TW200923584A - Photosensitive resin composition for interlayer insulation film - Google Patents

Abstract

This invention provides a photosensitive resin composition for an interlayer insulation film, comprising an alkali soluble resin (A) and a sensitizer (B). The alkali soluble resin (A) comprises a copolymer (A1) having a structural unit (a1) including an acidic group, a structural unit (a2) including a cross-linked group, and a structural unit (a3) including alkoxysilane. The structural unit (a3) preferably is represented by formula (a-3), wherein R4 represents hydrogen or methyl, R5 represents alkylene with 1 to 5 carbons, R6, R7, and R8 can be the same or different and represent alkyl or alkoxy with 1 to 5 carbons, and at least one of R6, R7, and R8 is alkoxy.

Description

[Technical Field] The present invention relates to a photosensitive resin composition for an interlayer insulating film. [Prior Art] Since the prior art, in electronic components such as liquid crystal display elements, integrated circuit elements, and image pickup elements An interlayer insulating film or the like provided in a layered shape for insulating between them is formed. This interlayer insulating film is always formed using a photosensitive resin composition (for example, refer to Patent Document 4). For example, a TFT (Thin Film Transistor) type liquid crystal display element is generally manufactured by the following steps. A polarizing plate is disposed on the glass substrate to form a dielectric layer and TF T , and then coated with an interlayer insulating film to form a back surface plate. On the other hand, a polarizing plate is disposed on the glass substrate to form a black matrix and a color filt pattern, and then a transparent conductive circuit layer and an interlayer insulating film are sequentially formed to manufacture the upper panel. Then, the spacer is separated. The spacer is opposed to the upper surface of the back surface, and a liquid crystal is sealed between the two sheets to fabricate a TFT crystal display device. The interlayer insulating film is generally formed by applying a photosensitive resin composition by the following method. The pattern is developed to form a pattern, and the pattern is thermally cured. The photosensitive resin composition for forming the interlayer insulating film is required to have a high insulating property. [Patent Document 1] Japanese Patent Laid-Open No. Hei 8 - 2 6 2 7 0 Since the solid wiring has been manufactured, the black er is manufactured by the illuminator, and the plate and the molding liquid are: , the missing material, 200923584 [Patent Document 2] Japanese Patent Laid-Open No. 2 0 0 0 - 1 6 2 7 6 9 [Patent Document 3] Japanese Patent Laid-Open No. Hei 2 - 3 3 0 1 8 0 [Patent Document 4] Japanese Patent Laid-Open No. Hei 2 - 2 5 9 Ο 8 3 [Invention] [Invention Wanted to solve However, in the photosensitive resin composition described in Patent Documents 1 to 4, for example, when the thickness of the interlayer insulating film is decreased as the number of layers increases, it is difficult to maintain a sufficiently high insulating property, and therefore it is necessary to have A photosensitive resin composition for an interlayer insulating film having higher insulating properties. The present invention has been developed in view of the above problems, and an object of the invention is to provide a photosensitive resin composition for an interlayer insulating film having higher insulating properties. [Means for Solving the Problem] The present inventors have found that the use of a copolymer having a specific structural unit in an alkali-soluble resin component of a photosensitive resin composition for an interlayer insulating film can improve insulation and finally complete the present invention. . The present invention provides a photosensitive resin composition for an interlayer insulating film comprising a testable resin component (A) and a sensitizer (Β); and the above-mentioned test component (A) contains a copolymer (A1), the copolymer (A1) The structural unit (a1) containing an acidic group, the structural unit (a2) containing a crosslinkable group, and the structural unit (a3) containing an alkoxyalkyl group. [Effect] According to the present invention, a photosensitive resin composition for an interlayer insulating film having higher insulating properties can be provided. [Embodiment] The photosensitive resin composition for interlayer insulating film of the present invention (hereinafter referred to as "photosensitive resin composition") contains a solvent-soluble resin component (also referred to as component (A), and is photosensitive). Agent (B) (hereinafter also referred to as ingredient). [Soliding Resin Component (A)] The component (A) in the present invention contains a copolymer (A1) containing a structural unit (a1) having an acidic group and a structure (a2) having a crosslinkable group. And a structural unit (a3) containing an alkoxyalkyl group. In the following description, the structural unit (a 1 ) containing an acidic group, the structural unit (a 2 ) containing a substituent group, and the structure (a 3 ) containing an alkoxyalkyl group are respectively referred to as a structural unit (a). 1), structural unit (a 2 ), and junction element (a3). The structural unit (al) in the present invention contains an acidic group which can react with a base. Examples of such an acidic group include a phenolic hydroxycarboxy group (including an acid anhydride). The structural unit containing such an acidic group has excellent developability. Further, the structural unit of the group contained in the component (A) is a structural unit having an intrinsic radical, that is, a structural unit containing only a phenolic hydroxyl group as an acid group-containing structural unit is improved. In addition to developability, the preservation property (especially the change in viscosity with change) can be improved. In the structural unit containing a phenolic hydroxyl group, a structural unit having a desired transradical represented by the following formula (a-1) is preferred. By retaining the structural unit 1 containing the desired transradical group, the preservative property can be improved, so that (i) the (B); A1 unit is crosslinked, and the acid is contained. The composition of the previous interlayer insulating film which can not be stored and which must be cryopreserved can be stored at room temperature by means of the element and the time. Specifically, the viscosity change rate was ±1% or less after storage for one month at 23 ° C, and showed excellent stability with time.

(a-1) [In the above formula, 1?° represents a hydrogen atom or a fluorenyl group, R1 represents a single bond or a carbon number of 1 to 5, and R2 represents a carbon number of 1 to 5, and a represents 1 An integer of ~5 'b denotes an integer of 0 to 4, and a+b is 5 or less. Further, 1/ when two R2 are present, the R2 may be different from each other or the same.] In the above formula (a-Ι), R is preferably a fluorenyl group. R1 represents a single bond or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include methylene, ethyl, propyl, isopropyl, n-butyl, isobutyl, butyl, pentyl, isoamyl, and new Amyl and so on. Among them, a single bond, an anthracene group, and an extended ethyl group are preferred. In particular, when R1 is a single bond, alkali solubility can be improved, and heat resistance at the time of forming an interlayer insulating film can be improved, which is preferable. 8 200923584 a represents an integer of 1 to 5, which is considered to be easy to manufacture, and a is preferably 1. The hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R1 is used as a reference (1 position). R2 is a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include an anthracenyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Among them, factors which are easy to manufacture are preferably sulfhydryl or ethyl. Specific examples of the structural unit represented by the above formula (a-Ι) include those represented by the following structural formula (a-1-1) or (a-1-2). Particularly preferred is a structural unit represented by the structural formula (a - 1 - 1 ). [Chemical 2]

(a-1-1) (a-1-2) The structural unit represented by the general formula (a-1) can be represented by a polymerizable monomer represented by the following general formula (a-Ι) Copolymerization with another polymerizable monomer is carried out into the copolymer (A1). [化3] 9 200923584 R°

I

H2C=CH person o / R1 /0\ (R2) b (〇H)a

(a-ΐΓ [In the above formula, R°, R1, R2, a, b are the same as described above] The structural unit (a2) in the present invention contains a crosslinkable group which is a group which is crosslinked by polymerization. By having such a crosslinkable group, the film can be cured after the pattern formation, and heat resistance and solvent resistance can be improved. Such a crosslinkable group is preferably a crosslinker by heating, and for example, An organic group having an epoxy group and an organic group having an oxetanyl group. Among them, in view of ease of production of the copolymer, an organic group having an epoxy group is preferred. In the structural unit (a2), the organic group having an epoxy group may be derived, for example, by copolymerizing the following polymerizable monomers: glycidyl acrylate, glycidyl methacrylate, Acrylic acid cold - methyl glycidol vinegar, mercapto acrylic acid / 3 - decyl glycidol vinegar, α - methacrylic acid glycidyl S, α - n-propyl methacrylate glycerol, α - n-butyl Glycidyl acrylate, 3,4-butylene acrylate, 3,4-ring of methacrylic acid Butyl ester, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate 6,7-10 200923584 epoxyheptyl ester, o-vinylbenzyl glycidyl ether, M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, (3,4-epoxycyclohexyl)methyl methacrylate, etc. These structural units (a 2 ) may be used singly or in combination. Among them, a structural unit derived from glycidol acrylate or glycidyl thioglycolate is particularly preferred, and such a structural unit is represented by the following formula (a-2).

(a-2) [In the above formula, R3 represents a hydrogen atom or a methyl group] The structural unit represented by the above formula (a-2) is easy to manufacture, cost-effective, and improved in the obtained interlayer The solvent resistance of the insulating film can be preferably used. The structural unit (a3) in the present invention contains an alkoxyalkyl group. By containing an alkoxyalkylene group, the insulating property of the resulting interlayer insulating film can be improved. Among them, a structural unit represented by the following formula (a - 3 ) is preferred. [化5] 200923584 R4

(a-3) [In the above formula, R4 represents a hydrogen atom or a fluorenyl group, R5 represents an alkylene group having a carbon number of 1 to 5, and R6, R7 and R8 may be different from each other or the same, and represent a carbon number of 1 to 5; An alkoxy group or an alkyl group, at least one of R6, R7 and R8 is an alkoxy group] In the above formula (a-3), R5, R6, R7 and R8 may be a straight chain or a branched chain. The alkyl group having a branched chain may, for example, be a normal, a second or a third butylmethylene group, a 1-mercapto-2-ethylexylethyl group, a 1-ethyl-2-indenyl group-extended group, 1-mercapto-2,2-dimethylexylethyl, 1,didecyl-2-indenylethyl, 1,dimethylpropyl, 1,2-dimethylpropane , 1,3-dimethylmethyl propyl, methyl butyl. The alkyl group having a branched chain may, for example, be: or 2-methylethyl, 1-, 2- or 3-mercaptopropyl, 1, bis-dipropylpropyl, 1,2-dimethyl Propyl, 1-, 2-, 3- or 4-methylbutyl. The alkoxy group having a branched chain may, for example, be 1- or 2-methylethoxy, 1-, 2- or 3-mercaptopropoxy, 1,1-didecylpropoxy, 1 , 2-dimercaptopropoxy, 1,3-dimercaptopropoxy, 1-, 2-, 3- or 4-mercaptobutoxy. When at least one of R6, R7 and R8 is an alkoxy group, the insulating property of the obtained interlayer insulating film can be improved, but the insulating property can be further improved by using two of the groups as alkoxy groups. Therefore, it is preferred to further preferably use all of the three groups as the alkane 12 200923584 oxy group. Further, the copolymer (A1) may contain a structural unit (a4) other than the structural units (al), (a2) and (a3). Examples of the structural unit (a4) include acrylates, methacrylates, acrylamides, mercapto acrylamides, maleimides, allyl compounds, and vinyl ethers. Structural units derived from the class, vinyl esters, and styrenes.

Specific examples of the acrylates include decyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate, octyl acrylate, and acrylic acid. a linear or branched alkyl acrylate such as octyl ester; cyclohexyl acrylate, dicyclopentanyl acrylate, 2-nonylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxy ethyl acrylate, Alicyclic acrylate, alicyclic acrylate, etc.; alicyclic acrylate, etc.; chloroethyl acrylate, 2,2-dimethacrylate Hydroxypropyl propyl ester, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, decyl benzyl acrylate, furfuryl acrylate ) tetrahydrofurfuryl acrylate, aryl acrylate (for example, benzoic acid benzoate). Specific examples of the methacrylates include decyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and methacrylic acid. Dibutyl ester, butyl methacrylate, amyl methacrylate, hexyl methacrylate, decyl 13 200923584

Linear or branched alkyl methacrylate such as octyl acrylate; cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-methylcyclohexanyl methacrylate Acrylic alicyclic aryl acrylate, isobornyl acrylate, mercaptopropionic acid [4-(transyl)cyclohexyl] methyl acetate, etc. Ester; benzyl methacrylate, chlorobenzyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, methacrylic acid 2, 2 - Mercapto-3-hydroxypropyl ester, trihydroxymercaptopropane monomethacrylic acid, pentaerythritol monomethacrylate, decyl methacrylate, tetrahydrofurfuryl methacrylate, aryl methacrylate (eg methacrylic acid) Phenyl ester, cresy 1 methacrylate, naphthyl methacrylate, and the like. Specific examples of the acrylamides include acrylamide and N-alkyl acrylamide (the number of carbon atoms of the alkyl group is preferably from 1 to 10, and examples thereof include a methyl group, an ethyl group, and a propyl group. , butyl, tert-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, benzyl, etc.), N-aryl acrylamide (for example, aryl, phenyl, tolyl, Nitrophenyl, naphthyl, hydroxyphenyl, etc.), N,N-dialkylpropenylamine (the carbon number of the alkyl group is preferably from 1 to 10), hydrazine, fluorene-aryl acrylamide (as aryl) Examples of the group include phenyl), fluorenyl-fluorenyl-fluorene-phenyl acrylamide, hydrazine-hydroxyethyl-fluorenyl decyl acrylamide, hydrazine-2-acetamidoethyl-hydrazine-acetic acid Acrylamide. Specific examples of the mercapto acrylamides include mercaptopropenylamine and fluorenyl-alkylmercaptopropenylamine (as the alkyl group, preferably having a carbon number of 1 to 14 200923584 10, for example, Examples thereof include a mercapto group, an ethyl group, a tributyl group, an ethylhexyl group, a hydroxyethyl group, a cyclohexyl group, etc., and an N-arylmethacrylamide (as an aryl group, a phenyl group, etc.), N , N-dialkylmercapto acrylamide (as an alkyl group, ethyl, propyl, butyl, etc.), N,N-diarylmethacrylamide (as an aryl group) Phenyl, etc.), N-hydroxyethyl-N-mercaptodecyl acrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmercaptopropene amine. Specific examples of the maleimide type include cyclohexylmaleimide and the like. Specific examples of the allyl compound include allyl esters (for example, acetic acid isopropyl acetate, hexanoic acid acrylic acid, octanoic acid propylene vinegar, lauric acid acrylic acid, allyl palmitate, and hard). Allyl fatty acid ester, allyl benzoate, allyl acetate, allyl lactate, etc.), allyloxyethanol, and the like. Specific examples of the vinyl ethers include alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, mercapto vinyl ether, ethylhexyl vinyl ether, and decyloxyethyl). Vinyl ether, ethoxyethyl vinyl ether, gas ethyl vinyl ether, 1-mercapto-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl Vinyl ether, diethylene glycol vinyl ether, diamylaminoethyl vinyl ether, dihexylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrogen Mercapto vinyl ether, etc., vinyl aryl ether (such as vinyl phenyl ether, vinyl phenyl phenyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl Naphthyl ether, vinyl decyl ether, etc.). Specific examples of the vinyl esters include vinyl butyrate and isobutyl 15 200923584 vinyl acetate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, and acid B. Dilute ester, vinyl chloroacetate, vinyl chloroacetate, methoxy vinyl acetate, butoxy vinyl acetate, ethylene sulfonate, vinyl acetate, vinyl lactate, -3-butyric acid Vinyl ester, vinyl benzoate, vinyl salicylate, chlorobenzoic acid ester, vinyl tetrabenzoate, vinyl naphthoate. Specific examples of the styrenes include styrene and alkyl benzene (for example, methyl styrene, dimethyl styrene, tridecyl styrene ethyl styrene, diethyl styrene, and isobutylene). Propyl styrene, butyl benzylidene styrene, cyclohexyl styrene, mercapto styrene, benzyl styrene gas methyl styrene, trifluorodecyl styrene, ethoxylated styrene, hydrazine Oxymethylstyrene, etc.), alkoxystyrene (for example: methoxyphenylene, 4-methoxy-3-mercaptostyrene, dimethoxy styrene, etc.), halostyrene (for example) : gas styrene, dichlorostyrene, trichlorostyrene, gas stupid ethylene, pentachlorostyrene, bromostyrene, dibromostyrene, iodobenzene, styrene, tris, styrene, 2_ Desert _4 - triseophenyl styrene, fluorine _3-trifluoromethyl styrene, etc.). As the structural unit (a4), it is particularly preferred to be derived from a body having an alicyclic group (especially an alicyclic alkyl acrylate or an alicyclic methacrylate). Thus, by introducing the alicyclic group into the polymer, the dielectric constant of the interlayer insulating film can be further reduced. Further, the quinone imines are also preferred because they also improve shape retention. The ratio of the structural unit (a 1 ) in the above copolymer (A1) is from 20 mol% to 70 mol%, more preferably from 20 mol% to 60 mol%. By acid, ethyl, ethyl, ethyl, ethyl, 4-, 4-, 4-,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Thereby, the formed angle can be made 45 degrees or more and 90 degrees or less, whereby a pattern having a ratio can be formed. The structural unit (a 2 ) in the above copolymer (A 1 ) is from 20 mol% to 70 mol%. By the structural unit (the chemical resistance of the interlayer insulating film can be sufficiently obtained by providing the photosensitive resin composition within the above range. Further, the structural unit in the copolymer (A1) (preferably 1 mol% 〜 When the structural unit is in the above range, the improvement of the photosensitive resin composition can be reduced as the insulating property of the interlayer insulating film. Further, the structural unit in the copolymer (A1) (preferably 0) Molar% to 40% by mole, more preferably 0% by mole - and preferably 0% by mole to 10% by mole. Weight average molecular weight of the above copolymer (A1) (by chromatography (GPC) The measured value in terms of styrene), .500 00, more preferably 50,000 to 30,000. By making the molecular weight easily formed into a film shape, further, by making the molecular weight available Moderate alkali solubility. The above copolymer (A1) can be produced by a known radical, that is, a polymerizable monomer which is derived from the above-mentioned knots (a2), (a3) and (a4) and polymerized by a known method. After the initiator is dissolved in the polymerization solvent, heating is applied to the side of the pattern of the photosensitive tree The wall is higher than the previous ratio, preferably the ratio of a 2 ) is the thermosetting property, the ratio of a 3 ), the ratio of the dielectric constant of (a 3 ), the ratio of a 4 ), ^ 3 0 Ear %, Mw: gel permeation is preferably 2 0 0 0~ 2 0 0 0 or more, 5 0 0 0 0 or less, and is produced by polymerization. The unit (al), known as free radicals, is stirred. Further, the test-soluble resin component (A) may contain other polymer (A2) in addition to the above copolymer (A1). The polymer (A2) may, for example, be a polymer or a copolymer composed of the structural unit (a4), a copolymer of the structural unit (al) and the structural unit (a4), a structural unit (a2) and a structural unit. Copolymer of (a4). The polymer (A2) may be used alone or in combination of two or more. The polymer (A2) is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, per 100 parts by mass of the copolymer (A1). The weight average molecular weight of the polymer (A2) (Mw: styrene-converted value of gel permeation chromatography (GPC)) is preferably from 20,000 to 50,000, more preferably 5 0. 0 0 ～3 0 0 0 0. [Photosensitive agent (B)] The photosensitive agent (B) is not particularly limited as long as it is a compound which can be used as a photosensitive component, but is preferably a compound containing a quinonediazide group. Specific examples of the diazonium-containing compound include a fully esterified or partially esterified compound of a phenolic thiol-containing compound and a naphthoquinone diazide s u 1 f ο n i c a c i d compound. Specific examples of the phenolic hydroxyl group-containing compound include polyhydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone. Ketones; tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylbenzene -2 -hydroxyphenyl 18 200923584 methane, bis(4-hydroxy-3,5-dimercaptophenyl)-4-hydroxyphenyldecane, bis(4-hydroxy-3, 5-didecyl) Phenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3, 5-dimercaptophenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2, 5-dimethylphenyl) -4 -hydroxyphenylmethane, bis(4-hydroxy-2,5-dimercaptophenyl)-3-hydroxyphenyldecane, bis(4-hydroxy-2, 5-dimethylphenyl) 2-hydroxyphenylmethane, bis(4-cyano-3,5-dimethylphenyl)-3,4-di-phenylphenylnonane, bis(4-hydroxy-2, 5-di Nonylphenyl)-3,4-dihydroxyphenylnonane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxybenzene -3 -methoxy-4-hydroxyphenyl decane, bis (5-ring 4-hydroxy-2-mercaptophenyl)-4-hydroxyphenyl decane, bis(5-cyclohexyl-4-hydroxy-2-mercaptophenyl)-3-hydroxyphenylmethane, bis ( 5-cyclohexyl-4-hydroxy-2-indenylphenyl)-2-hydroxyphenyldecane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-di Triphenyl-type compound such as phenylphenyl f; 2,4-bis(3,5-dimethyl-4-hydroxyl)-5-hydroxyphenol, 2,6-bis (2, Linear 3-nuclear benzene compound such as 5-dimethyl-4-hydroxybenzyl)-4-methylphenol; 1,1-bis[3-(2-hydroxy-5-fluorenylbenzyl)-4 Hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimercapto-3-(4-hydroxy-5-fluorenylbenzyl)-4-hydroxyphenyl]decane, bis[2, 5-dimercapto-3-(4-hydroxybenzyl)-4-hydroxyphenyl]decane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5 -nonylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methyst, bis[3-(3,5 -diethyl-pyridyl)-4-hydroxy-5-methylphenyl]decane, bis[3-(3,5-diethyl-4-hydroxybenzyl 19 200923584)-4 - Base _5-ethylphenyl] sputum, [2-Pentyl-3-(3,5-dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-fluorenyl) Benzyl)-5-nonylphenyl]decane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-nonylphenyl]decane, bis[2, 5 a linear 4-nuclear phenol compound such as dimethyl 3-(2-hydroxy-5-fluorenylbenzyl)-4-hydroxyphenyl]decane; 2,4-bis[2-hydroxy-3-(4) -hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxyfyl)-5-mercaptobenzyl]-6 Linear 5-core of cyclohexylphenol, 2,6-bis[2,5-dimercapto-3-(2-hydroxy-5-fluorenylbenzyl)-4-hydroxybenzyl]-4-methylphenol Steroidal polyphenolic compound such as phenolic compound; bis(2,3,4-trihydroxyphenyl)decane, bis(2,4-dihydroxyphenyl) fluorene, 2,3,4-trisylphenyl _4'_Phenylphenyl brothel, 2-(2,3,4-trisylphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2 ,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-p-phenyl)propane, 2 -(3-fail-4-phenylphenyl)-2-(3 - gas _4'_ mercaptophenyl) propane, 2-(2,4-di-phenyl)-2-(4'- mercaptophenyl)propane, 2-(2,3,4 ~Trisylphenyl)-2-(4'-pyridylphenyl)propane, 2-(2,3,4-trisylphenyl)-2-(4'-pyridyl_3', a bisphenol type compound such as 5'-dimethylphenyl)propane; [1-(4-hydroxyphenyl)isopropyl]-4-[l,l-bis(4-hydroxyphenyl)ethyl] Benzene, 1-[1-(3-mercaptophenyl)isopropyl]-4-[l,l-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, etc. a branched form compound; a condensed phenol compound such as 1,1-bis(4-hydroxyphenyl)cyclohexane. 20 200923584 These may be used alone or in combination of two or more. Further, examples of the diazonaphthoquinone sulfonic acid compound include naphthoquinone-1,2-diazo-5-sulfonic acid or naphthoquinone-1,2-diazo-4sulfonic acid. Further, other compounds containing a diazonium group include, for example, ortho-benzoquinone diazide, ortho-naphthoquinone diazide, ortho-nitrogen onion (ortho-ortho-). Anthraquinone diazide) or a similar nuclear substituted derivative such as the diazonaphthoquinone.

Further, it is also possible to use anthraquinone sulfonium chloride and a compound having a hydroxyl group or an amine group (for example, phenol, p-methoxyphenol, dinonylphenol, hydroquinone, bisphenol A, naphthol, ortho-benzene) Phenol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1, 3-dioxime ether, gallic acid, gallic acid which is esterified or etherified with a part of hydroxyl groups remaining, A reaction product of aniline, p-aminodiphenylamine or the like. These may be used singly or in combination of two or more. The diazonium-containing compound can be produced, for example, by the following method: in the presence of a triethanolamine, a carbonic acid test, or a hydrogencarbonate test in a suitable solvent such as dioxane The triphenyl-type compound is subjected to a condensation reaction with naphthoquinone-1,2-diazo-5-sulfonyl chloride or naphthoquinone-1,2-diazo-4-sulfonyl chloride for complete acetification or Part of the purpose. As the diazonium-containing compound, a diazonaphthoquinone sulfonate is preferred. Further, as the component (B), a non-benzophenone-containing compound containing a diazo group is preferably used, and a multinuclear branched compound is preferably used. Further, 21 200923584 The phenolic hydroxyl group-containing compound preferably has a gram extinction coefficient of 1 or less at a wavelength of 350 nm. Thereby, the photosensitive resin composition can obtain higher sensitivity and can improve the transmittance (transparency) when the interlayer insulating film is formed. Further, the decomposition temperature of the phenolic hydroxyl group-containing compound is more preferably 300 ° C or higher. Thereby, the transparency of the interlayer insulating film can be ensured. As such a component (B), diazo naphthalene of 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,b-bis(4-hydroxyphenyl)ethyl]benzene is particularly preferably used. An oxime sulfonate. Further, the sensitizer can maintain good stability over time. The content of the component (B) is from 10% by mass to 40% by mass, preferably from 20% by mass to 30% by mass, based on the total solid content. By setting the content of the component (B) to 10% by mass or more, the resolution can be improved. Further, the amount of film reduction of the pattern after patterning can be reduced. Further, by setting the content of the component (B) to 40% by mass or less, an appropriate sensitivity or transmittance can be imparted. [Organic solvent (C)] The photosensitive resin composition of the present invention may contain an organic solvent (C) (hereinafter also referred to as a component (C)) in order to improve coatability or adjust viscosity. Examples of the component (C) include stupid, toluene, xylene, mercaptoethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, decyl alcohol, ethanol, propanol, butanol, and hexanol. Cyclohexanol, ethylene glycol, diethylene glycol, glycerol, ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monoterpene ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate (MA), 3-methoxybutanol 22 200923584 (BM), 3-mercaptoacetate- 3-methoxy butyl acrylate, propylene glycol monoterpene ether acetate (PGMEA ) 'propylene glycol monoterpene ether propionate, propylene glycol monoethyl ether propionate, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate or Mixtures of these, etc. Among them, a mixed solvent of MA or MA and BM is preferably used. The amount of the organic solvent (C) to be used is not particularly limited, and the concentration which can be applied to the substrate or the like is appropriately set depending on the thickness of the coating film. Specifically, it is preferred to use an organic solvent in such a manner that the solid content concentration of the photosensitive resin composition is in the range of 10% by mass and 50% by mass, preferably 15 parts by mass or less by mass. ). [Others (D)] The photosensitive resin composition of the present invention may contain various additives such as a surfactant, a sensitizer, an antifoaming agent, and a crosslinking agent. The surfactant can be a conventionally known one, and examples thereof include compounds such as anionic, cationic, and nonionic. Specifically, X - 7 0 - 0 9 0 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like are mentioned. By adding an interface active agent, coatability and flatness can be improved. As the sensitizer, those used in the previously known positive type resist can be used. For example, a compound having a phenolic hydroxyl group having a molecular weight of 1 〇 〇 or less may be mentioned. The antifoaming agent may be a conventionally known one, and examples thereof include a Shishi compound and a fluorine compound. Further, examples of the crosslinking agent include a polymerizable compound having an ethylenically unsaturated bond. As such a compound, among them, a monofunctional, bifunctional or (23) 200923584 functional or higher (mercapto) acrylate having a polymerizability is preferred, and a factor for increasing the strength of the resulting film-like film can be preferably used. As the monofunctional (meth) acrylate, for example, (mercapto) acrylate 2-ethylidene ethyl ester, carbitol (meth) acrylate, (mercapto) propylene Isobornyl ester, (3-mercapto)acrylic acid 3-methoxybutyl ester, 2-(indenyl)acryloxyethyl 2-hydroxypropyl phthalate, and the like. As a commercial item, for example, Aronix M-101, Aronix M-lll, Aronix M-114 (manufactured by East Asia Synthetic Chemical Industry Co., Ltd.); KAYARAD TC-1 10S, KAYARAD TC-12 0S (Japanese Chemicals) Manufactured by the company); BISC0AT 158, BISC0AT 2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). Examples of the above-mentioned bifunctional (fluorenyl) acrylate include ethylene glycol (mercapto) acrylate, 1,6-hexanediol bis(indenyl) acrylate, and 1,9-nonanediol bis ( Mercapto acrylate, polypropylene glycol di(decyl) acrylate, tetraethylene glycol di(meth) acrylate, bisphenoxyethano 1 fluorene diacrylate, and the like. As a commercial item, for example, Aronix M-210, Aronix M-240, Aronix M-6200 (manufactured by East Asian Synthetic Chemical Industry Co., Ltd.); KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (曰本Manufactured by Chemical Pharmaceutical Co., Ltd.; BISCOAT 260 'BISCOAT 312, BISCOAT 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the above-mentioned trifunctional or higher (meth) acrylate include tris(hydroxyl) propane tri(indenyl) acrylate, pentaerythritol tris(fluorenyl) acrylate, and tris((fluorenyl) propylene oxy group. Ethyl)phosphate, pentaerythritol 24 200923584 tetrakis(yl) acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexakisyl acrylate, and the like. As a commercial item, for example, Aronix M-309, Aronix M-400, Aronix M-402, Aronix M-40 5 ' Aron ix M-45 0, Aronix M-7100, Aronix M-8 0 3 0, Aronix M-8060 (manufactured by East Asia Synthetic Chemical Industry Co., Ltd.); KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (manufactured by Sakamoto Chemical Co., Ltd.) ; BISC0AT 2 9 5, BISC0AT 3 0 0, BISC0AT 360, BISCOAT GPT, BISCOAT 3PA, BISC0AT 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). These crosslinking agents may be used singly or in combination. Further, since the photosensitive resin composition of the present invention contains the above-mentioned test-soluble component (A), sufficient thermosetting property can be obtained without adding the above-mentioned crosslinking agent, and a good interlayer insulating film can be formed. The photosensitive resin composition of the present invention can be produced, for example, by the following methods: (A) component, (B) component, (C) component, and (D) component by a mixer such as a roll mill, a ball mill, or a sand mill. Mixing (dispersion and kneading) 'Filtering with a filter such as a 5 era film passer as needed. The photosensitive resin composition of the present invention can be applied to an interlayer, a film or a film which is provided in an electronic component such as a liquid crystal display device, a chip circuit device or a solid-state image sensor for insulating a wiring layer arranged in a layer. . [Method of Forming Interlayer Insulating Film] 25 200923584 Hereinafter, a method of forming an interlayer film using the photosensitive resin composition of the present invention will be described. The method of forming an interlayer insulating film includes the steps of: applying a coating step of coating a photosensitive resin composition on a substrate, and performing an exposure step of selectively exposing the coated photosensitive resin composition after the exposure to use an alkali development after the above exposure The developing step of developing the liquid. Hereinafter, each step will be described. First, in the coating step, the photosensitive resin composition of the present invention is applied to a substrate or the like by a spinner, a roll coater, a spray coater or a slit coater. The body is dried to form a photosensitive tree composition layer. For example, a glass plate or a matte substrate having a wiring such as a transparent conductive path and a black matrix, a color filter, or a polarizing light, if necessary, may be used. The drying method of the substrate coated with the photosensitive resin composition may be any one of the following methods: (1) using a hot plate at a temperature of 80 ° C 1 2 0 ° C for 60 seconds to 1 The method of drying for 20 seconds, (2) the method of placing in the chamber for several hours to several days, and (3) the method of removing the solvent by placing it in a hot air heater or an infrared heater for several tens of minutes to several hours. Further, the film thickness of the upper photosensitive resin composition layer is not particularly limited, but is preferably about 1.0 m to 5.0 /zm. Then, in the exposure step, exposure is performed by interposing a specific mask. The exposure is performed by irradiating an active energy ray such as ultraviolet rays or excimer laser light. Examples of the light source of the active energy ray include a low pressure mercury welding high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, and an excimer laser generating device. The amount of energy ray to be irradiated is also determined by the example of a stepwise cloth-forming resin plate of a photosensitive resin composition/-S»/temperature line β, which is different from, for example, 30 mJ/cm2 to 2000. It can be around mJ/cm2. Then, in the developing step, the exposed photosensitive resin composition layer is developed with a developing solution to form a pattern. As the developer, an aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as TMAH) of 1% by mass to 3% by mass is used. 8%质量质量。 The concentration of the concentration of the general solution is 2. 3 8 % by mass. By setting the concentration of the developer to 3% by mass or less, the amount of film reduction of the formed pattern can be reduced. Then, the above pattern is heat-hardened. The temperature for the heat curing is, for example, preferably from 1 50 ° C to 2 50 ° C. [Examples] [Example 1] The composition was adjusted by (C) and mixed so that the concentration of the solid component containing the following components (A), (B) > (D) was 25 mass%, and the photosensitive film was prepared. Resin composition. (A) component: structural unit of the following formula (a -1 -1 ): structural unit (a-2-l): structural unit (a-3-l): structural unit (a-4-l) = 31 : 3 9 : 2 0 : 1 0 (Morby) resin (weight average molecular weight 1 1 5 0 0 ) 8 0 parts by mass [Chem. 6] 27 200923584

(a-1-1) (a-2-1) (a-3-1) (a-4-1) (B) Component: Bu [1-(4-hydroxyphenyl)isopropyl]-4 -[l,:l-bis(4-hydroxyphenyl)ethyl]benzene-1,2-diazonaphthoquinone-5-sulfonate (esterification rate 67%) 20 parts by mass (C) Ingredients: 3-methoxypropenyl acetate (D) component: surfactant (trade name: X - 7 0 - 0 9 3 ) 0.1 parts by mass

Here, the thermal decomposition temperature of the above 1_[1-(4-pyridylphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene is 3 65 ° C, The gram absorption coefficient at a wavelength of 350 nm is 0.003. [Example 2] A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (A) was replaced with the following components. (A) component: structural unit (a-1 -1 ): structural unit (a-2- 1 ): structural unit of the following formula (a-3-2): structural unit (a-4-1) = 31 : 39: 28 200923584 20 : 1 0 (Mohrby) resin (weight average molecular weight 1 3 5 0 0 ) 80 parts by mass [Chem. 7]

\si(OC2H5)3 0-3-2) [Comparative Example 1] A photosensitive resin was prepared in the same manner as in Example 1 except that the component (A) in Example 1 was replaced with the following components. Composition. (A) component: structural unit (a-1-l): structural unit (a-2-l) = 44: 56 (mole ratio) resin (weight average molecular weight 1 800) 0 0 parts by mass [ Comparative Example 2 A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (A) in Example 1 was replaced with the following components. (A) Component··Structural unit (a - Bu 1) ··Structural unit (a - 2 - 1 ): Structural unit (a-4-l) = 35: 45: 20 (mole ratio) resin (weight 29 200923584 Average molecular weight 1 1 3 0 0 ) 80 parts by mass (hardened film formation method) The above-prepared photosensitive resin composition was applied to a 6-inch ruthenium substrate by a spinner (manufactured by Shin-Etsu Chemical Co., Ltd.: low resistance) The film was made to have a film thickness of 1 μm, and then dried on a hot plate at 110 ° C for 2 minutes, and then subjected to full exposure using an ultrahigh pressure mercury lamp at 230 ° in a clean oven (c 1 ean oven). C was allowed to heat harden for 30 minutes. (Pattern forming method) The photosensitive resin composition prepared above was applied to a glass & plate (manufactured by Dow Corning Co., Ltd., 0.7 mm λ 1 G mm (thickness χ diameter)) to make a film thickness. It became 3.4 /zm, and then it was dried at 110 ° C for 2 minutes on a hot plate to obtain a coating film. Mirror Projection Aligner (product name: MPA-600 0FA, Canon), separated by 5 //m line-pattern/ 5 /zm gap-patterned positive mask pattern The coating film is exposed to light. Then, it was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (developing solution) for 1 minute for development, rinsed with pure water to remove unnecessary portions, and then subjected to full exposure using an ultrahigh pressure mercury lamp. The pattern was obtained by heat-hardening at 30 ° C for 30 minutes in a dust-free oven. [Evaluation] The photosensitive resin compositions of the above examples and comparative examples were evaluated. The dielectric constant, sensitivity, and transmission of the cured film were evaluated for the rate of 200923584. The evaluation method is as follows. Dielectric constant: The dielectric constant of the cured film obtained above was measured using SSM 49 5CV SYSTEM (manufactured by SSM Corporation, Japan). Transmittance · For the pattern formed by the pattern forming method, the transmittance is measured using a spectrophotometer (trade name: UV-2500PC, manufactured by Shimadzu Corporation), and the lowest transmittance at a wavelength of 400 nm to 800 nm. As the transmittance. The results of these are shown in Table 1. [Table 1] Dielectric constant (〖MHz') 栾射栾 Example 1 4.0 95 Example 2 4.0 95 Comparative Example 1 4.5 94 Comparative Example 2 4.4 94 From the above, the photosensitive resin composition of the present invention is previously Since the photosensitive resin composition has a smaller dielectric constant, it has higher insulation properties. [Simple description of the diagram] None [Key component symbol description] None 31

Claims (1)

200923584 X. Patent application scope: 1 . A photosensitive resin composition for interlayer insulating film, comprising an alkali-soluble resin component (A) and a sensitizer (B); and the above-mentioned solvent-soluble resin component (A) contains a copolymer (A1) The copolymer (A1) contains a structural unit (a) containing an acidic group, a structural unit (a2) containing a crosslinkable group, and a structural unit (a3) containing an alkoxyalkyl group. 2. Photosensitive tree for interlayer insulating film as described in the scope of application of the patent application a lipid composition in which the above structural unit containing an alkoxyalkyl group is represented by the formula (a-3), (a-3) [In the above formula, R4 represents a hydrogen atom or a methyl group, and represents a carbon number. /-Sfc / alkylene, R6, R7 and R8 may be different from each other or the same, 5 alkoxy or alkyl, at least 1 of R6, R7 and R8 and represent a carbon number of a methoxy group. 3. If you apply for a patent range! The photosensitive resin composition for an interlayer insulating film according to the invention, wherein the alkali-soluble resin component (A) contains only a structural unit containing a phenolic hydroxyl group as a structural unit containing an acidic group. 32 200923584 4. The photosensitive resin composition for interlayer insulating film described in the patent dry 帛 i, wherein the acidic group-containing structural unit U1) is expressed by the formula U]), [Chemical 2] (a-1) When the number is 1 to R2, 〇~ [In the above formula, R° represents a hydrogen atom or methyl 4 represents a single bond or an alkylene group of carbon 5, and R 2 represents an alkyl group of carbon number 5] When there are two or more of these R2, they may be different from each other, and a may be an integer of b, b is an integer of Table 4, and a+b is 5 or less]. The photosensitive layer for the interlayer insulating film described in the first paragraph of the patent range of the first aspect of the invention is "the above-mentioned structural unit (a2) containing a crosslinkable group is a general formula (a % > [化3] 33 200923584 (a-2) [In the above formula, R3 represents a hydrogen atom or a methyl group]. 6. If you apply for a patent range! The layer (5) is a 9-light resin composition for an insulating film, wherein the content of the acidic group-containing structural unit (ai) in the copolymer (A1) is 20 mol% to 70 mol%, and the above-mentioned The content of the structural unit (a2) of the crosslinkable group is from 20 mol% to 70 mol%, and the content of the alkoxyalkyl group-containing structural unit (a3) is from 1 mol% to 40 mol%. 34 200923584 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: