IIIHI||||||||III US005304628A United States Patent (19) (11) Patent Number: 5,304,628 Kinoshita et al. (45) Date of Patent: Apr. 19, 1994 (54) RADIATION-CURING RESIN (56) References Cited COMPOSITION U.S. PATENT DOCUMENTS 3,280,078 10/1966 Hostettler et al. .................. 522/163 (75) Inventors: Masashi Kinoshita, Tokyo; Hidenobu 4,500,704 2/1985 Kruper, Jr. et al. o Ishikawa, Chiba, both of Japan 4,686,276 8/1987 Myers ................. 4,808,658 2/1989 Walz et al. ..... - . 528/49 73) Assignee: Dainippon Ink and Chemicals, Inc., 4,948,700 8/1990 Maeda et al. ...... 522A101 Tokyo, Japan 5, 100,767 3/1992 Yanagawa et al. 522/100 5,102,702 4/1992 Grundke et al........ ... 525/526 (21) Appl. No.: 924,748 5,175,231 12/1992 Rappaport et al. ................. 528/106 Primary Examiner-Susan Berman 22 Filed: Aug. 4, 1992 Attorney, Agent, or Firm-Armstrong, Westerman, 30 Foreign Application Priority Data Hattori, McLeland & Naughton (57) ABSTRACT Aug. 5, 1991 JP Japan .................................. 3-195340 A radiation-curing resin composition comprising (A) a 51) Int. Cl......................... C08F 2/50; C08G 63/52; resin having a carboxylic acid group and an unsaturated C08G 18/OO double bond and (B) a compound containing a cyclo 52 U.S.C. ...................................... 528/370; 528/44; carbonate group. The composition is excellent in stabil 528/75; 528/306; 522/16; 522/97; 522/100; ity and curing properties and provides a cured film 522/101; 522/163 excellent in water resistance, solvent resistance, chemi 58) Field of Search ..................... 522/163, 92,93, 94, cal resistance, and heat resistance. 522/100, 101, 60, 68, 16, 97; 528/370, 44, 75, 306; 525/485, 524,526 2 Claims, No Drawings 5,304,628 1. 2 group and an unsaturated double bond, particularly a RADIATION-CURING RESIN COMPOSITION reaction product obtained from a compound containing an epoxy group, a compound containing a functional FIELD OF THE INVENTION group reactive with the epoxy group of said epoxy This invention relates to a novel radiation-curing group-containing compound and an unsaturated double resin composition. Specifically, it relates to a radiation bond, and a compound containing an acid anhydride curing resin composition comprising (A) a resin having group, and (B) a cyclocarbonate-containing compound a carboxylic acid group and an unsaturated double bond is an extremely stable one-pack type radiation-curing and (B) a compound containing a cyclocarbonate resin composition which, on ultraviolet curing followed group. Particularly, it relates to a radiation-curing resin 10 by postcure, provides a cured film satisfying all the composition comprising (A) a reaction product ob above-described performance requirements. The pres tained from a compound containing an epoxy group, a ent invention has been completed based on this finding. compound containing a functional group reactive with The present invention provides a radiation-curing the epoxy group of said epoxy group-containing com resin composition comprising, as essential components, pound and a reactive unsaturated double bond, and a 15 (A) a resin having a carboxylic acid group and an unsat compound containing an acid anhydride group and (B) urated double bond (hereinafter referred to as com a compound containing a cyclocarbonate group. pound (A)) and (B) a compound containing a cyclocar The radiation-curing resin composition according to bonate group (hereinafter referred to as compound (B)), the present invention cures on irradiation with so-called and particularly the present invention provides (A) a radiation, such as ultraviolet light and electron beam, 20 reaction product obtained from a compound containing and is suitable for a variety of uses as a coating com an epoxy group, a compound containing a functional pound, a printing ink, an adhesive, etc. The resin com group reactive with the epoxy group of said epoxy position is particularly suitable for the use in which group-containing compound and an unsaturated double durability is required after subjecting to a pattern mak bond, and a compound containing an acid anhydride ing step by development. 25 group. BACKGROUND OF THE INVENTION DETAILED DESCRIPTION OF THE Known radiation-curing resins, particularly resins INVENTION which cures on radical polymerization, include unsatu Compound (A) having a carboxylic acid group and rated polyester resins, vinyl ester resins (epoxy-acrylate 30 resins), various acrylate oligomers, and diallyl phthalate an unsaturated double bond which can be preferably prepolymers. These resins are widely employed with used in the present invention is a reaction product ob their respective characteristics being taken advantage of tained from a compound containing an epoxy group, a in the respective field of application. compound containing a reactive unsaturated double With the recent broadening of uses of radiation-cur 35 bond, and a compound containing an acid anhydride ing resin compositions, demands for higher perfor group, or a reaction product obtained from a compound mance properties have ever been increasing. However, containing an epoxy group, a compound containing an there has not yet been obtained a highly practical radia unsaturated monocarboxylic acid, and a compound tion-curing resin composition which satisfies all the containing an acid anhydride group. requirements. More specifically, while not limiting, resin (A) in Further, with the recent broadening of uses of radia cludes those having a structure resulting from the reac tion-curing resin compositions, demands as pattern tion between a compound containing an epoxy group making materials have been increasing. As alkali deve (hereinafter referred to as compound (a-1)) and an un lopment-type pattern making materials, those contain saturated monocarboxylic acid (hereinafter referred to ing a carboxylic acid group have been generally used. 45 as compound (a-2)). However, when the alkali development-type pattern Typical examples of compound (a-1) include glycidyl making materials containing a carboxylic acid group are ether type epoxy resins, such as a bisphenol A type used especially as electric materials, the carboxylic acid epoxy resin obtained by reacting bisphenol A and epi group affects the water resistance and the chemical chlorohydrin in the presence of an alkali and an epoxy resistance. In order to remove such a defect, there has 50 resin obtained by using brominated bisphenol A in place been proposed to use a resin composition containing an of bisphenol A in the above reaction. epoxy compound together with the alkali development In addition, novolak type epoxy resins, phenol novo type pattern making material containing a carboxylic lak type epoxy resins, and orthocresol novolak type acid group wherein a carboxylic acid is consumed by epoxy resins, which are obtained by reacting a novolak postcure. However, the conventional resin composition 55 resin with epichlorohydrin, are also used as compound which contains epoxy compound has had serious de (a-1). fects for reducing pattern developing property due to Also included in compound (a-1) are bisphenol F type poor stability. epoxy resins obtained by reacting bisphenol F and epi chlorohydrin, brominated epoxy resins derived from SUMMARY OF THE INVENTION tetrabromobisphenol A, cyclic aliphatic epoxy resins An object of the present invention is to provide an having a cyclohexene oxide group, a tricyclodecene extremely practical radical-curing resin which is excel oxide group or a cyclopentene oxide group; glycidyl lent in water resistance, solvent resistance, chemical ester resins, such as diglycidyl phthalate, diglycidyl resistance, heat resistance, and curing properties, and a tetrahydrophthalate, diglycidyl hexahydrophthalate, resin composition which has excellent stability. 65 diglycidyl p-hydroxybenzoate, and dimeric acid glyci As a result of extensive investigations, the inventors dyl esters; glycidylamine resins, such as tetraglycidyl have found that a combination of (A) a specific radia diaminodiphenylmethane, triglycidyl-p-aminophenol, tion-curing resin, i.e., a resin having a carboxylic acid diglycidylaniline, diglycidyltoluidine, tetraglycidyl-m- 5,304,628 3 4. xylylenediamine, diglycidyltribromoaniline, and tetra reactive diluents, organic solvents, and catalysts of glycidylibisaminomethylcyclohexane; hydantoin type epoxy ring opening. epoxy resins having a glycidylated hydantoin ring; and While a broad range of reactive diluents, from mono triglycidyl isocyanurate having a triazine ring. functional to polyfunctional, may be employed, typical These epoxy group-containing compounds (a-1) may examples of usable reactive diluents are 2-hydroxyethyl be used either individually or in combination of two or (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2 more thereof. ethylhexyl (meth)acrylate, N-vinylpyrrolidone, 1 Typical examples of compound (a-2) include acrylic vinylimidazole,isobornyl (meth)acrylate, tetrahydrofur acid, methacrylic acid, crotonic acid, and cinnamic furyl (meth)acrylate, carbitol (meth)acrylate, phenoxy acid, with acrylic acid being preferred. These con 10 ethyl (meth)acrylate, dicyclopentadiene (meth)a- pounds may be used either individually or in combina crylate, 1,3-butanedioldi(meth)acrylate, 1,6-hexanediol tion of two or more thereof. di(meth)acrylate, polyethylene glycol di(meth)acrylate, Typical examples of the compound containing an hydroxypivalic esters neopentylglycol di(meth)acry acid anhydride group include acid anhydrides of maleic late, trimethylolpropane