JPWO2006006581A1 - Photosensitive insulating resin composition, cured product thereof and use thereof - Google Patents

Abstract

Photosensitive insulating resin composition suitable for surface protective film and interlayer insulating film applications that can be cured at low temperature and can obtain cured products with excellent properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. Product, its cured product and its use. The photosensitive insulating resin composition is a copolymer obtained by copolymerizing a (meth) acrylic acid ester having an oxetanyl group and a specific hydroxy or alkoxystyrene derivative, preferably a (meth) acrylic acid having an oxetanyl group. A copolymer (A) obtained by copolymerizing an ester, a specific hydroxy or alkoxy styrene derivative, and another vinyl monomer, a light-sensitive acid generator (B), a cross-linking agent (C), and an adhesion Contains auxiliary agent (D).

Description

  The present invention relates to a photosensitive insulating resin composition used for a surface protective film (overcoat film) such as an organic semiconductor element, an interlayer insulating film (passivation film) and the like, a cured product obtained by curing the same, and use thereof. More specifically, a cured product that can be developed with an alkali, has excellent resolution as a resist, and has excellent properties such as low-temperature curability, electrical insulation, thermal shock resistance, chemical resistance, and such a cured product. The present invention relates to the obtained photosensitive insulating resin composition and its use.

  In recent years, organic materials have attracted attention as next-generation electronic device materials. Organic semiconductor materials are attracting attention as a third semiconductor material following Si and GaAs, and are being actively developed. Organic semiconductor materials are formed at a low temperature of 150 ° C. or lower, and the degree of freedom in selecting a substrate to be used is improved. Therefore, when organic semiconductor materials are used, a semiconductor device can be easily manufactured with a relatively inexpensive manufacturing apparatus. There is an advantage that you can. For example, many devices such as organic electroluminescence (EL) display devices with luminescent properties, organic memory devices using vinylidene fluoride as a ferroelectric layer, and organic photoelectric conversion devices that convert light energy into electrical energy have been studied and Has been developed.

However, the organic semiconductor material has a problem that it has low heat resistance and cannot be applied to conventional materials and manufacturing processes when forming a passivation film, a buffer coat layer, and the like. That is, photosensitive polyimides widely used for these applications usually require heating at 300 ° C. or higher for curing, and thus cannot be applied to organic semiconductor manufacturing processes.
As a result of the study by the present inventors in view of such a conventional technique, a copolymer formed by copolymerizing a (meth) acrylate having an oxetanyl group and a specific hydroxy or alkoxystyrene derivative, a photosensitive acid generator, It has been found that a composition containing a specific cross-linking agent and an adhesion assistant can solve the above-mentioned problems, and the present invention has been completed.

  As the photosensitive resin composition, for example, an alkali-soluble resin, a crosslinking agent, a compound having an oxetane structure in the molecule, rubber, a radiation-sensitive resin composition containing a radiation polymerization initiator (see Patent Document 1), Photosensitive resin containing compound (A) having oxetane structure, compound (B) having radical polymerizable unsaturated group, photo radical initiator (C), cationic polymerization initiator (D) and alkali-soluble resin (E) In the photocurable composition containing a composition (see Patent Document 2), an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent, the alkali-soluble resin has a polymerizable double bond, and Among these photocurable compositions, photocurable compositions containing an organic peroxide (see Patent Document 3) are known, but the resins used in these resin compositions are known. Cali soluble resin does not include having an oxetanyl group and (meth) acrylate as a monomer component of the resin.

  Further, the photosensitive resin composition is a negative resist composition containing an alkali-soluble resin as a base resin, wherein the oxetane is contained in the structure of the alkali-soluble resin or the compound used in combination with the alkali-soluble resin. Although a negative resist composition containing a structure (see Patent Document 4) is also known, this composition uses a specific silicon-containing compound as a crosslinking agent.

  The photosensitive resin composition is a photosensitive resin composition containing an alkali-soluble resin, a crosslinking agent, and a photopolymerization initiator, and the organic polymer having a phenolic hydroxyl group is converted to an oxirane compound and / or Or the photosensitive resin composition which is a polymer containing the compound represented by following General formula (1) modified | denatured by the oxetane compound in a structural unit, and the photosensitive resin composition containing alkali-soluble resin, a crosslinking agent, and a photoinitiator A photosensitive resin composition in which the alkali-soluble resin is a modified poly (p-hydroxystyrene) represented by the following general formula (2) containing an oxirane ring and / or an oxetane ring (see Patent Document 5) As is well known, this composition is a composition obtained by modifying the phenolic hydroxyl group of the alkali-soluble resin to be used with an oxetane compound. Those having the unit.

(In the formula, m and n represent an integer of 1 or more, and X represents a functional group containing an oxirane ring and / or an oxetane ring.)
Moreover, as a photosensitive resin composition, the radiation sensitive resin composition containing the high molecular compound (A) which has a carboxyl group and an oxetane skeleton, a quinone diazide compound (B), and a polyhydric phenol compound (C) (patent document 6). See also).
JP-A-11-65116 JP 2001-228610 A JP 2004-83754 A JP 2001-343748 A JP 2002-229204 A JP 2003-156843 A

  An object of the present invention is to obtain a cured product that can be cured at low temperature without hindering the function of an organic semiconductor element and has excellent properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. It is providing the photosensitive insulating resin composition suitable for the surface protection film which can be used, and an interlayer insulation film use, its hardened | cured material, and its use.

According to the present invention, the following photosensitive insulating resin composition, cured product thereof and use thereof are provided, and the above-described problems of the present invention are solved.
(1) (A) a copolymer obtained by copolymerizing a (meth) acrylic acid ester having an oxetanyl group and a monomer represented by the following general formula (3),
(B) a photosensitive acid generator,
(C) containing at least one crosslinking agent selected from epoxy compounds, isocyanate compounds and blocked products thereof, nitrogen-containing compounds obtained by alkyl etherifying all or part of the active methylol groups, and (D) an adhesion assistant. A photosensitive insulating resin composition.

(3)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
(2) The photosensitive insulating resin composition according to (1), wherein the component (A) is a copolymer obtained by copolymerizing another vinyl monomer.

(3) The component (B) is at least one selected from an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Photosensitive insulating resin composition.
(4) The photosensitive insulating resin composition according to (1), wherein the component (D) is a silane coupling agent.

(5) A cured product obtained by curing the photosensitive insulating resin composition according to (1).
(6) An electronic component comprising an insulating layer formed using the photosensitive insulating resin composition according to (1).

By using the photosensitive insulating resin composition according to the present invention, an alkali development and low-temperature curing are possible, and a cured product having excellent resolution, electrical insulation, heat resistance, thermal shock resistance, and chemical resistance is obtained. be able to.
That is, the cured product of the photosensitive insulating resin composition according to the present invention is excellent in electrical insulation, heat resistance, thermal shock resistance, and chemical resistance.

FIG. 1 is a cross-sectional view of a thermal shock evaluation substrate. FIG. 2 is a schematic diagram of a thermal shock evaluation substrate.

Explanation of symbols

1. 1. Silicon substrate Copper plating pattern

Hereinafter, the photosensitive insulating resin composition according to the present invention, its cured product, and its use will be specifically described.
The photosensitive insulating resin composition according to the present invention contains (A) a copolymer, (B) a photosensitive acid generator, (C) a crosslinking agent, and (D) an adhesion assistant.
[(A) Copolymer]
The (A) copolymer used in the present invention is a copolymer obtained from a (meth) acrylic acid ester having an oxetanyl group and a monomer represented by the following general formula (3), preferably It is a copolymer obtained from a (meth) acrylic acid ester having an oxetanyl group, a monomer represented by the following general formula (3), and another vinyl monomer.

(Meth) acrylic acid ester having oxetanyl group:
Examples of the (meth) acrylic acid ester having an oxetanyl group include (meth) acrylic acid (3-ethyl-3-oxetanyl) methyl.
Monomer represented by the general formula (3):

(3)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
Specific examples of the monomer represented by the general formula (3) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p-hydroxystyrene, and α-methyl-. m-hydroxystyrene, α-methyl-o-hydroxystyrene, p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, o-ethoxystyrene, pt-butoxystyrene M-t-butoxystyrene, ot-butoxystyrene, α-methyl-pt-butoxystyrene, α-methyl-pt-butoxystyrene, α-methyl-pt-butoxystyrene, etc. It is done.

In the above examples of monomers, vinyl monomers having a phenolic hydroxyl group are exemplified, but after copolymerizing a vinyl monomer in which this group is protected with a protective group, The protective group can be deprotected to form a copolymer having a phenolic hydroxyl group.
Other vinyl monomers:
Examples of other vinyl monomers include aromatics such as styrene, α-methylstyrene, o-methylstyrene, o-chlorostyrene, m-chlorostyrene, N, N-dimethyl-p-aminostyrene, and divinylbenzene. Vinyl compounds;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl acrylate, tricyclo [5.2.1.0 ^2,6 ] alkyl (meth) acrylates such as decanyl (meth) acrylate;
Unsaturated monocarboxylic esters such as methyl crotonate, ethyl crotonate, methyl cinnamate, ethyl cinnamate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, heptafluorobutyl (meth) acrylate;
Siloxanyl compounds such as trimethylsiloxanyldimethylsilylpropyl (meth) acrylate, tris (trimethylsiloxanyl) silylpropyl (meth) acrylate, di (meth) acryloylpropyldimethylsilyl ether;
Mono- or di- (meth) acrylates of alkylene glycols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol;
Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate;
Cyanalkyl (meth) acrylates such as cyanoethyl (meth) acrylate and cyanopropyl (meth) acrylate, and cyano compounds such as acrylonitrile and methacrylonitrile;
Polyhydric alcohols such as glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms, for example) and tetramethylolalkane (alkane has 1 to 3 carbon atoms, for example) Oligo (meth) acrylates such as di (meth) acrylates, tri (meth) acrylates or tetra (meth) acrylates;
Epoxy group-containing monomers such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, and allyl glycidyl ether;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate;
Hydroxyalkyl esters of unsaturated carboxylic acids such as 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, 2-hydroxypropyl cinnamate;
Unsaturated alcohols such as (meth) allyl alcohol;
Unsaturated (mono) carboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid;
Unsaturated polycarboxylic acids (anhydrides) such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid, and their mono- and diesters;
Examples include vinyl chloride, vinyl acetate, cinnamic acid ester, crotonic acid ester, dicyclopentadiene, and ethylidene norbornene.

The monomers exemplified above can be used alone or in combination depending on the purpose.
<Synthesis of copolymer>
The copolymer which is the component (A) of the present invention can be produced by, for example, a known solution polymerization in the presence of a chain transfer agent, if necessary, using a radical polymerization initiator.

As the polymerization medium used for the solution polymerization, an organic solvent can be suitably used. Specific examples of the organic solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate. ;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
and lactones such as γ-butyrolacun.

These organic solvents can be used alone or in admixture of two or more.
When the copolymer (A) is a copolymer of a (meth) acrylic acid ester having an oxetanyl group and a hydroxy or alkoxystyrene derivative represented by the general formula (3), the copolymer (A) has an oxetanyl group (meta ) Acrylic acid ester is obtained in an amount of 5 to 95% by weight, preferably 10 to 90% by weight, and the hydroxy or alkoxystyrene derivative in an amount of 5 to 95% by weight, preferably 10 to 90% by weight. It is desirable.

  When the copolymer (A) is a copolymer of a (meth) acrylic acid ester having an oxetanyl group, a hydroxy or alkoxystyrene derivative represented by the general formula (3), and other vinyl monomers The (meth) acrylic acid ester having an oxetanyl group is 5 to 90% by weight, preferably 10 to 85% by weight, the hydroxy or alkoxy styrene derivative is 5 to 85% by weight, preferably 10 to 80% by weight, etc. It is desirable to be obtained using 1 to 50% by weight, preferably 2 to 40% by weight of the vinyl monomer.

The number average molecular weight (hereinafter referred to as “Mn”) of the copolymer (A) by gel permeation chromatography (GPC) is typically 1,000 to 100,000, preferably 3,000 to 50. 1,000.
[(B) Photosensitive acid generator]
The photosensitive acid generator (B) used in the present invention is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation or the like. For example, an onium salt compound, a halogen-containing compound, a sulfone compound, and a sulfonic acid compound are used. , A sulfonimide compound, and a diazomethane compound. Specific examples are shown below.

Onium salt compounds:
Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
Specific examples of preferred onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluorochlorosulfonate, Phenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyl diphenylsulfonium p-toluenesulfonate, 4,7-di-n- Butoxynaphthyltetrahydrothiophenium trifluorome Examples thereof include tansulfonate, (4-phenylthio) phenyldiphenylsulfonium hexafluorophosphate, (4-phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, and the like.

Halogen-containing compounds:
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of preferred halogen-containing compounds include 1,10-dibromo-n-decane, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, phenyl-bis (trichloromethyl) -S-triazine. S-triazine derivatives such as 4-methoxyphenyl-bis (trichloromethyl) -S-triazine, styryl-bis (trichloromethyl) -S-triazine, naphthyl-bis (trichloromethyl) -S-triazine, and the like.

Sulfone compounds:
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, And bis (phenacylsulfonyl) methane.

Sulfonic acid compounds:
Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Preferred specific examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate and the like.

Sulfonimide compounds:
Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

Diazomethane compounds:
Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.
In the present invention, these photosensitive acid generators (B) can be used alone or in combination of two or more.

  The blending amount of the photosensitive acid generator (B) is 0.1 to 100 parts by weight of the copolymer (A) from the viewpoint of ensuring the sensitivity, resolution, pattern shape and the like of the resin composition of the present invention. 20 parts by weight, preferably 0.5 to 10 parts by weight. When the blending amount of the photosensitive acid generator (B) is less than 0.1 parts by weight, curing may be insufficient, heat resistance is lowered, and when it exceeds 20 parts by weight, transparency to radiation is lowered, The pattern shape may be deteriorated.

[(C) Crosslinking agent]
The crosslinking agent (C) used in the present invention is a compound having a group capable of reacting with the copolymer (A). The crosslinking agent (C) used in the present invention is at least one selected from an epoxy compound, an isocyanate compound, a blocked product thereof, and a nitrogen-containing compound obtained by alkyl etherifying all or part of the active methylol group.

Specifically, epoxidized polybutadiene, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin, phenol novolac resin type epoxy resin, etc. Epoxy compounds;
Isocyanate compounds such as tolylene diisocyanate and blocked products thereof;
Examples include (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, nitrogen-containing compounds in which all or part of the active methylol group such as (poly) methylolated urea is alkyletherified. .

The amount of the crosslinking material (C) is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, based on 100 parts by weight of the copolymer (A). If the blending amount of the crosslinking agent (C) is less than 1 part by weight, curing may be insufficient, and if it exceeds 50 parts by weight, the resolution may be deteriorated.
[(D) Adhesion aid]
The adhesion assistant (D) used in the present invention is a compound that improves the adhesion to an inorganic substance serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, or aluminum. is there. Specific examples include silane coupling agents and thiol compounds.

  Specific examples of silane coupling agents include γ- (2-aminoethyl) aminopropyltrimethoxysilane), γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and ureapropyltrimethoxy. Silane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane and the like can be mentioned, and examples of the thiol compound include monothiols such as t-dodecyl mercaptan and polyvalent thiols such as trithiocyanuric acid. Is preferably a silane coupling agent.

The amount of the adhesion assistant (D) is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the copolymer (A). If the blending amount of the adhesion assistant (D) is less than 0.5 parts by weight, the adhesion may be insufficient, and if it exceeds 10 parts by weight, the thermal shock resistance of the cured film may be lowered.
[solvent]
In the present invention, a solvent may be added to improve the handleability of the photosensitive insulating resin composition or to adjust the viscosity and storage stability. The type of such a solvent is not particularly limited, and examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve;
Carbitols such as butyl carbitol;
Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate;
Aliphatic carboxylic acid esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate;
Other esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, methyl amyl ketone;
Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
and lactones such as γ-butyrolacun.

These solvents can be used alone or in combination of two or more.
The amount of the solvent used can be appropriately determined according to the application, coating method, and the like.
[Additive]
Various additives can be blended in the photosensitive insulating resin composition according to the present invention as necessary. For example, polyimide, acrylic polymer, polyolefin elastomer, styrene butadiene elastomer, silicon elastomer, compound and resin having phenolic hydroxyl group, resin having oxetanyl group;
High density polyethylene, medium density polyethylene, polypropylene, polycarbonate, polyarylate, aliphatic polyamide, polyamideimide, polysulfone, polyethersulfone, polyetherketone, polyphenylene sulfide, (modified) polycarbodiimide, polyetherimide, polyesterimide, modified polyphenylene Examples thereof include thermoplastic or thermosetting resins such as oxides.

In addition, sensitizers, leveling agents, organic fillers such as silicone rubber particles or crosslinked rubber particles, inorganic fillers such as silica or alumina, and the like can also be included.
Such additives can be used alone or in combination of two or more.
[Preparation of photosensitive insulating resin composition]
The photosensitive insulating resin composition of the present invention includes, for example, the components of the copolymer (A), the photosensitive acid generator (B), the crosslinking agent (C), and the adhesion assistant (D), as necessary. And by mixing with other ingredients. As a method for producing the photosensitive insulating resin composition according to the present invention, conventionally known methods can be used as appropriate, and each component may be added at once or in any order, and stirring, mixing and dispersion may be performed. .

[Cured product]
The photosensitive insulating resin composition according to the present invention is excellent in resolution, and the cured product is excellent in electrical insulation, thermal shock, adhesion, solvent resistance, and the like. Therefore, the photosensitive insulating resin composition of the present invention can be suitably used particularly as a material for an interlayer insulating film or a surface protective film of a semiconductor element.

  For example, in order to form an interlayer insulating film using the photosensitive insulating resin composition according to the present invention, first, the photosensitive insulating resin composition is applied to a substrate such as a silicon wafer on which a wiring pattern has been applied, and then dried. Then, the solvent is volatilized to form a coating film. Then, it exposes through a desired mask pattern, Then, it develops with an alkaline developing solution, The coating film in which the desired pattern was formed is obtained by melt | dissolving and removing a non-exposed part. Furthermore, a cured film is obtained by performing heat treatment after development in order to develop the insulating film characteristics.

That is, as a method for applying the photosensitive insulating resin composition of the present invention to a substrate, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, or a curtain coating method is used. The coating thickness can be appropriately controlled by adjusting the solid content concentration and viscosity of the coating means and the photosensitive insulating resin composition.
Examples of radiation used for exposure include low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, i-line steppers, and other ultraviolet rays, electron beams, and laser beams. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, when the resin film thickness is 5 to 50 μm, it is about 1,000 to 20,000 J / m ² .

Then, it develops with an alkaline developing solution, and a desired pattern is formed by melt | dissolving and removing an unnecessary non-exposed part. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, a paddle developing method and the like. The developing conditions are usually about 20 to 40 ° C. for about 1 to 10 minutes.
Examples of the alkaline developer include an alkaline aqueous solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, and choline is dissolved in water so as to have a concentration of about 1 to 10% by weight. Is mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution. In addition, after developing with an alkaline developer, it is washed with water and dried.

  Further, after development, the film is cured by performing a heat treatment in order to sufficiently develop the characteristics as an insulating film. At this time, the photosensitive acid generator (B) is decomposed to generate an acid. The curing reaction between the crosslinking agent (C) and the copolymer (A) is promoted by the catalytic action of the acid. The photosensitive insulating resin composition according to the present invention can be heat-treated at a lower temperature than conventional photosensitive insulating resin compositions.

  Although said hardening conditions are not specifically limited, According to the use of hardened | cured material, it heats for about 30 minutes-10 hours at the temperature of 50-300 degreeC, and hardens a coating film. Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained pattern shape, it can also heat in two steps, for example, in the 1st step, it is 10 minutes-2 hours at the temperature of 50-150 degreeC. It can be heated to a certain degree, and further cured by heating at a temperature of 100 to 300 ° C. for about 20 minutes to 8 hours. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as heating equipment.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In the following examples and comparative examples, parts are used in terms of parts by weight unless otherwise specified.
Moreover, about the evaluation of each characteristic of hardened | cured material, it implemented in the following way.

Resolution:
A photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 10 μm. Thereafter, using an aligner (MA-100 manufactured by Karl Suss), UV light from a high-pressure mercury lamp was exposed through a pattern mask so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Next, the substrate was heated (PEB) at 110 ° C. for 3 minutes on a hot plate, and developed by immersing in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide (TMAH) at 23 ° C. for 60 seconds. The minimum dimension of the obtained pattern was taken as the resolution.

Adhesion:
A photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 10 μm. The exposure was performed with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 5,000 J / m ² . Subsequently, after heating (PEB) at 110 ° C. for 3 minutes on a hot plate, the ultraviolet rays from the high-pressure mercury lamp were again exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film. The obtained substrate was subjected to a resistance test by treating it with a pressure cooker tester (manufactured by Tabai Espec Co., Ltd.) at a temperature of 121 ° C. and a humidity of 100% for 168 hours. The adhesion after the test was determined by performing a cross-cut test (cross cut tape method) according to JIS K5400.

Electrical insulation (volume resistivity):
The photosensitive insulating resin composition was applied to a SUS substrate and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform resin coating film having a thickness of 10 μm. Ultraviolet rays from a high-pressure mercury lamp were exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Next, after heating (PEB) at 110 ° C. for 3 minutes on a hot plate, UV light from a high pressure mercury lamp was again exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film. The obtained cured film was treated with a pressure cooker test apparatus (manufactured by Tabai Espec) at a temperature of 121 ° C., a humidity of 100%, and a pressure of 2.1 atmospheres for 168 hours. The volume resistivity between the layers before and after the test was measured to confirm the resistance.

Thermal shock resistance:
The photosensitive insulating resin composition was applied to the substrate shown in FIGS. 1 and 2, and heated on a hot plate at 110 ° C. for 3 minutes to produce a 10 μm thick resin coating on the conductor. The exposure was performed with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 5,000 J / m ² . Subsequently, after heating (PEB) at 110 ° C. for 3 minutes on a hot plate, UV light from a high-pressure mercury lamp was again exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film. This substrate was subjected to a resistance test using a thermal shock tester (Tabaye Spec Co., Ltd.) at -50 ° C / 30 minutes to 125 ° C / 30 minutes as one cycle. The number of cycles until a defect such as a crack occurred in the cured film was confirmed.

Solvent resistance:
A photosensitive insulating resin composition was spin-coated on a 6-inch silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to prepare a uniform coating film having a thickness of 10 μm. The exposure was performed with ultraviolet rays from a high-pressure mercury lamp so that the exposure amount at a wavelength of 350 nm was 5,000 J / m ² . Subsequently, after heating (PEB) at 110 ° C. for 3 minutes on a hot plate, the ultraviolet rays from the high-pressure mercury lamp were again exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 J / m ² . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film. The obtained substrate was immersed in isopropyl alcohol at 60 ° C. for 10 minutes, and the surface of the cured film was observed with an optical microscope. The result was determined as follows.

○: No abnormality is observed on the surface of the cured film.
X: Whitening or roughening was recognized on the cured film surface.
[Synthesis Example 1]
In a 1 L separable flask, 18 g of acrylic acid, 98 g of α-methyl-p-hydroxystyrene, OXE-10 (trade name, manufactured by Osaka Organic Chemical Industry) 208 g, 26 g of styrene, 2,2′-azobisisobutyronitrile (hereinafter, (Referred to as “AIBN”) 15 g and 350 g of 2-heptanone were added and stirring was started. Under a nitrogen gas atmosphere, heating was started and stirring was continued at 70 ° C. for 3 hours. Thereafter, 10 g of AIBN was added, and stirring was continued for another hour at the same temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., stirring was continued for 3 hours, and then the heating was stopped to complete the reaction, whereby a 2-heptanone solution of copolymer (A-1) having a solid content of 49% was obtained.

[Synthesis Example 2]
138 g of α-methyl-p-hydroxystyrene, 156 g of OXE-30 (trade name, manufactured by Osaka Organic Chemical Industry), 12 g of styrene, 44 g of butyl acrylate, 15 g of AIBN and 350 g of 2-heptanone were added to a 1 L separable flask and stirring was started. . Under a nitrogen gas atmosphere, heating was started and stirring was continued at 70 ° C. for 3 hours. Thereafter, 10 g of AIBN was added, and stirring was continued for another hour at the same temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and stirring was continued for 3 hours. Then, the heating was stopped to complete the reaction, whereby a 2-heptanone solution of a copolymer (A-2) having a solid content of 49% was obtained.

[Synthesis Example 3]
To a 1 L separable flask, 70 g of pt-butoxystyrene, 30 g of OXE-10 (trade name, manufactured by Osaka Organic Chemical Industry), 3 g of AIBN and 100 g of propylene glycol monomethyl ether were added and stirring was started. Under a nitrogen gas atmosphere, heating was started and stirring was continued at 70 ° C. for 3 hours. Thereafter, 2 g of AIBN was added, and stirring was continued for another hour at the same temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and the stirring was continued for 3 hours, and then the heating was stopped to complete the reaction. Subsequently, 20 g of 20% hydrochloric acid aqueous solution was added, and hydrolysis was performed at 80 ° C. for 6 hours. 100 g of ethyl acetate was added to the solution, 200 g of distilled water was added, and the mixture was shaken well and allowed to stand to remove the aqueous layer. Thereafter, washing with water was repeated until the aqueous layer became neutral. Next, the solution was solidified in a large amount of hexane and vacuum dried to obtain a copolymer (A-3).

[Synthesis Example 4]
Synthesis of partial 3-ethyl-3-methyloxetane-4′-ether (modification rate 20%) of poly (p-hydroxystyrene) 3-ethyl-3-hydroxymethyloxetane (EOXA, manufactured by Toagosei Co., Ltd.) 10.2 g and 14.2 g of thionyl chloride were reacted by stirring in toluene, and the reaction product was taken out and purified by silica gel chromatography to obtain 8.4 g of 3-chloromethyl-3-ethyloxetane. Got. 2.5 g of the 3-chloromethyl-3-ethyloxetane and 10 g of poly (p-hydroxystyrene) (manufactured by Maruzen Petrochemical Co., Ltd.) were added to 60 ml of ethyl acetate and stirred for 1 hour, and then 0.75 g of sodium hydroxide was added. The mixture was further stirred at 60 ° C. for 6 hours. Reprecipitation with toluene, the resulting precipitate was vacuum-dried, and 10.1 g of a partial 3-ethyl-3-methyloxetane-4′-ether of poly (p-hydroxystyrene) having a modification rate of 20% ( A-4) was obtained.

[Example 1]
As shown in Table 1, 100 parts by weight of copolymer (A-1), 5 parts by weight of acid generator (B-1), 5 parts by weight of cross-linking agent (C-1) and adhesion aid (D-1) 2 A part by weight was dissolved in 50 parts of a solvent (ethyl lactate). The properties of this composition were measured according to the evaluation method. The obtained results are shown in Table 1.

[Examples 2-3]
A photosensitive insulating resin composition having the composition shown in Table 1 was prepared in the same manner as in Example 1, and these characteristics were measured in the same manner as in Example 1. The obtained results are shown in Table 1.
[Comparative Examples 1-2]
A photosensitive insulating resin composition having the composition shown in Table 2 was prepared in the same manner as in Example 1, and these characteristics were measured in the same manner as in Example 1. The obtained results are shown in Table 2.
(B) Photosensitive acid generator B-1: SP-152 (trade name, manufactured by Asahi Denka Kogyo)
B-2: SP-172 (Asahi Denka Kogyo brand name)
(C) Crosslinking agent C-1: Epicoat 152 (trade name, manufactured by Japan Epoxy Resin)
C-2: OXT-121 (trade name, manufactured by Toagosei)
C-3: Epicoat 828 (trade name, manufactured by Japan Epoxy Resin)
(D) Adhesion aid D-1: γ-glycidoxypropyltrimethoxysilane D-2: Ureapropyltrimethoxysilane D-3: Isocyanuric acid tris (3-trimethoxysilylpropyl)

Claims (6)

(A) a copolymer obtained by copolymerizing a (meth) acrylic acid ester having an oxetanyl group and a monomer represented by the following general formula (3),
(B) a photosensitive acid generator,
(C) containing at least one crosslinking agent selected from epoxy compounds, isocyanate compounds and blocked products thereof, nitrogen-containing compounds obtained by alkyl etherifying all or part of the active methylol groups, and (D) an adhesion assistant. A photosensitive insulating resin composition.

(3)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)   2. The photosensitive insulating resin composition according to claim 1, wherein the component (A) is a copolymer obtained by copolymerizing another vinyl monomer.   The photosensitive insulation according to claim 1, wherein the component (B) is at least one selected from an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. Resin composition.   The photosensitive insulating resin composition according to claim 1, wherein the component (D) is a silane coupling agent.   A cured product obtained by curing the photosensitive insulating resin composition according to claim 1.   An electronic component comprising an insulating layer formed using the photosensitive insulating resin composition according to claim 1.

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