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 tri(meth)acrylate, pentaeryth acid, fumaric acid, itaconic acid, citraconic acid, tetra 5 ritol tri(meth)acrylate, pentaerythritol tetra(meth)acry hydrophthalic acid, HET acid, hymic acid, chlorendic late, and dipentaerythritol hexa(meth)acrylate. acid, dimeric acid, adipic acid, succinic acid, alkenyl Typical but non-limiting examples of usable organic succinic acids, sebacic acid, azelaic acid, 2,2,4-trime solvents include aromatic hydrocarbons, e.g., toluene thyladipic acid, terephthalic acid, 2-potassium sul and xylene, ketones, e.g., methyl ethyl ketone, methyl foterephthalic acid, 2-sodium sulfoterephthalic acid, isobutyl ketone, and cyclohexanone; esters, e.g., methyl isophthalic acid, 2-potassium sulfoisophthalic acid, 2 acetate, ethyl acetate, and butyl acetate; alcohols, e.g., sodium sulfoisophthalic acid, and 5-sodium sulfoisoph methanol, ethanol, propanol, and butanol; aliphatic thalic acid; orthophthalic anhydride, 4-sulfophthalic hydrocarbons, e.g., hexane and heptane; and also cello anhydride, 1,10-decamethylenedicarboxylic acid anhy solve acetate, carbitol acetate, dimethylformamide, and dride, muconic anhydride, oxalic anhydride, malonic 25 tetrahydrofuran. anhydride, glutaric anhydride, trimellitic anhydride, The term "radiation' as used herein means ionizing hexahydrophthalic anhydride, tetrabromophthalic an radiations and light inclusively, such as electron beams, hydride, methylcyclohexenetricarboxylic acid anhy a-rays, 3-rays, y-rays, X-rays, neutron rays, and ultravi dride, and pyromellitic anhydride. olet light. Typical but non-limiting specific examples of com 30 Where ultraviolet light are used as radiations for pound (B) include those obtained by converting epoxy curing the resin composition of the present invention, it groups of the above-mentioned epoxy group-containing is preferably to use a photo initiator which is dissociated compounds (a-1), e.g., tris(2,3-epoxypropyl) isocyanu by ultraviolet light having a wavelength of from 1,000 rate (trifunctional epoxy compound having a triazine to 8,000 A to generate a radical. Any of commonly ring), to cyclocarbonate groups. 35 employed photo initiators may be used. Typical exam The compounds obtained by converting epoxy ples of usable photo initiators are acetophenones, benzo groups to cyclocarbonate groups can generally be pro phenone, Michler's ketone, benzil, benzoin benzoate, duced by dissolving an epoxy resin in propylene car benzoin, benzoin methyl ethers, benzyl dimethyl ketal, bonate, blowing carbon dioxide (CO2) into the solution, a-acyloxime ester, thioxanthones, anthraquinones, and and then allowing to react by using a tertiary amine derivatives thereof. such as dimethylbutylamine as a catalyst at usually from The photo initiator may be used in combination with 100 to 120 C. for 3 to 6 hours. a known photosensitizers. Typical examples of usable In the resin composition of the present invention, the photosensitizers include amine compounds, urea com proportion of compound (A) to compound (B) is set so pounds, sulfur-containing compounds, phosphorus-con that the cyclocarbonate group equivalent in compound 45 taining compounds, chlorine-containing compounds, (B) to the carboxylic acid group equivalent in com nitriles, and other nitrogen-containing compounds. pound (A) is 20/80 to 80/20, preferably 25/75 to 55/45 The catalyst for epoxy ring opening includes amine (equivalent ratio). If the ratio of the equivalent of car compounds, acid anhydrides, inidazole derivatives, boxylic acid groups to the equivalent of cyclocarbonate Lewis acids, Lewis acid salts, and phosphorus con groups is less than 20/80, heat resistance is decreased, 50 pounds. and if it is larger than 80/20, the resulting resin composi The radiation-curing resin composition of the present tion is insufficient in water resistance and alkali resis invention is usually cured as such by irradiation with tance. radiation or actinic radiation using the above-mentioned The radiation-curing resin composition of the present energy source and then postcured by heating. invention is of one-pack type and excellent in storage 55 The present invention is now illustrated in greater stability. The UV-non-irradiated resin composition of detail with reference to Synthesis Examples and Exam the invention, which is easily soluble in both alkaline ples, but it should be understood that the present inven solution and solvents, provides on UV irradiation fol tion is not construed as being limited thereto. All the lowed by postcure a cured film excellent in water resis parts and percents are by weight unless otherwise indi tance, solvent resistance, chemical resistance, and heat cated. resistance. If desired, the radiation-curing resin composition SYNTHESIS EXAMPLE 1 comprising resin (A) and compound (B) may further In a flask equipped with a thermometer, a stirrer, and contain other known epoxy compounds and/or com a reflux condenser were charged 213 g of a cresol novo monly employed additives as far as the purposed char 65 lak type epoxy resin having an epoxy equivalent of 213 acteristics, especially storage preservability, water resis ("Epiclon N-695' produced by Dainippon Ink and tance, solvent resistance, chemical resistance, and heat Chemicals, Inc.), 72.0 g of acrylic acid, and 1.2 g of resistance are not impaired. Usable additives include triphenylphosphine. The mixture was allowed to react 5,304,628 5 6 at 110' C. until the acid value became 3 or less. Thereaf -continued ter, 152 g of tetrahydrophthalic anhydride was added to Resin (B-1) 30 parts the reaction mixture, and the reaction was further con 1-Hydroxyhexyl phenylketone 3 parts ducted at 100 C. until the acid value reached 130 to Imidazoleamine 1 part obtain a resin having a carboxylic acid group and an 5 Methyl ethyl ketone 30 parts unsaturated double bond. The resulting resin was desig nated resin (A-1). The resulting coating composition was evaluated for SYNTHESIS EXAMPLE 2 storage stability according to the following test method. Tris(2,3-epoxypropyl) isocyanurate was treated with 10 1) Test on Stability carbonic acid gas to convert the epoxy group to a cy clocarbonate group in a usual manner to obtain a car The coating composition was preserved in a thermo bonate-containing triglycidyl isocyanurate. The result stat set at 80' C. with light shielded, and any change of ing resin was designated resin (B-1). the solution state was observed and rated as follows. 15 Excellent: No change after 5 hrs' preservation SYNTHESIS EXAMPLE 3 Good: No change after 3 hrs' preservation In a flask equipped with a thermometer, a stirrer, and Medium: Gelation observed after 3 hrs' preservation a reflux condenser were charged 187 g of a bisphenol A Poor: Gelation observed after 1 hr's preservation type epoxy resin having an epoxy equivalent of 187 The coating composition was coated on a wet-sanded ("Epiclon 850” produced by Dainippon Ink and Chemi 20 tinplate to a thickness of 20 um. The wet coating was cals, Inc.), 72.0 g of acrylic acid, and 1.2 g of triphenyl cured by ultraviolet irradiation and then postcured by phosphine. The mixture was allowed to react at 110° C. heating under the respective conditions shown in the until the acid value became 3 or less. Thereafter, 152 g following test methods. Each of the uncured wet coat of tetrahydrophthalic anhydride was added to the reac ing film, the UV-cured film (before postcure) and the tion mixture, and the reaction was further conducted at 25 postcured film was evaluated according to the follow 100 C. until the acid value reached 137 to obtain a resin ing test methods. having a carboxylic acid group and an unsaturated dou ble bond. The resulting resin was designated resin (A-2). 2) Test on Curing Properties The wet coating film was dried in hot air at 80 C. for SYNTHESIS EXAMPLE 4 30 15 minutes and then passed 15 cm below a medium-pres In a flask equipped with a thermometer, a stirrer, and sure mercury lamp (80 W/cm) at a speed of 50 m/min. a reflux condenser were charged 213 g of a cresol novo lak type epoxy resin having an epoxy equivalent of 213 The number of passes required for curing was recorded. ("Epiclon N-695'), 72.0 g of acrylic acid, and 1.2 g of 3) Test on Resistance to Water, Solvent, or Alkali triphenylphosphine. The mixture was allowed to react 35 at 110' C. until the acid value became 3 or less. Thereaf The wet coating film was irradiated with ultraviolet ter, 76.0 g of tetrahydrophthalic anhydride was added light emitted from a 80 W/cm medium-pressure mer to the reaction mixture, and the reaction was further cury lamp placed 15 cm above for 60 seconds and then conducted at 100 C. until the acid value reached 76 to postcured in a heating furnace at 140 C. for 40 minutes. obtain a resin having a carboxylic acid group, an unsatu The postcured film was given 40 rubbings with gauze rated double bond, and a hydroxyl group. The resulting impregnated with deionized water, acetone, or a 10% resin was designated compound (m-1). sodium hydroxide aqueous solution. The loss in film In a separate flask equipped with a thermometer, a thickness was measured and rated as follows. stirrer, and a reflux condenser were charged 1 mol of 45 Excellent: 0 to 5 um tolylene diisocyanate and 1 nol of 2-hydroxyethyl acry Good: 5 to 10 um late, and the mixture was subjected to a urethanation Medium: 10 to 15 um reaction in a usual manner to obtain an unsaturated Poor: 15um or more urethane compound having an unreacted isocyanate group at the urethane acrylate-terminated end group. 4) Test on Heat Resistance The resulting compound was designated compound 50 The wet coating film was dried in hot air at 80' C. for (u-1). 15 minutes and then passed 10 times under a medium In a separate flask equipped with a thermometer, a pressure mercury lamp (80 W/cm) placed 15 cm above stirrer, and a reflux condenser was added 285g of com at a speed of 50 m/min. The thus UV-cured film was pound (n-1), and 290 g of compound (u-1) was then postcured by heating in a furnace at 140 C. for 40 added thereto slowly to conduct a urethanation reac 55 minutes, followed by allowing to cool to room tempera tion until the unreacted isocyanate group disappeared. ture. The cured film was placed in a heating furnace at There was obtained a compound having a carboxylic 200 C. for 40 seconds. Immediately thereafter, gauze acid group and an unsaturated double bond. This com was stuck on the coating film. After cooling, the gauze pound was designated resin (A-3). was stripped off, and any change of the coating film was EXAMPLE 1. observed with the naked eye. The changes were rated as follows. Resin (A-1) prepared in Synthesis Example 1 was Excellent: No change observed at all. mixed with other components as shown below, fol Good: Slight traces of gauze observed. lowed by thoroughly stirring to prepare a coating com 65 Poor: The coating film melted and peeled away to position. gether with gauze. The results of the evaluation are shown in Table 1 Resin (A-1) 100 parts below. 5,304,628 7 8 with the same amount of a bisphenol A type epoxy resin EXAMPLE 2 (“RE-310S' produced by Nippon Kayaku Co., Ltd.; A coating composition was prepared in the same epoxy equivalent=185). The resulting coating composi manner as in Example i, except for replacing resin (A-1) tion was coated and cured in the same manner as in with resin (A-2) obtained in Synthesis Example 3. The 5 Example 1, and evaluation was made in the same man resulting coating composition was coated and cured in ner as in Example 1. The results obtained are shown in the same manner as in Example 1. Table 1. TABLE 1. Comparative Comparative Example Example Example Example Example Example 2 3 4. 2 Stability Excellent Excellent Excellent Excellent Poor Medium Curing Properties 2 1 1 2 2 5 (times) Water Resistance Excellent Excellent Excellent Excellent Medium Mediurn Solvent Resistance Excellent Excellent Excellent Excellent Good Poor Akali Resistance Excellent Excellent Excellent Excellent Good Poor Heat Resistance Excellent Good Excellent Excellent Good Poor The coating composition and the cured film were As is apparent from the results in Table 1, the radia evaluated in the same manner as in Example 1. The 20 tion-curing resin composition according to the present results obtained are shown in Table i. invention can be cured with radiation either at room temperature or even under heating. The composition is EXAMPLE 3 a one-pack type coating composition exhibiting excel A coating composition was prepared in the same lent stability owing to the structure of the cyclocarbon manner as in Example 1, except for replacing resin (A-1) 25 ate compound. Further, the structure based on the with resin (A-3) obtained in Synthesis Example 4. The epoxy compound and the cyclocarbonate compound resulting coating composition was coated and cured in makes the composition excellent in not only curing the same manner as in Example i. properties but resistance to water, solvents and chemi The coating composition and the cured film were cals as well as heat resistance. Accordingly, the resin evaluated in the same manner as in Example l. The 30 composition of the present invention is of high use in results obtained are shown in Table 1. various applications. As described and demonstrated above, the radiation EXAMPLE 4 curing resin composition of the present invention is of Resin (A-1) prepared in Synthesis Example 1 was one-pack type having excellent stability and provides a mixed with other components as shown below, fol 35 cured film excellent in water resistance, solvent resis lowed by thoroughly stirring to prepare a coating corn tance, chemical resistance, and heat resistance. Thus, position. the composition is very useful in a wide variety of appli cations as coating compounds, printing inks, adhesives, and so on. Resin (A-1) 100 parts While the invention has been described in detail and Resin (B-1) 40 parts 1-Hydroxyhexyl phenyl ketone 3 parts with reference to specific examples thereof, it will be Trimethylolpropane triacrylate 20 parts apparent to one skilled in the art that various changes Methyl ethyl ketone 20 parts Imidazoleanine 3 parts and modifications can be made therein without depart 45 ing from the spirit and scope thereof. What is claimed is: The resulting coating composition was coated and 1. A radiation-curing resin composition comprising, cured in the same manner as in Example 1, and evalua as essential components, tion was made in the same manner as in Example 1. The (A) a resin having a carboxylic acid group and an results obtained are shown in Table 1. unsaturated double bond, said resin being a reac SO tion product obtained from a compound containing COMPARATIVE EXAMPLE 1 an epoxy group, a compound containing a reactive A coating composition was prepared in the same unsaturated double bond, and a compound contain manner as in Example 1, except for replacing resin (B-1) ing an acid anhydride group, and with the same amount of a cresol novolak type epoxy (B) a compound containing a cyclocarbonate group. resin ("EOCN' produced by Nippon Kayaku Co., Ltd.; 55 2. A radiation-curing composition comprising, as epoxy equivalent=220). The resulting coating composi essential components, tion was coated and cured in the same manner as in (A) a resin having a carboxylic acid group and an Example 1, and evaluation was made in the same man unsaturated double bond, said resin being a reac ner as in Example 1. The results obtained are shown in 60 tion product obtained from a compound containing Table . an epoxy group, an unsaturated monocarboxylic acid, and a compound containing an acid anhy COMPARATIVE EXAMPLE 2 dride group, and A coating composition was prepared in the same (B) a compound containing a cyclocarbonate group. a manner as in Example 1, except for replacing resin (B-1) 65