TW201831999A - Photosensitive resin composition, cured film and production method therefor, and electronic component - Google Patents

Abstract

To simultaneously achieve chemical resistance and crack resistance in a cured film obtained from a photosensitive resin composition comprising a phenolic hydroxyl-containing resin as an alkali-soluble resin. This photosensitive resin composition comprises a phenolic hydroxyl-containing resin (A), a photoacid generating agent (B), and a maleimide group-containing compound (C).

Description

Photosensitive resin composition, cured film, manufacturing method thereof, and electronic component

The present invention relates to a photosensitive resin composition which is preferably used for forming a surface protective film and an interlayer insulating film, etc., which are included in electronic parts and the like, and further relates to a cured film formed from the composition, and A manufacturing method thereof, and an electronic component having the cured film.

Conventionally, various photosensitive resin compositions have been proposed as materials used when forming a surface protective film, an interlayer insulating film, and the like for a semiconductor element in an electronic component. For example, a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin has been studied (Patent Literature 1 and Patent Literature 2). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-186300 [Patent Document 2] Japanese Patent Laid-Open No. 2013-210606

[Problems to be Solved by the Invention] In a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin, it is difficult to balance chemical resistance and turtle resistance of a cured film obtained from the photosensitive resin composition. The problem of cracking is presumed to be the following reason. When only a epoxy-based crosslinking agent is used for the crosslinking of a resin having a phenolic hydroxyl group, a hydroxyl group is generated by ring opening of an epoxy ring in a crosslinking reaction, and if only a methylol-based crosslinking is used, Agent, phenolic hydroxyl groups remain after the cross-linking reaction, so chemical resistance is poor. On the other hand, in order to improve chemical resistance, if an epoxy-based crosslinking agent or a methylol-based crosslinking agent is used to increase the crosslinking density of a cured film, the elongation physical properties of the cured film are reduced, and crack resistance is deteriorated. [Means for solving problems]

The present inventors have made intensive studies in order to solve the problems. As a result, it was found that a photosensitive resin composition of the following composition containing a resin having a phenolic hydroxyl group can solve the above problems, and completed the present invention.

The present invention is, for example, the following [1] to [8]. [1] A photosensitive resin composition comprising a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a compound (C) containing a maleimide group.

[2] The photosensitive resin composition according to the above [1], wherein the maleimide group-containing compound (C) includes a compound (C1) having two or more maleimide groups .

[3] The photosensitive resin composition according to the above [1] or [2], further comprising a crosslinking agent (D) (except for a compound (C) containing a maleimide group).

[4] The photosensitive resin composition according to the above [3], wherein the cross-linking agent (D) includes an epoxy-based cross-linking agent (D1) and has at least two groups consisting of -CH ₂ At least one type of crosslinking agent (D2) among the groups represented by OR (wherein R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorenyl group having 2 to 10 carbon atoms).

[5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the photoacid generator (B) contains a quinonediazide compound (B1).

[6] A method for producing a cured film, comprising: forming a resin film of the photosensitive resin composition according to any one of [1] to [5] on a support; A step of exposing the film; a step of developing the resin film with an alkaline developer to form a patterned resin film; and a step of heating the patterned resin film.

[7] A cured film formed from the photosensitive resin composition according to any one of [1] to [5].

[8] An electronic part having the hardened film of [7]. [Effect of the invention]

According to the present invention, it is possible to achieve both chemical resistance and crack resistance of a cured film obtained from a photosensitive resin composition containing a resin having a phenolic hydroxyl group as an alkali-soluble resin.

Hereinafter, the form for implementing this invention is demonstrated including a preferable aspect. [Photosensitive resin composition] The photosensitive resin composition of the present invention contains a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C) described below. ).

<Resin (A)> The resin (A) having a phenolic hydroxyl group includes, for example, a polymer (a1) containing a structural unit derived from a radically polymerizable monomer having a phenolic hydroxyl group (hereinafter, also referred to as fluorene polymerization). (A1) ｣), novolac resin (a2), polybenzoxazole precursor (a3), polyfluorene imide with phenolic hydroxyl group, phenol-xylylene glycol condensation resin, formazan Phenol-glycol condensation resin, phenol-dicyclopentadiene condensation resin. Among these, the polymer (a1), the novolac resin (a2), and the polybenzoxazole precursor (a3) are more preferable from the viewpoint of the hardenability of the composition, and the polymer (a a1). The resin (A) may be used singly or in combination of two or more kinds.

<< Polymer (a1) >> Examples of the polymer (a1) include homopolymers or copolymers of radical polymerizable monomers having a phenolic hydroxyl group, radical polymerizable monomers having a phenolic hydroxyl group, and other radicals. Copolymer of polymerizable monomers.

Examples of the radically polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, and p-isopropenylphenol Isohydroxystyrene monomer; one or more hydrogen atoms of the hydroxystyrene monomer are bonded to the aromatic ring carbon via an alkyl, alkoxy, halogen, haloalkyl, nitro or cyano group Substituted monomers; vinyl hydroquinone, 5-vinyl gallic phenol, 6-vinyl gallic phenol. In addition, a monomer in which the phenolic hydroxyl group of the monomer is protected by an alkyl group, a silyl group, or the like can also be mentioned. When using the monomer which protected the said phenolic hydroxyl group, the polymer (a1) which has a phenolic hydroxyl group can be obtained by removing this protection after formation of a polymer. These monomers may be used alone, or two or more of them may be used in combination.

Examples of other radical polymerizable monomers include styrenes such as styrene, α-methylstyrene, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Monomers; monomers in which styrenic monomers are substituted on the aromatic ring carbon with one or more hydrogen atoms substituted by alkyl, alkoxy, halogen, haloalkyl, nitro or cyano groups; Diene such as butadiene, isoprene, chloroprene; unsaturated carboxylic acids such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and their half esters; o-vinyl benzoic acid, m-vinyl benzoic acid, P-vinylbenzoic acid or monomers in which one or more hydrogen atoms bonded to an aromatic ring carbon are substituted with alkyl, alkoxy, halogen, haloalkyl, nitro or cyano ; (Meth) acrylates such as glycidyl (meth) acrylate, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl Pyrrolidone, vinylpyridine, vinyl acetate, N-phenylmaleimide, N-cyclohexyl horse (PEI), N- (meth) Bing Xixi phthalimide (PEI) oxy, (meth) acrylate, (3,4-epoxycyclohexyl) methyl methacrylate. These monomers may be used alone, or two or more of them may be used in combination.

In the polymer of the said radically polymerizable monomer, the total of the content ratio of the structural unit derived from the radically polymerizable monomer which has a phenolic hydroxyl group, and the structural unit derived from other radically polymerizable monomers 100 mol%, and the content ratio of the structural unit derived from the radically polymerizable monomer having a phenolic hydroxyl group is preferably 30 mol% or more, more preferably 40 mol% to 95 mol%.

Preferred examples of the polymer of the radical polymerizable monomer include polyparahydroxystyrene, m-hydroxystyrene / p-hydroxystyrene copolymer, p-hydroxystyrene / styrene copolymer, and p-hydroxystyrene / P-vinylbenzyl glycidyl ether / styrene copolymer, p-hydroxystyrene / (3,4-epoxycyclohexyl) methyl methacrylate copolymer, p-hydroxystyrene / methacrylic acid (3,4- A hydroxystyrene polymer such as epoxycyclohexyl) methyl ester / styrene copolymer.

<< Novolak Resin (a2) >> The novolak resin (a2) can be obtained, for example, by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2, 3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, gallophenol, α-naphthol, β-naphthol. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and salaldehyde.

Specific examples of the novolak resin (a2) include phenol / formaldehyde condensation novolac resin, cresol / formaldehyde condensation novolac resin, cresol / salaldehyde condensation novolac resin, phenol-naphthol / formaldehyde condensation novolac resin, A novolak resin is a resin modified from a rubbery polymer having a polymerizable vinyl group such as a butadiene-based polymer (for example, a resin described in Japanese Patent Laid-Open No. 2010-015101).

"Polybenzoxazole precursor (a3)" Examples of the polybenzoxazole precursor (a3) include polymers having a structural unit represented by formula (1). The polybenzoxazole precursor (a3) may be a polymer having one structural unit or a polymer having two or more structural units.

[Chemical 1] In formula (1), X is a divalent organic group, and Y is a tetravalent aromatic ring-containing group. N and OH bonded to Y form a pair, and N and OH of each pair are bonded to the same aromatic ring. Adjacent carbon atoms.

X is a divalent organic group include for example: carbon atoms may be halogenated, an arylene group having 6 to 20, by the formula ^{(g1): - Ar 1 -R} 1 -Ar 1 - represents a divalent group, the carbon The alkanediyl group having 1 to 10 and the cycloalkanediyl group having 3 to 20 carbon atoms. In the formula (g1), Ar ^{1 is} each independently an arylene group having 6 to 20 carbon atoms which can be halogenated, and R ¹ is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfofluorenyl group, a carbonyl group, and an alkanediyl group having 1 to 10 carbon atoms which can be halogenated.

Examples of the arylene group having 6 to 20 carbon atoms which can be halogenated include phenylene, methyl phenylene, third butyl phenylene, fluorophenylene, chlorophenylene, bromophenylene, and phenylene. Naphthyl. Examples of the alkanediyl group having 1 to 10 carbon atoms include methylene and ethane-1,2-diyl. Examples of the alkanediyl group having 1 to 10 carbon atoms that can be halogenated include methylene, dimethylmethylene, and bis (trifluoromethyl) methylene. Examples of the cycloalkanediyl group having 3 to 20 carbon atoms include cyclobutanediyl group, cyclopentanediyl group, and cyclohexanediyl group.

Examples of the tetravalent aromatic ring-containing group in Y include a tetravalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, and an anthracene ring, and the formula (g2):> Ar ² -R ² -Ar ² A tetravalent base represented by <.

In formula (g2), Ar ^{2 is} each independently a trivalent group derived from an aromatic hydrocarbon such as a benzene ring, a naphthalene ring, or an anthracene ring, and R ² is a direct bond or a divalent group. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfofluorenyl group, a carbonyl group, and an alkanediyl group having 1 to 10 carbon atoms which can be halogenated.

Examples of the aromatic hydrocarbons that form Y or Ar ² include aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene. Examples of the alkanediyl group having 1 to 10 carbon atoms that can be halogenated include methylene, dimethylmethylene, and bis (trifluoromethyl) methylene.

In the polybenzoxazole precursor (a3), the content ratio of the structural unit represented by formula (1) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The content ratio can be measured by, for example, a nuclear magnetic resonance method.

"Other resins" Other specific examples of the resin (A) include: Japanese Patent Laid-Open No. 2002-139835, Japanese Patent Laid-Open No. 2004-240144, Japanese Patent Laid-Open No. 2007-056108, and Japanese Patent Laid-Open No. 2010 -102271, Japanese Patent Laid-Open No. 2007-192936, Japanese Patent Laid-Open No. 2009-237125, and Japanese Patent Laid-Open No. 2012-123378. The details of the method for producing the resin (A) are also described in these documents.

"Composition of Resin (A)" From the viewpoint of the resolution of a photosensitive resin composition, the elastic modulus of a cured film, and crack resistance, the resin (A) is subjected to gel permeation chromatography (Gel Permeation Chromatography, The weight average molecular weight (Mw) measured by the GPC) method is generally 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 50,000 in terms of polystyrene. The details of the Mw measurement method are as described in the examples.

The resin (A) is preferably a resin in which 0.001 mg / ml or more is dissolved in a tetramethylammonium hydroxide aqueous solution (23 ° C.) having a concentration of 2.38% by mass. The content of the resin (A) is usually 30% to 95% by mass, preferably 40% to 90% by mass, and more preferably 50% by mass based on 100% by mass of the solid content of the photosensitive resin composition of the present invention. ~ 85% by mass. When the content ratio of the resin (A) is within the above range, there is a tendency that a photosensitive resin composition capable of forming a cured film having excellent resolution can be obtained. The solid content means all components other than the solvent mentioned later.

<Photoacid generator (B)> The photosensitive resin composition of this invention contains a photoacid generator (B). The photoacid generator (B) is a compound which generates an acid by a process including light irradiation. By the exposure processing performed on the resin film formed from the photosensitive resin composition of the present invention, an acid is generated in the exposed portion based on the photoacid generator (B), and based on the action of the acid, the exposed portion faces the alkaline developer. Change in solubility.

The photosensitive resin composition of the present invention may be either a positive type or a negative type. The type of the photoacid generator (B) can be appropriately selected depending on the positive or negative type. Examples of the photoacid generator (B) include a photoacid generator that can be used in a positive resist such as a compound having a quinonediazide group (quinonediazide compound); an onium salt compound and a halogen-containing compound Photoacid generators that generate strong acids upon irradiation with light, such as fluorene compounds, sulfonic acid compounds, sulfonylimine compounds, and diazomethane compounds, can be used in negative resists. Hereinafter, the quinonediazide compound is also referred to as fluorene quinonediazide compound (B1) ｣, and the other exemplary photoacid generators are also referred to as｢ other photoacid generators (B2) ｣.

The quinonediazide compound (B1) generates a carboxylic acid by a process including light irradiation and development using an alkaline developer. The resin film obtained from the composition containing a quinonediazide compound (B1) is a film which is hardly soluble with respect to an alkaline developing solution. Therefore, by using a quinonediazide compound (B1), a positive pattern can be formed.

The other acid generator (B2) is a compound that generates a strong acid upon irradiation with light. A resin film obtained from a composition containing another acid generator (B2) forms a crosslinked structure by acting on the below-mentioned crosslinking agent (D) and the like with the acid generated by light irradiation. Therefore, by using another acid generator (B2), a negative pattern can be formed.

"Quinonediazide compound (B1)" Examples of the quinonediazide compound (B1) include naphthoquinonediazide compounds, and compounds having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4 An ester compound of a sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of Japanese Patent Laid-Open No. 2014-186300, and these are described in this specification.

Specific examples of the quinone diazide compound (B1) include, for example, selected from 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, and 2,3,4-trihydroxy Benzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2 ', 4'-pentahydroxybenzophenone, tris (4-hydroxydiphenyl) methane , Tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methyl Ethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methyl Ethyl] -1,3-dihydroxybenzene, and 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] Phenyl] ethane compounds, and ester compounds with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid.

One kind of quinonediazide compound (B1) may be used, or two or more kinds may be used in combination. In the photosensitive resin composition of the present invention, when a quinonediazide compound (B1) is used as the photoacid generator (B), the content of the quinonediazide compound (B1) is 100 masses relative to the resin (A). The part is usually 5 to 50 parts by mass, preferably 10 to 40 parts by mass, and more preferably 15 to 35 parts by mass. When the content of the quinonediazide compound (B1) is equal to or more than the lower limit value, the residual film rate of the unexposed portion is increased, and an image faithful to the pattern mask is easily obtained. When the content of the quinonediazide compound (B1) is equal to or less than the above-mentioned upper limit value, it is easy to obtain a resin film having an excellent pattern shape, and it is also possible to prevent foaming during film formation.

<< Other acid generator (B2) >> The other acid generator (B2) is, for example, at least one selected from the group consisting of an onium salt compound, a halogen-containing compound, a sulfonium compound, a sulfonic acid compound, a sulfonylimine compound, and a diazomethane compound. . Specific examples of these compounds include compounds described in paragraphs [0074] to [0079] of Japanese Patent Laid-Open No. 2014-186300, and these are described in this specification.

In the photosensitive resin composition of the present invention, when another acid generator (B2) is used as the photoacid generator (B), the content of the acid generator (B2) is usually 100 parts by mass of the resin (A). 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 5 parts by mass. When content of other acid generator (B2) is more than the said lower limit, hardening of an exposure part will become sufficient and it will become easy to improve heat resistance. When the content of the other acid generator (B2) is at most the above-mentioned upper limit value, it is easy to obtain a pattern with a high resolution without lowering the transparency with respect to the exposure light.

<Maleimide imide group-containing compound (C)> The photosensitive resin composition of the present invention contains a maleimide imine group-containing compound (C). The compound (C) containing a maleimidine imine group is a compound having one or more maleimide imine groups, and the upper limit of the number of maleimide imine groups is preferably 10, more preferably 5.

The maleimide group is a group which directly acts on a phenolic hydroxyl group at the time of thermal cross-linking or the like, and for example, the following reaction is considered to proceed. In this reaction, the hydroxyl group is not a new generator, and a phenolic hydroxyl group is consumed.

[Chemical 2] Therefore, when the photosensitive resin composition contains a maleimide group-containing compound (C), for example, a crosslinked structure can be formed in a form that consumes the phenolic hydroxyl group of the resin (A) during post-baking. Here, by reducing the phenolic hydroxyl group in the cured film, chemical resistance can be improved even if the crosslinking density is not so increased.

The compound (C) containing a maleimide imine group is preferably a compound (C1) having two or more maleimide imine groups (hereinafter, also referred to as a “crosslinkable maleimide compound (C1)”. ), The ｢crosslinkable maleimide imine compound (C1) may, for example, be a compound represented by formula (C1). By using a crosslinkable maleimide compound (C1), it is composed of a photosensitive resin The hardened film formed from the object can further exert the effect of improving the chemical resistance.

[Chemical 3] In the formula (C1), R ^C1 is an organic group. Examples of the organic group include an aromatic ring-containing group such as an alkanediyl group and an arylene group; an alicyclic group such as a cycloalkyl group; The dimer acid obtained.

The carbon number of the alkanediyl group is usually 1 to 20, and preferably 2 to 10. Examples of the group containing an aromatic ring and the group containing an alicyclic ring include a group having 6 to 20 carbon atoms and a group having 3 to 20 carbon atoms. Examples thereof include a group represented by -AXA- and a group represented by -AOAXAOA- the group represented by -R ^C2 -AR ^C2 - group represented. A is a benzene ring or a cyclohexane ring, and each may independently have one or two or more substituents such as an alkyl group having 1 to 10 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. X is a direct bond, -O-, -SO _2- , an alkanediyl group having 1 to 10 carbon atoms, or an alicyclic group containing 3 to 20 carbon atoms. R ^C2 is an alkanediyl group having 1 to 10 carbon atoms.

Examples of the alkanediyl group include methylene, ethanediyl, propanediyl, hexanediyl, octanediyl, nonanediyl, and decanediyl. Examples of the arylene group include phenylene, methyl phenylene, tertiary butyl phenylene, and naphthyl. Examples of the cycloalkylene include cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl. Examples of the alkyl group include methyl, ethyl, and propyl. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alicyclic ring include a cyclohexane ring and a tricyclodecane ring.

Specific examples of the crosslinkable maleimide compound (C1) include N, N'-ethylidenebismaleimide, and N, N'-hexamethylenebismaleimide Amine, N, N '-(2,2,4-trimethylhexane) bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-methylene Phenylbismaleimide, N, N'-2,4-Methylphenylbismaleimide, N, N'-2,6-Methylphenylbismaleimide, N , N'-p-xylylenebismaleimide, N, N'-m-xylylenebismaleimide, N, N '-(1,3-dimethylenecyclohexane) bis Maleimide, N, N '-(1,4-dimethylenecyclohexane) bismaleimide, N, N'-(4,4'-biphenyl) bismaleimide Imine, N, N '-(4,4'-diphenylmethane) bismaleimide, N, N'-(4,4'-dicyclohexylmethane) bismaleimide, N , N '-(4,4'-diphenyloxy) bismaleimide, N, N'-(4,4'-diphenylfluorene) bismaleimide.

Examples of other specific examples of the crosslinkable maleimide compound (C1) include bis [4- (4-maleimidephenoxy) phenyl] methane and 2,2-bis [4 -(4-maleimide phenoxy) phenyl] propane, bis [4- (4-maleimide phenoxy) phenyl] octane, bis [4- (4-maleimide Imine phenoxy) phenyl] decane, bis [4- (4-maleimidoimidephenoxy) phenyl] cyclohexane, bis [4- (4-maleimidoimidephenoxy) ) Phenyl] -tricyclo- [5.2.1.O ^2.6 ] decane.

At least one hydrogen atom in a benzene ring and a cyclohexane ring in the exemplified compound may be independently substituted with a C _1-10 alkyl group, respectively. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group.

In addition, a bismaleimide compound having both ends of polyoxyalkylene diamine sealed with maleic anhydride may also be used. Examples thereof include a bismaleimide compound having both ends of polyoxyethylene diamine sealed with maleic anhydride, a bismaleimide compound having both ends of polyoxypropylene diamine sealed with maleic anhydride, and A bismaleimide compound whose both ends are sealed with maleic anhydride.

In addition, the compound (C) containing a maleimidine imine group (C2) (hereinafter, also referred to as a non-crosslinkable maleimide compound (C2)) may be used. ｣). When a non-crosslinkable maleimide compound (C2) is used, for example, the phenolic hydroxyl group of the resin (A) can also be consumed during post-baking, so that the chemical resistance of the obtained film can be improved. Moreover, when using a non-crosslinkable maleimide compound (C2), it is preferable to use a crosslinking agent (D) from a hardening viewpoint.

Examples of the non-crosslinkable maleimide compound (C2) include NC _6-20 arylmaleimide such as N-phenylmaleimide and N-o-methylphenylmaleimide. Amine; N-methyl maleimide, N-propyl maleimide, N-butyl maleimide, N-decyl maleimide, etc. NC _1-20 alkyl maleimide Fluorene imine; NC _3-20 cycloalkylmaleimide, such as N-cyclohexylmaleimide.

The maleimide group-containing compound (C) may be used singly, or two or more kinds may be used in combination. The content of the maleimide group-containing compound (C) in the photosensitive resin composition of the present invention is usually 0.1 to 200 parts by mass, and preferably 1 to parts by mass, based on 100 parts by mass of the resin (A). 100 parts by mass, more preferably 5 to 50 parts by mass. If the content of the maleimide-imide-containing compound (C) is within the above range, the cured film obtained from the photosensitive resin composition is excellent in both chemical resistance and crack resistance.

<Crosslinking agent (D)> The photosensitive resin composition of the present invention may contain a crosslinking agent (D) as an optional agent in order to improve the hardenability of the resin film and to balance the chemical resistance and crack resistance of the cured film. ingredient. The self-crosslinking agent (D) excludes the maleimide group-containing compound (C). The cross-linking agent (D) functions as a resin (A) or a cross-linking component (hardening component) that reacts with the cross-linking agent.

The cross-linking agent (D) preferably contains an epoxy-based cross-linking agent (D1) and has at least two groups represented by -CH ₂ OR (wherein R is a hydrogen atom and the number of carbon atoms is 1 to 2) At least one kind of crosslinking agent (D2) is an alkyl group having 10 alkyl groups or a fluorenyl group having 2 to 10 carbon atoms.

Examples of the epoxy-based crosslinking agent (D1) include phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, and naphthol-phenol co-condensation novolac epoxy Resin, naphthol-cresol co-condensation novolac epoxy resin, bisphenol epoxy resin, biphenyl epoxy resin, triphenol epoxy resin, tetraphenol epoxy resin, phenol-xylyl type Epoxy resin, naphthol-xylyl epoxy resin, phenol-dicyclopentadiene epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, biphenylarene Basic epoxy resin, resorcin epoxy resin, hydroquinone epoxy resin, catechol epoxy resin, dihydroxynaphthalene epoxy resin, alicyclic epoxy resin , Aliphatic epoxy resin.

The cross-linking agent (D2) has at least two groups represented by -CH ₂ OR. In the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorenyl group having 2 to 10 carbon atoms, and is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, and butyl. Examples of the fluorenyl group include ethenyl and the like. Here, regarding the group represented by -CH ₂ OR, it is considered that a methylene group reacts with an aromatic ring of the resin (A) by a heat or an acid, and a cross-linking reaction is performed.

Examples of the crosslinking agent (D2) include compounds having two or more groups represented by the formula (d2-1), compounds having two or more groups represented by the formula (d2-2), and methylol-containing phenols. Compounds, alkylhydroxymethyl-containing phenol compounds, fluorenylmethyl-containing phenol compounds.

[Chemical 4] In formula (d2-1) and formula (d2-2), m is 1 or 2, n is 0 or 1, m + n is 2, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 2 carbon atoms. A fluorenyl group of 10 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * is a bonding bond.

Examples of the crosslinking agent (D2) include nitrogen compounds such as polymethylolated melamine, polymethylolated glycoluril, polymethylolated guanamine, and polymethylolated urea; and the activity in the nitrogen compounds A compound in which all or part of a methylol group (a CH ₂ OH group bonded to an N atom) is alkyl etherified or fluorinated. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, a propyl group, and a butyl group. These may be the same as or different from each other. In addition, the reactive methylol group which is not alkyl etherified or fluorinated may be self-condensed in one molecule or condensed between two molecules. As a result, an oligomer component may be formed.

Examples of the crosslinking agent (D2) include the crosslinking agents described in Japanese Patent Laid-Open No. 6-180501, Japanese Patent Laid-Open No. 2006-178059, and Japanese Patent Laid-Open No. 2012-226297. Specific examples include melamine-based crosslinking agents such as polymethylolated melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine. ; Glycolil-based cross-linking agents such as polymethylolated glycoluril, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril; 3,9-bis [2- (3,5-diamine group -2,4,6-triazaphenyl) ethyl] 2,4,8,10-tetraoxospiro [5.5] undecane, 3,9-bis [2- (3,5-diamine -Methyl-2,4,6-triazaphenyl) propyl] 2,4,8,10-tetraoxospiro [5.5] undecane and other guanamine methylolated compounds, and the compounds A guanamine-based cross-linking agent such as a compound in which all or part of the active methylol groups are alkyl etherified or fluorinated. Among these, a melamine-based crosslinking agent and a guanamine-based crosslinking agent are preferred.

Examples of the hydroxymethyl-containing phenol compound, the alkylhydroxymethyl-containing phenol compound, and the methoxymethyl-group-containing phenol compound include, for example, a compound represented by the following formula, and 2,6-dimethoxymethyl Methyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethoxymethyl-p-cresol.

[Chemical 5] One type of crosslinking agent (D2) may be used, or two or more types may be used in combination.

As the crosslinking agent (D), other crosslinking agents (D3) other than the epoxy-based crosslinking agent (D1) and the crosslinking agent (D2) may be used. Examples of the other crosslinking agent (D3) include oxetane-containing compounds, oxazoline ring-containing compounds, isocyanate group-containing compounds (including those obtained by blocking), and aldehyde group-containing phenol compounds. .

In the photosensitive resin composition of the present invention, the content of the cross-linking agent (D) is usually 1 to 60 parts by mass, preferably 3 to 50 parts by mass, and more with respect to 100 parts by mass of the resin (A). It is preferably 5 parts by mass to 40 parts by mass. When the content of the crosslinking agent (D) is within the above range, a cured film having excellent chemical resistance and crack resistance can be formed. In addition, the composition has excellent curability.

<Solvent> The photosensitive resin composition of the present invention may contain a solvent. By using a solvent, the operability of the photosensitive resin composition of the present invention can be improved, and viscosity or storage stability can be adjusted.

Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol Propylene glycol monoalkyl ethers such as monobutyl ether; Propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, and other propylene glycol dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and other propylene glycol monoalkyl ether acetates; cellosolvents such as ethyl cellosolve and butyl cellosolve; carbitols such as butylcarbitol Alcohols; lactates such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid Aliphatic carboxylic acid esters such as n-pentyl ester, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc .; methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate Other esters such as esters; Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-dimethylformamide, N-methylacetamide, N, N-dione Methylamines such as methylacetamide and N-methylpyrrolidone; lactones such as γ-butyrolactone; aromatic hydrocarbons such as toluene and xylene.

Among these, lactones, lactates, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers are preferred; γ-butyrolactone, ethyl lactate, and propylene glycol monomethyl ether ethyl are more preferred. Acid ester, propylene glycol monomethyl ether.

One kind of solvent may be used, or two or more kinds may be used in combination. When using a solvent, the content ratio of the solvent in the photosensitive resin composition of this invention is 10 to 95 mass% normally, Preferably it is 30 to 90 mass%.

<Other Additives> In addition to the photosensitive resin composition of the present invention, it may contain an adhesion promoter, crosslinked fine particles, a leveling agent, a surfactant, and a sensitizer within a range that does not impair the object and characteristics of the present invention. Additives, inorganic fillers, quenchers, and alkali solubility promoters.

<The manufacturing method of a photosensitive resin composition> The photosensitive resin composition of this invention can be prepared by mixing each component uniformly. In addition, in order to remove foreign matter, the components may be uniformly mixed, and then the obtained mixture may be filtered through a filter or the like.

[Curable Film and Production Method thereof] The cured film of the present invention is formed from the photosensitive resin composition. By using the photosensitive resin composition, a patterned cured film having high chemical resistance and crack resistance and high resolution can be produced.

Therefore, the photosensitive resin composition of the present invention can be preferably used for forming a cured film and an insulating film. For example, the photosensitive resin composition can be preferably used as a surface of an electronic component such as a circuit board (semiconductor element), a semiconductor package, or a display element. Forming materials such as a protective film, an interlayer insulating film, and a planarization film, or an insulating film material for a high-density mounting substrate.

A production example of the cured film of the present invention is shown below. This manufacturing example includes a step of forming a resin film of the photosensitive resin composition of the present invention on a support (film forming step); and a step of exposing the resin film through a desired pattern mask (exposure step) ; Developing the resin film with an alkaline developing solution, dissolving and removing the exposed portion in the case of the positive type, and dissolving and removing the non-exposed portion in the case of the negative type, thereby forming on the support; A step of developing a desired patterned resin film (development step); and a step of heating the patterned resin film (heating step).

[1] Film formation step In the film formation step, the photosensitive resin composition is coated on a support such that the film thickness of the finally obtained cured film becomes, for example, 0.1 μm to 100 μm. This is heated using an oven or a hot plate at, for example, 50 ° C to 140 ° C for 10 seconds to 360 seconds (pre-baking). In this manner, a resin film is formed on a support.

Examples of the support include a silicon wafer, a compound semiconductor wafer, a wafer with a metal film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, and a substrate having a semiconductor wafer on the surface of the support. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a screen printing method, and an inkjet method.

[2] Exposure step In the exposure step, a desired pattern mask is separated, and the resin film is exposed using, for example, a contact aligner, a stepper, or a scanner. Examples of the exposure light include ultraviolet rays and visible rays. For example, light having a wavelength of 200 nm to 500 nm (for example, i-rays (365 nm)) is used. The irradiation dose of actinic rays varies depending on the type of each component in the photosensitive resin composition, the blending ratio, the thickness of the resin film, etc., but the exposure dose is usually 100 mJ / cm ² to 5,000 mJ / cm ² .

Moreover, in the case of a negative type, you may heat-process a resin film after exposure. The conditions for the heat treatment vary depending on the content of each component of the photosensitive resin composition, the film thickness, and the like, but they are usually performed at 70 ° C to 150 ° C, preferably 80 ° C to 120 ° C, for about 1 minute to 60 minutes. .

[3] Development step In the development step, the resin film is developed with an alkaline developer, and the exposed portion is dissolved and removed in the case of a positive type, and the non-exposed portion is dissolved and removed in the case of a negative type. , Thereby forming a desired pattern on the support. Examples of the development method include a liquid-covered development method and the like. The development conditions are, for example, performed at 5 ° C to 40 ° C for about 1 minute to 10 minutes.

Examples of the alkaline developer include those obtained by dissolving a basic compound such as sodium hydroxide, potassium hydroxide, ammonia, tetramethylammonium hydroxide, and choline in water at a concentration of 1 to 10% by mass. Alkaline aqueous solution. For example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like may be added to the alkaline aqueous solution. After the resin film is developed with an alkaline developer, the resin film may be washed with water and dried.

[4] Heating step The heating step is, for example, a step performed to fully express the characteristics of an insulating film, and the pattern is hardened (post-baked) by heating. The curing conditions are not particularly limited, but depending on the use of the cured film, for example, heating at a temperature of 100 ° C to 350 ° C for about 30 minutes to 10 hours. In order to sufficiently harden or prevent deformation of the pattern shape, heating may be performed in multiple stages. As described above, a cured film can be obtained.

[Electronic Components] Using the photosensitive resin composition of the present invention, an electronic component having the cured film can be produced, for example, one having one or more cured films selected from a surface protection film, an interlayer insulating film, and a planarization film, Electronic components such as circuit boards (semiconductor elements), semiconductor packages, or display elements. [Example]

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the descriptions of the following examples and the like, as long as it is not specifically mentioned, ｢part｣ is used in the meaning of ｢part by mass｣.

1. Method for measuring physical properties The method for measuring the weight average molecular weight (Mw) of the resin (A) is to measure Mw by gel permeation chromatography under the following conditions. · Column: TSK-M and TSK2500 columns manufactured by Tosoh Corporation are connected in series. Solvent: Tetrahydrofuran. Temperature: 40 ° C. Detection method: Refractive index method. Standard material: Polystyrene. GPC device: manufactured by Tosoh. Device name ｢HLC-8220-GPC｣ Method for measuring the content of the structural unit of the resin (A) The content of the structural unit was measured by ¹³ C-NMR.

2. Synthesis of Resin (A) [Synthesis Example 1] Synthesis of copolymer (a-1): 70 parts of p-third butoxystyrene and 10 parts of styrene were dissolved in 150 parts of propylene glycol monomethyl ether, and nitrogen Under the environment, the reaction temperature was maintained at 70 ° C, and polymerization was performed for 10 hours using 4 parts of azobisisobutyronitrile. Then, sulfuric acid was added to the reaction solution, the reaction temperature was maintained at 90 ° C., and a reaction was performed for 10 hours to deprotect and convert the third butoxystyrene unit into a p-hydroxystyrene unit. Ethyl acetate was added to the obtained copolymer, and water washing was repeated five times, the ethyl acetate layer was sorted, and the solvent was removed to obtain a p-hydroxystyrene / styrene copolymer (a-1).

The weight average molecular weight (Mw) of the copolymer (a-1) was 10,000. The copolymer (a-1) is a copolymer having 80 mol% p-hydroxystyrene units and 20 mol% styrene units.

3. Production of Photosensitive Resin Composition [Example 1] 95 parts of copolymer (a-1) as Synthesis Example 1 of resin (A) and 1,1-bis ( 4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid 27.5 parts of the condensate (mol ratio = 1: 2) (b-1) of 4,4'-biphenylmethanebismaleimide (c) as the maleimide group-containing compound (C) -1) 30 parts and polyglycidyl ether of a dicyclopentadiene · phenol polymer as a cross-linking agent (D) (trade name "XD-1000" manufactured by Nippon Kayaku Co., Ltd.) (d-1) 10 Parts were uniformly dissolved in 300 parts of γ-butyrolactone, and then a foreign matter was removed from the solution by a membrane filter, thereby producing a photosensitive resin composition of Example 1. A predetermined evaluation was performed using the obtained photosensitive resin composition.

[Examples 2 to 11 and Comparative Examples 1 to 3] Except that the components shown in Table 1 below were used, the components were uniformly mixed in a solvent in the same manner as in Example 1 to prepare Examples 2 to The photosensitive resin composition of Example 11 and Comparative Examples 1 to 3. A predetermined evaluation was performed using the obtained photosensitive resin composition.

[Table 1]

Details of the components described in Table 1 are shown below. "Resin (A)" a-1: Copolymer (a-1) of Synthesis Example 1 a-2: Cresol novolac resin (m-cresol: p-cresol = 6: 4 (molar ratio), polybenzene Weight-average molecular weight in terms of ethylene = 6,000) "Photoacid generator (B)" b-1: 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl)- Condensate of 1-methylethyl] phenyl] ethane and 1,2-naphthoquinonediazide-5-sulfonic acid (Molar ratio = 1: 2) C)》 c-1: 4,4'-diphenylmethane bismaleimide c-2: N, N'-m-phenylene bismaleimide c-3: 1,6-bis horse Lycoimide- (2,2,4-trimethyl) hexane "crosslinking agent (D)" d-1: Polyglycidyl ether of dicyclopentadiene · phenol polymer (manufactured by Nippon Kayaku Co., Ltd.) Trade name (XD-1000)) d-2: Polymethylolated melamine-based crosslinking agent represented by the following formula

[Chemical 6] "Additives (E)" e-1 (adhesion aid): tris (trimethoxysilylpropyl) isocyanurate e-2 (alkali solubility promoter): 4,4 '-[1- [ 4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene] bisphenol "solvent (F)" f-1: γ-butyrolactone f-2: ethyl lactate ester

4. Evaluation The evaluation method of the photosensitive resin composition is as follows.

4-1. Resolution The photosensitive resin composition was spin-coated on a 6-inch silicon wafer, and then heated at 120 ° C. for 3 minutes using a hot plate to produce a uniform resin film with a thickness of 7 μm. Then, using an alignment machine (type 水 MA-150 ｣manufactured by SussMicrotec), with a pattern mask, the ultraviolet light from the high-pressure mercury lamp was exposed at a wavelength of 350 nm and an exposure of 800 mJ / cm ² . Irradiate the resin film. Then, the resin film was immersed and developed at 23 ° C. for 240 seconds using a 2.38% by mass tetramethylammonium hydroxide aqueous solution. Next, the developed resin film was washed with ultrapure water for 60 seconds, and air-dried with air, and then observed with an optical microscope, and the pattern size of the smallest pattern analyzed was set to the resolution.

4-2. Chemical resistance A photosensitive resin composition was coated on a 4-inch silicon wafer and heated at 120 ° C for 3 minutes using a hot plate to prepare a resin film having a thickness of 10 μm. Then, in a convection oven, heating was performed at 120 ° C for 30 minutes, and 150 ° C for 30 minutes, and then in Example 1, Example 2, and Comparative Example 1 at 250 ° C for 1 hour, and in Example 3 In Examples 11 and Comparative Examples 2 and 3, a cured film was obtained by heating at 200 ° C. for 1 hour. The obtained cured film was coated with a flux (product name: WF-6317), manufactured by Senju Metals Co., Ltd., under a nitrogen atmosphere, by a reflow device (type: STR-2010N2M-III) heated at 260 ° C. Alas, Senju Metal Co., Ltd.) was heated for 3 minutes, and the swelling ratio (%) of the cured film ((film thickness after immersion-film thickness before immersion) / film thickness before immersion × 100 (%)) was measured.

4-3. Crack resistance Evaluation of the crack resistance is performed by measuring the storage elastic modulus (E '). The photosensitive resin composition was coated on a substrate with a release material, and heated at 120 ° C. for 5 minutes using a hot plate to form a uniform resin film having a thickness of 15 μm. Then, in a nitrogen environment, the resin film was heated at 120 ° C. for 30 minutes and 150 ° C. for 30 minutes by a convection oven, and then at 250 ° C. in Example 1, Example 2, and Comparative Example 1. Heating was performed for 1 hour, and in Examples 3 to 11, and Comparative Examples 2 and 3, heating was performed at 200 ° C. for 1 hour to form a cured film.

The cured film was peeled from the substrate with a release material, and the cured film was cut into a strip shape of 2.5 cm × 0.3 cm. Using a thermomechanical analysis (TMA) device (device name ｢TMA / SS6100｣, manufactured by SII Nanotechnology (Nanotechnology) Co., Ltd.), the storage elastic coefficient (E ') of the long hardened film was measured. . The conditions at the time of measurement are as follows. Chuck distance: 2 cm Measurement frequency: 0.1 Hz Measurement temperature range: 23 ℃ ～ 330 ℃, Heating rate: 5 ℃ / min

[Table 2]

A cured film obtained from a photosensitive resin composition containing a maleimide imide group-containing compound (C) and a cured film obtained from a photosensitive resin composition not containing a maleimide imide group-containing compound (C) Compared with the cured film, even if it has the same chemical resistance, the curing temperature is higher than that (Examples 1 to 2 and Comparative Example 1 are 250 ° C or higher, Examples 3 to 11 and Comparative Examples 2 to Comparative Examples) 3 is 200 ° C. or higher) The storage elastic modulus (E ′) in a high-temperature region is also low, that is, the crosslinking density is low, so it is judged that the crack resistance is excellent.

no

FIG. 1 shows the storage elastic modulus (E ′) of the cured films of Examples and Comparative Examples. FIG. 2 shows the storage elastic coefficient (E ′) of the cured film of the example. FIG. 3 shows the storage elastic coefficient (E ′) of the cured film of the example. FIG. 4 shows the storage elastic coefficient (E ′) of the cured film of the comparative example.

Claims (8)

A photosensitive resin composition comprising: a resin (A) having a phenolic hydroxyl group, a photoacid generator (B), and a maleimide group-containing compound (C). The photosensitive resin composition according to item 1 of the scope of the patent application, wherein the compound (C) containing a maleimide group includes a compound (C1) having two or more maleimide groups. The photosensitive resin composition according to claim 1 or claim 2, further comprising a crosslinking agent (D) (excluding the maleimide-imide-containing compound (C)). The photosensitive resin composition according to item 3 of the scope of patent application, wherein the crosslinking agent (D) includes an epoxy-based crosslinking agent (D1) and has at least two represented by -CH ₂ OR At least one type of crosslinking agent (D2) among the crosslinking groups (in the formula, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a fluorenyl group having 2 to 10 carbon atoms). The photosensitive resin composition according to any one of claims 1 to 4, in which the photoacid generator (B) contains a quinonediazide compound (B1). A method for manufacturing a cured film, comprising: forming a resin film of a photosensitive resin composition according to any one of claims 1 to 5 on a support body on a support; A step of exposing; a step of developing the resin film with an alkaline developing solution to form a patterned resin film; and a step of heating the patterned resin film. A cured film formed from the photosensitive resin composition according to any one of claims 1 to 5 in the scope of patent application. An electronic part having a hardened film of the seventh scope of the patent application.