WO2006006581A1

WO2006006581A1 - Photosensitive insulating resin composition, cured product thereof and use thereof

Info

Publication number: WO2006006581A1
Application number: PCT/JP2005/012806
Authority: WO
Inventors: Hirofumi Gotou; Katsumi Inomata; Shin-Ichirou Iwanaga
Original assignee: Jsr Corporation
Priority date: 2004-07-14
Filing date: 2005-07-12
Publication date: 2006-01-19
Also published as: JPWO2006006581A1; TW200615693A

Abstract

Disclosed is a photosensitive insulating resin composition which can be cured at low temperatures and enables to obtain a cured product excellent in various characteristics such as resolution, electrical insulation, impact resistance and chemical resistance. Such photosensitive insulating resin composition is suitable for the use as surface protective films and interlayer insulating films. Also disclosed are a cured product of such a photosensitive insulating resin composition and use thereof. The photosensitive insulating resin composition contains a copolymer (A) obtained by copolymerizing a (meth)acrylate having an oxetanyl group and a specific hydroxy- or alkoxy-styrene derivative, preferably a copolymer (A) obtained by copolymerizing a (meth)acrylate having an oxetanyl group, a specific hydroxy- or alkoxy-styrene derivative and an additional other vinyl monomer, a photosensitive acid generator (B), a crosslinking agent (C) and an adhesion assistant (D).

Description

Specification

Photosensitive insulating resin composition, cured product thereof and use thereof

Technical field

[0001] The present invention relates to a photosensitive insulating resin composition used for a surface protective film (overcoat film) or an interlayer insulating film (nobation film) for organic semiconductor elements, a cured product obtained by curing the same, and Regarding its use. More specifically, a cured product that can be alkali-developed, has excellent resolution as a resist, and has excellent properties such as low-temperature curability, electrical insulation, thermal shock resistance, and chemical resistance, and such a cured product. The present invention relates to a photosensitive insulating resin composition that can be obtained and its use.

Background art

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 the substrate to be used is improved. Therefore, when organic semiconductor materials are used, semiconductor devices can be easily manufactured with relatively inexpensive manufacturing equipment. There is an advantage that it can be manufactured. For example, many elements such as organic electroluminescence (EL) display elements with luminescent properties, organic memory elements that use polyvinylidene fluoride as a ferroelectric layer, and organic photoelectric conversion elements that convert light energy into electrical energy Has been researched and developed.

[0003] However, organic semiconductor materials have a problem that they have 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. In other words, photosensitive polyimides widely used in these applications usually cannot be applied to organic semiconductor manufacturing processes because they require heating at 300 ° C. or higher for curing. As a result of the study by the present inventors in view of such a conventional technique, a copolymer obtained by copolymerizing a (meth) atalylate having an oxetanyl group and a specific hydroxy or alkoxystyrene derivative, a photo-sensitive acid A composition containing a generator, a specific cross-linking agent, and an adhesion assistant. The present inventors have found that the above problems can be solved, and have completed the present invention.

[0004] The photosensitive resin composition includes, for example, alkali-soluble resin, cross-linking agent, intramolecular A compound having an oxetane structure, a rubber, a radiation-sensitive resin composition containing a radiation polymerization initiator (see Patent Document 1), a compound having an oxetane structure (A), a compound having a radical polymerizable unsaturated group (B ), Photoradical initiator (C), cationic polymerization initiator (D), and photosensitive resin composition containing alkali-soluble resin (E) (see Patent Document 2), alkaline-soluble resin, photopolymerizable The alkali-soluble resin has a polymerizable double bond over a photocurable composition containing a monomer, a photopolymerization initiator, and a solvent, and the photocurable composition further contains an organic compound. A photocurable composition containing a peroxide (see Patent Document 3) is known, but the alkali-soluble resin used in these resin compositions contains a (meth) acrylate having an oxetal group. Containing as a monomer component of rosin is not.

[0005] The photosensitive resin composition is a negative resist composition containing an alkali-soluble resin as a base resin, and is used in the structure of the alkali-soluble resin or in combination with the alkali-soluble resin. A negative resist composition containing an oxetane structure in the structure of the compound to be prepared (see Patent Document 4) is also known, but this composition uses a specific cadmium-containing compound as a crosslinking agent.

[0006] The photosensitive resin composition is a photosensitive resin composition containing an alkali-soluble resin, a crosslinking agent, and a photopolymerization initiator, and the alkali-soluble resin has an organic polymer having a phenolic hydroxyl group. A photosensitive resin composition which is a polymer containing a compound represented by the following general formula (1) in which structural unit is modified with an oxsilane compound and Z or oxetane compound as a structural unit, and an alkali-soluble resin, a crosslinking agent A modified poly (p-hydroxystyrene) represented by the following general formula (2), wherein the alkali-soluble resin contains an oxsilane ring and a Z or oxetane ring: This photosensitive resin composition (see Patent Document 5) is also known in the art. This composition is a compound in which the phenolic hydroxyl group of the alkali-soluble resin used is modified with an oxetane compound. It has a return unit.

[0007] [Chemical 1]

[Wherein, m and n represent an integer of 1 or more, and X represents a functional group containing an oxsilane ring and a Z or oxetane ring.]

The photosensitive resin composition also includes a radiation-sensitive composition containing a polymer compound (A) having a carboxyl group and an oxetane skeleton, a quinonediazide compound (B), and a polyvalent phenolic compound (C). An active rosin composition (see Patent Document 6) is also known.

Patent Document 1: Japanese Patent Laid-Open No. 11 65116

Patent Document 2: JP 2001-228610 A

Patent Document 3: Japanese Patent Application Laid-Open No. 2004-83754

Patent Document 4: Japanese Patent Laid-Open No. 2001-343748

Patent Document 5: Japanese Patent Application Laid-Open No. 2002-229204

Patent Document 6: Japanese Patent Laid-Open No. 2003-156843

Disclosure of the invention

Problems to be solved by the invention

[0009] An object of the present invention is to provide a cured product that can be cured at a low temperature without hindering the function of an organic semiconductor element or the like and has excellent properties such as resolution, electrical insulation, thermal shock resistance, and chemical resistance. It is an object of the present invention to provide a photosensitive insulating resin composition suitable for use in a surface protective film and an interlayer insulating film, a cured product thereof, and a use thereof.

Means for solving the problem

[0010] 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 oxetal group and a monomer represented by the following general formula (3),

(B) a photosensitive acid generator, (c) Epoxy compounds, isocyanate compounds and blocked products thereof, nitrogen-containing compounds having all or part of the active methylol group alkylated, and at least one cross-linking agent selected

(D) A photosensitive insulating resin composition comprising an adhesion assistant.

[Chemical 2]

[0012] (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.

[0013] (3) At least the component (B) is selected from an onion salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound. The photosensitive insulating resin composition according to (1), wherein the composition is one type.

(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).

The invention's effect

[0015] By using the photosensitive insulating resin composition according to the present invention, alkali development and low-temperature curing are possible, and excellent resolution, electrical insulation, heat resistance, thermal shock resistance, and chemical resistance are achieved. Have It is possible to obtain hard objects.

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.

Brief Description of Drawings

FIG. 1 is a cross-sectional view of a thermal shock resistance evaluation substrate.

FIG. 2 is a schematic diagram of a thermal shock evaluation substrate.

Explanation of symbols

[0017] 1. Silicon substrate

2. Copper plating pattern

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] 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 Is a copolymer obtained from a (meth) acrylic acid ester having an oxetal group, a monomer represented by the following general formula (3), and another vinyl monomer.

[0019] (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-oxetal) methyl.

Monomer represented by the general formula (3):

[0020] [Chemical 3]

[0021] (3)

Specific examples of the monomer represented by the general formula (3) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-ρ-hydroxystyrene, α-methylm-hydroxystyrene, α-methyl o-hydroxystyrene, p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-etoxystyrene, m-etoxystyrene, o-etoxystyrene, p-t-butoxystyrene, m-t-butoxystyrene O-t-butoxystyrene, α-methyl p-t-butoxystyrene, α-methyl p-t-butoxystyrene, α-methyl-p-t butoxystyrene, and the like.

[0022] In the above examples of monomers, vinyl monomers having a phenolic hydroxyl group are exemplified. However, a vinyl monomer in which this group is protected by a protective group is copolymerized to form a copolymer. After that, the protective group is deprotected to form a copolymer having a phenolic hydroxyl group.

Other vinyl monomers:

Examples of other butyl monomers include aromatic vinyl compounds such as styrene, α-methyl styrene, ο methyl styrene, ο chloro styrene, m chloro styrene, Ν, Ν dimethylolene, amino styrene, and divinyl benzene;

Methyl (meth) acrylate, ethyl (meth) acrylate, η-propyl acrylate, η-butyryl acrylate, 2-ethyl hexyl (meth) acrylate, stearyl (meth) acrylate, isobornyl acrylate , Tricyclo [5.2.1.0 ² , ⁶ ] force (meth) acrylate, etc. Rukyll (meth) atarylates;

Unsaturated monocarboxylic esters such as methyl crotonate, ethyl crotonate, methyl cinnamate, and ketyl cinnamate; fluoroalkyl (meth) acrylates such as ptafluorobutyl (meth) acrylate; trimethylsiloxa -Siloxal compounds such as dimethyldimethylpropyl (meth) acrylate and tris (trimethylsilyl ether);

Mono- or di (meth) acrylates of alkylene glycols such as ethylene glycolanol, 1,2-propanediol, 1,3-propanediol, 1,6-hexanediol; 2-methoxyethyl (meth) acrylate , 2-Ethoxyethyl (meth) ate, 3-Eto

(Meth) atarylates, and cyan compounds such as acrylonitrile and metathali-tolyl;

Polyhydric alcohols such as glycerin, 1,2,4-butanetriol, pentaerythritol, trimethylolalkane (alkane has 1 to 3 carbon atoms, for example), tetramethylolalkane (alkane has 1 to 3 carbon atoms, for example 1 to 3) Oligo (meth) acrylates such as di (meth) acrylate, tri (meth) acrylate or tetra (meth) acrylate;

Epoxy groups such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxy cyclohexyl) ethyl (meth) acrylate, allyl glycidyl ester Containing monomer;

Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 — hydroxypropyl (meth) acrylate; 2-hydroxyethyl crotonate, croton Hydroxyalkyl esters of unsaturated carboxylic acids, such as 2-hydroxypropyl acid and 2-hydroxypropyl quinoate;

Unsaturated alcohols such as (meth) aryl alcohol;

Unsaturated (mono) carboxylic acids such as (meth) acrylic acid, crotonic acid, and cinnamate; Unsaturated anhydrides such as (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid, and their diesters;

Examples include vinyl chloride, vinyl acetate, cinnamate, crotonic ester, dicyclopentadiene, and ethylidene norbornene.

[0023] The monomers exemplified above can be used alone or in combination depending on the purpose.

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.

[0024] 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 monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like. Glycol monoalkyl ether acetates;

Propylene glycol monoalkyl ethers such as propylene glycol monomethino ethenore, propylene glycol monomethino enoate, propylene glycol monopropyl ether, propylene glycol monomono butenoate;

Propylene glycol dialkyl ethers such as propylene glycol dimethylol ether, propylene glycol jetino ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethanolate acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;

Cellosonolevs such as echinorescerosolev, butinorescerosolev;

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, and 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, Ν, Ν-dimethylacetamide, Ν-methylpyrrolidone;

Ratatons such as γ-petit lolacun are listed.

[0025] These organic solvents can be used alone or in admixture of two or more.

When the copolymer (Α) is a copolymer of a (meth) acrylic acid ester having an oxetanyl group and a hydroxy or alkoxy styrene derivative represented by the general formula (3), it has an oxetal group. (meth) 5-95 acrylate ester ^_0/0, resulting preferably 10-9 0% by weight, the hydroxy or alkoxy styrene derivatives 5-95%, preferably used in a proportion of 10 to 90 wt% It is desirable that

[0026] Further, the copolymer (Α) (meth) acrylic acid ester having a force oxetal group and a general formula

(3) When a copolymer of hydroxy or alkoxy styrene derivatives and other Bulle monomer represented in, Okiseta - having Le based on (meth) Atari esters 5-90 wt ^_0/0 , preferably 10 to 85 weight ^_0/0, the hydroxy or alkoxy styrene induction member 5 to 85 wt%, preferably 10 to 80 wt%, the other Bulle monomer 1-50 by weight%, preferably 2 It is desirable to be obtained by using at a ratio of ˜40% by weight.

[0027] The number average molecular weight (hereinafter referred to as "Μη") of the copolymer (Α) by gel permeation chromatography (GPC) is typically 1,000 to 100,000, preferably 3,00 to 50,000.

[(B) Photosensitive acid generator]

The photo-sensitive acid generator (用い) used in the present invention generates acid by irradiation with radiation. The compound is not particularly limited, and examples thereof include at least one selected from onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds. Specific examples are shown below.

[0028] Onium salt compounds:

Examples of the onium salt compound include a ododonium salt, a sulfo-um salt, a phospho-um salt, a diazo-um salt, and a pyridi-um salt.

Preferable examples of o-um salt include diphloe rhodonyum trifluoromethanes norephonate, diphnenorehodenium p tonorenosnorehonate, diphnenorehodenium. Hexafnoreo Mouth Antimonate, Diphlo-Rhodonium Hexafluorophosphate, Diphlo-Rhedonium Tetrafunoleroborate, Trihue-Noresnorehon Triflorotantansnorephonate, Trifheninoresnorehoni Hum p-to-no-re-nos-no-rephonate, triphenylenosenole homeohexahexoleo mouth antimonate, 4 t butylphenol diphenol diphenol-nolesnorephonyl trifluoromethanesulfonate, 4 t butylphenol 'diphenylsulfo- Um-p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophene-muto Julio b methanesulfonate, (4 Hue - thio) Hue - Rujifue - Rusuruho - © Kisafunoreo port phosphate to beam, (4 Hue - Norechio) Hue - Rujifue - Noresunoreho - © into airless such fully O b antimonate and the like.

[0029] Halogen-containing compounds:

Examples of the compound containing a hydrogen atom and a rogen include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like. Preferable examples of halogen-containing compounds include 1,10 dibromo-1-n-decane, 1,1 bis (4-cylinder) -1,2,2 trichloroethane, phenol-bis (trichloro S-triazine derivatives such as methyl) S-triazine, 4-methoxyphenyl-bis (trichloromethyl) S-triazine, styryl-bis (trichloromethyl) S-triazine, naphthyl-bis (trichloromethyl) -S-triazine .

[0030] Sulfone compounds:

Examples of the sulfone compounds include 13-ketosulfone compounds, j8-sulfonylsulfone compounds, and (X diazo compounds of these compounds. Examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, and bis (phenacylsulfonyl) methane.

[0031] Sulfonic acid compounds:

Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and the like.

Preferable specific examples include benzoin tosylate, pyrogallol tristrifluormethane sulphonate, o ditrobenzino trifnore aromethanesulphonate, o ditrobenzinole p toluenesulfonate, and the like.

[0032] Sulfonimide compounds:

Specific examples of the sulfonimide compound include N (trifluoromethylsulfo-loxy) succinimide, N— (trifluoromethylsulfo-loxy) phthalimide, N— (trifluoromethylsulfo-loxy) diphenylmaleimide, N- (trifluoro) Fluoromethylsulfoloxy) bicyclo [2.2.1] hept-5ene-2,3 dicarboximide, N- (trifluoromethylsulfoloxy) naphthylimide, and the like.

[0033] Diazomethane Compound:

Specific examples of diazomethane compounds include bis (trifluoromethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (phenolsulfol) diazomethane, and the like.

In the present invention, these photosensitive acid generators (B) can be used alone or in combination of two or more.

[0034] The blending amount of the photosensitive acid generator (B) is 100 parts by weight of the copolymer (A) from the viewpoint of securing the sensitivity, resolution, pattern shape, etc. of the resin composition of the present invention. In contrast, 0.1 to 20 parts by weight, preferably 0.5 to: L0 parts by weight. When the blending amount of the light-sensitive acid generator (B) is less than 0.1 part by weight, curing may be insufficient and heat resistance is lowered. When it exceeds 20 parts by weight, transparency to radiation is lowered. The pattern shape may be deteriorated.

[0035] [(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). It is. 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 in which all or part of the active methylol group is alkyl etherified. is there.

[0036] 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 compounds such as epoxy resin, phenol novolac, and epoxy resin;

Isocyanate compounds such as tolylene diisocyanate and blocked products thereof; (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, (poly) methylol urea urea and other active methylol groups Examples thereof include nitrogen-containing compounds in which all or part of them are alkyl etherified.

[0037] The amount of the crosslinking material (C) is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, per 100 parts by weight of the copolymer (A). If the 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 an 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. It is a compound that improves Specific examples include silane coupling agents and thiol compounds.

[0038] Specific examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethylpyrutrimethoxysilane, urea propyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and the like. As the thiol-based compound, a monothiol such as t-dodecyl mercaptan and a polyvalent thiol such as trithiocyanouric acid are used. In the present invention, it is preferable to use a silane coupling agent.

[0039] The amount of the adhesion assistant (D) is 0.5 to LO parts by weight, preferably 1 to 5 parts by weight with respect to 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 will decrease. There is a fear.

圖]

In the present invention, a solvent may be added to improve the handleability of the photosensitive insulating resin composition and 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 monomethenoylethenore acetate and ethylene glycol monoethyl ether acetate;

Cellosonolevs such as echinorescerosolev, butinorescerosolev;

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, and 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, methylamylketone;

Amides such as N-dimethylformamide, N-methylacetamide, Ν, Ν-dimethylacetamide, Ν-methylpyrrolidone;

Ratatons such as γ-petit lolacun are listed.

[0040] These solvents may 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 having phenolic hydroxyl group and resin, resin having oxetal group;

High density polyethylene, Medium density polyethylene, Polypropylene, Polycarbonate, Polyarylate, Aliphatic polyamide, Polyamideimide, Polysulfone, Polyethersulfone, Polyetherketone, Polyphenylenesulfide, (Modified) Polycarbodiimide, Polyetherimide, Polyesterimide, Modified polyphenylene -Thermoplastic or thermosetting resin such as lenoxide.

[0041] In addition, organic fillers such as sensitizers, leveling agents, silicone rubber particles or crosslinked rubber particles, silica or inorganic fillers such as alumina may be contained. .

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, each component of the copolymer (Α), a photosensitive acid generator (Β), a crosslinking agent (C), and an adhesion assistant (D), and the necessary components. Depending on the condition, it is produced 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 an arbitrary order and stirred, mixed and dispersed. Oh ,.

[0042] [Curing 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. Accordingly, 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.

[0043] 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 to which a wiring pattern is applied. It is applied and dried to evaporate the solvent and form a coating film. Thereafter, the film is exposed through a desired mask pattern, and then developed with an alkaline developer to dissolve and remove the non-exposed portion to obtain a coating film on which the desired pattern is formed. 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, coating such as dating method, spray method, bar coating method, roll coating method, spin coating method, curtain coating method, etc. 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 with a high-pressure mercury lamp, the film thickness is 5 to 50; ζ ΐη is about 1,000 to ²⁰ , OOOjZm ² .

Thereafter, development is performed with an alkaline developer to dissolve and remove unnecessary non-exposed portions, thereby forming a desired pattern. Examples of the development method in this case include a shower development method, a spray development method, an immersion development method, and a paddle development method, and the development conditions are usually about 1 to 10 minutes at 20 to 40 ° C. .

As the alkaline developer, for example, an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethylammonium hydroxide, choline, etc. may be adjusted to a concentration of about 10 to 10% by weight. An alkaline aqueous solution dissolved in water can be 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. After developing with alkaline developer Wash with water and dry.

[0046] Further, after the development, in order to sufficiently develop the characteristics as an insulating film, the film is cured by heat treatment. At this time, the photosensitive acid generator (B) is decomposed to generate an acid. This acid catalysis promotes the curing reaction between the crosslinking agent (C) and the copolymer (A). The photosensitive insulating resin composition according to the present invention can be heat-treated at a lower temperature than conventional photosensitive insulating resin compositions.

[0047] The above curing conditions are not particularly limited, but the coating film is cured by heating at a temperature of 50 to 300 ° C for about 30 minutes to 10 hours depending on the use of the cured product. Also, it can be heated in two stages in order to sufficiently advance the curing and prevent deformation of the obtained pattern shape. For example, in the first stage, the temperature is 50 to 150 ° C. for 10 minutes to 2 It can be heated for about an hour, 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 or an infrared furnace can be used as a heating facility.

[0048] [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.

[0049] Resolution:

A 6-inch silicon wafer was spin-coated with a photosensitive insulating resin composition and heated on a hot plate at 110 ° C for 3 minutes to produce a uniform coating film having a thickness of 10 / zm. Then, using the Araina one (Karl Suss Co. MA- 100), the exposure amount at wavelength 350nm ultraviolet rays from a high-pressure mercury lamp through a patterned mask 3,000～5 was exposed so that OOOjZm ^2. Next, the plate was heated (110 ° C) for 3 minutes at 110 ° C on a hot plate, and developed by immersing in a 38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C for 60 seconds. The minimum dimension of the obtained pattern was taken as the resolution.

[0050] Adhesion:

A 6-inch silicon wafer is spin-coated with a photosensitive insulating resin composition and hot-played. Heated at 110 ° C for 3 minutes to produce a 10 m thick uniform coating. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm ^2. Next, after heating (PEB) at 110 ° C for 3 minutes on a hot plate, the ultraviolet ray from the high-pressure mercury lamp was exposed again 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 with a pressure tacker tester (manufactured by Tabai Espec Co., Ltd.) for 168 hours under conditions of a temperature of 121 ° C. and a humidity of 100%. The adhesion after the test was judged by performing a cross-cut test (cross cut tape method) in accordance with JIS K5400.

[0051] 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 produce a uniform resin film having a thickness of 10 m. UV light from a high-pressure mercury lamp was exposed so that the exposure amount at a wavelength of 350 nm was 3,000 to 5,000 jZm ² . Then, after heating for 3 minutes at 110 ° C on a hot plate (PEB), the exposure amount in the wavelength 350nm ultraviolet high-pressure mercury lamp power even again 3, 000-5, was exposed so that OOOjZm ^2. Then, it was heated at 120 ° C for 2 hours in a convection oven to obtain a cured film. The obtained cured film was treated with a pressure tacker test device (manufactured by Tabai Espec) for 168 hours under the conditions of a temperature of 121 ° C, a humidity of 100% and a pressure of 2.1 atm. The volume resistivity between the layers before and after the test was measured to confirm the resistance.

[0052] 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 m thick resin coating on the conductor. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm ^2. Next, 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, OOOOjZm ² . Thereafter, the film was heated in a convection oven at 120 ° C. for 2 hours to obtain a cured film. The substrate was subjected to a resistance test using a thermal shock tester (manufactured by Tabai Espec Co., Ltd.) at 50 ° CZ30 minutes to 125 ° CZ30 minutes for one cycle. The number of cycles until defects such as cracks occurred in the cured film was confirmed. [0053] Solvent resistance:

A 6-inch silicon wafer was spin-coated with a photosensitive insulating resin composition and heated at 110 ° C for 3 minutes on a hot plate to produce a 10 m thick uniform coating film. Exposure at a wavelength of 350nm ultraviolet rays from a high-pressure mercury lamp 5 was exposed so that OOOjZm ^2. Next, after heating (PEB) at 110 ° C for 3 minutes on a hot plate, the ultraviolet ray from the high-pressure mercury lamp was exposed again 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.

[0054] O: No abnormality is observed on the surface of the cured film.

X: Whitening or roughening was observed on the surface of the cured film.

[Synthesis Example 1]

18g acrylic acid in a 1L separable flask, 98g of a-methyl-p-hydroxystyrene, OXE-10 (trade name, manufactured by Osaka Organic Chemicals) 208g, 26g of styrene, 2,2 'azobis isobuti-trinore (hereinafter referred to as "AIBN") ) 15g and 2g heptanone 350g were added and stirring was started. Heating was started under a nitrogen gas atmosphere, 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, and a 2-heptanone solution of copolymer (A-1) having a solid content of 49% was obtained.

[0055] [Synthesis Example 2]

In a 1 L separable flask, stirring was started with 138 g of α-methyl ρ-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. In 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, heating was stopped and the reaction was completed to obtain a 2-heptanone solution of copolymer (A-2) with a solid content of 49%. .

[0056] [Synthesis Example 3] To a 1 L separable flask, 70 g of p-t-butoxystyrene, 30 g of OXE-10 (trade name, manufactured by Osaka Organic Chemical Industry), 3 g of AIBN and 10 Og of propylene glycol monomethyl ether were added and stirring was started. Heating was started under a nitrogen gas atmosphere 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 stirring was continued for 3 hours. Then, the heating was stopped and the reaction was completed. Next, 20 g of a 20% hydrochloric acid aqueous solution was hydrolyzed at 80 ° C. for 6 hours at V ヽ. Ethyl acetate (lOOg) was added to the solution, and then 200g of distilled water was added and shaken well, then allowed to stand to remove the aqueous layer. Thereafter, washing with water was repeated until the aqueous layer became neutral. Next, the mixture was coagulated in a large amount of hexane and vacuum dried to obtain a copolymer (A-3).

[0057] [Synthesis Example 4]

Synthesis of poly (p-hydroxystyrene) partial 3-ethyl 3-methyloxetane 4'-ether (modification rate 20%)

3 ethyl-3 hydroxymethyloxetane (EOXA, manufactured by Toa Gosei Co., Ltd.) 10. 2 g and 14.2 g of chlorothionyl were stirred and reacted in toluene, and the reaction product was taken out. Purification using silica gel chromatography gave 8.4 g of 3-chloromethyl-3-ethyloxetane. 2.5 g of 3 chloromethyl-13-ethyloxetane and 10 g of poly (phydroxystyrene) (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 and 60 g was added. The mixture was stirred at ° C for 6 hours. Reprecipitate with toluene and vacuum-dry the resulting precipitate to obtain a 10-lg poly (p-hydroxystyrene) partial 3-ethyl 3-methyloxetane 4 'monoether (A-4) )

[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 crosslinking agent (C1) and 2 parts by weight of adhesion assistant (D-1) The part was dissolved in 50 parts of a solvent (ethyl acetate). The properties of this composition were measured according to the evaluation method. The results obtained are shown in Table 1.

[0059] [Examples 2 to 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 results obtained are shown in Table 1. [Comparative Examples 1-2]

In the same manner as in Example 1, a photosensitive insulating resin composition having the composition shown in Table 2 was prepared.

Our special o o o υ

>>>> Property 111 was measured in the same manner as in Example 1. Table 2 shows the results obtained.

'1 1 11

(B) Photosensitive acid generator

B— 1: SP—Yes 152 (trade name, manufactured by Asahi Denki Kogyo)

B—2: SP—172 (Asahi Denka Kogyo brand name)

(C) Crosslinking agent

C—1: Epicoat 152 (Japan Epoxy Resin product name)

C 2: OXT—121 (trade name, manufactured by Toagosei)

C-3: Epicoat 828 (Product name made by Japan Epoxy Resin)

(D) Adhesion aid

D-2: Ureapropyltrimethoxysilane

D—3: Tris (3-trimethoxysilylpropyl) isocyanurate

[table 1]

1

Example 1 Example 2 Example 3

100

(Ii) Acid generator (part)

Β— 1 5 2

Β-2 5

Five

Ten

2

Five

(E) Solvent (part)

Ethyl lactate 50 50

Methinoreamilketone 150

Resolution (μm) 10 10 10

Adhesion 100/100 100/100 100

Volume resistivity (Ω-cm)

Before test 4X 10 ¹⁶ 7X 10 ¹⁶ 4X 10 ^ie

After test 3X 10 ¹⁴ 5X 10 ¹⁴ 5X 10 ¹⁴

Thermal impulse cycle (times) 1000 1000 1000

Solvent resistance ○ ○ ○ Table 2

Comparative Example 1 Comparative Example 2 Copolymer

A— 1 100

A—4 100

(B) Acid generator (part)

B— 1 5

B-2 5

(C) Cross-linking agent (part)

C 1 1 5

CD) Adhesion aid (part)

D— 1 2

(E) Solvent (part)

Luccinole

Methylamyl ketone 100 100 Resolution m) 10 20 Adhesion 100/100 0/100 Volume resistivity (Ω · cm)

Test i 4X 10 ¹⁶ 7 X 1 0 ¹⁴ After test 5X 10 ¹² 3 X 10 ⁹ Thermal shock cycle (times) 100 200 Solvent resistance X 〇

Claims

The scope of the claims

(A) a copolymer obtained by copolymerizing a (meth) acrylic acid ester having an oxetal group and a monomer represented by the following general formula (3),

(B) a photosensitive acid generator,

(C) an epoxy compound, an isocyanate compound and a blocked product thereof, a nitrogen-containing compound having all or part of the active methyl group substituted with an alkyl ether, at least one crosslinking agent selected

[Chemical 4]

(3)

[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. The photosensitive insulating resin composition according to claim 1, wherein the composition is a seed.

[4] The photosensitive insulating resin composition according to claim 1, wherein the component (D) is a silane coupling agent.

[5] A cured product obtained by curing the photosensitive insulating resin composition according to claim 1.

[6] An electronic component comprising an insulating layer formed using the photosensitive insulating resin composition according to [1].