KR100758867B1 - Photosensitive resin composition for interplayer insulating film - Google Patents

Abstract

Provided is a photosensitive resin composition for an interlayer insulating film having excellent heat resistance. As photosensitive resin composition containing alkali-soluble resin component (A) and the photosensitive agent (B), (A) component contains the resin component (a1) which has a structural unit (a1) represented by the following general formula (a1). The photosensitive resin composition for interlayer insulation films to be made.

(In said general formula, R <^0> represents a hydrogen atom or a methyl group, R <^1> represents a single bond or a C1-C5 alkylene group, R <^2> represents a C1-C5 alkyl group, and a is a 1-5 An integer is shown, b represents an integer of 0 or 1-4, and a + b is 5 or less, and when two or more R <^2> exists, these R <^2> may mutually differ or may be the same.)

Photosensitive resin composition

Description

Photosensitive resin composition for interlayer insulation films {PHOTOSENSITIVE RESIN COMPOSITION FOR INTERPLAYER INSULATING FILM}

[Patent Document 1] Japanese Patent Application Laid-Open No. 8-262709

[Patent Document 2] Japanese Unexamined Patent Publication No. 2000-162769

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-330180

The present invention relates to a photosensitive resin composition for an interlayer insulating film.

This application claims priority based on Japanese Patent Application No. 2005-74858 for which it applied to Japan on March 16, 2005, and uses the content here.

Conventionally, the photosensitive resin composition is used for formation of the protective film for preventing deterioration or damage of electronic components, such as a liquid crystal display element, an integrated circuit element, and a solid-state image sensor, or the interlayer insulation film formed in order to insulate between the wiring arrange | positioned in layers. Has been.

In the case of integrated circuit elements, for example, multilayer wiring of LSI (Large Scale Integration) is formed by alternately forming and processing metal wirings through which electricity passes and interlayer insulating films electrically insulating them.

In the case of a liquid crystal display element, for example, in a TFT (thin film transistor) type liquid crystal display element, a polarizing plate is formed on a glass substrate, a transparent conductive circuit layer such as ITO, and a TFT are formed, coated with an interlayer insulating film and back On the other hand, a polarizing plate is formed on a glass plate, the pattern of a black matrix layer and a color filter layer is formed as needed, Furthermore, a transparent conductive circuit layer and an interlayer insulation film are formed sequentially, and it is set as a top plate, and this back plate and a top surface are formed. It is manufactured by enclosing a liquid crystal between both plates by opposing the plates with spacers therebetween. Acrylic resin is used for the photosensitive resin composition for interlayer insulation films used for manufacture of a liquid crystal display element in that transparency is favorable (refer patent document 1, 2, 3).

However, in the conventional interlayer insulation film formation, the photosensitive resin composition has a problem that the heat resistance of the obtained interlayer insulation film is not enough.

As described above, the photosensitive resin composition for an interlayer insulating film is formed to insulate between a protective film for preventing deterioration and damage of electronic components such as a liquid crystal display device, an integrated circuit device, and a solid-state image sensor, or between wirings arranged in layers. In order to form another layer or component after forming a protective film and an interlayer insulation film used for manufacture of an insulating film, these protective films and an interlayer insulation film may be heated at high temperature. Therefore, if the heat resistance of the protective film or the interlayer insulating film is insufficient, for example, the shape can not be maintained by the heat treatment, or the characteristics will change.

This invention is made | formed in view of the said situation, and makes it a subject to provide the photosensitive resin composition for interlayer insulation films provided with the outstanding heat resistance.

In order to achieve the said objective, the photosensitive resin composition for interlayer insulation films of this invention is a photosensitive resin composition containing alkali-soluble resin component (A) and a photosensitive agent (B), The said (A) component is a following general formula (a1) It is characterized by containing the resin component (a1) which has a structural unit (a1) represented by the following.

(In said general formula, R <^0> represents a hydrogen atom or a methyl group, R <^1> represents a single bond or a C1-C5 alkylene group, R <^2> represents a C1-C5 alkyl group, and a is a 1-5 An integer is 0, b represents an integer of 0 or 1 to 4, and a + b is 5 or less, and when b is 2 or more, each R ² may be different.)

In addition, a "structural unit" represents the monomeric unit which comprises a polymer.

According to this invention, the photosensitive resin composition for interlayer insulation films with excellent heat resistance can be provided.

To practice the invention  Best form for

The photosensitive resin composition for interlayer insulation films of this invention contains alkali-soluble resin component (A) (hereinafter abbreviated as (A) component), and photosensitive agent (B) [hereinafter abbreviated as (B) component].

This photosensitive resin composition exhibits insoluble or poorly soluble characteristics with respect to the alkaline developer by dissolution inhibiting action of the component (B) before exposure, and has a characteristic of dissolving in the alkaline developer when the component (B) is changed by exposure. It's a positive change.

(A) component contains the resin component (A1) which has a structural unit (a1) represented by the said General formula (A1). It is preferable that a resin component (a1) is an alkali-soluble resin component. By containing a structural unit (a1), the effect of this invention is improved.

In general formula (a1), R <^0> represents a hydrogen atom or a methyl group, and it is preferable that it is a methyl group.

R ¹ represents a single bond or a linear or branched alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, tert-butylene group, pentylene group, isopentylene group and neopentylene group. As the alkylene group, a methylene group and an ethylene group are preferable.

Among these, R ¹ is a single bond, and ethylene groups are preferred, especially preferred is a single bond.

a represents the integer of 1-5, and 1 is preferable at an effect and manufacture.

In the benzene ring, it is preferable that at least one hydroxyl group is bonded to the 4 position when the bonding position of "-C (O) -OR ^1- " is 1 position.

R <^2> represents a C1-C5 linear or branched alkyl group, and is methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, tert- butyl group, a pentel group, isopentyl group, and neo Pentyl group etc. are mentioned. Industrially, a methyl group or an ethyl group is preferable.

b represents 0 or the integer of 1-4, and it is preferable that it is zero.

In this invention, a preferable structural unit is illustrated below.

(In said general formula, R <^0> is as above.)

Among these, the structural unit represented by general formula (a1-1) is preferable, and it is especially preferable that R <^0> is a methyl group.

A structural unit (a1) can be used 1 type or in mixture of 2 or more types.

In addition to the structural unit (a1), the component (A1) may contain one or two or more structural units copolymerizable with the structural unit (a1).

In all the structural units which comprise (A1) component, it is preferable that the ratio of a structural unit (a1) is 20 mol% or more, It is preferable that it is especially 50 mol% or more, and 100 mol% may be sufficient.

By setting it in this range, the effect of this invention can be improved.

Although the structural unit which can be used other than a structural unit (a1) in (A1) component is not specifically limited, For example, acrylic acid, methacrylic acid, acrylic acid ester, acrylamide, methacrylic acid ester, meta The unit derived from the compound which has a polymerizable unsaturated bond chosen from a krill amide, an allyl compound, vinyl ether, vinyl ester, styrene, and crotonic acid ester, etc. is mentioned.

 As acrylate ester, for example, alkyl (The carbon number of the alkyl group is 1-10 is preferable.) Acrylate (For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate. , Acrylic acid-t-octyl, chlorethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like), and aryl acrylate (for example, phenyl acrylate). .

As methacrylic acid ester, for example, alkyl (as for the carbon number of the alkyl group, 1-10 is preferable) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl meth) Acrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate Acrylate, 5-hydroxypentel methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), aryl methacrylate (for example phenyl methacrylate, cresyl methacrylate, Naphthyl methacrylate, etc.) is mentioned.

As acrylamide, acrylamide and N-alkyl acrylamide (C1-C10 is preferable as the alkyl group, for example, methyl group, an ethyl group, a propyl group, a butyl group, t-butyl group, a heptyl group) , Octyl group, cyclohexyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (The aryl group includes, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.). .), N, N-dialkylacrylamide (The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group and cyclohexyl group. ), N, N-diarylacrylamide (the aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N- ( 2-acetamide ethyl) -N-acetylacrylamide is mentioned.

As methacrylamide, For example, methacrylamide and N-alkyl methacrylamide (The alkyl group has preferable C1-C10, For example, a methyl group, an ethyl group, t-butyl group, an ethylhexyl group, Hydroxyethyl group, cyclohexyl group, etc.), N-aryl methacrylamide (The aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (The alkyl groups include ethyl group, propyl group, Butyl group, etc.), N, N-diaryl methacrylamide (The aryl group includes a phenyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmetha. Krillamide and N-ethyl-N-phenyl methacrylamide are mentioned.

As the allyl compound, for example, allyl esters (for example, allyl acetate, allyl capronate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetate, allyl lactate Etc.), allyloxyethanol is mentioned.

As vinyl ether, For example, alkyl vinyl ether (For example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether , Benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (e.g., vinyl phenyl ether, vinyl tol ether, vinyl chlor phenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl) Ether, vinyl anthranyl ether, etc.) is mentioned.

As vinyl esters, vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barate, vinyl caproate, vinyl chlor acetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl Butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butylate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorate, vinyl tetrabenzoate, vinyl naphthoate Can be mentioned.

As the styrene, for example, styrene, alkyl styrene (for example methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl Styrene, chlormethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (e.g. methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), Halogen styrenes (e.g. chlorstyrene, dichlorstyrene, trichlorstyrene, tetrachlorstyrene, pentachlorstyrene, bromine styrene, dibrom styrene, iodine styrene, fluorostyrene, trifluorostyrene, 2-brom-4- Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.) is mentioned.

As crotonic acid ester, For example, alkyl crotonate (For example, butyl crotonate, hexyl crotonate, glycerin monoclotonate etc.); Dialkyl itaconic acid (for example, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.); Dialkyls of maleic acid or fumaric acid (for example, dimethyl maleate, dibutyl fumarate and the like); Acronitrile and methacrylonitrile are mentioned.

Moreover, the following epoxy group containing polymerizable unsaturated compound is also mentioned.

It is preferable that a component (A1) contains the structural unit (a2) represented by the following general formula (a2) at the point which improves heat resistance.

(In said general formula, R <^0> is as above. R <^3> represents a C1-C5 alkyl group and c represents O or the integer of 1-5. Moreover, when c is 2 or more, each R <^3> is Can be different.)

In the general formula (a2), R ⁰ is as described above.

R <^3> represents a C1-C5 alkyl group and is the same as that of the said R <^2> .

c represents the integer of 0 or 1-5, and it is preferable that it is zero.

A structural unit (a2) can be used 1 type or in mixture of 2 or more types.

It is preferable to contain 80 mol% or less and 80-10 mol% in balance with a structural unit (a1) among all the structural units which comprise (A1) component, and 50-10 mol is especially preferable in a structural unit (a2). It is preferable to contain%.

Moreover, as another structural unit which can be used as (a1) component, For example, the structural unit derived from hydroxy styrene, the structural unit (a3) represented by the following general formula (a3), and the following general formula (a4) The structural unit (a4) etc. which are represented by these are mentioned. More preferably, it is 1 type chosen from a structural unit (a3) and a structural unit (a4).

(In said general formula, R <^0> is as above. R <^4> represents a C1-C5 alkyl group or a hydrogen atom. "

In the general formula (a3), R ⁰ is as described above.

R <^4> represents a C1-C5 alkyl group or hydrogen atom. As an alkyl group, the thing similar to the alkyl group in description of R <^2> can be mentioned. Especially, an alkyl group is preferable and especially a methyl group is preferable.

(In said general formula, R <^0> , R <^3> , c is as above. In addition, when two or more R <^3> exists, these R <^3> may mutually differ or may be the same.)

In General Formula (a4), R ³ and c are the same as described above.

The mass average molecular weight (Mw: measured value by styrene conversion of gel permeation chromatography (GPC)) of a component (A1) is 2000-50000, Preferably it is 5000-30000. By setting it as the lower limit or more, it can form easily in a film form, and setting it as an upper limit or less, suitable alkali solubility is obtained, and it is preferable.

In addition, (A1) component can be used 1 type or in mixture of 2 or more types.

In (A) component, alkali-soluble resin components other than (A1) component can be mixed and used. For example, it is an acrylic resin, hydroxy styrene resin, a novolak resin, etc. However, Preferably content of (A1) component in (A) component is 70 mass% or more, Preferably it is 80 mass% or more, and 100 mass% may be sufficient.

The photosensitive agent (B) improves the solubility with respect to the alkali solution (for example, tetramethylammonium hydroxide aqueous solution) of the photosensitive resin composition for interlayer insulation films of this invention by irradiation with an ultraviolet-ray or the like. As a photosensitizer (B), the photosensitizer (quinonediazide group containing compound) which has a quinonediazide group is preferable.

As a quinone diazide group containing compound, the complete ester and partial ester of a phenol compound and a naphthoquinone diazide sulfonic-acid compound are mentioned, for example.

As said phenolic compound, For example, Polyhydroxy benzophenone compounds, such as 2,3,4- trihydroxy benzophenone and 2,3,4,4'- tetrahydroxy benzophenone;

Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxy Phenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4 -Hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2, 5-dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl)- 3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl)- 2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4- Hydroxyphenylmethane, bis (5-hour Clohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl Trisphenol type compounds such as -4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol Linear three benzene ring type phenol compounds;

1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy- 5-methylbenzyl) -4-hydroxyphenyl] methane, bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl -4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4- Hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2 -Hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl Linear tetranuclear phenol compounds such as 3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;

2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxy Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4 Linear polyphenol compounds such as linear 5-nucleated phenol compounds such as -methyl phenol;

Bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- ( 2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- ( 3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-tri Hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) Bisphenol-type compounds such as propane;

1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl Multinuclear branched compounds such as) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

Condensation type phenol compounds, such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc. are mentioned.

These can be used 1 type or in combination or 2 or more types.

The naphthoquinone diazide sulfonic acid compound may include naphthoquinone-1,2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid.

In addition, other quinone diazide group-containing compounds such as ortho benzoquinone diazide, orthonaphthoquinone diazide, ortho anthraquinone diazide or orthonaphthoquinone diazide sulfonic acid ester, and the like, and further Compounds having orthoquinonediazidesulfonylchloride and hydroxyl or amino groups, for example phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthool, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, Pyrogallol 1,3-dimethylether, gallic acid, reaction products with esterified or etherified gallic acid, aniline, p-aminodiphenylamine and the like, with some hydroxyl groups, and the like can also be used. These may be used independently and may be used in combination of 2 or more type.

These quinonediazide group-containing compounds are, for example, the above-mentioned polyhydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sul Phenyl chloride can be manufactured by condensing in presence of alkali, such as triethanolamine, an alkali carbonate, and an alkali hydrogen carbonate, in a suitable solvent, such as dioxane, and fully esterifying or partial esterifying.

As a quinone diazide group containing compound, such a naphthoquinone diazide sulfonic-acid ester compound is preferable.

(B) A component can be used 1 type or in mixture of 2 or more types.

(B) A component is 5-200 mass parts with respect to 100 mass parts of (A) component, It is preferable to use in the range of 15-100 mass parts preferably.

By using it in this range, the homogeneity of a film | membrane becomes favorable and resolution will improve. Moreover, the fidelity of the pattern obtained by exposure and image development improves, and transferability improves.

Moreover, it is preferable to mix | blend a thermosetting component (C) [hereinafter, it will describe with (C) component] to the photosensitive resin composition for interlayer insulation films of this invention. Thereby, heat resistance can be improved.

As (C) component, it is preferable that it is a component which can form a crosslinked structure in (A1) component and (C) component by heating, For example, the component which has an epoxy group and an oxetane group is mentioned.

Specifically, the copolymer etc. of the polymerizable unsaturated compound containing various epoxy resins and an epoxy group containing polymerizable unsaturated compound are mentioned, for example.

As an epoxy resin, the thing of Unexamined-Japanese-Patent No. 8-262709 is mentioned, for example. Preferably bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, The resin etc. which co-polymerized glycidyl methacrylate are mentioned. Among these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins, and the like are preferable.

As an epoxy group containing polymerizable unsaturated compound, the compound which has a vinyl group and an epoxy group is mentioned, for example. A specific example is shown below.

For example, glycidyl acrylate, glycidyl methacrylate, glycidyl (alpha)-ethyl acrylate, glycidyl (alpha)-n-propyl acrylate, glycidyl (alpha)-n-butylacrylate, acrylic acid -3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, N- [4 -(2,3-epoxypropoxy) -3,5-dimethylbenzyl] acrylamide, N- [4- (2,3-epoxypropoxy) -3,5-dimethylphenylpropyl] acrylamide, acrylic acid-β -Methylglycidyl, methacrylic acid- (beta) -methylglycidyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned.

Moreover, as (C) component, what has an alicyclic epoxy group is preferable. As for carbon number of the alicyclic group of an alicyclic epoxy group, about 5-10 are preferable.

As an alicyclic epoxy group containing polymeric unsaturated compound, the alicyclic epoxy group containing polymeric unsaturated compound represented with the following general formula is mentioned.

(Wherein, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R ₅ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and R ₃ , R ₄ and R ₅ are It may be the same or different and w represents the number of 0-10.)

Among these, what is represented by the said General formula (4) is preferable.

In the "copolymer of a polymerizable unsaturated compound containing an epoxy group-containing polymerizable unsaturated compound", as the polymerizable unsaturated compound used together with the epoxy group-containing polymerizable unsaturated compound, as described above, in the component (A1) And monomer components copolymerizable with the structural unit (a1), for example, acrylic acid, methacrylic acid, acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, aryl compounds, and vinyl ethers. And compounds having a polymerizable unsaturated bond selected from vinyl esters, styrenes, crotonic acid esters and the like.

Among these, acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters are preferable, acrylic acid and methacrylic acid are particularly preferable, and methacrylic acid is more preferable.

In the polymerizable unsaturated compound used for the copolymer, the proportion of the epoxy group-containing polymerizable unsaturated compound is 5 to 90 mol%, preferably 50 to 85 mol%.

Among these, as (C) component, resin which has an epoxy group (for example, the copolymer of the polymerizable unsaturated compound containing the said epoxy resin and an epoxy group containing polymerizable unsaturated compound) is preferable.

It is especially preferable to have a unit derived from the epoxy group-containing polymerizable unsaturated compound because of its high heat resistance. And among these, it is preferable to use what has an alicyclic epoxy group.

(C) component can be used 1 type or in mixture of 2 or more types.

(C) component is 10-250 mass parts with respect to 100 mass parts of (A) component, Preferably it is 50-200 mass parts. By setting it as this range, the heat resistance improvement effect will become more favorable.

Moreover, you may mix | blend surfactant (D) [hereinafter, it is described with (D) component] in the photosensitive resin composition for interlayer insulation films of this invention in consideration of applicability | paintability.

As the component (D), any conventionally known compound may be used, and compounds such as anionic, cationic, and nonionic compounds may be mentioned. Specifically, X-70-090 (product name, the Shin-Etsu Chemical Co., Ltd. product) etc. are mentioned.

Moreover, you may add various additives, such as a sensitizer and an antifoamer, to the photosensitive resin composition for interlayer insulation films of this invention.

As a sensitizer, what is used for the conventionally well-known positive resist can be used. For example, the compound etc. which have phenolic hydroxyl group of molecular weight 1000 or less are mentioned.

What is necessary is just a conventionally well-known antifoamer, and a silicone type and a fluorine-type compound are mentioned.

Organic solvents

An organic solvent can be mix | blended with the photosensitive resin composition for interlayer insulation films of this invention for the improvement of applicability | paintability, and viscosity adjustment.

Organic solvents include benzene, toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , 3-methoxybutyl acetate (MBA), 3-methoxybutanol (MB), 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate, Propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate and the like. Especially, the mixed solvent of MBA and MB is preferable.

Although the usage-amount of an organic solvent is not specifically limited, It is a density | concentration which can be apply | coated to a board | substrate etc., and it sets suitably according to a coating film thickness. It is preferable to use so that solid content concentration of the photosensitive resin composition may be in the range of 10-50 mass%, Preferably it is 15-35 mass%.

The photosensitive resin composition for interlayer insulation films of this invention can be prepared, for example by the following method.

(A) component and (B) component are added to the organic solvent and other additives as needed, and mixed (dispersed and kneaded) with stirrers, such as three roll mills, a pole mill, and a sand mill, and filtered with a 5 micrometer membrane filter, and photosensitive A resin composition is prepared.

The photosensitive resin composition for interlayer insulation films of the present invention is an interlayer insulation film formed to insulate a protective film for preventing deterioration or damage of electronic components such as a liquid crystal display device, an integrated circuit device, a solid-state imaging device, or between wirings arranged in layers. It can be used preferably for formation.

Hereinafter, the example of the method of forming a protective film or an interlayer insulation film using the photosensitive resin composition for interlayer insulation films of this invention is demonstrated.

First, a silicon substrate in which metal wiring is formed; Polarizing plate which formed black matrix layer, color filter layer, etc .; Supports, such as a glass substrate in which the transparent conductive circuit layer was formed, are prepared.

And the photosensitive resin composition for interlayer insulation films of this invention is apply | coated to the surface of this support body with a spinner, a roll coater, a spray, etc., and it dries to form the photosensitive resin layer of about 1.0-5 micrometers in film thickness. A drying method is not specifically limited, For example, (1) The method of drying for 60 second-120 second at the temperature of 80 degreeC-120 degreeC on a hotplate, (2) The method of leaving for several hours-several days at room temperature, (3) Any of the methods of removing the solvent in a hot air heater or an infrared heater for several tens of minutes to several hours may be used.

And an active energy ray, such as an ultraviolet-ray and an excimer laser beam, is irradiated and partially exposed through a positive mask between them. Although the energy dose to irradiate changes also with the composition of the photosensitive resin composition, about 30-2000mJ / cm <2> is preferable, for example.

And the pattern after dissolving and removing an exposure part is developed by using an organic alkali aqueous solution, such as tetramethylammonium hydroxide (TMAH) aqueous solution, or inorganic alkaline aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium metasilicate, and sodium phosphate. Form. Thereby, a protective film and an interlayer insulation film can be formed in a desired range.

Then, heat processing is performed on the conditions of 150-250 degreeC after that. Moreover, it is preferable to expose the whole surface of the formed pattern.

According to this invention, the photosensitive resin composition for interlayer insulation films with favorable heat resistance can be provided.

Therefore, even if the interlayer insulating film is heated at a relatively high temperature, for example, about 200 to 250 ° C. in the process of manufacturing a device in which the protective film or the interlayer insulating film is formed, the effect that the characteristics of the protective film or the interlayer insulating film is hardly deteriorated is obtained.

Moreover, the photosensitive resin composition for interlayer insulation films of this invention has the effect that resolution is also favorable and the surface roughness of a pattern is also small.

EXAMPLE

The following component was mixed and the photosensitive resin composition of about 28 mass% of solid content concentration was manufactured.

Component (A): wherein the homopolymer (Mw: 19000) R ⁰ is composed of a structural unit of a methyl group in the general formula (a1-1) 30 parts by weight

(B) Component: 1 mol of 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene and naphthoquinone-1,2- 20 parts by mass of an esterified product with 2 moles of diazide-5-sulfonic acid chloride

(C) component: 50 mass parts of copolymers (Mw: 7000) with a molar ratio of 20:80 of methacrylic acid and (3,4-epoxycyclohexyl) methyl methacrylate

(D) Component: X-70-090 (Product Name, Shin-Etsu Chemical Co., Ltd.) 0.1 parts by mass

Organic solvent: Mixed solvent with mass ratio of MBA and MB 80: 20

(Comparative Example)

A photosensitive resin composition was produced in the same manner as in Example except that the component (A) was changed to a copolymer (Mw: 7000) having a molar ratio of methacrylic acid and styrene of 20:80.

The photosensitive resin composition of an Example and a comparative example was evaluated as follows.

`` Resolution ''

The photosensitive resin composition was apply | coated to a glass substrate by the spin coat, it dried on the hotplate on conditions of 100 degreeC and 120 second, and the photosensitive resin composition layer of 4.0 micrometers of film thicknesses was formed. Then, a pattern of 5 µm line & space was formed by exposure using an exposure machine (product name: Nikon G7E, manufactured by Nikon Corporation) with a mask in between, and development using a 0.4 mass% aqueous TMAH solution to form a pattern. It was. Both the Example and the comparative example could form a pattern.

`` Flatness ''

The surface of the pattern was observed with an electron microscope. As a result, there was almost no surface roughness in the Example. In contrast, surface roughness occurred in the comparative example.

`` Heat resistance ''

The board | substrate which formed the said pattern was left to stand in the oven of 220 degreeC for 30 minutes. In the Examples, the line width did not change and the heat resistance (shape stability) was good. In contrast, in the comparative example, the line width was changed (the line width was increased), and the heat resistance was poor.

In the above result, it was confirmed that the heat resistance was favorable in the Example concerning this invention. In addition, resolution was also good.

According to this invention, the photosensitive resin composition for interlayer insulation films with excellent heat resistance can be provided.

Claims (6)

It is a photosensitive resin composition containing an alkali-soluble resin component (A) and a photosensitive agent (B), The photosensitive resin composition for interlayer insulation films in which said (A) component contains the resin component (a1) which has a structural unit (a1) represented by the following general formula (a1).

(In said general formula, R <^0> represents a hydrogen atom or a methyl group, R <^1> represents a single bond or a C1-C5 alkylene group, R <^2> represents a C1-C5 alkyl group, and a is a 1-5 An integer is 0, b represents an integer of 0 or 1 to 4, and a + b is 5 or less, and when R is 2 or more, each R ² may be different.) The method of claim 1, The photosensitive resin composition for interlayer insulation films in which the said resin component (A1) further has a structural unit (a2) represented by the following general formula (a2).

(In the general formula, R ⁰ represents a hydrogen atom or a methyl group, R ³ represents an alkyl group having 1 to 5 carbon atoms, and c represents an integer of 0 or 1 to 5. In addition, when c is 2 or more, each of R ³ may be different.) The photosensitive resin composition for interlayer insulation films of Claim 1 which further contains (C) a thermosetting component. The photosensitive resin composition for interlayer insulation films of Claim 2 which further contains (C) a thermosetting component. The method of claim 3, wherein The said (C) thermosetting component is the photosensitive resin composition for interlayer insulation films which have an alicyclic epoxy group. The method of claim 4, wherein The said (C) thermosetting component is the photosensitive resin composition for interlayer insulation films which have an alicyclic epoxy group.