TWI328718B - Photosensitive resin composition for interplayer insulating film - Google Patents

Description

1328718 (1) The present invention relates to a photosensitive resin composition for an interlayer insulating film. The present invention claims priority from Japanese Patent Application No. 2000-74858, filed on Jan. [Prior Art] Conventionally, in order to prevent a liquid crystal display element, an integrated circuit element, a solid film, a protective film for deterioration or damage of an electronic component such as a solid phase pickup element, or to insulate a wiring disposed between layers. A photosensitive resin composition is used for the formation of the interlayer insulating film provided. In the case of an integrated circuit element, for example, an LSI (Large Scale Integration) multilayer wiring is formed by interposing a metal wiring that is energized and an interlayer insulating film that electrically exchanges the same. In the case of a liquid crystal display device, for example, a TFT (thin film transistor) liquid crystal display device is provided with a polarizing plate on a glass substrate to form a transparent conductive circuit layer such as IT0 and a TFT, and is covered with an interlayer insulating film to form a back surface plate. On the other hand, if a polarizing plate is provided on the glass plate, the pattern of the black matrix layer and the color filter layer may be formed as needed, and the transparent conductive circuit layer and the interlayer insulating film may be sequentially formed into the upper panel. The panel and the upper panel are manufactured by sealing a liquid crystal between the two plates by a spacer. The photosensitive resin composition for interlayer insulating film used for the production of the liquid crystal display element is excellent in transparency, so that propylene resin-5-(2)(2)1328718 can be used (see Patent Documents 1, 2, 3). ). [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2000-162769 (Patent Document 3). In the formation of a conventional interlayer insulating film, the photosensitive resin composition may have a problem that the heat resistance of the obtained interlayer insulating film may not be sufficient. As described above, the photosensitive resin composition for an interlayer insulating film is used for a protective film for preventing deterioration or damage of electronic components such as a liquid crystal display element, an integrated circuit element, a solid-state imaging solid-state element, or the like. The interlayer insulating film disposed in the layered wiring is provided for insulation. After forming the protective film or the interlayer insulating film, the protective film or the interlayer insulating film may be heated to form another layer or part. The situation of high temperature. Therefore, when the heat resistance of the protective film or the interlayer insulating film is insufficient, for example, the shape cannot be maintained by heat treatment, and the characteristic change or the like may be inappropriately generated. In view of the above, the present invention provides a photosensitive resin composition for an interlayer insulating film having excellent heat resistance. In order to achieve the above object, the photosensitive resin composition for an interlayer insulating film of the present invention is In the photosensitive resin composition containing the alkali-soluble resin component (A) and the photosensitive agent (B), the component (A) contains a resin component (A1) having the following structural formula (al): ) is characterized by it. -6- (3) 1328718

【化1】

(In the above general formula, 'Rfl represents a hydrogen atom or a methyl group, R1 represents a single bond or an alkylene group having a carbon number of 1 to 5', and R2 represents an alkyl group having a carbon number of 1 to 5, an abbreviated as an integer of 1 to 5' b represents an integer of 0 or 1 to 4, and a + b is 5 or less. Further, when R 2 is two or more, the R 2 may be different or the same with each other.) Further, the "constituting unit" means a constituent polymer. Monomer unit. According to the present invention, a photosensitive resin composition for an interlayer insulating film having excellent heat resistance is provided. [Best Mode for Carrying Out the Invention] The photosensitive resin composition for an interlayer insulating film of the present invention contains a soluble resin component (A) [hereinafter, abbreviated as (A) component]), and a photosensitive agent (B) "hereinafter, abbreviated ( B) Ingredients. (4) (4)

1328718 The photosensitive resin composition exhibits a positive type which changes the characteristics of the solution due to the change in the component (B) due to exposure due to the exposure suppressing action. The component (A) contains the resin component (A1) having the general formula a). The resin component is preferred. Since it contains a constituent unit (al in the formula (al), R° represents a hydrogen source. R1 represents a single bond or a straight group having a carbon number of 1 to 5. In terms of an alkylene group, a methylene propylene group may be mentioned. An n-butenyl group, an isobutenyl group, a tripentenyl group, a neopentenyl group, etc., preferably in an alkylene group. In the above, in the case of R1, a single bond is used, and a preferred one is a. The effect is good. Also, in the benzene ring, the bond position of the hydroxyl group (0) - the bond position of Ο-R'-" is one bit E is desired. R2 represents a linear or fraction of carbon number 1 to 5. Methyl, ethyl, propyl, isopropyl, and the insoluble or poorly soluble nature of the component (B) of the pre-butylation cause (B) is a constituent unit ((A 1 ) with respect to the alkali developer. The alkali-soluble resin) can enhance the effector or methyl group of the present invention, and the methyl group is a chain or branched chain alkylene group, a vinyl group, a propylene group, an isobutylene group, a pentenyl group, and a hetero face. Methylene group, vinyl alkenyl group is preferred, especially in the case of a single bond, in the case of at least one, "-C temple, a chain-bonded alkyl group bonded to the 4-position" ,can Base, isobutyl, secondary butyl-8- (5) 1328718 pentyl, isopentyl, neopentyl, etc. Industrially, methyl or ethyl is preferred b to represent an integer from 1 to 4, 〇 is desirable. In the present invention, preferred constituent units are as exemplified below. 'Chemical 2】

(a1-1) (al-2) (In the above general formula, RG is the same as before.) Among these, the unit represented by the chemical formula (al-Ι) is preferred, and especially W is preferably a methyl group. The constituent unit (al) may be used in combination of one type or two or more types. The component (A1) may contain one or two or more kinds of constituent units copolymerizable with the constituent unit (al), in addition to the constituent unit (al). In the total constituent unit of the component (A1), the ratio of the constituent units (al) -9 - (6) (6) 1328718 is expected to be 20 mol% or more, and particularly preferably 50 mol% or more. It is preferable that the effect of the present invention is improved within this range. The component (A1) may be used as a constituent unit other than the constituent unit (al), and is not particularly limited, and may, for example, be selected from the group consisting of acrylic acid, methacrylic acid, acrylates, acrylamides, and methacrylic acid. A unit derived from a compound having a polymerizable unsaturated bond, such as an ester, a methacrylamide, an allyl compound, a vinyl ether, a vinyl ester, a styrene, or a crotonate. The acrylate type may, for example, be an oxime group (the alkyl group has a carbon number of preferably 1 to 10) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, Ethylhexyl acrylate, octyl acrylate, acrylic acid-trioctyl octyl ester, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate Ester, trimethylolpropane monoacrylate, neopentyl alcohol monoacrylate, epoxy propyl acrylate, benzyl acrylate, methoxy benzyl acrylate, mercapto acrylate, tetrahydrofurfuryl acrylate , etc.), aryl acrylate (such as phenyl acrylate, etc.). The methacrylate type may, for example, be an alkyl group (the alkyl group preferably has a carbon number of 1 to 10) a methacrylate (for example, methyl methacrylate, ethyl methacrylate, or propyl group). Acrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxy-10-(7) 1328718 butyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxyl Propyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, mercapto methacrylate, tetrahydrofurfuryl methyl Acrylate, etc.), aryl methacrylate (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.).

The acrylamide may, for example, be acrylamide or N-alkyl acrylamide (the alkyl group preferably has a carbon number of from 1 to 10, and has, for example, a methyl group, an ethyl group, a propyl group, a butyl group, Tertiary butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, benzyl, etc.), N-aryl acrylamide (for aryl, for example, phenyl, tolyl, nitrophenyl, naphthalene Base, hydroxyphenyl, etc., hydrazine, hydrazine-dialkyl acrylamide (the alkyl group, preferably having a carbon number of 1 to 10, such as methyl, ethyl, butyl, isobutyl, ethyl Hexyl, cyclohexyl, etc.), anthracene, fluorene-diaryl acrylamide (for aryl, for example, phenyl, etc.), hydrazine-methyl-hydrazine-phenylpropenylamine, hydrazine-hydroxyethyl - Ν-methacrylamide, Ν-(2-acetamidoethyl)-fluorene-ethenyl acrylamide. The methacrylamide may, for example, be methacrylamide or fluorenyl-alkyl methacrylamide (the alkyl group is preferably a carbon number of 1 to 10, for example, a methyl group or an ethyl group). , tert-butyl, ethylhexyl, hydroxyethyl, cyclohexyl, etc.), fluorenyl-aryl methacrylamide (the aryl group, phenyl, etc.), hydrazine, hydrazine-dialkylmethacryl Indoleamine (the alkyl group, having ethyl, propyl, butyl, etc.), hydrazine, hydrazine-diarylmethyl acrylamide (the aryl group, having a phenyl group, etc.), hydrazine-hydroxyethyl- Ν-Methyl methacrylamide, Ν-methyl-Ν-phenylmethacrylamide, Ν-ethyl-Ν-phenylmethacrylamide.

-11 - (8) (8) 1328718 The allyl compound may, for example, be an allyl ester (for example, acetic acid propylene vinegar, caproic acid propylene vinegar, octanoic acid propylene vinegar, lauric acid propylene vinegar, palm Acid allyl ester, allyl stearate, allyl benzoate, allyl acetate, allyl lactate, etc., allyloxyethanol. The vinyl ethers may, for example, be alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether) , chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl acid, dimethylamine Ethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ether (eg vinyl phenyl ether) , vinyl toluene ether, ethylene chlorophenyl ether, ethylene-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl ether ether, etc.). Examples of the vinyl esters include, for example, ethylene butyrate, ethylene isobutyrate, ethylene trimethyl acetate, ethylene diethyl acetate, ethylene valerate, ethylene hexanoate, and ethylene chloroacetic acid. Ester, ethylene dichloroacetate, ethylene methoxy acetate, ethylene butoxy acetate, vinyl phenyl acetate, ethylene acetate, ethylene lactate, ethylene - / 3-benzene Butyrate, ethylene cyclohexyl carboxylate, ethylene benzoate, ethylene salicylate, ethylene chlorobenzoate, ethylene tetrachlorobenzoate, (L) ethylene formate. Examples of the styrenes include styrene, alkylstyrene (e.g., methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene'diethylstyrene, cumene. Ethylene, butyl styrene, hexyl styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene, chloromethyl-12- (9) 1328718 styrene, trifluoromethyl styrene, ethoxylate Styrene, ethoxymethyl styrene, etc., alkoxy styrene (eg methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), Halogenated styrene (eg chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodine styrene, fluorostyrene, trifluorostyrene , 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.). The crotonate may, for example, be an alkyl crotonate (e.g., butyl crotonate, hexyl crotonate, glycerol monobutyrate, etc.): a dialkyl itaconate (e.g., itaconic acid) Ester, diethyl itaconate, dibutyl itaconate, etc.): dialkyl ester of maleic acid or fumaric acid (eg dimethyl maleate, dibutyl anti- Butylene diester, etc.); acrylonitrile, methacrylonitrile. Further, the following epoxy group-containing polymerizable unsaturated compound may also be mentioned. The component (A1) is preferably a component (a2) represented by the following general formula (a2), and is preferably improved in heat resistance. [化3] R0

(R3)c (a2)

-13- (10) 1328718 (In the above general formula, 'RG is the same as above', R3 represents an alkyl group having 1 to 5 carbon atoms, and C represents an integer of 0 or 1 to 5. Further, when R3 is present in two or more cases, R3 may be different or identical to each other.) In the above general formula (a2), rQ is the same as above. R3 represents an alkyl group having 1 to 5 carbon atoms, which is the same as the description of the former R2. c represents 〇 or an integer from 1 to 5, which is expected. The constituent unit (a2) is used in combination of one type or two or more types. In the total constituent unit of the component (A1), the constituent unit (a2) is equal to or less than 8 〇mol% in terms of the balance with the constituent unit (a 1 ). The ear % is preferably 'in particular, it contains 50 to 1% of the molar %, and the other constituent units which can be used for the component (A1) may, for example, be a constituent unit derived from hydroxystyrene, or the following The constituent unit (a3) shown in the general formula (a3) 'constituent unit (a4) shown in the following general formula (a4). More preferably, it is one selected from the constituent unit (a3) and the constituent unit (a4). [化4] R0

R4 (a3)

• 14-(11) 1328718 (In the above general formula, R is the same as above. R4 represents a carbon number of 1 to 5 atoms.) In the above general formula (a3), RD is the same as above. R4 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. The alkyl group is the same as the alkyl group in the description of R2. Among them, an alkylmethyl group is preferred. In terms of alkyl or hydrogen, it can be exemplified, especially

(In the above general formula, !^'113, (: the same as above. Also in the case of '113, the R3s may be different or identical to each other.) - In the general formula (a4), R3, c is the same as above. The mass average molecular weight of the component (A1) (measured by styrene in terms of Mw: GPC) is 2,000 Å, preferably 5,000 to 30,000. It is easy to make it equal to or lower than the lower limit ,, and the upper limit is 値 or less. Obtaining moderate alkali solubility. There are two kinds of gel permeation chromatography -50000. The film is formed into a film-like -15- (12) 1328718. The (A1) component can be used in combination of one type or two or more types. It can be used by mixing an alkali-soluble tree-fat component other than the component (A1), for example, a propylene resin, a hydroxystyrene resin, a novolac: a lacquer resin, etc. However, it is preferably a component (A1) in the component (A). 70% by mass or more, preferably 80% by mass or more, and 100% by mass, the photosensitive agent (B) can be irradiated with ultraviolet rays or the like to improve the photosensitive resin composition for the interlayer insulating film of the present invention. Solubility of an alkaline solution (for example, aqueous tetramethylammonium hydroxide solution). Photosensitive agent (B) The sensitizer having a benzoquinonediazide group (containing a benzoquinonediazide compound) is preferably a benzoquinonediazide compound, and examples thereof include a phenol compound and a naphthoquinonediazidesulfonate. The fully esterified product or partially esterified product of the acid compound 〇 can be exemplified by, for example, 2,3,4-trihydroxydiphenylφ ketone, 2,3,4,4··tetrahydroxydiphenyl ketone, etc. Polyhydroxydiphenyl ketone compound; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane 'bis(4-hydroxy-2, 3,5-trimethylphenyl)-2-hydroxyphenylmethane '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-di Methylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2j-dimethylphenyl)-3-hydroxyphenylmethane 'bis(4-hydroxy-2,5-dimethylphenyl) -16- (13) (13)

1328718)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethyldihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenylylphenylmethane, double (4-hydroxy-2,5-dimethylphenyl)methane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxybis(5-cyclohexyl-4-hydroxy-2-methyl Phenyl)-4-hydroxybenzene (5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenyl 5-cyclohexyl-4-hydroxy-2-methylphenyl)-2 -hydroxyphenyl-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylphenol type compound; 2,4-bis(3,5-dimethyl-4-hydroxybenzyl) ))-5-hydroxyl | bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol; etc.; Linear benzene ring compound; 1,1-double 3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-4-hydroxyphenyl)methane , bis[2,5-dimethyl-3-(4-hydroxyphenyl)methane, bis[3-(3,5-dimethyl-4-hydroxybenzylmethylphenyl)methane, double [ 3-(3,5-Dimethyl-4-hydroxy-5-ethylphenyl)methane, bis[3-(3,5-diethyl-4-hydroxyhydroxy-5-methylphenyl] Methane , bis[3-(3,5-diethyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylphenyl Methane, bis[2-hydroxy-3methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-methylbenzyl)-5-methylphenyl]methane, double [ 2,5-Dimethylphenyl)-3,4-;)-3,4-dihydroxy 14-dihydroxybenzene: phenylmethane, methane, bis & methane, bis(3 alkane, bis(5- ; three S phenols such as methane; 2,6-L linear 3-nuclear type phenol group-5-cyclohexylmethylbenzyl)-benzyl)-4-hydroxy)-4-hydroxy-5-benzyl)- 4-hydroxybenzyl)-4--4-hydroxybenzyl 3,5-dimethyl-(2-hydroxy-5-(2-m--5-yl-3-(2-hydroxy-17-) (14) (14) 1328718 linear 5-nuclear phenol compound such as 5-methylbenzyl)-4-hydroxyphenyl]methane; 2,4-bis[2-hydroxy-3-(4-hydroxyl) Benzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, Linear 5-nuclear benzoquinone compound such as 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-cardohydroxybenzyl]-4-methylphenol Linear polyphenol combination ; 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-(31 -fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl) )-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4-hydroxy-3',5'-dimethylphenyl)propane, etc. a biguanide type compound; 1-[1-(4-hydroxyphenyl)isopropyl]-4-[l,l-bis(4-hydroxyphenyl)ethyl)]benzene, 1-[1-( 3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, etc., a multinuclear branched compound; A condensed phenol compound such as 1-bis(4-hydroxyphenyl)cyclohexane. These may be one type or a combination of two or more types. Further, the naphthoquinonediazidesulfonic acid compound may, for example, be naphthalene-18-(15)(15)1328718醌-1,2-diazido-5-sulfonic acid or naphthoquinone-1,2 · Diazido-4-sulfonic acid and the like. Further, for other benzoquinonediazide-based compounds, for example, n-benzoquinonediazide, n-naphthoquinonediazide, n-quinonediazide or n-naphthoquinonediazidesulfonate can be used. Such a nuclear-substituted derivative, such as n-benzoquinonediazidesulfonyl chloride and a compound having a hydroxyl group or an amino group, such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, double Phenol A, naphthol, pyrocatechol, gallicol, gallophenol monomethyl ether, gallicol-1,3-dimethyl ether, gallic acid, hydroxyl residue for partial esterification or An etherified gallic acid, an aniline, a reaction product of an aminodiphenylamine or the like. These may be used alone or in combination of two or more. The benzoquinonediazide-containing compound, for example, the polyhydroxydiphenyl ketone, and naphthoquinone-1,2-diazido-5-sulfonium chloride or naphthoquinone-1,2-di The azido-4 sulfonium chloride is condensed in a suitable solvent such as dioxane in the presence of a base such as triethanolamine, a carbonic acid base or a hydrogencarbonate base, and is produced by complete esterification or partial esterification. In the case of the phenylhydrazine diazide-containing compound, such a naphthoquinonediazidesulfonate is preferred. The component (B) may be used alone or in combination of two or more. The component (B) is preferably in the range of 5 to 200 parts by mass, preferably 15 to 100 parts by mass, per 100 parts by mass of the component (A). Within this range, the film homogeneity is good and the resolution is improved. Further, by exposure and development, the faithfulness of the obtained pattern can be improved, and the transfer property can be improved. -19- (16) (16) 1328718 Further, the photosensitive resin composition for an interlayer insulating film of the present invention is preferably a thermosetting component (C) (hereinafter referred to as a component (C)). Thereby, heat resistance can be improved. In the component (C), a component having a crosslinked structure formed by heating the component (A1) or in the component (C) is desirable, and examples thereof include an epoxy group and an oxetane group. . Specifically, for example, various epoxy resins, copolymers containing a polymerizable unsaturated compound containing an epoxy group-containing unsaturated compound, and the like. The epoxy resin may, for example, be described in JP-A-8-262709. Preferably, a bisphenol A type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a cyclic aliphatic epoxy resin, and a glycidyl ester type are exemplified. Epoxy resin, epoxypropylamine type epoxy resin, heterocyclic epoxy resin, epoxy methacrylate, (co)polymerized resin, and the like. Among these, a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, a glycidyl ester type epoxy resin or the like is preferred. The epoxy group-containing polymerizable unsaturated compound may, for example, be a compound having a vinyl group and an epoxy group. Specifically, for example, the following is shown. For example, epoxy acrylate, epoxy methacrylate, α-ethyl acrylate epoxy, α-η-propyl acrylate epoxy propyl, α-n-butyl acrylate epoxy propyl, acrylic acid - 3,4-Ethoxybutyl, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, (1-ethylacrylic acid-6,7-epoxyheptyl,^[4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl]propenylamine, hydrazine- [4-( -20- (17) 1328718 2,3-epoxypropoxy)-3,5-dimethylphenylpropyl]propenylamine, acryl-β-methylepoxypropyl, Methacrylic acid-β-methylepoxypropyl group, o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, p-vinylbenzyl epoxypropyl ether, etc. Further, (C) component In the aspect of the invention, those having an alicyclic epoxy group are preferred. The number of carbon atoms of the alicyclic group of the alicyclic epoxy group is preferably from about 5 to 10. The polymerizable unsaturated compound containing an alicyclic epoxy group. The alicyclic epoxy group-containing polymerizable unsaturated compound represented by the following general formula is exemplified.

(4) r3 〇

I II CH2= c_c —〇 —r4 (18)1328718

(5)

[化1 Ο]

[化1 1] r3 ο

I II CH2_C — C—〇——

(7)

-22- (19) 1328718 【化1 2】 R3 ο ο

_l II II CH2= c —c —〇—R4—]~CH2—〇—c 【化1 3】

(8)

C-c-o-r4-ch——ch2=

(9)

-23- (20)1328718 【化1 5】r3 οI II ch2=c-c-o-

,Ο-CH 2\ ,CH- Ό (11) , 0-CH5

[Chemical 1 6] R3 Ο Ο 〇 R3 R3 I 11 Γιι Ί II I 1 CH2= C A C —O — R4—O—C— R5—O.—C—N—R5—N—L Jw

(12) [Chem. 1 7] R3 O O 〇 R3 R3

-24- (13) (21) 1328718 [Chem. 1 8]

(14)

[Chemical 1 9] R3 〇 R3 I II I ch2=c-c-n-r4

(15)

[化2 0]

(16) (22) 1328718 [Chem. 2 1]

(17) [Chem. 2 2]

R3 ο I II ch2=c-c-r4

(18)

[Chemical 2 3] R3 O R3 o 〇 I II I II r iu CH2= C — C — N — C — N — R 5 — N — C — 0 — R 4 Η H ” w

(19) -26- (23) 1328718 [Chem. 2 4]

(20) [Chem. 2 5]

(twenty one)

(twenty two)

-27- (24) 1328718 [Chem. 2 8]

OH ch2=ch-ch2-o-r4-c [Chemical 2 9]

[化3 0] ch2=ch-o-r4

(27) (25) 1328718 [Chem. 3 1]

[化3 2]

(28) [Chem. 3 3]

-29- (26) 1328718 [Chem. 3 5]

(32) (wherein R3 represents no hydrogen atom or methyl group, R4 represents a divalent hydrocarbon group having 1 to 8 carbon atoms, R5 represents a divalent hydrocarbon group of carbon 1 to 20, and R3 'R4 and R5 may be the same or different 'w indicates the number of 0 to 10) These objects are expected to be represented by the general formula (4). In the "copolymer containing a polymerizable unsaturated compound containing an epoxy group-containing polymerizable unsaturated compound", the polymerizable unsaturated compound used together with the epoxy group-containing polymerizable unsaturated compound is as described above. In the component (A1), the monomer component copolymerizable with the constituent unit (al) is, for example, selected from the group consisting of acrylic acid, methacrylic acid, acrylate ester, acrylamide, methacrylate, A compound having a polymerizable unsaturated bond such as a methacrylamide, an allyl compound, a vinyl ether, a vinyl ester, a styrene, or a crotonic acid vinegar. -30- (27) (27) 1328718 Among these, acrylic acid, methacrylic acid, acrylates, and methacrylates are preferred, and acrylic acid and methacrylic acid are preferred, and methacrylic acid is preferred. In the polymerizable unsaturated compound used in the copolymer, the ratio of the epoxy group-containing polymerizable unsaturated compound is from 5 to 90 mol%, preferably from 50 to 85 mol%. In the above (C) component, a resin having an epoxy group (e.g., a copolymer containing the above epoxy group-containing polymerizable unsaturated compound or a polymerizable unsaturated compound) is preferred. In particular, those having a unit derived from the above epoxy group-containing polymerizable unsaturated compound are preferred because of high heat resistance. Preferably, those having an alicyclic epoxy group are preferred in the above. (C) The component may be used alone or in combination of two or more. The component (C) is 10 to 250 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the component (A). Within this range, the heat resistance improving effect can be further improved. Further, in the photosensitive resin composition for an interlayer insulating film of the present invention, the surfactant (D) (hereinafter referred to as (D) component) can be blended in consideration of coatability. (D) The component may be a conventional one, and examples thereof include an anionic, cationic or nonionic compound. Specifically, X-70-090 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) or the like can be exemplified. Further, in the photosensitive resin composition for an interlayer insulating film of the present invention, various additives such as a sensitizer and an antifoaming agent may be added. -31 - (28) 1328718 For sensitizers, users of conventional positive-type photoresists can be used. There is a compound having a phenolic hydroxyl group having a molecular weight of 100 or less. The antifoaming agent may be a conventional one, and a polyfluorene-fluorine-based compound may, for example, be mentioned. Organic solvent The photosensitive resin composition for an interlayer insulating film of the present invention is improved in properties, and the viscosity can be adjusted to match an organic solvent. In terms of organic solvents, there are benzene, toluene, xylene, methyl ethyl acetonate, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, hexanol, cyclohexanol, ethylene glycol, diethyl Glycol, glycerin, ethylene glycol ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene Methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate ( ), 3-methoxybutanol (MB), 3-methyl-3-methoxybutyl B , propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ester, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl acrylate carbonate, butyl carbonate and the like. Among them, the combination of MBA and MB is good. The amount of the organic solvent to be used is not particularly limited, but the substrate may be equal to the concentration of the cloth, and may be appropriately set depending on the thickness of the coating film. The solid content of the photosensitive resin is preferably from 10 to 50% by mass, preferably from 15 to 35%. The interlayer insulating film of the present invention is composed of a photosensitive tree jg, and the composition is, for example, coated with ketone, butanol monomethylol di MBA ether ethyl ester, and the carbon agent is a coatable mass of -32- (29). ) (29)^287i8 & method modulation. The (A) component and the (B) component are added with an organic solvent or other additives as needed, and mixed (dispersed/kneaded) in a three-roller 'ball mill' sand mill or the like, and filtered by a 5 μm membrane filter to prepare photosensitivity. Resin composition. The photosensitive resin composition for interlayer insulating film of the present invention is a protective film for preventing deterioration or damage of electronic components such as liquid crystal display elements, integrated circuit elements, solid imaging solid-phase elements, or layered. The formation of the interlayer insulating film provided for insulation in the wiring of the wiring is appropriate. Hereinafter, an example of a method of forming a protective film or an interlayer insulating film using the photosensitive resin composition for an interlayer insulating film of the present invention will be described. First, a germanium substrate formed of a metal wiring is prepared; a polarizing plate such as a black matrix layer or a color filter layer; and a support such as a glass substrate provided with a transparent conductive circuit layer are provided. Next, on the surface of the support, the photosensitive resin composition of the interlayer insulating film of the present invention is applied by a spinner, a roll coater, spray coating or the like, and dried to form a film thickness of about 1·〇5 to 5 μm. A photosensitive resin layer. The drying method is not particularly limited. For example, (1) drying at a temperature of 80 ° C to 120 ° C for 60 seconds to 120 seconds, (2) placing at room temperature for several hours to several 曰The method, (3) in the warm air heater or the infrared heater, the method of removing the solvent in a few ten to several hours, any method can be followed by 'through the positive mask, ultraviolet rays, excimer Laser light and other activities -33- (30) (30) 1328718 Performance line illumination for partial exposure. The amount of the energy ray to be irradiated varies depending on the composition of the photosensitive resin composition, but is preferably, for example, about 30 to 2000 mJ/cm2. Next, using an aqueous solution of an organic alkali such as an aqueous solution of tetramethylammonium hydroxide (TMAH) or an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium methyl citrate or sodium phosphate, the exposed portion is dissolved and removed to form a solution. Graphic type. Thereby, a protective film or an interlayer insulating film can be provided in a desired range. Thereafter, heat treatment was carried out under the conditions of 150 to 2 50 °C. Moreover, it is better to fully expose the pattern formed. According to the invention, it is possible to provide a photosensitive resin composition for an interlayer insulating film having good heat resistance. Therefore, in the manufacturing process of the element in which the protective film or the interlayer insulating film is provided, even if the interlayer insulating film is heated at a relatively high temperature, for example, about 200 to 250 ° C, it is difficult to lower the characteristics of the protective film or the interlayer insulating film, and the effect is extremely good. . Further, in the photosensitive resin composition for an interlayer insulating film of the present invention, the resolution is also good, and the surface roughness of the pattern is small. [Embodiment] (Example) The following components were mixed to prepare a photosensitive resin composition having a solid content concentration of about 28% by mass. (A) component: In the general formula (al-Ι), RG is a homopolymer of a methyl group (Mw: 1 9000) 30 parts by mass - 34 - (31) (31) 1328718 (B) Component: L-[l-(4-Hydroxyphenyl)isopropyl]-4-[l,l-bis(4-hydroxyphenyl)ethyl)benzene 1 molar with naphthoquinone-1,2-diazide Base-5-sulfonic acid chloride 2 molar ester 20 parts by mass (C) Component: molar ratio of methacrylic acid to (3,4-epoxycyclohexyl)methyl methacrylate 20 : 80 Copolymer (Mw : 7〇〇〇) 50 parts by mass (D) Component: X-70-O90 (product name, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by mass of organic solvent: mass ratio of MBA to MB 80 : 20 Mixed solvent (Comparative Example) A photosensitive resin was produced in the same manner as in the Example except that the component (A) was changed to a copolymer of methacrylic acid and styrene of 20:80 (Mw: 7000). Composition. In the examples, the photosensitive resin compositions of the comparative examples were evaluated in the following manner. "Resolution property j is applied by a spin coating method on a glass substrate by a spin coating method". The film is dried on a hot plate at 100 ° C for 120 seconds to form a photosensitive resin composition layer having a film thickness of 4.0 μm. Subsequently, it was exposed to a exposure machine (product name: Nikon G7E, manufactured by Nikon Co., Ltd.) through a mask, and developed using a TMAH aqueous solution having a concentration of 44 mass% to form a pattern of 5 μm line and gap when forming a pattern. In the examples, any of the comparative examples can be formed as shown in Fig. 35-(32), (32) 1328718. "Flatness" The surface of the above pattern was observed by an electron microscope. As a result, there is substantially no surface roughness in the examples. In contrast, in the comparative example, there is surface roughness.

Health. "Heat resistance J The substrate of the above pattern was formed and placed in an oven at 220 ° C for 30 minutes. In the examples, the line width was not changed 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. From the above results, it was confirmed that the heat resistance was good in the examples of the present invention, and the resolution was also good. [Industrial use possibility] According to the present invention, there is provided a photosensitive resin composition for an interlayer insulating film having excellent heat resistance

Claims (1)

1328718 --- Announcement 10, Patent Application No. 9 5 1 03 924 Patent Application Revision of Chinese Patent Application Revision of the Republic of China on April 9, 1999 1. A photosensitive resin composition for interlayer insulating film, which is A photosensitive resin composition containing an alkali-soluble resin component (A), a photosensitive agent (B), and an organic solvent, wherein the component (A) contains a constituent unit represented by the following general formula (ai) (a 1 The resin component (A1), the ratio of the constituent unit (al) in the resin component (A1) is 20 mol% or more and 100 mol% or less, and the mass average molecular weight of the resin component (A1) is 2,000 or more and 50,000 or less. The content of the resin component (A1) in the component (A) is 70% by mass. The amount of the component (B) is a compound containing quinonediazide, and the content of the component (B) is 5 to 2 〇0 based on 100 parts by mass of the component (A). In the range of the mass fraction, the organic solvent is used in an amount such that the solid content concentration of the photosensitive resin composition is in the range of 10 to 5 % by mass. 1328718 [Chemical 1] R° (al) (In the above general formula, a hydrogen atom or a methyl group, R1 represents a single bond or an alkylene group having 1 to 5 carbon atoms, R2 represents an alkyl group having 1 to 5 carbon atoms, and a represents an integer of 1 to 5, b represents an integer of 0 or 1 to 4, and a + b is 5 or less. Further, when R 2 is present in two or more, the R 2 may be mutually different or the same). 2. The photosensitive resin composition for interlayer insulating film according to the first aspect of the invention, wherein the resin component (A1) further has a structural unit (a2) represented by the following general formula (a2), -2- I32S718 (In the above general formula, RG represents a hydrogen atom or a methyl group, R3 represents a fluorenyl group having 1 to 5 carbon atoms, c represents an integer of 0 or 1 to 5, and when R3 is present in two or more, the R3 may mutually A photosensitive resin composition for an interlayer insulating film, which is characterized in that it is a photosensitive resin composition for an interlayer insulating film according to the first aspect of the invention, and further contains an epoxy resin or a The copolymer of the epoxy group-containing polymerizable unsaturated compound is (C) a thermosetting component. The content of the (C) thermosetting component is 1 〇 to 250 by mass based on 100 parts by mass of the component (A). Within the scope of the share. 4. A photosensitive resin composition for an interlayer insulating film, which is characterized in that it is a photosensitive resin composition for an interlayer insulating film according to the second aspect of the invention, and further contains an epoxy resin or an epoxy group-containing polymerizable property. The content of the (C) thermosetting component of the (C) thermosetting component is in the range of 10 to 250 parts by mass based on 100 parts by mass of the component (A). 5. The photosensitive -3- 1328718 resin composition for an interlayer insulating film according to the third aspect of the invention, wherein the (c) thermosetting component has a copolymerization of a polymerizable unsaturated compound containing an alicyclic epoxy group; Things. The photosensitive resin composition for interlayer insulating film according to the fourth aspect of the invention, wherein the (C) thermosetting component has a copolymer of a polymerizable unsaturated compound containing an alicyclic epoxy group. -4-