TWI373482B - - Google Patents

Description

</ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The protective film, such as the heat-resistant or chemical-resistant, insulating and flexible, and the protective insulating film for semiconductor elements, the insulating film for multilayer printed circuit boards, the solder protective film, Cover lay • film, etc. [Prior Art] - As a photosensitive polyimine-based material, a material of polyamic acid belonging to the precursor of polyimine is used, for example, a proposal is: In the carboxy group, the photosensitive group is introduced into the carboxyl group of the polyproline (Japanese Patent Laid-Open Publication No. SHO-49-1 1 554 1 and JP-A-5-45-746) A material having a polyfluorene acid and a photosensitive group (Japanese Patent Laid-Open Publication No. SHO 54-145794) and the like. However, in these inventions, in order to obtain a polyimide film which is a target product after forming a patterned film, it is necessary to carry out a bismuth imidization treatment at a high temperature of 300 or more. Such a high temperature has a problem that the substrate is limited or the copper of the wiring is oxidized. In order to improve such a problem, there has been a proposal to use a photosensitive polyimide which is a solvent-soluble resin which is imidized by a hydrazine for the purpose of lowering the hardening temperature (Japanese Patent Laid-Open No. 10- Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In addition, it is easy to suffer from oxygen hindrance, and it is easy to cause film fading during development, and it is difficult to improve the resolution, so that materials satisfying all the characteristics are not obtained. On the other hand, there is also a polyimine skeleton having a phenolic hydroxyl group (Japanese Patent Laid-Open No. Hei 3-209478) or a polyamine skeleton (Japanese Patent Laid-Open No. Hei 1-46862, No. 1 Proposal for the positive form of 1 -65 1 07 public φ report) and diazonaphthoquinone. However, in view of the light transmittance of the composition, it is difficult to form a thick film of 20 micrometers or more, and in order to ensure development, the molecular weight of the resin belongs to a low molecular weight, or - as a photosensitizer Since the amount of addition of the nitrogen naphthoquinone is excessive to the resin, it is difficult to obtain the original hardening property of the resin. [Patent Document] Japanese Patent Laid-Open Publication No. SHO-54-45 No. 5-5-45 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei-5-5-45 746 (Patent Document 3) Japanese Patent Laid-Open No. 54-1 45794 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Contents] [The subject of the invention] -6- 1373482

(11) (11) 1373482 and f is 0 or 1. Also, D may be the same or different from each other. For the case of Z, the following structure can be exemplified [Chemical Formula 15]

-15- (13) 1373482 . * 4 Phenyl, vinyl. Further, g is a positive number of 1 to 80, preferably 3 to 70, more preferably 5 to 50. Further, l, m, and n in the general formula (1) are positive numbers of 2000, 0 SmS 2000, and n$n core 2000, respectively, and can satisfy 0.24 1/( 1 + m + n ) ^ 1.0 ' ml ( 1 + m + n) ^ 0.8 ' n/ ( 1 + m + n ) The positive number of SO.8. When 丨/(丨 + m + n) is 0.2 or less, it is not preferable because it is difficult to exhibit the effect of the primary alcoholic hydroxyl group. In addition, φ is selected such that the alcohol equivalent of the primary alcohol derived from (the primary alcohol can be 200 or more and 3,500 or less, preferably 300 or more and 300 or less), and the alcohol equivalent of the primary alcohol derived from &lt; When it is less than 50,000, it is not preferable because it can obtain sufficient photocurability, and if it is 200 or less, it is not preferable because the film properties such as film strength after hardening are deteriorated. In the synthesis method of the first-order alcohol, it is not limited to such a method, and may be utilized in the synthesis of the resin (1) without affecting the target characteristics. The aromatic diamine or the aliphatic diamine other than the general formula # (3) and (4). The molecular weight of the polyimine which can be represented by the general formula (1) of the present invention is usually from 5,000 to 500,000. It is preferably 10,000 to 30,000,000. If the molecular weight is 5,000 or less, the film strength of the polyimide resin is lowered, and if it is 500,000 or more, it is not preferable because the compatibility with the solvent is lowered. Photocurable resin composition of the present invention The invention comprises: (A) the above polyimine-based polymer compound, (B) an amine-based condensate modified by formaldehyde water or formalin-alcohol, a melamine resin, and a urea tree-17-1373482 Any one or more of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups in one molecule, and (C) photo-initiating acid generating agents for generating acid by irradiation with light in a range of 24 nm to 500 nm The component (B) used in the present invention is a component which is used for the hardening reaction with the above component (A) to facilitate the formation of the pattern, and further enhances the strength of the cured product. The resin of the component (B) has a weight average molecular weight of from 150 to 10,000, particularly preferably from 200 to 3,000. If the weight average molecular weight is 150 or less, sufficient photocurability may not be obtained, such as When it is more than 10,000, the heat resistance after curing of the composition may be deteriorated. The amine-based condensate modified with the formalin or the formalin/alcohol of the above component (B) may, for example, be: Modified by formalin or formalin-alcohol a cyanamide condensate or a urea condensate modified with formalin or formalin-alcohol. The preparation of the modified melamine condensate is, for example, first, methylolification of a melamine monomer using formaldehyde water according to a well-known method. The modified melamine may be represented by the following formula (5) by modifying it with alkane or by alkoxylation with an alcohol. Here, as the above alcohol, a lower alcohol is preferable, for example. An alcohol having 1 to 4 carbon atoms is preferred.

R3 R3 (wherein R3 may be the same or different methylol group, and contains an alkoxymethyl group or a hydrogen atom of a carbon number to -18-(15) 1373482 • 4 4 , but at least one of them The hydroxymethyl group or the above alkoxymethyl group. The above R3 may, for example, be an alkoxymethyl group such as a methylol group, a methoxymethyl group or an ethoxymethyl group, or a hydrogen atom. The denatured melamine of the above general formula (5) may specifically be exemplified by trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, hexamethylol melamine or hexamethoxymethylol melamine. Wait. • Next, the modified melamine represented by the general formula (5) or the oligomer (for example, an oligomer such as a dimer or a trimer) may be subjected to addition condensation condensation with formaldehyde to a desired molecular weight. To obtain the melamine condensate modified by formaldehyde water or formal water-alcohol. Here, one or more modified melamine condensates of the monomer of the general formula (5) and the condensate thereof can be used as the component (B). Further, the preparation of the urea condensate modified by formalin or formalin-alcohol is carried out, for example, by a known method, by subjecting a urea condensate of a desired molecular weight to hydroxymethylation using formaldehyde water for modification, or This is further alkoxylated with an alcohol for modification. Specific examples of the modified urea condensate include a methoxymethylated urea condensate, an ethoxymethylated urea condensate, and a propoxymethylated urea condensate. Here, one or more of the modified urea condensates may be used as the component (B). Further, the phenol compound having an average of two or more methylol groups or alkoxymethyl groups in one molecule of the component (B) may, for example, be (2-hydroxy-5-methyl)-1,3. Diphenylmethanol, 2,2,6,6'-tetramethoxymethylbisphenol A, and the like. -19- (16) 1373482 The amine condensate and the phenol compound of the component (B) may be used singly or in combination of two or more. The amine condensate or the phenol compound of the component (B) of the present invention is preferably 0.5 to 50 parts by mass, particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the polyamidimide-based polymer compound of the component (A). . When the amount is 0.5 parts by mass or less, sufficient hardenability may not be obtained at the time of light irradiation. Conversely, when the amount is 50 parts by mass or more, the proportion of the polyamidene linkage of the photocurable resin composition may be lowered. On the other hand, it is possible that the cured product does not exhibit sufficient effects of the present invention. In the photo-initiating acid generator of the component (C), an acid is generated by irradiation with light having a wavelength of from 240 to 500 nm, and the acid becomes a hardening contact. Since the resin composition of the present invention is excellent in compatibility with an acid generator, a wide range of acid generators can be used. The acid generator may, for example, be a key salt, a diazomethane derivative, a glyoxaldehyde derivative, a ruthenium oxide derivative, a second derivative, or a nitrite group. a sulfonate derivative, a sulfonate derivative, a quinone imide sulfonate derivative, an oxime sulfonate derivative, an imido sulfonate derivative, a tri-agricultural derivative, etc. The compound (R4) „M + K- (6) which can be represented by the following general formula (6) is exemplified (wherein R4 represents a linear -20- having a carbon number of 1 to 12 which may have a substituent ( 17) 1373482 Alkyl, branched or cyclic alkyl, aryl having 6 to 12 carbons or aralkyl having 7 to 12 carbons, M + representing iodonium or hydrazine, and K- representing non-nucleophilic two-way Non-nucleophilic two way ion, and h means 2 or 3 °. In the above R4, the alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group or a 2-oxy group. Cyclohexyl, norbornyl, adamantyl, etc. Further, in the case of aryl, phenyl; o-, m- or p-methoxyphenyl, φ ethoxyphenyl, m- or p-butoxybenzene Alkoxyphenyl; 2-, 3-' or 4. Alkylphenyl group such as tolyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl or xylyl, etc. Further, in the case of an aralkyl group, a benzyl group or a phenyl group is exemplified. Base, etc. - each group. The non-nucleophilic two-way ion of _K- may, for example, be a chloride ion, a bromide ion or the like; a triflate, 1,1, Fluoroalkyl sulfonate such as 1-trifluoroethane sulfonate or nonafluorobutane sulfonate; tosylate, tosylate, 4-fluorobenzenesulfonate, An aryl sulfonate such as 1,2,3,4,5-pentafluorobenzenesulfonate; an alkylsulfonate such as mesylate or butyl sulfonate; In addition, a compound represented by the following general formula (7) can be exemplified. [Chemical 20] ^2 (7) r5-so2*c-so2-r5 (wherein R5 represents the same or different 8 linear, branched or cyclic alkyl or halogenated alkyl groups having 1 to 12 carbon atoms, aryl or halogenated aryl groups having 6 to 12 -21 - (18) 1373482, or 7 to 12 carbon atoms The aralkyl group.) In the above R5, the alkyl group may, for example, be a methyl group, an ethyl group, a propyl group or a butyl group. The pentyl group, the cyclopentyl group, the cyclohexyl group, the norbornyl group, the adamantyl group, etc., and the halogenated alkyl group may, for example, be a trifluoromethyl group, a trifluoroethyl group, a 1,1 or a trichloro group. Ethyl, nonafluorobutyl, etc. The aryl group may, for example, be a phenyl group; an ortho, meta, or p-methoxyphenyl group, an ethoxyphenyl group, an intermediate or an alkane such as p-yttrium tributoxyphenyl. Oxyphenyl; an alkylphenyl group such as 2, 3- or 4-tolyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl or xylyl. The halogenated aryl group may, for example, be fluorobenzene, chlorobenzene or 1,2,3,4,5-pentafluorobenzene or the like. The aralkyl group may, for example, be a benzyl group or a phenethyl group. The glyoxal dioxime derivative may, for example, be a compound represented by the following general formula (8). [Chemical 2 1] ψψ 瘫 R6-S02O-N=cC=N - 0-S02-R6 (8) (wherein, R6 and R7 represent linear and branched carbon atoms of 1 to 12 which may be different from each other. a branched or cyclic alkyl or halogenated alkyl group, an aryl group having 6 to 12 carbon atoms or a halogenated aryl group, or an aralkyl group having 7 to 12 carbon atoms. Further, R7 may be bonded to each other to form a cyclic structure, such as formation. In the ring structure, 'r7' represents a linear or branched alkyl group having the same or different carbon number of 1 to 6. The above alkyl group of R6, R7, halogenated alkyl group, aryl group, and tooth The aryl group and the aralkyl group are exemplified by the above R5. Above -22- (19) (19)

1373482 alkylene, methylene, ethyl, propyl, and the like. Specific examples of the photoinitiated acid generator of the component (C): diphenyl iodonium trifluoromethanesulfonate, phenyl phenyl iodonium triphenylmethanesulfonate, diphenyl iodine iron p-toluenesulfonate, Tributoxyphenyl)phenyliodonium, trifluoromethanesulfonate fluoromethanesulfonic acid (p-butoxyphenyl)diphenylphosphonium, bis(p-butoxyphenyl)phenylhydrazine, trifluoro Methane with butoxyphenyl) hydrazine, triphenylphosphonium p-toluenesulfonate, tributyloxyphenyl p-tert-butylphenylate, bis(love)phenylhydrazine p-toluenesulfonate, p-toluenesulfonic acid Triphenylsulfonium tert-butoxyphenylsulfonate, triphenylsulfonium butanesulfonate, trisyl glucan, p-toluene acid trimethylsulfonium, Sandaijiayuan awakening 2·oxycyclohexyl)铳, p-toluenesulfonic acid cyclohexylmethyl thiol), dimethylphenyl sulfonium trifluoromethanesulfonate, p-tolyl fluorene, dicyclohexylphenyl fluorene trifluoromethanesulfonate, hexylphenyl hydrazine, double (4-tert-butylphenyl) iodine gun hexaphenyl (4-thiophenoxyphenyl) hexafluoroantimonate and other mirror salts bis(phenylsulfonyl)diazomethane, bis(p-toluene methane, Bis (xylene sulfonate) diazo Methane 'double (diazo carbamide, bis(cyclopentyl) diazonyl sulfonium) diazomethane, bis(isobutyl sulfonium) heavy gas, second butyl oxime, diazo In the case of thiol, bis(n-propyl), bis(isopropylsulfonyl)diazomethane, bis(butylene, hexyl), it can be exemplified (for the third butoxy-p-toluenesulfonic acid ( Triphenylsulfonium, trifluoromethanesulfonic acid acid (p-tert-benzenesulfonic acid (p-tert-butoxyphenyl) hydrazine, hexafluorobutanesulfonic acid trimethylcyclohexylmethyl ((2. oxy ring) Dimethyl benzene benzene sulfonate, acid ring, diuretic acid, _, ~ sulphur, diazocyclohexyl fluorene, bis (n-butyl ketone, bis ( guanidine) diazo carbene Benzene sulfonate) -23- (20) 1373482 Diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isosulfonyl)diazomethane, bis(second pentylsulfonate) Nitromethane (third pentylsulfonium) diazomethane, 1-cyclohexylsulfonium-1-(disulfonyl)diazomethane, 1-cyclohexylsulfonium-1-(third pentyl) Sulfodiazomethane, 1-tripentylsulfonium-1-(third) Sulfonium) a diazomethane derivative such as heavy methane; bis(p-tolylsulfonyl)-α-dimethylglyoxal dioxime, • (p-tolylsulfonyl)-α-diphenylethylene Aldehyde dioxane, bis(p-sulfonyl)-α-dicyclohexyl glyoxal dioxime, bis(p-tolyl)-2,3-pentanedione glyoxal dioxime, bis(p-toluene) Benzene oxime). -yl-3,4-pentanedione glyoxal dioxime, di-n-(n-butanesulfonate). methylglyoxal dioxime, di-n-(n-butanesulfonate)- --diphenylethylenedifluoride, di-n-(n-butanesulfonyl)-α-dicyclohexylglyoxal dioxo(n-butanesulfonate)-2,3-pentanedione glyoxal Bismuth, bis(alkylsulfonyl)-2-methyl-3,4-pentanedione glyoxal dioxime, di-ortho ( # sulfonate)-α-dimethylglyoxal dioxime, double neighbor (Three methane sulfonate g £^-dimethylglyoxal dioxime, di-ortho (1,1,1-trifluoroethanesulfonyl) dimethylglyoxal dioxime, di-butyl (t-butyl) Sulfonium)-α-dimethylaldehyde dioxime, di-ortho (perfluorooctanesulfonyl) dimethylglyoxal, di-o-(cyclohexanesulfonyl)-α-dimethylglyoxal dioxime , O-sulfonyl)-α-dimethylglyoxal dioxime, di-ortho (p-fluorobenzenesulfonyl) dimethylglyoxal dioxime, di-ortho (p-butylbutasulfonyl)-α-diethyl Dialdehyde dioxime, di-ortho (xylylene)-α-dimethylglyoxal di-double (camphorsulfonate)-α-dimethylglyoxal and other diuretic dialdehyde quinone, dibutyrate醯) Nitrogen di-o-toluenesulfonyl 2-methyl 2-dialdehyde, di-n-butymethane I )--a-ethylidene (Benzene-a-methylindole, iso--24- 1373482 • i ( 21) % hydrodialdehyde dioxane derivative: oxidative irony such as 2-cyclohexylcarbonyl-2-(p-toluenesulfonyl)propane (p-toluenesulfonyl)propane such as α-(phenylhydrazino)-I-tolylacetonitrile Derived 2,6-dinitrobenzyl dis-selenate, 2,4-dinitroester derivative of p-toluenesulfonic acid, diphenyl difluorene, dicyclohexyl di-roll, etc.; • 1,2,3-parameter (methane Sulfonium oxy)benzene, 1,2,3·oxy)benzene, 1,2,3·g (p-toluenesulfonyloxy)benzimidimide-yl-trifluoromethanesulfonate, citric acid-jun Ester, 5-norbornene 2,3. dicarboxy quinone imine-based. _ norbornene 2,3. dicarboxy quinone imine-yl-methanesulfonate dicarboxy quinone imine-based A quinone imine-based sulfonate derivative such as n-butyl sulfonate or n-trifluoroamine. Furthermore, (5- '(4-tolyl)sulfonyl 3 • )-(2-tolyl)acetonitrile, (5-(4-(4-methylsulfonyl)-5H-thiophene-2· A subunit-(2-toluene i acid ester. Among them, a guanamine-based sulfonate or an imide ester is suitable. The above acid generator (C) can be used alone. The amount of the compound of the polyimine-based polymer compound is 100 parts by mass, particularly preferably 0.2 to 5 parts by mass. If the amount is adjusted, sufficient photocurability, an oxime sulfonate derivative may not be obtained; , 2-isopropylortyl-2-J; derivative; p-toluenesulfonyl b-benzyl benzyl nitrate sulfonate (trifluoromethanesulfonate I sulfonate derivative; imine-yl-p-toluene Sulf-trifluoromethanesulfonate, 5-, 5-norbornene 2,3-methylsulfonylnaphthylquinone ylide-5H-thiophene-2-ylidenephenylsulfonyloxy)phenyl g ( Ethylene sulfonate such as acetonitrile or hydrazine sulfonate or a mixture of two or more thereof, and the component (A) is 0.05 to 20 masses in an amount of 0.05 parts by mass or less as in 20 parts by mass to 25-(22) 1373482. Above, it may be due to the light absorption of the acid generator itself, and the light under the thick film In the photocurable resin composition of the present invention, an organic solvent may be blended as an ingredient of rD) when necessary. In the case of an organic solvent, it is preferred to dissolve the above-mentioned polyimine resin. a solvent such as an amine condensate modified with formal water or a formaldehyde water/alcohol, a phenol compound, and a photo-initiating acid generator; and the organic solvent may, for example, be cyclohexanone or cyclopentanone. Ketones such as methyl-2-pentanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol; propylene glycol monomethyl ether, B Ethers such as diol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, third derivative of propionate Esters such as esters, propylene glycol mono-tert-butyl ether acetate, r-butyrolactone, phthalamides such as φ N-methyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, etc. These organic solvents are used singly or in combination of two or more. Among these organic solvents, ethyl lactate, cyclohexanone, cyclopentanone, and r- which are most preferable in solubility of the acid generator are particularly preferred. Butyrolactone, hydrazine, hydrazine-dimethylacetamide, and a mixture thereof The amount of the organic solvent used in the above (D) is 50 to 2,000 by weight of the total solid content of the components (Α) to (C). The mass fraction is particularly preferably from 100 to 1,000 parts by mass. If it is 50 parts by mass or less, the compatibility of the above components (Α) to (C) may be insufficient, and conversely, -26- (23) 1373482, even if it is 2,000 parts by weight or more, there is still little change in compatibility, and there is a possibility that the viscosity is too low to be suitable for the coating of the resin. Further, in the photocurable resin composition of the present invention, in addition to the above components, cerium may be blended with other additive components. For such an additive component, for example, a surfactant which is conventionally used for improving coatability can be added. In the case of a surfactant, preferably a nonionic one, for example, a fluorine-containing surfactant surfactant, φ may specifically be exemplified by perfluoroalkyl polyethylene oxide ethanol, fluorinated alkyl ester, perfluoroalkylamine oxidation. A fluorine-containing organic siloxane compound or the like. These compounds can be used by commercially available companies, for example, Florat ^ FC· , 4430 (both Sumitomo 3M (shares)), Shafron "S-141" and "S-145" (all are Asahi Glass) (shares), Unida because of "DS-401", "DS-403 1" and "DS-451" (both Taijin Industrial (share) system), US and Canada "F-8151" (large Japan ink industry (shares) system, "X-70-093" (both Shin-Etsu Chemical Co., Ltd.), etc. The best # is Florat "FC-44 30" (Sumitomo 3M (shares) And "X_7 0-093" (Shin-Etsu Chemical Co., Ltd.). In addition, other additives may also add a light absorbing agent to enhance the light absorption efficiency of the photo-initiating acid generator. In other words, a diaryl argon, a diaryl sulfonium, a 9,10-dimethyl hydrazine, a 9-fluorenone, etc. may be added. a compound, specifically, a tertiary amine compound such as triethanolamine or a nitrogen atom-containing compound such as benzotriazole or pyridine, and a decane coupling agent as an adhesion improving agent, for example, a ring The decane coupling agent KBM-403 (Shin-Etsu (25) 1373482 resin is coated on the substrate. The substrate may be, for example, a crystal substrate or a ceramic circuit board. Further, the solution may be further thinned. Then, the film is bonded to the substrate. The coating method can be carried out by a well-known lithography method, and can be applied by a dipping method, a spin coating method, a roll coating method or the like. Alternatively, it is preferably made to 0.1 to ΙΟΟμιη. First, a film of such a composition is formed, and then the film is bonded to the substrate φ. Here, for the purpose of effective photohardening reaction, it is preliminarily made by preliminary heating as needed. The solvent is volatilized, and the preliminary heating can be carried out at a temperature of 140 ° C for 1 minute to 1 hour, and then hardened by exposure to light having a wavelength of 240 to 500 nm. The above light is, for example, a desired pattern. Here, the material of the mask is such that it can shield light having a wavelength of 240 to 500 nm, for example, chromium, but is not limited to chromium. For the light having a wavelength of 240 to 500 nm, it can be exemplified by # Various waves that occur in the device Long light, for example, g line, i ultraviolet light, far ultraviolet light (248 nm), etc. The exposure amount is 10 to 2000 mJ/cm 2 . Here, when needed, it can The heat treatment may be carried out, for example, at 40 to 140 ° C for 0.5 to 10 minutes. After the above exposure or after the exposure, the developer is used after heating. The developing solution 'is preferably used as a solvent. The organic solvent to be used is, for example, methylacetamide or cyclohexanone, and the development can be carried out by a usual method, impregnation of a pattern formation or the like. Then, if necessary, t round, plastic | external. For example, the amount of coating can also be expected. It can be covered by, for example, a 40 mask, but it is preferably suitable for radiation, etc., such as sensitivity heat treatment, line imaging, for example, two, for example, washing, -29-(26) 1373482 rining, drying, etc. Then, a composition film having a desired pattern can be obtained. Here, the method of forming the pattern is as described above, but if it is not necessary to form a pattern, for example, if a simple uniform film is to be formed, the above-mentioned pattern is used except for the above-mentioned mask. The same method as described in the type forming method can be used. Moreover, the obtained pattern is heated by using an oven or a hot plate at 120 to 300 ° C for 10 minutes to 10 hours to increase the crosslinking density and remove the volatile components remaining in the φ, thereby forming a close contact with the substrate. A film that is excellent in strength, heat resistance, strength, and electrical properties. The cured film obtained from the photocurable resin composition in this manner is excellent in adhesion to the substrate, heat resistance, and electrical insulation, and is suitable for use as an electrical, electronic component, or semiconductor element. In addition to the film, a fine pattern can be formed, and the formed film is excellent in adhesion to the substrate, electrical characteristics, and mechanical properties, and is suitably used as a protective film for a semiconductor element, a wiring protective film, and a cap film. , solder resistance, etc. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the following examples. Here, in the following examples, the parts are by mass. Adjustment of Polyimine Resin Solution [Synthesis Example 1] -30- (27) 1373482 In a flask equipped with a stirrer, a thermometer, a nitrogen gas replacement device, and an ester adapter, 2,2-double (3) was fed. 4-4-g of 4-phenyldicarboxylic anhydride) perfluoropropane and 200.0 g of cyclohexanone as a solvent. Under stirring, 36.6 g of 2,2-bis(3-hydroxy-4-aminephenyl)perfluoropropane dissolved in 124.Og of cyclohexanone was added dropwise. After dropping, continue stirring for another 10 hours. Then, 50.0 g of toluene was added to the reaction solution, and the whole system was heated to 150 ° C and left for 6 hours. At this time, an ester was taken through the ester to recover 3.5 g of φ water. After the completion of the heating, the mixture was cooled to room temperature to obtain a polyimine resin which was obtained by a repeating unit which can be represented by the formula (9). 〔化22〕

(9) In the IR (infrared) spectrum analysis of the resin, no absorption derived from polyglycolic acid was observed, and absorption by the quinone imine group was observed at wavelengths of 1 78001^1 and 1 720CHT1. Further, absorption from a phenol group was observed in the vicinity of 3400 CHT1. Further, as a result of gel permeation chromatography analysis using tetrahydrofuran as a solvent, the weight average molecular weight in terms of styrene was 45,000 0. 220.0 g (resin solid content 17.6%) of the resin solution thus obtained and 7.4 g of glycidol were fed to the flask. Heat at 120 ° C for 6 hours. After the reaction was completed, it was cooled to room temperature, and the reaction solution was placed in a resin of 1 liter of methanol. After the precipitated resin was dried under reduced pressure at 40 ° C, 42.5 g of a resin was recovered. When using NMR (nuclear resonance) observation, it is considerable -31 - 1373482

[Synthesis Example 5] The resin having the structure represented by the formula (9) obtained in Synthesis Example 1 was added with a glycidyl hydrazine solution of 15 g of a cyclohexanone solution containing 14.6% of a resin solid content, followed by a synthesis example. The method of 1 carries out the reaction. However, only the heating conditions are made at 1 20 ° C for 1 hour. As a result, the resin solution (A-2) which is a resin represented by the following formula (14) and which is contained in a resin solid content of 17.9% can be obtained by the following formula (14). [27]

[Examples] • ··... -35- (32) 1373482 A solution of the polyimine resin synthesized from the above Synthesis Examples 1 to 4 was used, and a crosslinking agent and light were prepared according to the compositions described in Table 1. An acid generator, other additives, a solvent, and the like were initiated, and then stirred, mixed, and dissolved, and then subjected to precision filtration using a 0.2 micron filter made of Teflon to obtain the photohardening of the present invention from Examples 1 to 6. Resin composition. Further, for the sake of comparison, the resin represented by the formula (9) which is an intermediate for the production of the formula (10) of Synthesis Example 1 can be dissolved in cyclohexanone so that the solid content of the resin can be φ 20.0%. The solution was prepared as a resin solution E-1, followed by 2 wafers of 6 吋矽 wafers treated with hexamethyldioxane, and 2 micron membranes on the surface of 6 Å wafers. The composition of each example was coated on one piece of a copper substrate plated with a thickness of electrolytic copper, using a spin coater in accordance with the film thickness described in the table. In the three wafers prepared, for each of the ruthenium substrates, for the purpose of solvent removal, heat drying was performed on a hot plate at 1 ° C for 2 minutes, followed by a line having equal intervals. And • A quartz mask made of a line width of 1 μm to 20 μm is irradiated with light of a wavelength and an exposure amount as described in Table 1. Here, the NSR-1 755i7A represents a Nikon (Nicon) stop-type exposure device, and the PLA-600FA represents a Canon contact-contact type exposure device. After the irradiation, it was heated at 80 ° C for 1 minute and then cooled. Thereafter, the coated substrate was immersed in dimethylacetamide for 3 minutes to carry out development. The line width of the resolved image at this time is shown in Table 2. Further, the film thickness after the image formation is also described together. On the other hand, the composition of the examples (33) and (33) 1373482 described in Table 1 was applied to the remaining ruthenium wafer and copper substrate under the same conditions, and the solvent was removed. Prebake treatment (prebake). Further, after the entire substrate is irradiated with light without using a mask made of quartz, the heating after the exposure is continued, and the immersion in the dimethyl ketone g is continued. The film remaining after the operation was further heated in an oven at 200 ° C for 3 hours to obtain a cured film. Using this film, the insulation and adhesion of each film were measured in the manner described in Table 2 below.

-37- 8, (35) 1373482. PG-1 : [Chem. 2 8]

PG-2 : [Chem. 2 9]

Further, the crosslinking agents CL-1 to LC-3 used are as follows: CL : 1 [Chemical 3 1] H3COH2C\ &gt; (: Η 2 ΟΟΗ 3

H3COH2Csn/Nv^N, n_^CHj〇CH3 &lt;!; H2OCH3 CHjzOCHs (36) 1373482. CL : 2 [Chem. 3 2] Ο

Further, the contents of other additives used are as follows. FC-4430: Fluorinated surfactant (product name KBE-403 manufactured by Sumitomo 3: Co., Ltd.: epoxy modified sand oxide sanding adhesive (Shin-Etsu Chemical Co., Ltd.) X-70-0 93: Fluoride-containing 矽Ketone surfactant (Shin-Etsu Chemical Industrial Name)) Industrial Co., Ltd. -40 (37) 1373482. Example Electrical Characteristics S i Wafer Copper Substrate Insulation Failure Strength Example 1 0/100 0/100 3 00 ν /μιη Example 2 0/100 0/100 3 00 V/μιη Example 3 0/100 0/100 3 00 V/μιη Example 4 0/100 0/100 300 V/μιη Example 5 0/100 0 /100 25 0 V/μπι Example 6 0/100 0/100 3 00 V/μιη • In the above Table 2, the adhesion was evaluated by placing the substrate in a saturated 2, air pressure pressure cooker for 24 hours. The format peel test 'measures the number of peels. From the above results, it is known that the compositions of Examples 1 to 6 have a wide range of film thicknesses from a film of about 1 μm to a film thickness of 20 μm or more, and exhibit good resolution without occurrence of film fading. When it is a photosensitive material, it has sufficient characteristics, and the cured film has good adhesion to various substrates or electrical properties such as insulation withstand voltage, and is suitable as a protective film for a circuit or an electronic component. -41 -

Claims (1)

1373482.. Patent Application No. 094,134,982 Patent Application Revision of the Chinese Patent Application Revision of the Republic of China on April 1, 101, Patent Application No. 1. A photocurable resin composition characterized by: (A) a compound having a polyimine skeleton dissolved in an organic solvent substantially yttrium imidized, having a weight average molecular weight of a primary alcohol of 5,0' in a molecule having an alcohol equivalent of 3 500 or less. 00 to 500,000 polyφ quinone imine polymer compound, (B) an amine condensate modified by formaldehyde water or formal water-alcohol, a melamine resin 'urea resin, or an average of 2 in one molecule Any one or more of a hydroxymethyl or alkoxymethylol phenol compound, or (C) an acid generating acid generating agent which generates an acid by irradiation with light in a range of from 240 nm to 500 nm. 2. The photocurable resin composition according to claim 1, wherein (A) component is 100 parts by mass, (B) component is 0.5 to 50 parts by mass, and (C) component is 0.05 to 20 parts by mass. to make. Φ 3 . The photocurable resin composition according to claim 1 or 2, wherein the component (D) has a total amount of the components (A) to (C) of 1 part by mass, and contains 50 to 2000 masses. A portion of the organic solvent. 4. The photocurable resin composition of claim 3, wherein the polyimine polymer compound of the component (A) of claim 1 is represented by the following general formula (1), (1) (1) CH3—C—丨53 £1373482 LLX Κ Λ Γ 1 ?—— NX Μ—Υ— &amp;&amp; _ 1 ϊ ι \ m II II ο ο [wherein X is a tetravalent organic group, Y is The divalent organic group represented by the general formula (2), Z is a divalent organic group, W is a divalent organic group having an organic decane structure, 1 is a positive number, and m and η are respectively 0 or a positive number, and 0.2 ^ 1/ ( 1 + m + n ) $ 1 , 〇 $ m / ( 1 + m + n ) S 0·8, OS η / ( 1 + m + n ) $0.8, 〔化 2〕. (2) In the middle, A is selected from the group consisting of (Chemical 3), CH2, I., _S〇2, and CONH— Any of the divalent organic groups may be the same or different, and B and C are each an alkyl group, an alkoxy group or a hydrogen group having 1 to 4 carbon atoms which may be the same or different from each other, and a and b are 〇 or 1' and c is an integer from 1 to 1〇, again, in the formula Ri -2- 1373482. It is a monovalent group of an alcoholic hydroxyl group selected from a phenolic hydroxyl group, a carboxyl group or a first stage, and at least one of R1 is an organic group containing a primary alcohol, and further, an alcohol equivalent of a first-order alcohol. It is selected by way of being able to become 3 500 or less. 5. The photocurable resin composition according to claim 3, wherein in the general formula (2), 'R1 is a polyacrylonitrile having an organic group containing a primary alcohol, and the candidate is selected as: The valence group of any one of the following, and the alcohol equivalent of the primary alcohol is selected in such a manner as to be 3,500 or less, [Chemical 4] h2 9H ch2oh ~〇H , —COOH , —〇-C — C-CH20H , -〇-C-CH2〇H , ? H2 ?h 〇ch2oh —c~o~c -c-ch2oh , —coc-ch2oh , Η H 2 O 6 ·Light as in item 3 of the patent application A curable resin composition, wherein in the general formula (1), X is a tetravalent organic group having at least a tetracarboxylic dianhydride residue selected from the group consisting of the following formula; Organic based polyimine, 1373482 1. The photocurable resin composition of claim 3, wherein in the general formula (1), W is a divalent organic group represented by the following general formula (4) and has a primary alcohol. Organic based polyimine, (4) (wherein R2 is a monovalent hydrocarbon group having 1 to 8 carbon atoms which may be the same or different from each other, and g is a positive number from 1 to 80). 9. The photocurable resin composition of claim 3, wherein η in the general formula (1) is 3/n$4 〇0 of a decane modified polyazide having an organic group containing a primary alcohol amine. A method for forming a pattern, comprising: (i) a step of forming a photocurable resin composition according to any one of claims 1 to 9 on a substrate, (Π) a step of exposing light by a light source having a wavelength of 240 to 50 〇 11111 by a photomask and a step of heating after selective exposure, (iii) a step of performing development using an organic solution. Wait for 3 steps. A protective film </ RTI> characterized in that the film formed by the method of the method of claim 10 is heated and hardened at a temperature ranging from 120 ° C to 300 ° C.