by 0.1 MPa from the atmospheric pressure, thereby obtaining a solution of the maleic imide compound (A-2) of the component (A).

[0135] (Synthesis Examples A3 to A6)

[0136] Except having changed the compounding amount of each component as shown in Table 1, it carried out similarly to Synthesis Example A2, and obtained the solution of the maleimide compound (A-3) - (A-6).

[0137] (Synthesis Example A7)

[0138] In a 0.3L flask container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, and a stirrer, 39.39 parts by mass of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride (BPAF), 165.77 parts by mass of T-SOL 100, and 35.04 parts by mass of solmix A-11 were added. After the addition, the temperature was raised to 80°C, kept warm for 0.5 hours, and 43.07 parts by mass of dimer diamine (DDA) was added dropwise. After the addition, 5.30 parts by mass of norbornane diamine (NBDA) was added dropwise, and after the addition, the temperature was kept warm at 80°C for 0.5 hours. After the temperature was kept warm, 2.20 parts by mass of a methanesulfonic acid aqueous solution was added. After that, the alcohol in the reaction solution was removed and the temperature was raised to 160°C. After the temperature was raised, 50.00 parts by mass of toluene was added, and a dehydration ring-closure reaction was carried out at 160° C. for 2 hours to remove water and alcohol in the reaction solution, thereby obtaining an intermediate polyimide resin. Next, the obtained polyimide resin was cooled to 130° C., 8.42 parts by mass of maleic anhydride was added, the temperature was raised to 160° C., a dehydration ring-closure reaction was carried out at 160° C. for 4 hours to remove water in the reaction solution, thereby obtaining a maleimide compound.

[0139] The obtained maleic imide compound was placed in a separatory funnel, 500 parts by mass of pure water was added, and the separatory funnel was shaken and allowed to stand. After standing, the aqueous layer and the organic layer were separated, and only the organic layer was recovered. The recovered organic layer was placed in a 0.3L glass container equipped with a cooler, a nitrogen inlet pipe, a thermocouple, a stirrer, and a vacuum pump, and the temperature was raised to 88-93°C. After removing water, the temperature was raised to 100°C, and a portion of the solvent was removed over 0.5 hours under a state of reducing the pressure by 0.1MPa from the atmospheric pressure, thereby obtaining a solution of the maleic imide compound (A-7) of component (A).

[0140] (Synthesis Example A8)

[0141] Except having changed the compounding amount of each component as shown in Table 2, it carried out similarly to Synthesis Example A7, and obtained the solution of the maleimide compound (A-8).

[0142] (Synthesis Example A9)

[0143] A solution of maleimide compound (A-9) was obtained in the same manner as in Synthesis Example A7, except that BPAF was changed to 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione (TDA-100), norbornanediamine was changed to 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene (BPF-AN), and the amount of each component was changed as shown in Table 2.

[0144] (Non-volatile ingredients)

[0145] After 0.75 g±0.25 g of the solution of the maleimide compound was weighed with a precision balance and placed in a metal petri dish, it was dried at 150° C. for 0.5 hours with a hot air dryer, and the nonvolatile content (NV) was calculated by the following formula.

[0146] NV (mass %) = {(W3-W1) / W2} × 100

[0147] W1: Mass of the empty metal petri dish (g)

[0148] W2: Mass of the maleimide compound solution before drying (g)

[0149] W3: Mass of the dried metal petri dish + maleimide compound (g)

[0150] [Table 1]

[0151]

[0152] [Table 2]

[0153]

[0154] As the component (B), the following compounds were prepared.

[0155] A-DCP: tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

[0156] A-DOG: dioxane glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

[0157] A-9300: Tris-(2-acryloyloxyethyl)isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

[0158] DCP: tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name)

[0159] TA-G: 1,3,4,6-Tetraallyl glycoluril (manufactured by SHIKOKU KASEI HOLDINGS CORPORATION, product name)

[0160] TAIC: Triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, product name)

[0161] L-DAIC: Diallyl isocyanurate (manufactured by SHIKOKU KASEI HOLDINGS CORPORATION, product name)

[0162] Polyvinyl benzyl ether compound: the compound prepared in Synthesis Example B1 was used.

[0163] (Synthesis example B1)

[0164] 90 parts by mass of phenol aralkyl resin (manufactured by AIR WATER PERFORMANCE CHEMICAL INC., product name "HE100C-30", hydroxyl equivalent 174 g / eq), 83 parts by mass of chloromethylstyrene (manufactured by Linchuan Chemical Co., Ltd., a mixture of 17% by mass of o-chloromethylene and 83% by mass of p-chloromethylene), 17 parts by mass of tetrabutylphosphonium bromide (manufactured by Kanto Chemical Co., Inc.), 6 parts by mass of pure water, 113 parts by mass of toluene and 23 parts by mass of 2-propanol were placed in a 500 mL reaction container equipped with a stirring device, a thermometer, a reflux tube and an air pump, and air was blown in at a flow rate of 50 mL / min and mixed while stirring at 40° C. Then, the temperature was raised to 70° C., and 30 parts by mass of a 48% by mass sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 20 minutes. After the dropwise addition, the reaction was carried out while stirring at 70° C. for 4 hours, and the reaction solution was cooled at 25° C. and neutralized with a 10 mass % hydrochloric acid aqueous solution. The organic layer of the neutralized reaction solution was washed three times with pure water, and then the organic layer was put into methanol to recover the precipitate, thereby obtaining a polyvinyl benzyl ether compound. By measuring the infrared absorption (IR) spectrum of the polyvinyl benzyl ether compound, it was confirmed that the phenolic hydroxyl group of the phenol aralkyl resin had a structure substituted by a vinyl benzyl ether group.

[0165] The following compounds were prepared as the component (C), the component (D), a coupling agent, a polymerization inhibitor, a rust inhibitor, and a solvent.

[0166] (C) Component: Oxime ester photopolymerization initiator (manufactured by BASF Japan Ltd., product names "Irgacure OXE01" and "Irgacure OXE02")

[0167] (D) Component: α,α'-bis(tert-butylperoxy)diisopropylbenzene (manufactured by NOF CORPORATION, product name "PERBUTYL P")

[0168] Coupling agent: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KBM-503")

[0169] Polymerization inhibitor: 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical (TEMPOL) (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0170] Rust inhibitor: 1,2,3-benzotriazole (manufactured by JOHOKU CHEMICAL CO., LTD., product name "BT-120")

[0171] Solvent: Mesitylene (manufactured by Toyo Gosei Co., Ltd.)

[0172] [Photosensitive resin composition]

[0173] The components in the amounts (parts by mass, solid content) shown in Table 3 were mixed, stirred at 25° C. for 30 minutes or more, and then filtered through a filter having a mesh size of 0.5 μm to prepare photosensitive resin compositions of Examples 1 to 10.

[0174] (Dielectric properties)

[0175] The photosensitive resin composition was applied onto a copper foil using a knife coater, air-dried for 15 minutes, and dried in a dryer at 90° C. for 15 minutes to form a coating film. The coating film was exposed to light using a high-pressure mercury lamp (exposure: 1000 mJ / cm 2 ) and post-exposure baking (100°C, 1 minute) was performed on a hot plate to form a resin film with a thickness of 100 μm. Thereafter, the resin film was cured at 200°C for 2 hours in a nitrogen atmosphere using a clean oven. Next, the copper foil was dissolved and removed using ammonium persulfate to obtain a cured film.

[0176] The cured film was cut into pieces with a length of 80 mm and a width of 80 mm to prepare evaluation samples. The evaluation samples were measured for relative dielectric constant (Dk) and dielectric loss tangent (Df) at 10 GHz at room temperature using a SPDR dielectric resonator (manufactured by QWED) and an analyzer (manufactured by Agilent Technologies, product name "PNA Network Analyzer N5227A").

[0177] (5% weight loss temperature)

[0178] 6.0 to 10.0 mg of the cured film was weighed and placed in an open sample container (manufactured by Hitachi High-Tech Corporation, product name "GCA-0055"), and the 5% weight loss temperature (T) was measured under the conditions of a nitrogen flow rate of 300 mL / min, a starting temperature of 40°C, and a heating rate of 10°C / min. d5 ). As a measuring apparatus, NEXTA STA200RV (manufactured by Hitachi High-Tech Corporation) was used.

[0179] (photosensitive characteristics)

[0180] The photosensitive resin composition was spin-coated on the silicon wafer and heated and dried at 90° C. for 5 minutes using a hot plate to form a resin film with a thickness of 8 μm. Next, an i-ray stepper (manufactured by CERMA PRECISION, INC., product name “Sc6k”) was used at an exposure dose of 300 mJ / cm 2 After exposing the resin film to a pattern under the conditions of , it was heated at 100°C for 1 minute using a hot plate. Thereafter, it was immersed in a developer (a mixture of cyclopentanone and propylene glycol monomethyl ether acetate (PGMEA)) at 25°C for 20 seconds and cleaned with PGMEA. A metal microscope was used to confirm the peeling of the developed resin film from the silicon wafer, the cracks in the resin film, the roughness at the ends of the pattern, and the residue at the bottom of the pattern of the developed resin film. The case where these undesirable conditions could not be confirmed and the minimum through-hole diameter was less than 20μm was evaluated as "A", and the case where the minimum through-hole diameter exceeded 20μm was evaluated as "B".

[0181] [Table 3]

[0182]

[0183] The components in the amounts (parts by mass, solid content) shown in Table 4 were mixed, stirred at 25° C. for 30 minutes or more, and then filtered through a filter having a mesh size of 0.5 μm to prepare photosensitive resin compositions of Examples 11 to 15.

[0184] (photosensitive characteristics)

[0185] The photosensitive resin composition was spin-coated on the silicon wafer and dried by heating at 90°C for 5 minutes to form a resin film with a thickness of 7 μm. Then, a mask alignment exposure machine (MA-20) was used to expose the silicon wafer at an exposure dose of 1000 mJ / cm 2 After the resin film was pattern-exposed under the conditions of , it was heated at 100°C for 1 minute. The silicon wafer with the exposed resin film was developed with a developer (a mixture of cyclopentanone and PGMEA) at 25°C for 15 seconds and then cleaned with PGMEA. The presence or absence of cracks in the developed resin film was confirmed with a metal microscope. The case where these defects could not be confirmed was set as "A", and the case where defects were confirmed was set as "B" for evaluation.

[0186] [Table 4]

[0187]

[0188] The components in the amounts (parts by mass, solid content) shown in Table 5 were mixed, stirred at 25°C for 30 minutes or more, and then filtered through a filter with a mesh size of 0.5 μm to prepare photosensitive resin compositions of Examples 16 to 18. Dielectric properties, 5% weight loss temperature, and photosensitivity were evaluated in the same manner as in Examples 1 to 10.

[0189] [Table 5]

[0190]

Claims

1. A photosensitive resin composition comprising a base resin containing a maleimide compound, a crosslinking agent and a photopolymerization initiator, in, The maleimide compound is a reaction product of tetracarboxylic dianhydride, diamine, and maleic anhydride, and the diamine includes a dimer diamine and a second diamine other than the dimer diamine.

2. The photosensitive resin composition according to claim 1, in, The tetracarboxylic dianhydride includes at least one selected from the group consisting of 4,4′-(4,4′-isopropylidenediphenoxy)diphthalic anhydride, 4,4′-oxydiphthalic anhydride, and 1,2,3,4-butanetetracarboxylic dianhydride.

3. The photosensitive resin composition according to claim 1, in, The tetracarboxylic dianhydride includes 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-C]furan-1,3-dione.

4. The photosensitive resin composition according to any one of claims 1 to 3, in, The second diamine includes at least one selected from the group consisting of meta-xylylenediamine, 4,4′-diaminodiphenylmethane, 1,3-diaminopropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

5. The photosensitive resin composition according to any one of claims 1 to 3, in, The second diamine includes norbornanediamine.

6. The photosensitive resin composition according to any one of claims 1 to 5, in, The crosslinking agent includes a polymerizable crosslinking agent having a (meth)acryloyl group.

7. The photosensitive resin composition according to claim 6, in, The polymerizable crosslinking agent having a (meth)acryloyl group includes at least one selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, tri-(2-(meth)acryloyloxyethyl)isocyanurate, and dioxane glycol di(meth)acrylate.

8. The photosensitive resin composition according to any one of claims 1 to 6, in, The cross-linking agent includes a polymerizable cross-linking agent having an allyl group or a vinyl group.

9. The photosensitive resin composition according to claim 8, in, The polymerizable crosslinking agent having an allyl group or a vinyl group includes at least one selected from the group consisting of 1,3,4,6-tetraallyl glycoluril, triallyl isocyanurate, diallyl isocyanurate, and polyvinyl benzyl ether compounds. 10 . The photosensitive resin composition according to claim 1 , further comprising a thermal polymerization initiator. 11 . A cured product, which is a cured product of the photosensitive resin composition according to claim 1 . 12 . A semiconductor element comprising a redistribution layer comprising a cured product of the photosensitive resin composition according to claim 1 .

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