TW583510B - Ultraviolet-curing resin composition and photo solder resist ink containing the same - Google Patents

Abstract

An ultraviolet-curing resin composition comprises (A) an ultraviolet-curing resin prepared by reacting an epoxy component comprising (a) an epoxy polymer prepared by polymerizing an ethylenically unsaturated monomer component containing (i) an epoxy-bearing ethylenically unsaturated monomer and (b) an epoxy-bearing isocyanurate derivative with (c) a carboxyl-bearing ethylenically unsaturated monomer, and then reacting the obtained intermediate with (d) a saturated or unsaturated polybasic acid anhydride; (B) an epoxy compound having two or more epoxy groups in the molecule; (C) a photopolymerization initiator; and (D) a diluent. A photo solder resist ink containing the composition can be developed with a dilute aqueous solution of an alkali and can form on a substrate a solder resist excellent in resistances to soldering heat and gold plating.

Description

583510 发明 Description of the invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the contents, the embodiments, and the drawings are simply explained) FIELD OF THE INVENTION A photoresist ink developed by an aqueous solution is used for a protective film of a color filter and an ultraviolet curable resin composition of a pixel. Known technology Since the beginning, in order to support the fine and high density of conductor patterns on printed circuit boards, liquid photoresist inks that can be developed have been used. For example, the liquid photoresist ink disclosed in Japanese Patent Application Laid-Open No. 61-243869 can be developed using a dilute aqueous alkali solution and composed of a soluble ultraviolet curing resin, a photopolymerization initiator, and an epoxy compound in a dilute aqueous alkali solution. In order to develop this ultraviolet curable resin in a dilute aqueous alkali solution, a considerable amount of carboxyl groups are introduced. However, since an epoxy compound needs to be compounded in the above photoresist ink, the carboxyl group existing in the ultraviolet curable resin and the like will react with the epoxy compound, and it is quite easy to react in the thermal curing pre-drying process, and It is quite easy to produce poor development and poor resolution. According to the results, the amount of the epoxy compound used must be limited to a range where such problems do not occur, and the solder heat resistance and electric corrosion resistance of the photoresist-improving coating film produced by the compound cannot be fully exerted. Sexual characteristics. Disclosure of the Invention 8229pif 1 .doc / 015 (Underlined) 5 583510 In view of the above problems, the present invention aims to provide an ultraviolet curable resin composition having excellent developability, resolution, and development width, that is, The ultraviolet curable resin composition invented by the invention is characterized in that it is composed of the following components: (A) The ethylenically unsaturated monomer component of the ethylenically unsaturated monomer ⑴ having an epoxy group is superimposed. An epoxy-containing polymer (a) and an epoxy-containing compound containing an epoxy-containing trimeric isocyanate derivative (b) are reacted with an ethylenically unsaturated monomer (c) having a carboxyl group to obtain an intermediate product. UV-curable resin obtained by reacting a substance with a saturated or unsaturated polybasic acid anhydride (d); (B) an epoxy compound having two or more epoxy groups in a molecule; (C) a photopolymerization initiator; and ( D) Among the thinners, the purpose of improving the heat resistance, developability, and softening point of the resin composition can be achieved by the ultraviolet curable resin of the component (A). Another object of the present invention is to provide a photoresist ink containing the resin composition. This photoresist ink can be developed with a dilute aqueous alkali solution and exhibits excellent substrate adhesion and electrical corrosion resistance, as well as excellent solder heat resistance and gold plating resistance, and can be provided as a photoresist formed on a substrate. The development width here refers to the width of the pre-drying conditions obtained by maintaining the possibility of development, or the width of the pre-drying management or the allowable range of the pre-drying. Still another object of the present invention is to provide a substrate or a printed circuit board on which a hardened film formed of the resin composition or a photoresist ink is formed on the substrate or the printed circuit board. 8229pifl.d0C / 015 (Unlined underline) 6 Another object of the present invention is to provide a dry film. The dry film is formed from the resin composition or the photoresist ink described above on the support by drying the film. On the income. By using this dry film, the photoresist formed by the above resin composition or photoresist ink can be easily provided on a substrate. The further formed features of the present invention and the effects obtained by the present invention 'Please refer to the attached drawings, and clearly understand the best embodiment for implementing the present invention in detail below. A UV-curable resin (A) used in the present invention is an epoxy-containing polymer (a) obtained by polymerizing an ethylenically unsaturated monomer component of an ethylenically unsaturated monomer ⑴ having an epoxy group. And an epoxy compound component containing an epoxy-containing trimeric isocyanate derivative (b), the ethylenically unsaturated monomer (c) having a carboxyl group is reacted, and the intermediate product obtained by the reaction is saturated or unsaturated Saturated polybasic acid anhydride (d). As the epoxy-group-containing polymer (a), an ethylene-based unsaturated monomer (i) having an epoxy group and an ethylene-based unsaturated monomer (H) copolymerizable with the monomer 与 此 can be used. Copolymer obtained by polymerizing the unsaturated unsaturated monomer component. In addition, the epoxy-containing polymer (a) may use an ethylenically unsaturated monomer having an epoxy group (0, and the ethylenic property of two or more ethylenically unsaturated monomers (iii) in one molecule. Copolymers obtained by polymerizing unsaturated monomer components 0 More 'epoxy-containing polymers (a), 7 8229pifl.d〇C / 〇15 (without underline) with epoxy groups can also be used. The ethylenically unsaturated monomers (i), ethylenically unsaturated monomers (iii) having two or more in one molecule, and the ethylenically unsaturated monomers (Π) that can be copolymerized with these monomers are not ethylenically unsaturated. The ethylenically unsaturated polymer of the saturated monomer component is polymerized. The ethylenically unsaturated monomer (i) contained in the epoxy group is introduced into the epoxy-containing polymer to add an epoxy group. The ethylenically unsaturated monomer based on ethyl group imparts photohardenability to the ethylenyl-containing polymer by combining ethylenically unsaturated double bonds. 尙 Furthermore, when using ethylenically unsaturated monomers contained in epoxy groups, i has more than two ethylenically unsaturated monomers (out) and ethylenic properties that are copolymerizable with these monomers I When the ethylenically unsaturated monomer component of the saturated monomer (丨 丨) is used, the content of the ethylenically unsaturated monomer ⑴ is preferably the ethylenically unsaturated monomer used in the production of the epoxy-containing polymer ⑷ About 40 to 99.9 mole percent of the entire ingredients, more preferably about 55 to 95 mole percent. In addition, an ethylenically unsaturated monomer containing no compound (iii) and ethylenically unsaturated monomer (^) is used. In the case of components, the content of the ethylenically unsaturated monomer ⑴ is 100 mole percent of the entire ethylenically unsaturated monomer component used in the production of the epoxy-containing polymer (a). Within the above range, The ultraviolet curable resin composition of the present invention is particularly capable of exhibiting excellent photohardenability and resolution, and the cured film finally formed by using the same composition has excellent heat resistance, and is particularly suitable as a permanent skin month. When this permanent film is used as a photoresist, it is particularly shown to have excellent solder heat resistance and electrical corrosion resistance. For ethylenically unsaturated monomers, for example, epoxypropyl 8 8229pif can be used. l.doc / 〇15 (underlined) 583510 (meth) propionic acid esters, (3,4-epoxycyclohexyl) (meth) propanoic acid methyl esters and other (meth) acrylic acid rings Oxycyclohexyl derivatives, alicyclic epoxy derivatives of (meth) acrylic acid esters, β-methylglycidyl (meth) propanoic acid esters, and monoallyl propylene oxide Trimeric isocyanate, etc. The above-mentioned substances may be used alone or in combination. In particular, if it is based on the ease of availability, it is preferred to use an epoxypropyl (meth) acrylate. In addition, in the present specification (Meth) acrylic is the general name of acrylic acid and methacrylic acid, and (meth) acrylic group is the general name of propenyl group and methacryl group. It has two or more ethylenically unsaturated groups in one molecule. The compound (iii) is an optional component, and is used for the purpose of further improving the heat resistance and softening point of the ultraviolet curable resin composition of the present invention. When the above-mentioned compound (iH) is used, its content rate is preferably in a range of 0.1 to 10 mole% of the total amount of the ethylenically unsaturated monomer component used in the production of the epoxy-containing polymer (a). Within this range, the polymerization reaction for forming the epoxy group-containing polymer (a) can be performed under good conditions, and is particularly effective for anti-gelling. In addition, the hardened film formed by the ultraviolet curable resin composition of the present invention has excellent heat resistance, and particularly when used as a solder resist, it exhibits excellent solder heat resistance. In addition, when it is in the range of 0 to 7 mol%, it is most suitable because it has both a heat-resistance improving effect and good polymerizability. As the compound (iii) having two or more ethylenically unsaturated groups in one molecule, for example, diethylene glycol di (meth) acrylate and triethylene glycol di (methyl) can be used. Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (formaldehyde 9 8229pif 1 .doc / 015 (underlined) 583510 ) Acrylate, polypropylene glycol di (meth) acrylate, EOPO modified dimethacrylate, bisphenol AEO adduct di (meth) acrylate, bisphenol FEO adduct di (methyl) ) Acrylate, bisphenol APO adduct di (meth) acrylate, bisphenol AEOP adduct di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Ethylene glycol di (meth) acrylate, neopentyl ethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, cyclopentyl di (meth) acrylate , Cyclopentenyl di (meth) acrylate, diallyl monoglycidyl trimer isocyanate, etc. Two ethylenically unsaturated compound having a group. In addition, compounds having three or more ethylenically unsaturated groups in one molecule can also be used, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (methyl) Base) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and polyesters of two, three or more composed of polybasic acid and hydroxy (meth) alkyl acrylate, etc. , And polyester (meth) acrylate. The above-mentioned compound (iii) can be used alone or in combination. The compound (iii) mentioned above can reinforce the main chain by containing the epoxy-group-containing polymer (a), thereby obtaining effects such as improvement of solder heat resistance, adjustment of softening point, and development width. Specifically, it is preferable to use bis (meth) acrylate in the compound (iii). As for the di (meth) acrylate, it is particularly preferable to use, for example, a hydroxyalkylene unit having at least one hydroxyethylene, hydroxypropylene, etc. in the molecule. In this case, not only can the ultraviolet curing of the present invention be improved The heat resistance of the resin composition can also provide a particularly excellent development width. At 8229pifl.d0C / 015 (without underline) 10 583510 Here, the appropriate number of hydroxyalkylene units in one molecule of di (meth) acrylate is 1 to 40, preferably 4 to 30 And more preferably 4 to 10. In this way, the reactivity at the time of manufacturing the ultraviolet curable resin (A) can be stabilized, the development width of the ultraviolet curable resin composition of the present invention can be widened, and the cured film thereof can also exhibit excellent solder heat resistance. Sex. In addition, when a substance having both a hydroxyalkylene unit and a bisphenol backbone is used as the di (meth) acrylate, it is more preferable because it has particularly excellent solder heat resistance and particularly excellent development width. As a di (meth) acrylate having a hydroxyalkylene unit which can be used as the compound (iii), ethylene ethylene represented by the following general formula (1) can be used

ch3 ch3 CH2 = c—coo — (CH2CH2〇) n — OCC = CH (1) Here, n 値 in the formula is an integer from 1 to 40. In addition, propylene glycol dimethyl propionate or polypropylene glycol dimethacrylate shown in the following general formula (2) may be used: a group CH,

ch3 ch3 ch3 ch3 CO—O— (CH-CH20) m (CH2 —CHO) n —oc -C = CH. (2) Here, n and m in the formula are integers of 0 or more, and n and m The total is 1 to 40. Furthermore, the ethylene glycol diacrylate or polyethylene glycol diacrylate shown in the following general formula (3) may be used: 8229pifl.doc / 015 (underlined) 11… (3) CH2 = CH—C0—0 (CH2—CH2〇) n—oc—ch = ch where n 値 is an integer from 1 to 40. In addition, as the bis (meth) acrylate having a hydroxyalkylene unit and a bisphenol backbone, a compound represented by the following general formula (4) can be used:

Here, 値 of η and m in the formula is an integer of 0 or more, and 値 of n + m is 1 to 40. Examples of such compounds include: 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) ) Phenyl] propane or 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane and the like. Alternatively, a compound shown in the following general formula (5) can be used:

Here, 値 of η and m in the formula is an integer of 0 or more, and 値 of n + m is 1 to 40. Examples of such compounds include: 2,2-bis [4- (propenyloxyethoxy) phenyl] propane, 2,2-bis [4- (propyleneoxydiethoxy) phenyl] propane Or 2,2-bis [4- (propyleneoxypolyethoxy) phenyl] propane, and bisphenol a 8229pifl · ς! (Κ / 015 (Unlined) 12 583510 Polyethylene glycol polypropylene B Dihydric adducts of diols, etc. Specifically, for a bis (meth) acrylate having a hydroxyalkylene unit, for example, NK ESTER 4G shown in formula (1) ( Trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., polyethylene glycol # 200 dimethacrylate (average 値 of η: 4)); NK ESTER 9G (trade name, new Manufactured by Nakamura Chemical Industry Co., Ltd., polyethylene glycol # 400 dimethacrylate (average η of 9); NK ESTER 9PG (trade name, Shin Nakamura Chemical Industry) shown in formula (2) Co., Ltd., polypropylene glycol # 400 dimethacrylate (average 値 of m + n: 7)); NK ESTER A-200 (trade name, Shin Nakamura Chemical Industry) shown in formula (3) Co., Ltd., Poly Ethylene Glycol # 200 diacrylate (average 値 of η: 4)); NK ester A-400 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., polyethylene glycol, shown in Formula (3)) # 400 diacrylate (average 値 of η: 9)); NK ESTER A-600 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., polyethylene glycol # 600 diacrylic acid) shown in formula (3) Esters (average 値 of η: 14)), etc. In addition, for a di (meth) acrylate having a hydroxyalkylene unit and a bisphenol backbone, for example, NK shown in formula (4) ESTER-BPE-100 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., 2,2-bis [4- (methacryloxyethoxy) phenyl] propane (m + n average 値: 2. 6)), NG ESTER-BPE-200 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane (m + n Average 値: 4)), NK ESTER-BPE-500 (trade name, manufactured by Shin Nakamura Chemical Industry Co., Ltd., 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane 13 8229pifl. doc / 015 (underlined) 583510 (average 値 of m + n: 10)); NK ESTER A-BPE-4 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) shown in formula (5), 2, 2-bis [4- (propyleneoxydiethoxy) phenyl] propane (average fluorene of m + n: 4)); blend 43DB-40B (manufactured by Nippon Oil & Fats Co., Ltd.) , Bisphenol A polyethylene glycol polypropylene glycol adduct dimethacrylate) and so on. The ethylenically unsaturated monomer (ii) which can be copolymerized with the ethylenically unsaturated monomer 具有 having an epoxy group and the compound (Hi) having two or more ethylenically unsaturated groups in one molecule is an optional component. If necessary, it can be used for adjusting the photocurability of the ultraviolet curable resin composition of the present invention and adjusting the physical properties of the cured film. The ethylenically unsaturated monomer (ii) as described above is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) ) Butyl acrylate, isobutyl (meth) acrylate, 3 butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid N-decyl ester, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate Alkyl, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc., linear, branched, or cycloaliphatic (however, it may have a partially unsaturated bond in the ring) (Meth) acrylates; ethyl hydroxy (meth) acrylate, ethyl methoxy (meth) acrylate, ethyl ethoxy (meth) acrylate, diethylene glycol mono (meth) acrylate , Triethylene glycol mono (meth) acrylate, methoxydiethylene glycol mono (meth) acrylate, etc. Alcohol ester (meth) acrylate; same propylene glycol ester (meth) acrylate, butene glycol ester mono (meth) acrylate, glycerol mono (meth) acrylate And so on; (meth) acrylic acid T ester and other aromatic 8229pifl. doc / 015 (underlined) 14 583510 (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N-propyl (meth) acryl (Meth) ammonium amine, N-third butyl (meth) propenylamine, N-third octyl (meth) propenylamine, diacetone (meth) propenylamine, etc. Acrylamido-based compounds; N-phenylmaleic anhydride imine, N- (2-methylphenyl) maleic anhydride imine, N-cyclohexylmaleic anhydride imine, N- (2 , 6-diethylphenyl) maleic anhydride imine, N-dodecyl maleic anhydride imine, N-benzyl maleic anhydride imine and other maleimide imine-based compounds; And vinylpyrrolidone, (meth) acrylonitrile, ethyl acetate, styrene, α-methylstyrene, vinyl ether, and the like. These substances can be used individually or in combination. Among them, from the viewpoint of the ease of adjusting the film hardness, oiliness of the ultraviolet curable resin composition, and the adjustment of the photoresist hardness finally formed, it is used: linear or branched aliphatic, aromatic or (Meth) acrylates, hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, alicyclics (however, they may have a partially unsaturated bond in the ring), Maleic anhydride imine-based compounds and the like are suitable. When the above ethylenically unsaturated monomer (Π) is used, its content rate is not particularly limited, and generally it is 1 to 60 mole% of the total amount of ethylenically unsaturated monomer components, and it is 1 to 55 Molar% is preferred, and 10-50 mole% is particularly preferred. Within the above range, a sufficient introduction amount of the ethylenically unsaturated group to be introduced into the ultraviolet curable resin composition (A) can be ensured. In addition, adjustment of the hardness and the hydrophilic group of the cured film can be performed particularly easily. The epoxy group-containing polymer (a) can be obtained by a known polymerization method such as solution polymerization or latex polymerization. When solution polymerization is used, for example, the presence of the above ethylenically unsaturated monomers and, if necessary, the corresponding 8229 pif 1. doc / 015 (Unlined) 583510 The ethylenically unsaturated monomer (ii) or compound (iii) is used as a suitable organic solvent for the ethylenically unsaturated monomer component. A polymerization initiator is added, and under a nitrogen stream Heat and stir. Alternatively, a method of polymerizing under reflux may be adopted. As the organic solvent used in the above polymerization method, for example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate Acetates, ethylene glycol ether acetate, butyl glycol ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like; and dialkylethyl Glycol ethers and so on. These substances can be used individually or in combination. As for the polymerization initiator used for polymerization, for example, 3rd butyl hydroperoxide, di-3rd butyl peroxide, dodecyl peroxide, phenylfluorenyl peroxide, Peroxides such as diisopropylperoxydicarbonate, and azo compounds such as azobisisobutyronitrile, 2,2'-azobisisobutyric acid methyl ester, and azodicyanovaleronitrile and many more. These substances can be used alone or in combination. The ultraviolet curable resin composition (A) of the present invention can be obtained by allowing the ethylenically unsaturated monomer (c) having a residue to be obtained from the epoxy-containing polymer (a) and An epoxy compound containing an epoxy group-containing trimeric isocyanate derivative (b) is reacted, and then the obtained intermediate product is subjected to an addition reaction with a saturated or unsaturated polybasic acid anhydride (d) to form the reaction. By the addition reaction of the ethylenically unsaturated monomer (c) having an end group, an epoxy group-containing triisocyanate derivative (b) and an epoxy group-containing polymer (a) can be imparted. The epoxy compound component is derived from ethylenically unsaturated double bond 8229pifl. doc / 015 (Underlined) 16 Knot photohardenability. In addition, in order to make the characteristics of the epoxy-containing trimeric isocyanate derivative (b) apparent, 'the epoxy-containing polymer (a) used in the production of the ultraviolet-curable resin composition (a) In the epoxy compound component composed of the epoxy group-containing trimeric isocyanate derivative (b), the amount of the epoxy group-containing trimeric isocyanate derivative (b) is preferably 1 to 50% by weight, and 1 to 35% by weight. % Is more preferred, and 2 to 20% by weight is particularly preferred. The epoxy compound-containing polymer (a) and the epoxy-group-containing trimeric isocyanate derivative (b) contain the epoxy compound-containing polymer (a) in an amount of 50 to 99% by weight is preferred, 65 to 99% by weight is more preferred, and 80 to 98% by weight is particularly preferred. In addition, in the present invention, the above-mentioned epoxy compound component used for generating the ultraviolet curable resin (A) may also contain (a) component, (b) component, and other epoxy compounds. In this case, the Among the epoxy compound components used to generate the ultraviolet curable resin (a), the preferred amount of the epoxy group-containing trimeric isocyanate derivative (b) is in the above-mentioned range. As for the epoxy-containing trimeric isocyanate derivative (b), for example, triglycidyltrimeric isocyanate, monoallyldiglycidyltrimeric isocyanate, diallylmonoepoxy Propyl trimer isocyanate, etc. These substances may be used singly or in combination. Specifically, for example, TEPIC (trade name, manufactured by Sanko Chemical Co., Ltd., triglycidyl trimer isocyanate), monoallyl diglycidyl trimer isocyanate (trade name, Shikoku Chemical Co., Ltd.) Industrial Co., Ltd., monoallyl diglycidyl trimeric isocyanate), diallyl monoglycidyl trimeric isocyanate (trade name, manufactured by Shikoku Chemical Industry Co., Ltd., diallyl Mono-glycidyl-trimeric isocyanate) and the like. Among them, three 17 8229 pif 1 is used in particular. doc / 015 (Unlined) 583510 Epoxypropyltrimeric isocyanate is preferred as the epoxy-containing trimeric isochloroacetate derivative (b). To correspond to other epoxy compounds in the epoxy compound component used to generate ultraviolet curable resin when used together with epoxy-containing polymer (a) and epoxy-containing trimeric isocyanate derivative (b) when necessary. For example, a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A epoxy resin, a bisphenol A-phenol novolac epoxy resin, a bisphenol 酹 ρ epoxy resin, YX4000 (manufactured by Petrochemical Shell Epoxy Co., Ltd.), alicyclic epoxy resin (such as "EHPE-3150" manufactured by DAICEL Chemical Industry Co., Ltd.), multifunctional epoxy resin based on tris (phenylphenyl) methane (Japan) EPPN-502H manufactured by Chemical Pharmaceutical Co., Ltd., and TACTX-742 and XD-9035 manufactured by Dow Chemical Co., Ltd.), hydrogenated bisphenol A type epoxy resin, dicyclopentadiene-phenol type epoxy resin, and naphthalene type epoxy resin Wait. On the other hand, as the ethylenically unsaturated monomer (c) having a carboxyl group, for example, (meth) acrylic acid, butenoic acid, cinnamic acid, and 2- (meth) acrylfluorenylhydroxyethylbutyl Diacid, 2- (meth) acrylfluorenyl hydroxyethyl phthalic acid, β-carboxyethyl acrylate, acrylfluorenyl hydroxyethyl succinate, 2-acrylic acid, 3- (2-carboxyethoxy ) -3-carboxypropyl ester, 2- (meth) acrylfluorenylhydroxyethyltetrahydrophthalic acid, 2- (meth) acrylfluorenylhydroxyethylhexahydrophthalic acid, etc. have only 1 Those with ethylenically unsaturated groups; and those with plural ethylenically unsaturated groups such as pentaerythritol tri (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. This ethylenically unsaturated group is obtained by reacting a dibasic acid anhydride in a polyfunctional acrylate having a hydroxyl group. The above substances can be used individually 8229pif 1. doc / 015 (Underlined) 18 Use them in combination. Among the above substances, those having only one carboxyl group are preferred, and (meth) acrylic acid or those containing (meth) acrylic acid as a main component are preferred. Since the ethylenically unsaturated group introduced by (meth) acrylic acid is excellent in photoreactivity, it is preferable to use (meth) acrylic acid as the ethylenically unsaturated monomer (c) having a carboxyl group. The blending amount of the ethylenically unsaturated monomer (C) having a carboxyl group is such that the molar amount of the epoxy group in the epoxy compound component used to form the ultraviolet curable resin (A) is 1 mole. The carboxyl group of the ethylenically unsaturated monomer (e) becomes an amount of 0.7 to 1.2 moles, and becomes 0.1. 9 ~ 1. 1 mole is better, 0. 95 ~ 1. 1 Morteja. Within the above range, the ultraviolet-curable resin composition (a) of the present invention can exhibit a particularly wide development width, and further, the residual influence of the unreacted ethylenically unsaturated monomer (c) having a carboxyl group is small. In terms of saturated or unsaturated polybasic anhydride (d), for example, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, Tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylorbornene 2,3-dicarboxylic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Dibasic acid anhydrides; and tribasic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarbonic anhydride, and methylcyclohexene tetracarbonic anhydride. These substances may be used singly or in combination. The main purpose of using the above-mentioned saturated or unsaturated polybasic acid anhydride (d) is to impart ultraviolet curable resin acid hydrazone so as to obtain properties capable of being redispersed and re-dissolved by dilute aqueous alkali solution 'and thus obtain heat. Sclerosing. The amount used is a UV-curable tree composed of a polybasic anhydride addition reaction. 19 8229pifl. doc / 015 (Unlined) The acid value of the lipid is preferably 25 to 150 mgKOH / g, and particularly preferably 45 to 100 mgKOH / g. Within the above-mentioned range, the ultraviolet-curable resin composition of the present invention exhibits particularly good developability, and the cured film formed therefrom is also particularly excellent in electric characteristics, electric corrosion resistance, and water resistance. In addition, the best results are obtained when the acid sulfonium is in the range of 50 to 85 mgKOH / g. The ultraviolet curable resin (A) of the present invention can be obtained by allowing the ethylenically unsaturated monomer (c) having a carboxyl group to be obtained from the epoxy-containing polymer (a) and epoxy-containing polymer obtained as described above. The epoxy compound component composed of the trimeric isocyanate derivative (b) is reacted, and a saturated or unsaturated polybasic acid anhydride (d) is added to the obtained intermediate product, and then there are at least two in the molecule. An isocyanate group-containing isocyanate compound (e) is reacted to produce it. As for the isocyanate compound (e), for example, 2,4-methylphenyl diisocyanate, 2,6-methylphenyl diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and the like can be used. Isocyanate, isophorone diisocyanate, 4,4, -diphenylmethane diisocyanate, toluidine diisocyanate, lysine diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethyl Hexamethylene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl polyisocyanate, etc. These substances can be used alone or in combination. In addition, the above substances are preferably those having only two isocyanate groups in the molecule, especially isophorone diisocyanate, hydrogenated xylylene diisocyanate, methylenephenyl diisocyanate, and xylylene. Diisocyanates and the like are more preferred. In addition, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and the like having only two isocyanate groups and no aromatic ring in the molecule are most suitable. 8229pif 1. doc / 015 (Unlined bottom line) 20 583510 By adding the above isocyanate compound (e) ', excellent film properties can be obtained after pre-drying, and at the same time, light with excellent developability, resolution, and heat resistance can be obtained. Resistance performance. The amount of the isocyanate compound (e) used is 1 mole relative to the hydroxyl group of the secondary hydroxyl group in the product obtained by the reaction of the epoxy compound component and the ethylenically unsaturated monomer (c) having a carboxyl group. For the purpose of making the isocyanate group of the isochlorosulfonium compound (e) 0. The amount is from 01 to 0.90 mole, and the amount from 0 to 0.05 to 0.4 mole is preferable. Within the above range, the solubility of the ultraviolet curable resin (A) to the diluent (D) becomes particularly good. The addition reaction of an ethylenically unsaturated monomer (c) having a carboxyl group and a saturated or unsaturated polyanhydride (d) can be performed by a known method. For example, the addition reaction of an ethylenically unsaturated monomer (c) having a carboxyl group is an epoxy resin composed of an epoxy group-containing polymer (a) and an epoxy group-containing trimeric isocyanate derivative (b). To the compound component, an ethylenically unsaturated monomer (c) having a carboxyl group, methoxyhydroquinone as a thermal polymerization stopper, and tertiary ammonium, quaternary ammonium or dibenzyl as a catalyst are added. Dihydrogen is chained and stirred and mixed, and then the reaction is performed at a reaction temperature of preferably 60 to 150 ° C, particularly preferably 80 to 12 (rc) according to a general method. A saturated or unsaturated polybasic acid anhydride The addition reaction of (d) can also be carried out by the same method as described above. When the isocyanate compound (e) as an optional component is added to the saturated or unsaturated polybasic acid field (d) and the reaction is carried out, : Adding an ethylenically unsaturated monomer (c) having a carboxyl group to a solvent solution containing an epoxy compound component composed of an epoxy group-containing polymer (a) and an epoxy group-containing polyisocyanate derivative (b) The intermediate product obtained after the reaction is saturated or unsaturated 21 8229pifl. doc / 015 (without underline) The isocyanate compound (e) is added to react before, after or at the same time as the addition reaction of the polybasic acid anhydride (d). For the above reaction, for example, a general method may be used, and an organic tin compound such as dibutyltin dilaurate or a tertiary amine such as benzyldimethylamine may be added as a catalyst, or the above reaction may not be added in the previous reaction. Under the blended catalyst, heating and stirring are performed at a reaction temperature of 20 to 10 ° C. The weight-average molecular weight of the ultraviolet curable resin (A) prepared as described above is not particularly limited, and it is preferably The range is a weight average molecular weight of 3000 to 400,000. In the above range, the ultraviolet curable resin composition of the present invention can have particularly excellent sensitivity and resolution. The blending amount of the ultraviolet curable resin (A) is in order to be able to The ultraviolet curable resin composition of the present invention is ensured to have good sensitivity, operating characteristics, and photoresist energy formed at the end, and has good physical properties. Therefore, it is to account for the organic content in the thinner (D) used in addition to the contract. 10 to 80% by weight of the total amount of the components of the ultraviolet curable resin composition of the present invention other than the solvent is preferred. Within the above range, the ultraviolet curable properties of the present invention The lipid composition is particularly excellent in ultraviolet curability, and is particularly capable of reducing the adhesion of the pre-dried film. For the epoxy compound (B) having two or more epoxy groups in one molecule, for example, ·· Solvent-insoluble epoxy compounds, solvent-soluble epoxy compounds, etc., for example, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol A-phenolaldehyde Type epoxy resin, bisphenol F type epoxy resin, triglycidyl trimer isocyanate, monoallyl diglycidyl trimer isocyanate, YX4000 (made by Sinopec Shell Epoxy Co., Ltd.), sorbitol poly Glycidyl ether, N-glycidyl epoxy resin, 8229pifl. doc / 015 (Unlined) 22 cycloaliphatic epoxy resin (such as "EHPE-3150" manufactured by DAICEL Chemical Industry Co., Ltd.), polyol polyglycidyl ether compound, glycidyl ester compound, N-epoxypropyl group Type epoxy resin, trifunctional epoxy resin based on tris (hydroxyphenyl) methane (EPPN-502H manufactured by Nippon Kayaku Co., Ltd., and TACTX-742 and XD-9035 manufactured by Dow Chemical Co., Ltd.), hydrogenated bisphenol A-type epoxy resin, dicyclopentadiene-phenol-type epoxy resin, naphthalene-type epoxy resin, and ethylene polymer with epoxy group. The above substances can be used singly or in combination, or cross-linking modification can be used. Among them, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, bisphenol A-phenol novolac epoxy resin, triglycidyl trimer isocyanate, and YX4000 are particularly preferred. . The blending amount of the epoxy compound (B) in the ultraviolet curable resin composition of the present invention is to account for the ultraviolet ray of the present invention, in addition to the organic cereals in the diluent (0) used in the contract with the blender. 0.1 to 50% by weight of the total amount of the components of the curable resin composition is preferred. Within the above range, the ultraviolet curable resin composition of the present invention can exhibit particularly excellent thermosetting properties and has a particularly wide development width. As the photopolymerization initiator (C), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin and its alkyl ethers, and acetophenone can be used. , 2,2-monomethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylbenzene Acetophenones such as ketones; anthracenes such as 2-methylanthracene, 2-pentylanthracene, etc .; 2, 'dimethylthioxanthone, 2,4-diethylthioxanthone, 2 -Thioxanthones such as chlorothioxanthone, 2,4-diisopropylthioxanthone, i-chloro-4-propoxythioxanthone; acetophenone dimethyl ketal, 8229pifl. doc / 015 (Unlined) 23 Acetals such as benzyldimethylketal; benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 3,3 ', 4,4'-tetra- (3rd butylperoxyquinyl) -benzophenone, 4-benzofluorenyl-4'-methyldiphenyl sulfide, etc. Ton ketones; 2-methylmethylthio) phenyl > 2-morpholine-propan-1_one, 2-phenylfluorenyl-2-dimethylamino-1- (4-morpholinebenzene Group) -butanone-1, 4,4'-bis-diethylaminobenzophenone and other substances containing nitrogen atoms; and 2,4,6-trimethylphenylfluorenyldiphenylphosphine oxidation Things. The above substances may also be related to benzoic acid or ethyl p-dimethylaminobenzoate, iso-p-dimethylaminobenzoate, 2-dimethylpentylethylbenzoate, etc. Well-known photopolymerization accelerators such as tertiary amines and sensitizers are used together. The above-mentioned photopolymerization initiators can be used individually or in combination with each other as appropriate. As the sensitizer for the laser exposure method, for example, 7-diethylamino-4_methylcoumarin, 4,6-diethyl-7-ethylamine Coumarin derivatives such as legumin, quinoline blue pigment, glutin pigment, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1Η_pyrrole small group) -phenyl) titanium and other aromatic cycloolefin metal derivatives, etc. In addition, the ultraviolet curable resin composition of the present invention can also be used as a visible light or near-infrared curable substance. The blending amount of the photopolymerization initiator (C) in the ultraviolet curable resin composition of the present invention is in order to make a good balance between the photocurability and the properties of the solder resist obtained. In the diluent (D) used at the time, the total amount of the components of the ultraviolet curable resin composition of the present invention other than the organic solvent is 0. 1 to 30% by weight is preferred. Within the above range, the UV-curable resin composition of the present invention will exhibit particularly excellent UV-hardening properties, and at the same time, the heat resistance and electro-corrosion resistance of its cured film will become particularly excellent. 8229pifl. doc / 015 (Underlined) 24 Differences. The diluent (D) can be used alone or in combination with a photopolymerizable ethylenically unsaturated monomer or an organic solvent. As the photopolymerizable ethylenically unsaturated monomer, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-vinylpyrrolidone, ( Methyl) propanylmorpholine, methoxytetraethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol di (methyl) Acrylic acid, N, N-dimethyl (meth) acrylamide, N-methylol (methyl) acrylamide, N, N-dimethylaminopropyl (meth) acrylamine, N, N-dimethylamino (meth) acrylate, N, N-dimethylamino (meth) acrylate, trihydroamine (meth) acrylate; diethylene glycol di (methyl) Base) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, phenoxyethyl (methyl Based) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (Meth) acrylate, cyclopentyl mono (meth) acrylate, cyclopentenyl mono (meth) acrylate, cyclopentyl di (meth) acrylate, cyclopentenyl di (methyl) Base) acrylic esters; mono-, di-, tri- or more polyesters of polybasic acids and hydroxy (meth) acrylic acid alkyl esters; and polyester (meth) acrylic acid esters, urethane (meth) acrylic acid esters, etc. (Meth) acrylate monomers and the like. The photopolymerizable ethylenically unsaturated monomers can be used individually or in combination with each other as appropriate. 8229Pifl. cl〇C / 015 (Underlined) 25 In addition, as the organic solvent, for example, ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, and ethyleneethylene Alcohols, such as linear, branched, second- or polyvalent alcohols; ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; SWASOL series (Jiushan Petrochemical Company) Made), SOLVESSO series (manufactured by EXXON Chemical Co., Ltd.) and other petroleum-based aromatic mixed solvents; ethylene glycol ethers such as ethylene glycol ether and butyl ethylene glycol ether; carbitol, butyl carbitol, etc. Carbitols; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; ethyl acetate, butyl acetate, ethylene glycol Ethyl acetates such as alcohol ether acetate, butyl glycol ether acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and dialkyl glycol ethers Wait. The above-mentioned substances may be used singly or in appropriate combination with each other. The photopolymerizable ethylenically unsaturated monomer used as the diluent (D) can dilute the ultraviolet curable resin (A) to make it easy to apply, and can also adjust its acid value to give it photopolymerization. Sex. In addition, the organic solvent used as the diluent (D) can be dissolved and diluted into a coatable liquid state such as the ultraviolet curable resin (A), and can be formed into a film by drying. In addition, as a diluent (D), although the photopolymerizable components such as the above-mentioned photopolymerizable ethylenically unsaturated monomers are not necessarily blended in the ultraviolet curable resin composition of the present invention, When incorporated, the total amount is preferably 50% by weight or less of the total amount of the components of the ultraviolet curable resin composition of the present invention other than the organic solvent used at the time of the contract. If the blending amount exceeds 50% by weight, the surface adhesion of the pre-dried film will become too strong. Therefore, the patterned negative mask is directly abutted on 8229Pifl. doc / 015 (Underlined) 26 When the dried coating film surface is exposed, the problem of smearing of the negative mask may occur. On the other hand, the organic solvent used as the diluent (D) in the same manner as the photopolymerizable ethylenically unsaturated monomer is the ultraviolet curable resin composition of the present invention, and is particularly used as a dilute alkali. A necessary component for the use of developable photo-solder photoresist ink in a water-based aqueous solution is a necessary choice to achieve rapid volatilization during pre-drying without remaining in the pre-dried film. The blending amount of the organic solvent in the composition is preferably more than 5% of the total amount of the components of the ultraviolet curable resin composition of the present invention. If it is less than the above ratio, application of the composition becomes easy and difficult. In addition, since the above-mentioned preferable blending amount varies depending on the coating method, and must be appropriately adjusted according to the coating method, the upper limit of the blending amount is not particularly limited. In the ultraviolet curable resin composition of the present invention, in addition to the above-mentioned components, it may be blended with, for example, the following materials: thermosetting components such as blocked isocyanate, amine resin, etc .; ultraviolet curable epoxy groups (methyl ) Acrylic esters, such as: bisphenol A type, phenol novolac type, cresol novolac type, those with (meth) acrylic acid added to alicyclic epoxy resin, or Malay added to the above substances Acid anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride and other saturated or unsaturated polybasic acid anhydrides, such as alkyl (hydroxy) (meth) acrylate, ( UV-curable polymer obtained by reacting alkyl meth) acrylate with copolymers of maleic anhydride and other ethylenically unsaturated monomers; styrene- (meth) acrylic acid- (meth) acrylate copolymerization Products such as ethylenically unsaturated compounds copolymers or styrene-meth (meth) acrylic acid (meth) acrylate copolymers, such as ethylene 8229pifl. dooC / 015 (Unlined) 27 Copolymers of unsaturated unsaturated compounds, or UV-curable polymers obtained by reacting with the above-mentioned substances by further adding an ethylenically unsaturated monomer having an epoxy group ; UV-curable polymer to which (meth) acrylic acid is added to a vinyl copolymer having an ethylenically unsaturated monomer having an epoxy group as a monomer unit, styrene-maleic resin, Polymer compounds such as allyl phthalate resin, phenoxy resin, melamine resin, urethane resin, and fluorine-containing resin. In addition, the ultraviolet curable resin composition of the present invention may be added with an epoxy resin hardener, a hardening accelerator, a filler, a colorant, a leveling agent, a tackifier, a thixotropic agent, and a polymerization agent, if necessary. Various additives such as stop agents, anti-halo agents, flame retardants, defoamers, dispersion stabilizers, polymer dispersants and antioxidants. The ultraviolet curable resin composition of the present invention can be prepared by a conventional kneading method using, for example, a triaxial roller, a ball mill, a sand mill, or the like, for each formulation ingredient and additive. At this time, it may also be adopted: a part of the components (A) to (D), for example, a part of the component (D) and a component (B) are mixed / dispersed in advance to obtain a first mixture, and then, A part of the components (A), (C) and (D) are mixed / dispersed in advance to obtain a second mixture, and the above-mentioned first and second mixtures are mixed to prepare a blending method as described above when in use. The method of using the ultraviolet curable resin composition of the present invention is not particularly limited. For example, a photoresist ink used in the manufacture of a printed circuit board having a fine, high-density conductor pattern is preferably used. By using the above-mentioned photoresist ink, a photoresist pattern can be formed on a printed circuit board or a substrate. At this time, by using the above-mentioned photoresist ink on a printed circuit board or substrate 8229pifl. doc / 〇15 (Underlined) 28 Hardened and formed into an appropriate pattern shape to form a hardened film, and then use this hardened film to form a photoresist pattern. An example of forming a photoresist pattern on a substrate is described below. First, the photoresist ink is applied by a dipping method, a spray method, a spin coater, a roll coater, a curtain coater, or a screen printing method. Next, in order to volatilize the organic solvent of the diluent, pre-drying is performed at, for example, 60 to 120 ° C to form a pre-dried film. Secondly, a negative mask with a pattern is directly or indirectly arranged on the surface of the pre-dried film, and the chemical lamp, the low-pressure mercury lamp, the medium-pressure mercury lamp, the high-pressure mercury lamp, the ultra-high-pressure mercury lamp, and the xenon lamp are arranged through the negative mask through the negative mask. Or a metal halide lamp or the like is irradiated with ultraviolet rays, and then developed to form a pattern. Furthermore, by curing the epoxy compound by heating at 120 to 180 ° C for 30 to 90 minutes, a photoresist pattern capable of forming a hardened film having excellent film strength, hardness, and chemical resistance can be obtained. As the alkaline solution used in the development step, for example, an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, an aqueous solution of ammonium carbonate, an aqueous solution of sodium bicarbonate, an aqueous solution of potassium bicarbonate, an aqueous solution of ammonium bicarbonate, or an aqueous solution of sodium hydroxide can be used. , Potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution, lithium hydroxide aqueous solution, and the like. In addition to the bases described above, organic amines such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine can also be used. These materials can be used alone or in combination. As the solvent of the above-mentioned alkali solution, not only water but also a mixture of water and a hydrophilic organic solvent such as a lower alcohol may be used. In addition, the ultraviolet curable resin composition or photoresist ink 8229pifl of the present invention. doc / 015 (Unlined) 29 can be formed on the surface of the support, which is the so-called dry film photoresist. The film thickness in this case is preferably 10 to 100 m. For the support, for example, a film having a thickness of 5 to 100 / zm such as polyethylene terephthalate can be used. The ultraviolet curable resin composition or the photoresist ink film can be formed by coating the support film with the ultraviolet curable resin composition or the photoresist ink and drying it. The ultraviolet curable resin composition of the present invention is particularly suitable for use in a photoresist ink. However, it is not limited to this. For example, it can be used to form a protective film for a color filter. Organic pigments such as azolake, insoluble azo, and phthalocyanine; and inorganic pigments such as Milori Blue, iron oxide, and cobalt; and oil-soluble dyes and alkalis Suitable pigments such as basic dyes and disperse dyes, or a composition for color filter pixel modulation of fuel. Preferred Embodiments First Embodiment The following is a description of the present invention based on embodiments, but the present invention is not limited thereto. In addition, "part" and "%" used below are weight-based unless otherwise specified. [First Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate and methyl (meth) acrylate. 20 parts, 10 parts of 3 butyl (meth) acrylate, 100 parts of carbitol acetate, and 0.1 of dodecanethiol. 2 parts, 3 azobisisobutyronitriles, 8229pifl. doc / 015 (without underline) 30 Polymerization was carried out by heating under a nitrogen stream and stirring at 80 ° C for 5 hours to obtain a 50% epoxy group-containing copolymerization solution. To be continued, 10 parts of TEPIC-S (manufactured by Nissan Chemical, Triglycidyl Trimeric Isocyanate) and hydroquinone were added to the above-mentioned 50% epoxy-group-containing copolymerization solution. . 05, acrylic 43, dimethyl benzylamine 0. 2 parts, reacted at 100 ° C for 24 hours, followed by adding 45 parts of tetrahydrophthalic anhydride and 98 parts of carbitol acetate at 100 ° C for 3 hours, and A 50% ultraviolet-curable resin solution (A-1) was obtained. [Second Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate and NK ESTER 9G (trade name, Made by Shin Nakamura Chemical Co., Ltd. 10 polyethylene glycol methacrylate (n = 9) molecular weight = 536) 10, methyl (meth) acrylate 20, carbitol acetate 100, Dodecanethiol 2 parts, 3 parts of azobisisobutyronitrile, were heated under nitrogen flow, and continuously polymerized at 8 ° C. for 5 hours to obtain a 50% epoxy group-containing copolymerization solution. Continued, in the above-mentioned 50% epoxy-containing copolymerization solution, added TEPIC-S (made by Nissan Chemical, triglycidyl trimer isocyanate) 20, hydroquinone 0. 05 parts, 50 parts acrylic acid, divinyl benzylamine 0. Two parts were reacted at 100 ° C for 24 hours, followed by adding 45 parts of tetrahydrophthalic anhydride and 115 parts of carbitol acetate at 100 ° C for 3 hours to obtain 50% of the UV-curable resin solution (A-2). 8229pifl. doc / 015 (Unlined bottom line) 31 [Third Synthesis Example] In a four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer, epoxypropyl (meth) acrylate 70 was added. NK ESTER 9PG (trade name, manufactured by Shin Nakamura Chemical Co., Ltd., polypropylene glycol # 400 dimethacrylate polypropylene giycol methacrylate ^?) Molecular weight = 536) 10 parts (15) methyl (meth) acrylate, (methyl ) 5 parts of 3 butyl acrylate, 100 parts of carbitol acetate, 3 parts of azobisisobutyronitrile, heated under nitrogen flow, and continuously stirred at 80 ° C for 5 hours to obtain a 50% The epoxy group contains a copolymerization solution. Continuing, to the above 50% epoxy-group-containing copolymerization solution, TEPIC-S (Tris Glycidyl Trimeric Isocyanate, manufactured by Nissan Chemical Co., Ltd.) 20 parts, hydroquinone 0.05 part, Acrylic acid 50 parts, divinyl benzylamine 0.2 parts, react at 100 ° C for 24 hours, and then add isophorone diisocyanate 2. 7 parts and dibutyl tin dilam * ate 0. 01, at 50. (: Stir for 4 hours to carry out the reaction, and then add 45 parts of tetrahydrophthalic anhydride and 118 parts of carbitol acetate and react at 100 ° C for 3 hours to obtain a 50% UV-curable resin solution. (A-3) [Fourth Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate, NKESTERA-BPE-4 (trade name, manufactured by Shin Nakamura Chemical Co., Ltd., 2,2 · bis [心 (acryloxydiethoxy) phenyl] propane 2,2-bis [4- (acryloxydiethoxy) phenyl] propane , Molecular weight = 512) 5 32 8229pif 1. doc / 015 (without underline), 15 methyl (meth) acrylates, cyclohexylmaleimidelO, cyclohexylmaleimidelO, carbitol acetate 100, dodecanethiol 0.1 One part and three parts of azobisisobutyronitrile were heated under nitrogen flow and continuously stirred at 80 ° C for 5 hours to obtain a polymerization solution to obtain a 50% epoxy group-containing copolymerization solution. Continuing, in the above-mentioned 50% epoxy-group-containing copolymerization solution, TEPIC-S (three epoxypropyltrimeric isocyanate manufactured by Nissan Chemical) 50 parts, hydroquinone 0. 05, 72 acrylic, divinylamine. 2 parts, reacted at 100 ° C for 24 hours, followed by adding 56 parts of tetrahydrophthalic anhydride and 178 parts of carbitol acetate at 100 ° C for 3 hours to obtain 50% UV curing Resin solution (A-4). [Fifth Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate and BLEMER43DB-40B (trade name ' Bis-phenol A polyethylene glycol polypropylene glycol admixed dimethacrylate, molecular weight = about 1180) manufactured by Nippon Ozuki Corporation, 14 parts of (meth) acrylic acid 6 parts of methyl ester, 10 parts of 3 butyl (meth) acrylate, 100 parts of carbitol acetate, 3 parts of dodecanethiol, 3 parts of azobisisobutyronitrile, and heated under nitrogen flow And at 80T: continuous stirring for 5 hours of polymerization to obtain a 50% epoxy group-containing copolymerization solution. Continuing, in the above-mentioned 50% epoxy-group-containing copolymerization solution, 20 parts of TEPIC-S (Nissan Chemical Triglycidyl Trimeric Isocyanate) and p-benzene 8229pifl were added. doc / 015 (Unlined) 33 parts of diphenols 0.05, 50 parts of acrylic acid, 0.2 parts of divinylbenzylamine, reacted at 105 ° C for 24 hours, followed by tetrahydrophthalate The 38 anhydrides and 108 carbitol acetates were reacted at 100 ° C. for 3 hours to obtain a 50% ultraviolet curable resin solution (A-5). [Sixth Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate and NK ESTER TMPT (trade name, Manufactured by Shin Nakamura Chemical Co., Ltd., trimethylol propane trimethacylate molecular weight = 337) 10 parts, 15 methyl (meth) acrylates, 5 third butyl (meth) acrylates, 100 parts of carbitol acetate, 0.1 of dodecanethiol. Two parts, three parts of azobisisobutyronitrile, were heated under nitrogen flow, and continuously stirred at 80 ° C. for 5 hours of polymerization to obtain a 50% epoxy group-containing copolymerization solution. Continuing, in the above-mentioned 50% epoxy-containing copolymerization solution, TEPIC-S (made by Nissan Chemicals, triglycidyltriisocyanate) 10, hydroquinone 0. 05 parts, 43 parts of acrylic acid, and 0.2 parts of divinylbenzylamine were reacted at 105 ° C for 24 hours, followed by 38 parts of tetrahydrophthalic anhydride and 91 parts of carbitol acetate at 100 ° C was reacted for 3 hours to obtain a 50% ultraviolet curable resin solution (A-6). [Seventh Synthesis Example] A four-necked flask equipped with a reflux cooler, a thermometer, a glass tube for nitrogen exchange, and a stirrer was charged with 70 parts of epoxypropyl (meth) acrylate and methyl (meth) acrylate. 20 parts, 10 parts of (3) butyl (meth) acrylate, 100 parts of carbitol acetate, 0, dodecanethiol. 2 parts, 3 parts of azobisisobutyronitrile, 34 8229pifl. doc / 〇l5 (underlined) heating under nitrogen flow, and continuously stirring at 80 ° C. for 5 hours of polymerization to obtain a 50% epoxy group-containing copolymerization solution. Continuing, in the above-mentioned 50% epoxy-group-containing copolymerization solution, hydroquinone 0.05 part, acrylic acid 37 part, and divinylbenzylamine 0. Two parts were reacted at 100 ° C for 24 hours, followed by adding 45 parts of tetrahydrophthalic anhydride and 79 parts of carbitol acetate at 100 ° C for 3 hours to obtain 50. % UV-curable resin solution (E-1). [Eighth Synthesis Example] 214 parts of EPICLON N-680 (trade name: Dainippon Ink Chemical Industry Co., Ltd., cresolnovolac epoxyresin, epoxy equivalent weight: 214) were heated and dissolved in carbitol acetate In the solution of 60 esters, add acrylic acid under stirring: 74, hydroquinone 0. 1 part, phenyl divinyl benzylamine 0. Seven parts were reacted at 90 to 100 ° C for 24 hours according to the usual method. This reaction solution was added to 95 parts of carbitol acetate, and after stirring and cooling, an epoxy acrylate solution was obtained. Then, 76 parts of tetrahydrophthalic anhydride and 87 parts of carbitol acetate were added and reacted at 100 ° C for 3 hours to obtain a 60% ultraviolet curable resin solution (E-2). The mixture obtained by using the ultraviolet curable resin liquids (A-1) to (A-2) and (E-1) to (E-2) produced in the above synthesis example as shown in Table 1 Mixing with a three-axis roller to produce liquid photoresist inks in the first to sixth embodiments and the first to third comparative examples that can be developed with a dilute aqueous alkali solution. 8229pifl. doc / 015 (Unlined) 35 583510 Comparative Example ΓΟ ο Inch 〇o rH rr «H d rH CN ο Inch 〇o oo—H r * -H m ο Inch 〇o 1-HO rH Example vo Ο τ-Η inch 〇〇rH rH to o to ο inch 〇0 OrH o rH inch ο do ——H fH o rH 〇 inch > r > 〇 o rH o rH < N ο inch ο rH o H rH in O fH ο inch d 〇 rrH o Ultraviolet curable resin solution (Al) Ultraviolet curable resin solution (A-2) Ultraviolet curable resin solution (A-3): UV-curable resin solution (A-4) UV-curable resin solution (A-5) UV-curable resin solution (A-6) UV-curable resin solution (E-1) UV-curable resin solution (E-2) Dipentaerythritol hexaacrylate EPICL0N Ν-695 Υ400 TEPIC-S IRGACURE 907 KAYACURE DETX-S Modaflow silica (average particle size: 1 // m) boron sulfate melamine phthalocyanine green SWASOL 1500 8229pifl.d〇c / 015 (Unlined) 36. "EHCLON N-695" (trade name) in Table 1 is a cresol novolac epoxy resin manufactured by Daiyoshi Chemical Industry Co., Ltd. and "YX4000" (trade name) It is an epoxy compound made by Petrochemical Shell Epoxy Co., Ltd. with an epoxy equivalent of 195, and "TEPIC-S" (trade name) is a tripropylene oxide made by Nissan Chemical Industries, Ltd. with an epoxy equivalent of 100. Trimeric isocyanate. Also, "IRGACURE-907" is a photopolymerization initiator (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- made by Ciba-Geigy Corporation. Ketone, 2-methyl -1-[4- (methylthio) phenyl] -2-morpholinopropane -l-〇ne), and "KAYACURE-DETX-S" (trade name), manufactured by Yomoto Chemical Co., Ltd. Photopolymerization initiator (2,4-diethylthio, 2,4-diethylthio), and "Modaflow" (trade name) is a flattening agent manufactured by Monsanto. Also, "SWASOL 1500" (trade name) is a petroleum-based aromatic mixed solution manufactured by Maruzan Petrochemical Co., Ltd. The performances of each photoresist ink and a printed circuit board with a photoresist formed using the same photoresist ink were evaluated by the following test methods. Table 2 shows the results of these evaluations. 37 8229pif 1 .doc / 015 (underlined) 583510 Comparative example m < 3 〇 〇 〇 〇 〇 〇 〇 <] < 3 < X 00 〇 〇 〇 〇 < 3 X X 〇 (N < 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < X 〇〇〇〇〇〇〇〇 < 3 X X 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < < X 〇〇〇〇〇〇〇〇 < <] < 〇 Example 0000000000000000 ◎ ◎ 0000XV0000000000000000 ◎ ◎ ○ × 〇 〇 寸 〇〇〇〇〇〇〇〇〇〇〇 <] 〇〇〇〇〇 ◎◎ ◎ 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 ^ Τί 〇〇〇〇〇 ◎ ◎ 〇 〇〇〇〇 (N 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇〇〇〇〇〇 ◎ ◎ 〇〇K 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 < 00 〇〇 ◎ 〇〇〇〇ffi 〇〇 Test item drying time: 10 minutes: 20 minutes: 30 minutes: 10 minutes: 20 minutes: 30 minutes 1: 40 minutes: 50 minutes: 60 minutes: 70 minutes: 80 minutes 90 minutes exposure: 50mj / cm2 exposure: 150mj / cm2 Adhesiveness of resolving photoresist to substrate __ Adhesiveness m Adhesiveness Pencil hardness Gold-plating resistance Electro-resistance solder 1 time Soldering 5 times Drying time Drying time : Drying time: Drying time 1 Drying time: Drying time = Drying time = Drying time = 1 Drying time: Drying time = Drying time: Surface adhesion pre-drying time allowable range (developing width i degree)! Solder heat resistance «Ρ Shu The characteristics of the test piece with the most appropriate exposure conditions for varying the number of remaining steps 8229pifl.d0C / 015 (without underline) 38 [Performance Evaluation of Photoresist Ink]-Surface Adhesion-Glass Ring of Copper Foil with a Thickness of 35 / zm On the copper-plated laminated plate formed by the oxygen material, a full-screen photoresist ink is applied by screen printing. In order to volatilize the solvent, pre-dry at 80 ° C under the drying conditions of 10, 20 and 30 minutes. For each type of ink, each made separately Three types of test pieces having a pre-dried film with a thickness of 20 films. After that, on the RC HMW680GW (model, pressure-reduced close-type double-sided exposure machine manufactured by ORC), the patterned mask was directly placed on the surface of the pre-dried film, and the pressure-reduced close joint was performed together. After ultraviolet irradiation, the degree of adhesion when the mask was removed under each drying condition was evaluated. The evaluation method of surface adhesion is as follows. X: It is difficult to remove the cover. The cover is damaged and cannot be used again when it is forcibly peeled off. △: After the mask is taken off, there are patches on the pre-dried film. ○: The mask can be easily removed, and there are no marks on the mask on the pre-dried film. One development width (allowable time for pre-drying time) _ On a copper-clad laminate formed of a glass epoxy substrate with a thickness of 35 μm of copper foil, screen-printed photoresist ink is applied on the entire screen. In order to evaporate the solvent, Pre-drying at 80QC with drying conditions of 10, 20, 30, 40, 50, 60, 70, 80, and 90 minutes. For each type of ink, a pre-drying with a film thickness of 20 // m is prepared. Film of 9 types of test pieces. After that, the patterned mask is directly placed in close contact with the surface of the pre-dried film, and each photoresist ink is irradiated with an optimum exposure amount of ultraviolet rays. Next, a 1% 8229pifl.doc / 015 (underlined) 39 aqueous sodium carbonate solution was used as a developing solution, and the developability and pattern formation state were observed. The evaluation method of the development width is as follows. X: Removal of the unexposed portion of the development is difficult, and the pattern cannot be formed. Δ: The development of the unexposed part takes a long time, and the pattern of the fine pattern part cannot be formed. ○: The unexposed part is easy to develop and a clear pattern can be obtained. One remaining step: on a copper-plated laminate formed of a glass epoxy substrate with a copper foil thickness of 35 / zm, screen-printed photoresist ink was applied in full screen printing, in order to volatilize the solvent at 80 ° C Pre-drying was performed under the drying conditions with a drying time of 20 minutes, and test pieces having a pre-dried film with a film thickness of 20 // m were prepared for each type of ink. After that, on the ORC HMW680GW (model, pressure-reduced and tight-type double-sided exposure machine manufactured by Oak Manufacturing Co., Ltd.), the step PHOTEC21 section (exposure test mask made by Hitachi Chemical Industry Co., Ltd.) was directly arranged on the pre-dried film surface, and they were jointly The pressure-tight sealing was performed, and ultraviolet rays of 50 and 150 mJ / cm2 were irradiated respectively. Then, development was performed using a 1% sodium carbonate aqueous solution as a developing solution to obtain the number of steps after development to obtain a standard for exposure sensitivity. [Performance Evaluation of Printed Circuit Board] In order to confirm the performance of the printed circuit board manufactured by each photoresist ink, a test piece formed by the following steps 1 to V was manufactured. 1 < Coating process> A copper-plated laminate formed on a glass epoxy substrate of a copper foil with a thickness of 35 / zm, and a patterned printed circuit board previously etched to print a comprehensive coating solution on a screen. Photoresist ink to obtain a photoresist 8229pifl.dOC / 015 (underlined) 40 ink layer on the substrate surface. II < Pre-drying process > After the coating step, the film was dried at 8 CTC for 20 vol. The solvent in the photoresist ink layer on the substrate surface was pre-dried for 15 minutes to obtain a pre-111 with a film thickness of 20 / zm. < Exposure Step Process > ^ The patterned mask is directly placed in close contact with the pre-dried film, and the surface is irradiated with ultraviolet rays of the optimal exposure amount to each water. < Development process> Exposure of the cage. In the film, a 1% sodium carbonate aqueous solution was removed as a shadow, and the substrate was exposed and hardened. After the exposure process, pre-drying was performed as a developing solution, and a pattern of a pre-dried film showing the unexposed portion was formed. ~ v < Post-heat roasting process> Will have pre-dried leather tags. 〇 The hearty substrate is heated at 150 ° C for 30 minutes,

The dry film is hardened, and the test piece has a photoresist formed by the hardened film. '. The test piece obtained by evaluating the above-mentioned process was performed by the following methods: a resolvability, an observing line width and a concentric circle with a line width of 40 mm, and a pattern state of the formed pattern . The evaluation method of resolution is as follows. X: Cannot form a pattern. A: A pattern can be formed, but a part of the pattern is defective. 8229Pifl.d0C / 015 (Underlined) 41 °: A clear pattern can be obtained. -Solder heat resistance-LONCO 3355-1 1 (trade name, water-soluble flux from London Chemical Company) was used as the flux. First apply flux to the test piece, then immerse this in a molten solder bath at 260 ° C for 15 seconds, and then wash it with water. After one cycle or five cycles of this cycle, the degree of whitening of the surface was observed. In addition, the cross-cut transparent tape peeling test was performed in accordance with JIS D 0202, and the change in the adhesion state was observed. The evaluation method of surface whitening is as follows. X: Significant whitening. △: Whitening occurred. 〇: Only slight whitening occurred. :: No whitening occurred. The method of evaluating the adhesion is as follows. X: The photoresist swells and peels before the cross-cut test. △: Partial peeling occurred at the cross-cut portion when the tape was peeled. 〇. / · No peeling occurred in the cross section. :: No change occurred at all. —Pencil Hardness— The pencil hardness is measured and evaluated in accordance with JIS K 5400, and other items are evaluated by ordinary methods. —Mineral gold resistance— Using commercially available electroless nickel plating baths and electroless gold plating baths, the test pieces were plated with gold and the tightness of the coating film was observed. The evaluation method of the gold plating resistance is as described in 8229pifl.doc / 015 (underlined) 42 below. X: The coating film floats and peels off when the tape is peeled. △: The appearance is not changed, but some peeling occurs when the tape is peeled. ○: No change occurred at all. An electro-corrosion resistance- Use a comb electrode B coupon of IPC B-25 instead of a test piece, make a printed circuit board for evaluation under the above conditions, and apply a bias voltage of DC 100 volts to the comb electrode at 40, 90% R. After 500 hours under HL conditions, the presence or absence of migration was evaluated and evaluated. The evaluation method of the electric resistance is as follows. X: Confirmation of migration. △: It was confirmed that migration occurred only slightly. 〇: It was confirmed that migration did not occur at all. As is clear from Tables 1 and 2, compared with the first comparative example to the third comparative example, the development width, solder heat resistance, and gold plating resistance of the first to sixth examples are higher, and they are more excellent. Substrate adhesion and galvanic corrosion resistance. Industrial Applicability As described above, according to the present invention, it is possible to provide an ultraviolet curable resin composition having excellent developability, resolution, development width, and heat resistance. The photoresist ink contained in this composition can be developed with a dilute aqueous alkali solution, and can be formed on a substrate such as a printed circuit board, showing excellent substrate adhesion and resistance to electric corrosion, and exhibiting heat resistance and resistance. Gold-plated photoresist. 8229pifl.doc / 015 (underlined) 43

Claims (1)

Patent application scope 1 · A kind of ultraviolet curable resin composition, which is characterized by being composed of the following components: (A) an ethylenically unsaturated monomer having an epoxy-based ethylenically unsaturated monomer fluorene An epoxy-group-containing polymer (a) and an epoxy-group-containing compound containing a trimeric isocyanate derivative (b) containing an epoxy group, and an ethylenically unsaturated monomer having a carboxyl group. A UV-curable resin obtained by reacting an intermediate product with a saturated or unsaturated polybasic acid anhydride (d), the UV-curable resin excluding organic solvents in the diluent (D) 10% to 80% of the total amount of the ultraviolet curable resin composition; (B) a monoepoxy compound having two or more epoxy groups in a molecule, and the epoxy compound (B) is a diluent ( D) 0.1% to 50% of the total amount of the ultraviolet curable resin composition except organic solvents; (C) — a photopolymerization initiator, the photopolymerization initiator (c) is a diluent (D) UV-curable resin except organic solvents 0.1% ~ 30% of the total composition; and (D) -diluent. 2. The ultraviolet curable resin composition according to item 1 of the scope of the patent application, wherein the ethylenically unsaturated monomer component includes the ethylenically unsaturated monomer ⑴ and an ethylenically unsaturated monomer capable of copolymerization. Body (Π). 3. The ultraviolet-curable resin composition according to item 1 of the scope of the patent application, wherein the ethylenically unsaturated monomer component includes a compound having two or more ethylenically unsaturated groups in one molecule (out) . 8229pifl.doc / 015 (Unlined) 44 4. The UV-curable resin composition as described in item 3 of the scope of patent application, wherein the ethylenically unsaturated monomer component includes the ethylenically unsaturated monomer, (i) One or more compounds (iii) and a monoethylenically unsaturated monomer (Π) which can be copolymerized in the molecule. 5. The ultraviolet-curable resin composition according to item 1 of the scope of the patent application, wherein the ultraviolet-curable resin (A) is obtained by adding a saturated or an unsaturated polybasic acid anhydride (d) to the intermediate product, Then, an isocyanate compound (e) having at least two isocyanate groups in the molecule is reacted to form ^ 6. The ultraviolet curable resin composition according to item 1 of the patent application scope, wherein the ethylenically unsaturated monomer ⑴ Includes monoglycidyl (meth) acrylate. 7. The ultraviolet-curable resin composition according to item 1 of the scope of the patent application, wherein the epoxy-containing trimeric isocyanate derivative (b) includes a trioxypropyltrimeric isocyanate. 8. The ultraviolet curable resin composition according to item 3 of the scope of patent application, wherein the compound (iii) comprises a di (meth) acrylate. 9. The ultraviolet curable resin composition according to item 3 of the scope of the patent application, wherein the compound (iii) is -di (meth) acrylate having at least one hydroxyalkylene unit. 10. The ultraviolet curable resin composition according to item 3 of the scope of patent application, wherein the content of the compound (m) is the total amount of the ethylenically unsaturated monomer component used in the epoxy-containing polymer (a). 0.1% to 1Q% in stomach. 11. A substrate having the ultraviolet-hard 8229pifl.doc / 015 (without underline) as described in item 1 of the scope of patent application 45 583510 chemical resin composition. 12. A photoresist ink containing a UV-curable resin composition as described in item 1 of the scope of patent application. 13. A printed circuit board having a hardened film of a photoresist ink as described in claim 12 of the scope of patent application. 14. A dry film formed by drying a film obtained by drying the ultraviolet-curable resin composition as described in item 1 of the scope of patent application, formed on the surface of a support. 15. A dry film formed by forming a film obtained by drying the photoresist ink as described in item 12 of the patent application range on the surface of a support. 8229pifl.doc / 015 (underlined) 46