JPH01289819A - Actinic radiation-curable unsaturated resin composition - Google Patents
Actinic radiation-curable unsaturated resin compositionInfo
- Publication number
- JPH01289819A JPH01289819A JP11989988A JP11989988A JPH01289819A JP H01289819 A JPH01289819 A JP H01289819A JP 11989988 A JP11989988 A JP 11989988A JP 11989988 A JP11989988 A JP 11989988A JP H01289819 A JPH01289819 A JP H01289819A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin
- unsaturated
- meth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 11
- 239000002253 acid Substances 0.000 claims abstract description 38
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 18
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 16
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 abstract description 40
- 229920005989 resin Polymers 0.000 abstract description 40
- 238000000576 coating method Methods 0.000 abstract description 26
- 239000011248 coating agent Substances 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- -1 vinyl compound Chemical class 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000006386 neutralization reaction Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- ZGHFDIIVVIFNPS-UHFFFAOYSA-N 3-Methyl-3-buten-2-one Chemical compound CC(=C)C(C)=O ZGHFDIIVVIFNPS-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- WXUKWXKGNXTMLW-UHFFFAOYSA-N 2-nitro-9h-fluorene;(phenyldisulfanyl)benzene Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1.C1=CC=C2C3=CC=C([N+](=O)[O-])C=C3CC2=C1 WXUKWXKGNXTMLW-UHFFFAOYSA-N 0.000 description 1
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
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- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- HSOOVEKLGOIEFF-UHFFFAOYSA-N ethenyl nitrate Chemical class [O-][N+](=O)OC=C HSOOVEKLGOIEFF-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005650 polypropylene glycol diacrylate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は活性エネルギー線硬化型不飽和樹脂組成物に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an active energy ray-curable unsaturated resin composition.
（従来の技術及びその課題）
従来、活性エネルギー線硬化型不飽和樹脂組成物はすで
に種々のものが開発され、これらは塗装、複合材、電子
部品等の分野で広く利用されているが、近時それらの活
性エネルギー線硬化型不飽和樹脂組成物の一つとしてビ
ニル樹脂を主体とする樹脂組成物の開発が試みられてい
る。現在ビニル樹脂組成物を主体とする組成物として、
高酸価ビニル樹脂と脂肪族エポキシ基含有ビニル化合物
とを反応させて得られるものが知られているが、このも
のは高温での長期貯蔵安定性が劣り、しかも該組成物か
ら形成された被膜は被塗物に対する密着性及び耐水性が
劣り、いまだ・・に充分満足すべき性質を示すには至っ
ていない。(Prior art and its problems) Various active energy ray-curable unsaturated resin compositions have been developed and are widely used in the fields of coatings, composite materials, electronic parts, etc.; Attempts have been made to develop a resin composition based on vinyl resin as one of these active energy ray-curable unsaturated resin compositions. Currently, as a composition mainly composed of vinyl resin compositions,
A product obtained by reacting a high acid value vinyl resin with an aliphatic epoxy group-containing vinyl compound is known, but this product has poor long-term storage stability at high temperatures, and the coating formed from the composition has poor adhesion to coated objects and water resistance, and has not yet shown sufficiently satisfactory properties.
（課題を解決するための手段）
本発明は上記した問題点を解決するために鋭意研究を行
なった結果、活性エネルギー線硬化型不飽和樹脂組成物
として高酸価アクリル系樹脂と脂環式エポキシ基含有不
飽和化合物との反応物の水性化物を用いると上記した問
題点を全て解消することを見い出し、本発明を完成する
に至った。(Means for Solving the Problems) As a result of intensive research in order to solve the above-mentioned problems, the present invention has developed an active energy ray-curable unsaturated resin composition consisting of a high acid value acrylic resin and an alicyclic epoxy resin. It has been discovered that all of the above problems can be solved by using an aqueous product of the reaction product with a group-containing unsaturated compound, and the present invention has been completed.
即ち、本発明は高酸価アクリル系樹脂と脂環式エポキシ
基含有不飽和化合物とを反応させて得られる酸基及び不
飽和基を含有する反応物の水性化物であることを特徴と
する活性エネルギー線硬化型不飽和樹脂組成物に関する
。That is, the present invention is an aqueous product of a reactant containing an acid group and an unsaturated group obtained by reacting a high acid value acrylic resin with an alicyclic epoxy group-containing unsaturated compound. The present invention relates to an energy ray curable unsaturated resin composition.
本発明組成物で使用する高酸価アクリル系樹脂は、 （
メタ）アクリル酸、２−カルボキシエチル（メタ）アク
リレート、２−カルボキシプロピル（メタ）アクリレー
ト、（無水）マレイン酸などのエチレン性不飽和酸を必
須成分とし、これに（メタ）アクリル酸のエステル類［
例えばメチル（メタ）アクリレート、エチル（メタ）ア
クリレート、プロピル（メタ）アクリレート、ブチル（
メタ）アクリレート、２−エチルヘキシル（メタ）アク
リレート、ステアリル（メタ）アクリレート、ヒドロキ
シエチル（メタ）アクリレート、ヒドロキシプロピル（
メタ）アクリレートなど］ ：ビニル芳香族化合物［例
えばスチレン、α−メチルスチレン、ビニルトルエン、
ｐ−クロルスチレンなど］ ；アミド系不飽和化合物［
例えば（メタ）アクリルアミド、ダイア七トンアクリル
アミド、Ｎ−メチロールアクリルアミド、Ｎ−ブトキシ
メチルアクリルアミドなと］ ；ポリオレフィン系化合
物［例えばブタジェン、インプレン、クロロブレンなど
］及びその他［例えば（メタ）アクリロニトリル、メチ
ルイソプロペニルケトン２酢酸ビニル、ベオパモノマー
（シェル化学製品）、ビニルプロピオネート、ビニルピ
バレートなど］から選ばれる１種もしくは２種以上の単
量体とを共重合させた通常公知の共重合体が使用できる
。The high acid value acrylic resin used in the composition of the present invention is (
Ethylenically unsaturated acids such as meth)acrylic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, and (anhydrous) maleic acid are essential components, and esters of (meth)acrylic acid are [
For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (
meth)acrylate, 2-ethylhexyl(meth)acrylate, stearyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(
meth)acrylate, etc.]: Vinyl aromatic compounds [e.g., styrene, α-methylstyrene, vinyltoluene,
p-chlorostyrene, etc.] ; Amido-based unsaturated compounds [
For example, (meth)acrylamide, diaseptacrylamide, N-methylol acrylamide, N-butoxymethyl acrylamide]; polyolefin compounds [e.g. butadiene, imprene, chlorobrene, etc.] and others [e.g. (meth)acrylonitrile, methyl isopropenyl ketone A commonly known copolymer obtained by copolymerizing one or more monomers selected from vinyl diacetate, Veopa monomer (Shell Chemical Products), vinyl propionate, vinyl pivalate, etc. can be used.
上記高酸価アクリル系樹脂は、該樹脂に由来する酸基の
一部と脂環式エポキシ基含有不飽和化合物に由来°する
エポキシ基とを反応させて該樹脂中に不飽和基を導入す
ることが行なわれるが、該樹脂中に充分な不飽和基を導
入すること及び水性化に必要な酸基を残存させておく必
要があることから、樹脂の酸価は３０以上、好ましくは
６０〜５００範囲を有する。The above-mentioned high acid value acrylic resin is produced by introducing an unsaturated group into the resin by reacting a part of the acid groups derived from the resin with an epoxy group derived from an alicyclic epoxy group-containing unsaturated compound. However, since it is necessary to introduce sufficient unsaturated groups into the resin and leave acid groups necessary for aqueousization, the acid value of the resin is 30 or more, preferably 60-60. It has a range of 500.
本発明組成物で使用する脂環式エポキシ基含有不飽和化
合物は、−分子中に１個のラジカル重合性の不飽和基と
脂環式エポキシエ基とを有する化合物である。具体的に
は、例えば下記一般式％式％
［各一般式中、Ｒ１は水素原子又はメチル基を示す、Ｒ
２は炭素数１〜６の２価の脂肪族飽和炭化水素基を示す
、Ｒ３は炭素数１〜１０の２価の炭化水素基を示す、見
は０−１０の整数を示す、］
等が挙げることができる。The alicyclic epoxy group-containing unsaturated compound used in the composition of the present invention is a compound having one radically polymerizable unsaturated group and an alicyclic epoxy group in the molecule. Specifically, for example, the following general formula % formula % [In each general formula, R1 represents a hydrogen atom or a methyl group, R
2 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R3 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and 2 represents an integer from 0 to 10.] etc. can be mentioned.
上記において、Ｒ２によって示される炭素数１〜６の２
価の脂肪族飽和炭化水素基としては、直鎖又は分枝状の
アルキレン基例えばメチレン、エチレン、プロピレン、
テトラメチレン、エチルエチレン、ペンタメチレン、ヘ
キサメチレン基等を挙げることができる。また、Ｒ３に
よって示される炭素数１−１０の２価の炭化水素基とし
ては、例えばメチレン、エチレン、プロピレン、テトラ
メチレン、エチルエチレン、ペンタメチレン、ヘキサメ
チレン、ポリメチレン、フェニレ挙げることができる。In the above, 2 having 1 to 6 carbon atoms represented by R2
Examples of aliphatic saturated hydrocarbon groups include linear or branched alkylene groups such as methylene, ethylene, propylene,
Examples include tetramethylene, ethylethylene, pentamethylene, and hexamethylene groups. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R3 include methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, polymethylene, and phenyle.
また、上記した脂環式エポキシ基含有不飽和化合物以外
に、例えば（メタ）アクリル酸グルシジル、β−メチル
（メタ）アクリル酸グリシジル、アリルグリシジルエー
テル等の脂肪族エポキシ基含有不飽和化合物を脂環式エ
ポキシ基含有不飽和化合物との総合計量に対して９０重
量％以下の範囲で併用して使用できる。In addition to the above-mentioned alicyclic epoxy group-containing unsaturated compounds, aliphatic epoxy group-containing unsaturated compounds such as glycidyl (meth)acrylate, glycidyl β-methyl (meth)acrylate, allyl glycidyl ether, etc. It can be used in combination with the epoxy group-containing unsaturated compound in an amount of 90% by weight or less based on the total amount.
上記高酸価アクリル系樹脂及び脂環式エポキシ基含有不
飽和化合物を用いて酸基及び不飽和基を含有する樹脂を
製造する方法は１例えば高酸価アクリル系樹脂の不活性
有機溶剤溶液（例えばアルコール系、エステル系、芳香
族炭化水素系、脂肪族炭化水素系等が挙げられ色、中で
も好ましくはアルコール系等の親水性有機溶剤である。A method for producing a resin containing an acid group and an unsaturated group using the above-mentioned high acid value acrylic resin and alicyclic epoxy group-containing unsaturated compound is 1, for example, a solution of a high acid value acrylic resin in an inert organic solvent ( For example, alcohol-based, ester-based, aromatic hydrocarbon-based, aliphatic hydrocarbon-based, etc. may be mentioned, among which hydrophilic organic solvents such as alcohol-based are preferred.
）と脂環式エポキシ基含有不飽和化合物とを約２０〜１
２０°Ｃ１約１〜５時間の反応条件で反応させることに
より行なうことができる。) and the alicyclic epoxy group-containing unsaturated compound in about 20 to 1
This can be carried out by reacting at 20° C. for about 1 to 5 hours.
かくして得られる酸基及び不飽和基を含有する樹脂は、
分子量１０００当り不飽和基数を０．２〜４．０個、好
ましくは０．７〜３．５個の範囲で有することができる
。不飽和基数が０．２個より少ないと、被膜の硬化性が
不充分となって、被塗物に対する密着性、耐水性等が劣
り、またプリント配線板に適用すると塩化第２銅等のア
ルカリエツチング液に対する耐エツチングレジスト性が
劣り、そのためにプリント回路板の解像度が劣る、他方
、不飽和基数が４．０個より多いと高酸価アクリル系樹
脂との付加反応中に増粘、ゲル化する恐れがあり、また
該組成物を長期間保存すると増粘、ゲル化する恐れがあ
るので好ましくない。The resin containing acid groups and unsaturated groups obtained in this way is
The number of unsaturated groups per 1000 molecular weight can range from 0.2 to 4.0, preferably from 0.7 to 3.5. If the number of unsaturated groups is less than 0.2, the curability of the coating will be insufficient, resulting in poor adhesion to the object to be coated, water resistance, etc., and when applied to printed wiring boards, alkali such as cupric chloride Etching resist resistance against etching liquids is poor, resulting in poor resolution of printed circuit boards.On the other hand, if the number of unsaturated groups is greater than 4.0, viscosity increases and gelation occurs during addition reaction with high acid value acrylic resin. Furthermore, if the composition is stored for a long period of time, it may thicken or gel, which is not preferable.
また、該樹脂は、数平均分子量をｔ、ｏｏｏ〜１００．
０００、好ましくは３．０００〜７０．０００の範囲で
有することができる０分子量がｔ、ｏｏｏより小さいと
、被膜の耐水性や耐エツチングレジスト性に劣り、他方
、分子量がｔｏｏ、ｏｏｏより大きいと、高粘度となり
取り扱いが不便となり、また増膜性も悪くなり耐水性被
塗物に対する密着性、耐エツチングレジスト性に劣る被
膜となるので好ましくない。Further, the resin has a number average molecular weight of t, ooo to 100.
000, preferably in the range of 3.000 to 70.000. If the molecular weight is smaller than t, ooo, the water resistance and etching resistance of the film will be poor; on the other hand, if the molecular weight is larger than too, ooo. This is not preferable because it becomes highly viscous, making it inconvenient to handle, and also has poor film-thickening properties, resulting in a film with poor adhesion to water-resistant objects and poor etching resist properties.
更に、該樹脂は、樹脂酸価を２０以上、好ましくは３０
〜３００の範囲で有することができる。Furthermore, the resin has a resin acid value of 20 or more, preferably 30.
-300.
酸価が２０より小さいと、中和抜水中に水溶化もしくは
水分散化できなくなるので好ましくない。If the acid value is less than 20, it is not preferable because it cannot be water-solubilized or water-dispersed in the neutralized water.
本発明における活性エネルギー線硬化型不飽和樹脂の水
分散化または水溶化は樹脂骨格中に含まれる酸基をアル
カリ（中和剤）で中和することによって行なわれる。中
和剤としては、例えばモノエタノールアミン、ジェタノ
ールアミン、トリエタノールアミンなどのアルカノール
アミン類、トリエチルアミン、ジエチルアミン、モノエ
チルアミン、ジインプロピルアミン、トリメチルアミン
、ジイソブチルアミンなどのアルキルアミン類、ジメチ
ルアミノエタノールなどのアルキルアルカノールアミン
類、シクロヘキシルアミンなどの脂環族アミン類、カセ
イソーダ、カセイカリなどのアルカリ金属水酸化物、ア
ンモニアなどがあり、これらは単独または混合物として
使用できる。中和剤の使用量は樹脂骨格中に含まれるカ
ルボキシ基１モルに対して０．３〜１．０当量の範囲が
好ましく、０．３当量より少なくなると水分散性が悪く
、１．０当量より多くなると貯蔵安定性が劣るので好ま
しくない。In the present invention, the active energy ray-curable unsaturated resin is water-dispersed or water-solubilized by neutralizing the acid groups contained in the resin skeleton with an alkali (neutralizing agent). Examples of neutralizing agents include alkanolamines such as monoethanolamine, jetanolamine, and triethanolamine, alkylamines such as triethylamine, diethylamine, monoethylamine, diimpropylamine, trimethylamine, and diisobutylamine, and dimethylaminoethanol. Examples include alkyl alkanolamines, alicyclic amines such as cyclohexylamine, alkali metal hydroxides such as caustic soda and caustic potash, and ammonia, and these can be used alone or as a mixture. The amount of the neutralizing agent used is preferably in the range of 0.3 to 1.0 equivalents per mole of carboxyl groups contained in the resin skeleton, and if it is less than 0.3 equivalents, water dispersibility will be poor and 1.0 equivalents. If the amount is larger, the storage stability will be poor, which is not preferable.
水溶化または水分散化し樹脂成分の流動性をさらに向上
させるために親水性溶剤（たとえばインプロパツール、
ｎ−ブタノール、１−ブタノール、メトキシエタノール
、エトキシエタノール、ブトキシェタノール、ジエチレ
ングリコール、メチルエーテル、ジオキサン、テトラヒ
ドロフランなど）を加えることができる。親木性溶剤の
使用量は樹脂成分１００重量部に対し３００重量部以下
の範囲が望ましい。Hydrophilic solvents (e.g. Improper Tool,
n-butanol, 1-butanol, methoxyethanol, ethoxyethanol, butoxyethanol, diethylene glycol, methyl ether, dioxane, tetrahydrofuran, etc.) can be added. The amount of the wood-philic solvent used is preferably 300 parts by weight or less per 100 parts by weight of the resin component.
被塗物への塗布量を多くするため、疎水性溶剤（たとえ
ばトルエン、キシレン等の石油系溶剤、メチルエチルケ
トン、メチルイソブチルケトン等のケトン類、酢酸エチ
ル、酢酸ブチル等のエステル類、２−エチルヘキシルア
ルコール等のアルコール類など）も加えることができる
。疎水性溶剤の使用量は樹脂成分１００重量部に対し２
００重量部以下の範囲が望ましい。In order to increase the amount of coating on the object, use hydrophobic solvents (for example, petroleum solvents such as toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, and 2-ethylhexyl alcohol). alcohols, etc.) can also be added. The amount of hydrophobic solvent used is 2 parts per 100 parts by weight of the resin component.
A range of 0.00 parts by weight or less is desirable.
本発明で使用する活性エネルギー線硬化型不飽和樹脂組
成物には、用途及び要求される塗膜性能等に応じて適宜
、従来公知の重合性ビニル七ツマ−及び重合性プレポリ
マーを配合することができる。The active energy ray-curable unsaturated resin composition used in the present invention may be blended with conventionally known polymerizable vinyl nitrates and polymerizable prepolymers as appropriate depending on the intended use and required coating performance. I can do it.
重合性ビニルモノマーとしては、具体的には、例えば１
価ビニルモノマー類［例えば上記高酩価アクリル系樹脂
で使用した（メタ）アクリル酸のエステル、ビニル芳香
族化合物、アミド系不飽和化合物、ポリオレフィン系化
合物及びその他モノマー等のモノマー； 水酸ｘ含有モ
ノマーとモノイソシアネート （例えばブチルイソシア
ネート、フェニルイソシアネート等）との付加物；アジ
リジン基含有上ツマ−及び含リンビニルモノマー等が挙
げられる。］及び多価ビニルモノマー類［例えば多価ア
ルコールと（メタ）アクリル酸エステルとの反応物（例
えばブタンジオールジアクリレート、トリメチロールプ
ロパントリアクリレート、ペンタエリスリトールテトラ
アクリレート等）、ポリアルキレングリコールと（メタ
）アクリル酸エステルとの反応物（例えば、ジエチレン
グリコールジアクリレート、プロピレングリコールジア
クリレート、ポリエチレングリコールジアクリレート、
ポリプロピレングリコールジアクリレート等）、カプロ
ラクトン変性多価アルコールと（メタ）アクリル酸エス
テルとの反応物、含すンジビニル七ツマー等が挙げられ
る。］が挙げられる。Specifically, as the polymerizable vinyl monomer, for example, 1
Vinyl monomers [for example, monomers such as (meth)acrylic acid esters, vinyl aromatic compounds, amido unsaturated compounds, polyolefin compounds, and other monomers used in the above-mentioned high alcohol value acrylic resins; hydroxyl x-containing monomers and monoisocyanates (for example, butyl isocyanate, phenyl isocyanate, etc.); examples include aziridine group-containing monomers and phosphorus-containing vinyl monomers. ] and polyvalent vinyl monomers [e.g., reaction products of polyhydric alcohols and (meth)acrylic acid esters (e.g., butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, etc.), polyalkylene glycols and (meth) Reactants with acrylic esters (e.g. diethylene glycol diacrylate, propylene glycol diacrylate, polyethylene glycol diacrylate,
(polypropylene glycol diacrylate, etc.), reaction products of caprolactone-modified polyhydric alcohols and (meth)acrylic acid esters, divinyl heptamers, and the like. ].
重合性プレポリマーとしては、具体的には、例えば水性
化が可能な重合性不飽和基含有樹脂［例えばカルボキシ
ル基含有ポリオールにポリイソシアネート化合物を介し
てヒドロキシアルキル（メタ）アクリレートを導入した
樹脂等］及び重合性不飽和基含有樹脂［例えばポリエス
テルポリオールの（メタ）アクリル酸エステル、ポリエ
ーテルポリオールの（メタ）アクリル酸エステル、アク
リルポリオールの（メタ）アクリル酸エステル、ポリエ
ポキシと（メタ）アクリル酸との付加物及びポリオール
にポリイソシアネート化合物を介してヒドロキシアルキ
ル（メタ）アクリレートを導入した樹脂等］が挙げられ
る。Specifically, the polymerizable prepolymer includes, for example, a polymerizable unsaturated group-containing resin that can be water-based [for example, a resin in which hydroxyalkyl (meth)acrylate is introduced into a carboxyl group-containing polyol via a polyisocyanate compound, etc.] and polymerizable unsaturated group-containing resins [for example, (meth)acrylic esters of polyester polyols, (meth)acrylic esters of polyether polyols, (meth)acrylic esters of acrylic polyols, polyepoxy and (meth)acrylic acid and resins in which hydroxyalkyl (meth)acrylate is introduced into polyol via a polyisocyanate compound].
上記重合性ビニルモノマー及び重合性プロポリマーは活
性エネルギー線硬化型樹脂組成物の樹脂固形分１００重
量部に対して１００重量部以下、好ましくは５０重量部
以下の範囲で配合できる。The above-mentioned polymerizable vinyl monomer and polymerizable propolymer can be blended in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the resin solid content of the active energy ray-curable resin composition.
更に本発明組成物には、必要に応じて活性エネルギー線
の硬化性を阻害しない程度で顔料及び染料等を配合する
ことができる。Further, the composition of the present invention may contain pigments, dyes, etc., if necessary, to the extent that they do not inhibit the curability of active energy rays.
本発明組成物は塗料、印刷インキ、フォトレジスト、ソ
ルダーレジスト、接着剤、粘着剤等に特に有用なもので
ある。The compositions of the present invention are particularly useful in paints, printing inks, photoresists, solder resists, adhesives, pressure-sensitive adhesives, and the like.
本発明組成物を用いて被膜を形成する方法は、例えば木
材、無機質材料、プラスチック、金属等の被塗物に例え
ばナチュラルロールコータ、リバースロールコータ、グ
ラビアロールコータ、エアースプレー、エアレススプレ
ー、八−コーター、ナイフコーター、スピンコーター、
電着塗装機、刷毛、浸漬塗装機等の塗装機を用いて塗装
風
を行なった後、水分等を１００℃以下の熱・で除去し、
次いでこのものに電子線又は紫外線の活性エネルギー線
で照射を行なって塗膜を硬化させることができる。上記
塗装膜厚は乾燥膜厚で１００μ以下、好ましくは１〜７
０−の範囲である。膜厚が１００−より多いと塗着膜中
の水分等が除去できず残存し被膜硬化性が劣るので好ま
しくない。The method of forming a film using the composition of the present invention can be applied to a coated object such as wood, inorganic material, plastic, metal, etc. using a natural roll coater, reverse roll coater, gravure roll coater, air spray, airless spray, etc. coater, knife coater, spin coater,
After applying a coating style using a coating machine such as an electrodeposition coating machine, a brush, or a dip coating machine, moisture etc. are removed using heat below 100℃.
This material can then be irradiated with active energy rays such as electron beams or ultraviolet rays to cure the coating film. The above coating film thickness is 100μ or less in terms of dry film thickness, preferably 1 to 7
The range is 0-. If the film thickness is more than 100 mm, water, etc. in the applied film cannot be removed and remains, resulting in poor film curability, which is not preferable.
活性エネルギー線を放出させる電子線の加速器としては
、例えばコツククロフト型、コッククロフトワルトン型
、パン拳デ・グラーフ型、共振変圧器型、変圧器型、絶
縁コア変圧器型、ダイナミドロン型、リニアフィラメン
ト型、ブロードビーム型、エリアビーム型、カソード電
極型、高周波型等が挙げられる。又電子線の照射量は塗
膜を硬化させるに必要な線量を与えれば特に制限されな
いが、一般には約１００〜２０００ＫｅＶで約０．５〜
２０メガラド（Ｍｒａｄ）の線量を照射する。電子線を
照射する雰囲気は不活性気体中で行なうのが好ましい。Examples of electron beam accelerators that emit active energy rays include Cockcroft type, Cockcroft-Walton type, Panken de Graaf type, resonant transformer type, transformer type, insulated core transformer type, Dynamidron type, and linear filament type. , broad beam type, area beam type, cathode electrode type, high frequency type, etc. The amount of electron beam irradiation is not particularly limited as long as it provides the dose necessary to cure the coating, but generally it is about 100 to 2000 KeV and about 0.5 to 2000 KeV.
A dose of 20 megarads (Mrad) is applied. The atmosphere in which the electron beam is irradiated is preferably an inert gas.
また、活性エネルギー線を放出させる紫外線の照射源と
しては、例えば水銀ランプ、高圧水銀ランプ、キセノン
ランプ、カーボンアーク、メタルハライドランプ、太陽
光等を挙げることができる。紫外線を照射する雰囲気は
、空気中もしくは不活性気体中で照射することが好まし
い、また、照射する雰囲気が空気の場合は、高圧水銀ラ
ンプを照射源として用いるのが特に好ましい、また、照
射条件は光重合開始剤の吸収量によって異なるが３００
０〜４５００人の波長を有する光線を用いて数分以内、
通常は１秒〜２０分の範囲で行なわれる。Examples of the ultraviolet irradiation source that emits active energy rays include a mercury lamp, a high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. The atmosphere in which ultraviolet rays are irradiated is preferably air or an inert gas, and when the irradiation atmosphere is air, it is particularly preferable to use a high-pressure mercury lamp as the irradiation source, and the irradiation conditions are as follows: Although it varies depending on the absorption amount of the photopolymerization initiator, it is 300
Within a few minutes using a light beam with a wavelength of 0 to 4500,
This is usually carried out for a period of 1 second to 20 minutes.
また、本発明の塗料組成物を紫外線で硬化させる場合は
、該塗料組成物に光重合開始剤が添加され、その代表的
なものとしては、例えばベンゾイン、ベンゾインメチル
エーテル、ベンゾインエチルエーテル、ベンゾインｎ−
プロピルエーテル、ベンゾインｎ−ブチルエーテル、ベ
ンゾフェノン、Ｐ−メチルベンゾフェノン、ミヒラーケ
トン、アセトフェノン、２−クロロチオキサントン、ア
ンスラキノン、クロロアンスラキノン、２−メチルアン
スラキノン、フエニルジスルフィド２−ニトロフルオレ
ン、ブチロイン、アニソインエチルエーテル、アゾビス
イソブチロニトリル、テトラメチルチウラムジスルフィ
ド等が挙げることができる。これらの光重合開始剤は１
種もしくは２種以上を組合せて用いることができる。In addition, when the coating composition of the present invention is cured with ultraviolet rays, a photopolymerization initiator is added to the coating composition, typical examples of which include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n −
Propyl ether, benzoin n-butyl ether, benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, chloroanthraquinone, 2-methylanthraquinone, phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl Examples include ether, azobisisobutyronitrile, and tetramethylthiuram disulfide. These photoinitiators are 1
One species or a combination of two or more species can be used.
また、光重合開始剤の配合量は活性エネルギー線硬化塗
料に対して約０．１−１０重量％の範囲で配合すること
が好ましい、さらに上記した光重合開始剤による光重合
反応を促進させる目的で光重合促進剤を上記した光重合
開始剤と併用して用いることができ、その代表的なもの
としては、例えばトリエチルアミン、トリエタノールア
ミン、２−ジメチルアミノエタノール等の第３級アミン
類、トリフェニルホスフィンで代表されるアルキルホス
フィン類、β−チオグリコールで代表されるチオール類
等を挙げることができる。Further, the amount of the photopolymerization initiator is preferably blended in the range of about 0.1 to 10% by weight based on the active energy ray-cured paint, and the purpose is to promote the photopolymerization reaction by the above-mentioned photopolymerization initiator. A photopolymerization accelerator can be used in combination with the photopolymerization initiator described above, and typical examples thereof include tertiary amines such as triethylamine, triethanolamine, and 2-dimethylaminoethanol; Examples include alkyl phosphines represented by phenylphosphine, thiols represented by β-thioglycol, and the like.
本発明組成物を用いてプリント基板製造に適用した一例
を下記に示す。An example in which the composition of the present invention is applied to the manufacture of printed circuit boards is shown below.
本発明組成物をｐＨ５〜１０、固形分３〜３０重量％、
好ましくは５〜１５重量％に調整しアニオン電着塗料浴
とする。該塗料浴を１５〜４０℃、好ましくは１５〜３
０℃に管理する。ついで、この電着塗料浴に、銅箔を張
った絶縁体に銅めつきを施してなるプリント配線基板を
陽極として浸漬し、２０〜４００Ｖの直流電流を通電す
ることによって行なわれる。通電時間は３０秒〜５分が
適当であり、膜厚は乾燥膜厚で２〜１ｏｏｋ、好適には
３〜２０−であることが望ましい。The composition of the present invention has a pH of 5 to 10, a solid content of 3 to 30% by weight,
Preferably, the amount is adjusted to 5 to 15% by weight to form an anionic electrodeposition paint bath. The paint bath is heated to 15-40°C, preferably 15-3
Control at 0℃. Then, a printed wiring board made of an insulator covered with copper foil and plated with copper is immersed in this electrocoating paint bath as an anode, and a direct current of 20 to 400 V is applied thereto. The appropriate current application time is 30 seconds to 5 minutes, and the dry film thickness is preferably 2 to 1 ook, preferably 3 to 20 mm.
電着塗装後、電着浴から被塗物を引き上げ水洗したのち
、電着塗膜中に含まれる水分が熱風などで除去される。After electrodeposition coating, the object to be coated is taken out of the electrodeposition bath and washed with water, and then the moisture contained in the electrodeposition coating is removed with hot air or the like.
ついで、このように形成された感光性電着塗膜面にパタ
ーンマスク（写真ネガ）を重ねてから導体回路（回路パ
ターン）に紫外線などの活性光線を照射露光する。Next, a pattern mask (photographic negative) is placed on the surface of the photosensitive electrodeposition coating film thus formed, and the conductor circuit (circuit pattern) is exposed to active light such as ultraviolet rays.
更に、露光部以外の未硬化部分はアルカリ水溶液等の現
像処理によって除去される。現像処理は塗膜面上に弱ア
ルカリ水を吹きつけることによって塗膜の感光部分を洗
い流すことによって行なわれる０弱アルカリ水は通常ｐ
Ｈ８〜１０のカセイソーダ、炭酸ソーダ、カセイカリ、
アンモニア水など塗膜中に有する遊離にカルボン酸と中
和して水溶性を与えることのできるものが使用可能であ
る。Further, the uncured portions other than the exposed portions are removed by a development process using an alkaline aqueous solution or the like. The development process is carried out by spraying weakly alkaline water onto the coating surface to wash away the photosensitive areas of the coating.
H8-10 caustic soda, carbonated soda, caustic potash,
It is possible to use substances such as ammonia water that can be neutralized with free carboxylic acids in the coating film to impart water solubility.
現像処理によって基板上に露出した銅箔部分（非回路部
分）は例えば、塩化第２鉄溶液等を用いた通常のエツチ
ング処理によって除去される。The copper foil portion (non-circuit portion) exposed on the substrate by the development process is removed by a normal etching process using, for example, a ferric chloride solution.
しかる後、回路パターン上の露光塗膜もトリクロルエチ
レンなどのクロル系溶剤またはＰＨ１２以上のカセイソ
ーダ、カセイカリなどによって溶解除去されて基板上に
プリント回路が形成される。Thereafter, the exposed coating film on the circuit pattern is dissolved and removed using a chlorine solvent such as trichlorethylene, or caustic soda or caustic potash having a pH of 12 or higher, thereby forming a printed circuit on the substrate.
（作用及び効果）
本発明組成物は、特に脂環式エポキシ基含有不飽和化合
物に由来する脂環式エポキシ基と高酸価アクリル系樹脂
に由来する酸基との付加反応はエポキシ基の開環重合反
応の反応性が高いため容易に活性エネルギー線硬化可能
な不飽和基を樹脂中に導入することができる。また該組
成物は酸基と脂環式エポキシ基との反応で生じた化学結
合が比較的立体障害の大きな結合であるため組成物中の
加水分解促進物質（例えば水、酸、アルカリ等）に対し
て化学的に安定であり、長期間の貯蔵においても樹脂成
分の分離沈降等がなく貯蔵安定性に優れた性質を示す、
また、該組成物から形成される被膜は上記の化学結合を
有することから耐水性、被塗装物に対する密着性に優れ
た顕著な効果が奏される。特に該組成物をプリント基板
に適用すると解像度に優れたプリント配線板が形成され
るという顕著な効果が奏される。(Functions and Effects) In particular, the composition of the present invention is characterized in that the addition reaction between the alicyclic epoxy group derived from the alicyclic epoxy group-containing unsaturated compound and the acid group derived from the high acid value acrylic resin causes the opening of the epoxy group. Since the reactivity of the ring polymerization reaction is high, an active energy ray-curable unsaturated group can be easily introduced into the resin. In addition, since the chemical bond formed by the reaction between the acid group and the alicyclic epoxy group is a bond with relatively large steric hindrance, the composition is susceptible to hydrolysis accelerators (e.g. water, acids, alkalis, etc.) in the composition. In contrast, it is chemically stable and exhibits excellent storage stability without separation and sedimentation of resin components even during long-term storage.
Furthermore, since the film formed from the composition has the above-mentioned chemical bonds, it exhibits remarkable effects in terms of water resistance and adhesion to objects to be coated. In particular, when the composition is applied to a printed circuit board, a remarkable effect is produced in that a printed wiring board with excellent resolution is formed.
（実施例）
以下、本発明を実施例によってさらに具体的に説明する
。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples.
不飽和樹脂の合成例１
スチレン３０重量部、ブチルアクリレート３５重量部、
アクリル酸３５重量部およびアゾビスイソブチロニトリ
ル３重量部からなる混合液を窒素ガス雰囲気下において
１２０℃に保持した反応容器中のセロソルブ９０重量部
に３時間かけて滴下した０滴下後、１時間熟成させ、ア
ゾビスジメチルバレロニトリル１重量部とセロソルブ１
０重量部からなる混合液を１時間要して滴下し、さらに
５時間熟成させて高酸価アクリル樹脂（酸価２６０）溶
液を得た０次にこの溶液に下記化合物
Ｈ３０
ｓａｉ１部およびハイドロキノンモノメチルエーテル０
．３重量部を加えて空気を吹き込みながら８０℃５時間
反応させて不飽和樹脂（酸価的８０、不飽和基数１．５
３個／分子量１０００、数平均分子量的１５，０００）
溶液を得た。Synthesis example 1 of unsaturated resin: 30 parts by weight of styrene, 35 parts by weight of butyl acrylate,
A mixed solution consisting of 35 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was added dropwise over 3 hours to 90 parts by weight of Cellosolve in a reaction vessel maintained at 120°C under a nitrogen gas atmosphere. Aged for an hour, 1 part by weight of azobisdimethylvaleronitrile and 1 part of cellosolve.
A mixed solution consisting of 0 parts by weight was added dropwise over 1 hour and further aged for 5 hours to obtain a high acid value acrylic resin (acid value 260) solution.Next, 1 part of the following compound H30 sai and hydroquinone monomethyl were added to this solution. ether 0
．． Add 3 parts by weight and react at 80°C for 5 hours while blowing air to obtain an unsaturated resin (acid value: 80, number of unsaturated groups: 1.5).
3 pieces/molecular weight 1000, number average molecular weight 15,000)
A solution was obtained.
不飽和樹脂の合成例２
合成例１の高酸価アクリル樹脂溶液２０４重量部に下記
化合物
ハイドロキノンモノメチルエーテル ０ 、
３重ｆｆｉ部を加えて空気を吹き込みながら８０℃５
時間反応させて不飽和樹脂（酸価５２、不飽和基数１．
８２個／分子量１０００、数平均分子量的１６，０００
）溶液を得た。Synthesis Example 2 of Unsaturated Resin To 204 parts by weight of the high acid value acrylic resin solution of Synthesis Example 1, the following compounds hydroquinone monomethyl ether,
Add triple ffi parts and heat to 80℃5 while blowing air.
An unsaturated resin (acid value 52, number of unsaturated groups 1.
82 pieces/molecular weight 1000, number average molecular weight 16,000
) solution was obtained.
不飽和樹脂の合成例３
メチルメタクリレ−）４Ｏｆｆｉ量部、ブチルアクリレ
ート３５重量部、アクリル酸２５重量部およびアゾビス
イソブチロニトリル２重量部からなる混合液を窒素ガス
雰囲気下において１１０℃に保持した反応容器中のプロ
ピレングリコールモノメチルエーテル９０重量部に３時
間かけて滴下した０滴下後、１時間熟成させ、アゾビス
ジメチルバレロニトリル１重量部およびプロピレングリ
コールモノメチルエーテル１０重量部からなる混合液を
１時間要して滴下し、さらに５時間熟成させて高酸価ア
クリル樹脂（！１ｉ価１８４）溶液を得た０次にこの溶
液に下記化合物
３６ ｍ 置部およびハイドロキノンモノメチルエーテ
ル０．２５重量部を加えて空気を吹き込みながら８０°
Ｃで５時間反応させて不飽和樹脂（酸価５８、不飽和基
数１．４２個／分子量１ｏｏｏ、数平均分子量的２０，
０００）溶液を得た。Synthesis Example 3 of Unsaturated Resin A mixed solution consisting of 4 parts by weight of methyl methacrylate, 35 parts by weight of butyl acrylate, 25 parts by weight of acrylic acid, and 2 parts by weight of azobisisobutyronitrile was heated to 110°C under a nitrogen gas atmosphere. After the 0 dropwise addition over 3 hours to 90 parts by weight of propylene glycol monomethyl ether in the reaction vessel held, it was aged for 1 hour to form a mixed solution consisting of 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of propylene glycol monomethyl ether. It was added dropwise over a period of 1 hour, and further aged for 5 hours to obtain a high acid value acrylic resin (1i value: 184) solution.Next, 36 parts of the following compound and 0.25 parts by weight of hydroquinone monomethyl ether were added to this solution. 80° while blowing air.
C for 5 hours to form an unsaturated resin (acid value 58, number of unsaturated groups 1.42/molecular weight 1ooo, number average molecular weight 20,
000) solution was obtained.
不飽和樹脂の合成例４
メチルメタクリレ−）４Ｏｆｆｉ量部、ブチルアクリレ
ート２５重量部、２−ヒドロキシエチルメタクリレート
１５重量部、アクリル酸２ｏｆｆｉ量部およびアゾビス
イソブチロニトリル２重量部からなる混合系を窒素ガス
雰囲気下において１０５℃に保持した反応容器中のブチ
ルセロソルブ９０重量部に３時間かけて滴下した０滴下
後、１時間熟成させ、アゾビスジメチルバレロニトリル
１重量部およびプロピレングリコールモノメチルエーテ
ル１０重量部からなる混合液を１時間要して滴下し、さ
らに、５時間熟成させて高酸価アクリル樹脂（酸価１５
０）溶液を得た０次にこの溶液に下記化合物
２５重量部およびハイドロキノンモノメチルエーテル０
．１重量部を加えて空気を吹き込みなから８０°Ｃで５
時間反応させて不飽和樹脂（酸価６０、不悠和基数１．
１個／分子量１０００、数平均分子量２０，０００）溶
液を得た。Synthesis Example 4 of Unsaturated Resin Mixture system consisting of 4 parts by weight of methyl methacrylate, 25 parts by weight of butyl acrylate, 15 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of acrylic acid, and 2 parts by weight of azobisisobutyronitrile was added dropwise over 3 hours to 90 parts by weight of butyl cellosolve in a reaction vessel maintained at 105°C under a nitrogen gas atmosphere. After the dropwise addition, the mixture was aged for 1 hour, and 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of propylene glycol monomethyl ether were added. A mixed solution consisting of 50% of
0) A solution was obtained.Next, 25 parts by weight of the following compound and hydroquinone monomethyl ether were added to this solution.
．． Add 1 part by weight, blow in air, and heat at 80°C for 5 minutes.
An unsaturated resin (acid value 60, number of unsustainable groups 1.
1 piece/molecular weight 1000, number average molecular weight 20,000) solution was obtained.
比較樹脂の合成例°ｌ
スチレン３０重量部、ブチルアクリレート４０重量部、
アクリル酸３０重量部およびアゾビスイソブチロニトリ
ル３重量部から混合液を窒素ガス雰囲気下においてｉｚ
ｏ’ｃに保持した反応容器中のセロソルブ９０重量部中
に３時間かけて滴下した。Ｗ４下後、１時間熟成させ、
アゾビスジメチルバレロニトリル１重量部とセロソルブ
１０重量部からなる混合液を１時間要して滴下し、さら
に５時間熟成させて高酸価アクリル樹脂（酸価２２２）
溶液を得た０次にグリシジルメタクリレート３２重量部
、ハイドロキノンモノメチルエーテル０．２５重量部、
テトラエチルアンモニウムブロマイド０．６重量部を加
えて空気を吹き込みながら１１０℃５時間反応させて不
飽和樹脂（酸価７６、不飽和基数１．６７個／分子量１
０００、数平均分子量的１５，０００）溶液を得た。Synthesis example of comparative resin °l 30 parts by weight of styrene, 40 parts by weight of butyl acrylate,
A mixed solution of 30 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was heated to iz in a nitrogen gas atmosphere.
The mixture was added dropwise over 3 hours to 90 parts by weight of cellosolve in a reaction vessel kept at o'c. After lowering W4, let it mature for 1 hour,
A mixed solution consisting of 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of cellosolve was added dropwise over 1 hour, and the mixture was further aged for 5 hours to form a high acid value acrylic resin (acid value 222).
The solution obtained was 32 parts by weight of zero-order glycidyl methacrylate, 0.25 parts by weight of hydroquinone monomethyl ether,
Add 0.6 parts by weight of tetraethylammonium bromide and react at 110°C for 5 hours while blowing air to obtain an unsaturated resin (acid value 76, number of unsaturated groups 1.67/molecular weight 1).
000, number average molecular weight 15,000) solution was obtained.
実施例１
不飽和樹脂の合成例１の溶液２６２重量部にα−ヒドロ
キシイソブチルフェノン８重量部を加えた後、トリエチ
ルアミン１１．５重量部（中和度０．５）を添加し中和
した。この溶液をデイスパーを用いて高速攪拌しながら
脱イオン水１４１０重量部を徐々に加えて固形分１０重
量％の水分散溶液を得た。この水分散溶液をアルミニウ
ム板上にスプレーで塗装し、８０℃で１５分間乾燥させ
た後、１２０Ｗ／ｃｍ高圧水銀灯で５秒間ＵＶ照射し、
硬化させた。この塗膜厚は約２０゜であった、また、こ
の塗膜の付着性及び耐水性を調べた。Example 1 After adding 8 parts by weight of α-hydroxyisobutylphenone to 262 parts by weight of the solution of Synthesis Example 1 of unsaturated resin, 11.5 parts by weight of triethylamine (degree of neutralization 0.5) was added for neutralization. While stirring this solution at high speed using a disper, 1410 parts by weight of deionized water was gradually added to obtain an aqueous dispersion solution with a solid content of 10% by weight. This aqueous dispersion solution was spray-painted onto an aluminum plate, dried at 80°C for 15 minutes, and then exposed to UV light for 5 seconds using a 120W/cm high-pressure mercury lamp.
hardened. The thickness of this coating film was about 20°. The adhesion and water resistance of this coating film were also examined.
実施例２
不飽和樹脂の合成例２の溶液２７４重量部にα−ヒドロ
キシイソブチルフェノン８重量部を加えた後、トリエチ
ルアミン８重量部（中和度０．５）を添加して中和した
。以下、実施例１と同様にして固形分１０重量％の水分
散溶液を調製し、実施例１と同様の試験をした。Example 2 After adding 8 parts by weight of α-hydroxyisobutylphenone to 274 parts by weight of the solution of Synthesis Example 2 of unsaturated resin, 8 parts by weight of triethylamine (degree of neutralization 0.5) was added for neutralization. Thereafter, an aqueous dispersion solution having a solid content of 10% by weight was prepared in the same manner as in Example 1, and the same tests as in Example 1 were conducted.
比較例１
比較樹脂の合成例１の溶液２３６重量部にｄ−ヒドロキ
シイソブチルフェノン７重量部を加えた後、トリエチル
アミン９重量部（中和度０．５）を添加して中和した。Comparative Example 1 After adding 7 parts by weight of d-hydroxyisobutylphenone to 236 parts by weight of the solution of Comparative Resin Synthesis Example 1, 9 parts by weight of triethylamine (degree of neutralization 0.5) was added for neutralization.
以下、実施例１と同様にして固形分１０重量％の水分散
溶液を調製し、実施例１と同様の試験をした。Thereafter, an aqueous dispersion solution having a solid content of 10% by weight was prepared in the same manner as in Example 1, and the same tests as in Example 1 were conducted.
実施例３
不飽和樹脂の合成例１の溶液２６２重量部にチタン白２
４重量部を加えシェイカーで顔料分散した後、トリエチ
ルアミン１１．５重量部を添加し中和した。この溶液を
デイスパーで攪拌しながら脱イオン水４４７重量部を徐
々に加えて固形分２５重量％の水分散溶液を得た。Example 3 Titanium white 2 was added to 262 parts by weight of the solution of unsaturated resin synthesis example 1.
After adding 4 parts by weight and dispersing the pigment in a shaker, 11.5 parts by weight of triethylamine was added for neutralization. While stirring this solution with a disper, 447 parts by weight of deionized water was gradually added to obtain an aqueous dispersion solution with a solid content of 25% by weight.
この水分散溶液をアルミニウム板上にバーコーターで塗
装し、８０℃で１５分間乾燥させた後、電子線照射機を
用いて５メガラッド照射し、硬化させた。この塗膜厚は
約２０％であった。また、この塗膜の付着性及び耐水性
を調べた。This aqueous dispersion solution was applied onto an aluminum plate using a bar coater, dried at 80° C. for 15 minutes, and then irradiated with 5 megarads using an electron beam irradiator to cure it. The coating thickness was approximately 20%. Additionally, the adhesion and water resistance of this coating film were examined.
比較例２
比較樹脂の合成例１の溶液２３６重量部にチタン白２０
重量部を加えシェイカーで顔料分散した後、トリエチル
アミン９重量部を添加し中和した。以後、実施例３と同
様にして固形分２５重量％の水分散溶液を作り、実施例
３と同じ試験をした。Comparative Example 2 Titanium White 20 was added to 236 parts by weight of the solution of Comparative Resin Synthesis Example 1.
After adding parts by weight and dispersing the pigment in a shaker, 9 parts by weight of triethylamine was added for neutralization. Thereafter, an aqueous dispersion solution having a solid content of 25% by weight was prepared in the same manner as in Example 3, and the same test as in Example 3 was conducted.
実施例１〜３及び比較例１及び２の塗膜試験結果をまと
めて表−１に示す。The coating film test results of Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1.
１）付着性：ＪＩＳ Ｄ−０−２０２の試験法に従い
テストピースに１ｍｌ１１間隔で１００個のゴバン目状
のカットを入れて１次いでセロファン粘着テープでビー
リングを行ない、ハクリを生じていない桝目の数を分子
に、もとの桝目の数（１００ケ）を分母として表わした
。1) Adhesion: According to the test method of JIS D-0-202, 100 square cuts of 1 ml were made at 11 intervals on a test piece, and then beaded with cellophane adhesive tape. The number is expressed as the numerator and the original number of squares (100 cells) is expressed as the denominator.
２）浸水後の付着性
５０℃の温水中に１日塗板を浸漬した後、表面の水分を
拭きとり、室温で１時間放置した後ｌ）と同じ試験をし
た。2) Adhesion after immersion in water After the coated plate was immersed in warm water at 50°C for one day, the moisture on the surface was wiped off, and after being left at room temperature for 1 hour, the same test as in 1) was conducted.
３）貯蔵安定性
１文の褐色のポリエチレンビンに水分散溶液７００ｃｃ
を入れ、４０°Ｃで貯蔵し、半月毎に溶液状態を調べた
。3) Storage stability: 700 cc of water dispersion solution in a brown polyethylene bottle.
was stored at 40°C, and the state of the solution was checked every six months.
実施例４
不飽和樹脂の合成例３の溶液２３９重量部に２−メチル
−１−［４−（メチルチオ）フェニル］ ・２・モルフ
ォリノ−プロペン３重量部を加えて溶解した後、トリエ
チルアミン９重量部（中和度約０．６）を添加し中和し
た。この溶液をデイスパーを用いて高速攪拌しながら脱
イオン水１１７０重量部を徐々に加えて固形分１０重量
％の水分散液を得た。この水分散液をアニオン電着塗料
浴とし、該塗料浴中に銅張積層板を陽極及びステンレス
板を陰極を設け、両電極間に６０ｍＡ／ｄ１１の定電流
を３分間通電し、銅張積層板上に電着塗膜を析出させた
０次に、このものを塗料浴から引き上げ水洗後７０℃で
５分間乾燥し膜厚２０−の塗板を得た。この塗板上にプ
リント回路用のネガフィルムを真空密着し、３ＫＷ超高
圧水銀灯で３００ＩｌｌＪ／ｃ１１２照射（３６５ｎｍ
）した後、１％炭酸ソーダ溶液で未硬化部を除去した。Example 4 3 parts by weight of 2-methyl-1-[4-(methylthio)phenyl].2-morpholino-propene was added and dissolved in 239 parts by weight of the solution of Synthesis Example 3 of unsaturated resin, and then 9 parts by weight of triethylamine was added. (degree of neutralization about 0.6) was added to neutralize. While stirring this solution at high speed using a disper, 1170 parts by weight of deionized water was gradually added to obtain an aqueous dispersion having a solid content of 10% by weight. This aqueous dispersion was used as an anionic electrodeposition paint bath, a copper clad laminate was provided as an anode and a stainless steel plate was provided as a cathode in the paint bath, and a constant current of 60 mA/d11 was applied between the two electrodes for 3 minutes to form a copper clad laminate. After depositing an electrodeposited coating film on the board, this product was taken out of the paint bath, washed with water, and dried at 70°C for 5 minutes to obtain a coated board with a film thickness of 20°C. A negative film for printed circuits was vacuum-adhered onto this coated plate, and irradiated with 300IllJ/c112 (365nm) using a 3KW ultra-high pressure mercury lamp.
), the uncured portion was removed with a 1% sodium carbonate solution.
さらに、５０°Ｃの塩化第２鉄溶液をスプレーして、露
出している銅をエツチング除去した後、硬化した塗膜を
３重量％カセイソーダ溶液で除去し、シャープな画線を
形成したプリント回路板を得た。Furthermore, after spraying a 50°C ferric chloride solution to remove the exposed copper by etching, the cured coating was removed with a 3% by weight caustic soda solution to form a printed circuit with sharp lines. Got the board.
実施例５
不飽和樹脂の合成例４の溶液２２８重量部にカーボンブ
ラック２５重量部、ミロリーブルー５重量部を加えて３
本ロールで顔料分散したのち、トリメチロールプロパン
トリアクリレート１２重量部、２・２ジメトキシ２−フ
ェニルアセトフェノン７重量部を添加した。さらにジメ
チルエタノールアミン６重量部（中和度０．５）で中和
した。この溶液をデイスパーで攪拌しながら脱イオン水
３００重量部を徐々に加えて固形分（関西ペイント社製
、商品名、感光性樹脂板）を使用し印刷機で上質紙に印
刷したのち８０Ｗ／ｃｍ水冷高圧水銀灯でＵＶ照射し乾
燥硬化したところ、輪郭のはっきりし°た文字の印刷物
を得た。Example 5 25 parts by weight of carbon black and 5 parts by weight of Miloly Blue were added to 228 parts by weight of the solution of Synthesis Example 4 of unsaturated resin.
After the pigment was dispersed using this roll, 12 parts by weight of trimethylolpropane triacrylate and 7 parts by weight of 2.2 dimethoxy 2-phenylacetophenone were added. Further, the mixture was neutralized with 6 parts by weight of dimethylethanolamine (degree of neutralization: 0.5). While stirring this solution with a disper, 300 parts by weight of deionized water was gradually added, and the solid content (manufactured by Kansai Paint Co., Ltd., trade name, photosensitive resin plate) was printed on high-quality paper with a printing machine at 80 W/cm. When the material was dried and cured by UV irradiation using a water-cooled high-pressure mercury lamp, prints with clearly defined characters were obtained.
Claims (1)
和化合物とを反応させて得られる酸基及び不飽和基を含
有する反応物の水性化物であることを特徴とする活性エ
ネルギー線硬化型不飽和樹脂組成物。1. Active energy ray curing characterized by being an aqueous product of a reactant containing an acid group and an unsaturated group obtained by reacting a high acid value acrylic resin with an alicyclic epoxy group-containing unsaturated compound type unsaturated resin composition.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11989988A JPH01289819A (en) | 1988-05-17 | 1988-05-17 | Actinic radiation-curable unsaturated resin composition |
| GB8911194A GB2219591B (en) | 1988-05-17 | 1989-05-16 | Radiation curable unsaturated resin |
| CA000599789A CA1339485C (en) | 1988-05-17 | 1989-05-16 | Active energy ray-curable unsaturated resin composition |
| DE3916035A DE3916035C2 (en) | 1988-05-17 | 1989-05-17 | Unsaturated resin compound curable with active energy rays |
| US07/353,335 US5002977A (en) | 1988-05-17 | 1989-05-17 | Active energy ray-curable unsaturated resin composition |
| DE3943850A DE3943850B4 (en) | 1988-05-17 | 1989-05-17 | Active radiation curable unsatd. resin material - comprises reaction prod. of acid Gp.-contg. vinyl! resin and alicyclic epoxy! Gp.-contg. unsatd. cpd. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11989988A JPH01289819A (en) | 1988-05-17 | 1988-05-17 | Actinic radiation-curable unsaturated resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01289819A true JPH01289819A (en) | 1989-11-21 |
Family
ID=14772978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11989988A Pending JPH01289819A (en) | 1988-05-17 | 1988-05-17 | Actinic radiation-curable unsaturated resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01289819A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10161308A (en) * | 1996-11-26 | 1998-06-19 | Asahi Chem Ind Co Ltd | Photopolymerizable resin composition and its use |
| JP2004010779A (en) * | 2002-06-07 | 2004-01-15 | Nippon Paint Co Ltd | Ultraviolet curing type water-based coating material composition |
-
1988
- 1988-05-17 JP JP11989988A patent/JPH01289819A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10161308A (en) * | 1996-11-26 | 1998-06-19 | Asahi Chem Ind Co Ltd | Photopolymerizable resin composition and its use |
| JP2004010779A (en) * | 2002-06-07 | 2004-01-15 | Nippon Paint Co Ltd | Ultraviolet curing type water-based coating material composition |
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