JP2000256429A - Active energy ray-curable unsaturated resin composition - Google Patents
Active energy ray-curable unsaturated resin compositionInfo
- Publication number
- JP2000256429A JP2000256429A JP11064387A JP6438799A JP2000256429A JP 2000256429 A JP2000256429 A JP 2000256429A JP 11064387 A JP11064387 A JP 11064387A JP 6438799 A JP6438799 A JP 6438799A JP 2000256429 A JP2000256429 A JP 2000256429A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ethylenically unsaturated
- carboxylic acid
- active energy
- resin composition
- 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 abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 61
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 46
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 32
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims description 17
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- -1 propylene glycol ethers Chemical class 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 5
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- CSCSROFYRUZJJH-UHFFFAOYSA-N 1-methoxyethane-1,2-diol Chemical compound COC(O)CO CSCSROFYRUZJJH-UHFFFAOYSA-N 0.000 description 1
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-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
- UKQBWWAPJNHIQR-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCC(CO)(CO)CO UKQBWWAPJNHIQR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DPTGFYXXFXSRIR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl prop-2-enoate Chemical compound C1C(COC(=O)C=C)CCC2OC21 DPTGFYXXFXSRIR-UHFFFAOYSA-N 0.000 description 1
- 102100033007 Carbonic anhydrase 14 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101000867862 Homo sapiens Carbonic anhydrase 14 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
(57)【要約】
【課題】 被塗物に対する密着性及び耐水性に優れ、溶
剤の毒性の心配が殆どない活性エネルギー線硬化型不飽
和樹脂組成物を提供する。
【解決手段】 エチレン性不飽和基含有カルボン酸を重
合して得られた酸基含有樹脂と脂環式エポキシ基含有エ
チレン性不飽和化合物との変性重合体に、有機溶剤又は
有機溶剤と重合性ビニルモノマーを配合してなる。PROBLEM TO BE SOLVED: To provide an active energy ray-curable unsaturated resin composition which is excellent in adhesion to an object to be coated and water resistance and hardly causes solvent toxicity. The modified polymer of an acid group-containing resin obtained by polymerizing an ethylenically unsaturated group-containing carboxylic acid and an alicyclic epoxy group-containing ethylenically unsaturated compound is polymerized with an organic solvent or an organic solvent. It contains vinyl monomer.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、反応性官能基を含
む活性エネルギー線硬化型不飽和樹脂組成物に関する。[0001] The present invention relates to an active energy ray-curable unsaturated resin composition containing a reactive functional group.
【０００２】[0002]
【従来の技術】従来から、活性エネルギー線（紫外線、
γ線、電子線等）硬化型不飽和樹脂組成物として種々の
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。更に、近年それらの活性エ
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。しかし、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
十分でなく、また、使用される有機溶剤によっては、そ
の毒性に対する設備投資が必要となる等、いまだ実用に
十分満足すべき性質を示すには至っていない。2. Description of the Related Art Conventionally, active energy rays (ultraviolet rays,
Various types of curable unsaturated resin compositions have been developed as γ-rays, electron beams, etc., and these are widely used in the fields of coating, composite materials, electronic components and the like. Further, in recent years, development of a resin composition mainly composed of a vinyl resin has been attempted as one of the active energy ray-curable unsaturated resin compositions.
At present, as a composition mainly composed of a vinyl resin, a composition obtained by reacting a high acid value vinyl resin with a vinyl compound having an aliphatic epoxy group is known. However, the film formed from the composition has insufficient adhesion and water resistance to an object to be coated, and furthermore, depending on the organic solvent used, equipment investment for its toxicity is required. It does not show satisfactory properties.
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的は、被塗
物に対する密着性及び耐水性に優れ、溶剤の毒性の心配
が殆どない活性エネルギー線硬化型不飽和樹脂組成物を
提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide an active energy ray-curable unsaturated resin composition which is excellent in adhesion to an object to be coated and water resistance and hardly causes solvent toxicity. is there.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記した問
題点を解決するために鋭意研究を行った結果、活性エネ
ルギー線硬化型不飽和樹脂組成物として、特定構造を有
する脂環式エポキシ基含有エチレン性不飽和化合物と酸
基含有不飽和樹脂との反応物を、特定の有機溶剤及び重
合性ビニルモノマーで希釈してなる組成物が上記問題点
を解消し得ることを見出し、本発明を完成するに至っ
た。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as an active energy ray-curable unsaturated resin composition, an alicyclic epoxy resin having a specific structure was used. The present inventors have found that a composition obtained by diluting a reaction product of a group-containing ethylenically unsaturated compound and an acid group-containing unsaturated resin with a specific organic solvent and a polymerizable vinyl monomer can solve the above problems, and the present invention Was completed.
【０００５】すなわち本発明の第１は、エチレン性不飽
和基含有カルボン酸（ａ）を重合して得られた酸基含有
樹脂（ｐ）と脂環式エポキシ基含有エチレン性不飽和化
合物（ｃ）との変性重合体（Ａ１）に、有機溶剤（Ｓ）
又は有機溶剤（Ｓ）と重合性ビニルモノマー（Ｂ）を配
合してなる活性エネルギー線硬化型不飽和樹脂組成物を
提供する。本発明の第２は、酸基含有樹脂（ｐ）がエチ
レン性不飽和基含有カルボン酸（ａ）とエチレン性不飽
和基含有カルボン酸（ａ）以外の不飽和化合物（ｂ）を
重合して得られたものである本発明の第１に記載の活性
エネルギー線硬化型不飽和樹脂組成物を提供する。本発
明の第３は、脂環式エポキシ基含有エチレン性不飽和化
合物（ｃ）とエチレン性不飽和基含有カルボン酸（ａ）
を共重合して得られた脂環式エポキシ基含有樹脂（ｑ）
とエチレン性不飽和基含有カルボン酸（ａ）との変性共
重合体（Ａ２）に、有機溶剤（Ｓ）又は有機溶剤（Ｓ）
と重合性ビニルモノマー（Ｂ）を配合してなる活性エネ
ルギー線硬化型不飽和樹脂組成物を提供する。本発明の
第４は、脂環式エポキシ基含有樹脂（ｑ）が脂環式エポ
キシ基含有エチレン性不飽和化合物（ｃ）とエチレン性
不飽和基含有カルボン酸（ａ）とエチレン性不飽和基含
有カルボン酸（ａ）以外の不飽和化合物（ｂ）を共重合
して得られたものである本発明の第３に記載の活性エネ
ルギー線硬化型不飽和樹脂組成物を提供する。本発明の
第５は、有機溶剤にプロピレングリコールエーテル類を
用いることを特徴とする本発明の第１または３に記載の
活性エネルギー線硬化型不飽和樹脂組成物を提供する。
本発明の第６は、プロピレングリコールエーテル類がプ
ロピレングリコールモノメチルエーテルであることを特
徴とする本発明の第５に記載の活性エネルギー線硬化型
不飽和樹脂組成物を提供する。本発明の第７は、さらに
重合開始剤を含むことを特徴とする本発明の第１〜６の
いずれかに記載の活性エネルギー線硬化型不飽和樹脂組
成物を提供する。That is, a first aspect of the present invention is that an acid group-containing resin (p) obtained by polymerizing an ethylenically unsaturated group-containing carboxylic acid (a) and an alicyclic epoxy group-containing ethylenically unsaturated compound (c) )) And an organic solvent (S)
Alternatively, there is provided an active energy ray-curable unsaturated resin composition comprising an organic solvent (S) and a polymerizable vinyl monomer (B). A second aspect of the present invention is that the acid group-containing resin (p) is obtained by polymerizing an ethylenically unsaturated group-containing carboxylic acid (a) and an unsaturated compound (b) other than the ethylenically unsaturated group-containing carboxylic acid (a). The active energy ray-curable unsaturated resin composition according to the first aspect of the present invention, which is obtained, is provided. A third aspect of the present invention is that an alicyclic epoxy group-containing ethylenically unsaturated compound (c) and an ethylenically unsaturated group-containing carboxylic acid (a)
(Q) alicyclic epoxy group-containing resin obtained by copolymerizing
Organic solvent (S) or organic solvent (S) to modified copolymer (A2) of carboxylic acid (a) and ethylenically unsaturated group-containing carboxylic acid (a)
And a polymerizable vinyl monomer (B). A fourth aspect of the present invention is that the alicyclic epoxy group-containing resin (q) comprises an alicyclic epoxy group-containing ethylenically unsaturated compound (c), an ethylenically unsaturated group-containing carboxylic acid (a), and an ethylenically unsaturated group. The active energy ray-curable unsaturated resin composition according to the third aspect of the present invention is obtained by copolymerizing an unsaturated compound (b) other than the carboxylic acid (a) contained. A fifth aspect of the present invention provides the active energy ray-curable unsaturated resin composition according to the first or third aspect of the present invention, wherein a propylene glycol ether is used as an organic solvent.
A sixth aspect of the present invention provides the active energy ray-curable unsaturated resin composition according to the fifth aspect, wherein the propylene glycol ether is propylene glycol monomethyl ether. A seventh aspect of the present invention provides the active energy ray-curable unsaturated resin composition according to any one of the first to sixth aspects of the present invention, further comprising a polymerization initiator.
【０００６】また、本発明では以下の発明も開示され
る。脂環式エポキシ基含有エチレン性不飽和化合物
（ｃ）を重合して得られた脂環式エポキシ基含有樹脂
（ｑ）とエチレン性不飽和基含有カルボン酸（ａ）との
変性共重合体（Ａ２）に、有機溶剤（Ｓ）又は有機溶剤
（Ｓ）と重合性ビニルモノマー（Ｂ）を配合してなる活
性エネルギー線硬化型不飽和樹脂組成物が開示される。
脂環式エポキシ基含有樹脂（ｑ）が脂環式エポキシ基含
有エチレン性不飽和化合物（ｃ）とエチレン性不飽和基
含有カルボン酸（ａ）以外の不飽和化合物（ｂ）を重合
して得られたものである上記の発明に記載の活性エネル
ギー線硬化型不飽和樹脂組成物が開示される。以下、本
発明を詳細に説明する。The present invention also discloses the following invention. Modified copolymer of alicyclic epoxy group-containing resin (q) obtained by polymerizing alicyclic epoxy group-containing ethylenically unsaturated compound (c) and ethylenically unsaturated group-containing carboxylic acid (a) ( A2) discloses an active energy ray-curable unsaturated resin composition obtained by blending an organic solvent (S) or an organic solvent (S) with a polymerizable vinyl monomer (B).
The alicyclic epoxy group-containing resin (q) is obtained by polymerizing the alicyclic epoxy group-containing ethylenically unsaturated compound (c) and the unsaturated compound (b) other than the ethylenically unsaturated group-containing carboxylic acid (a). The active energy ray-curable unsaturated resin composition according to the invention described above is disclosed. Hereinafter, the present invention will be described in detail.
【０００７】[0007]
【発明の実施の形態】（Ａ）変性重合体 本発明において硬化型不飽和樹脂組成物に使用する変性
重合体（Ａ）は、下記変性重合体（Ａ１）又は変性重合
体（Ａ２）である。変性重合体（Ａ１）はエチレン性不
飽和基含有カルボン酸（ａ）を、必要に応じて加えられ
るエチレン性不飽和基含有カルボン酸（ａ）以外の不飽
和化合物（ｂ）と、ビニル重合して得られた酸基含有樹
脂（ｐ）が有するカルボキシル基に、脂環式エポキシ基
含有エチレン性不飽和化合物（ｃ）（以下、エポキシ基
含有不飽和化合物（ｃ）と略称する。）を付加させて得
られた変性重合体である。変性共重合体（Ａ２）は、エ
ポキシ基含有不飽和化合物（ｃ）とエチレン性不飽和基
含有カルボン酸（ａ）をビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ１）、エポキシ基含有不飽和
化合物（ｃ）とエチレン性不飽和基含有カルボン酸
（ａ）とエチレン性不飽和基含有カルボン酸（ａ）以外
の不飽和化合物（ｂ）とビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ２）、エポキシ基含有不飽和
化合物（ｃ）をビニル重合して得られた脂環式エポキシ
基含有樹脂（ｑ３）、又はエポキシ基含有不飽和化合物
（ｃ）とエチレン性不飽和基含有カルボン酸（ａ）以外
の不飽和化合物（ｂ）とビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ４）（ここで、ｑ１、ｑ２、
ｑ３又はｑ４を、区別が不要の場合には単にｑとい
う。）が有するエポキシ基に、エチレン性不飽和基含有
カルボン酸（ａ）を付加させて得られた変性重合体であ
る。BEST MODE FOR CARRYING OUT THE INVENTION (A) Modified Polymer The modified polymer (A) used in the curable unsaturated resin composition of the present invention is the following modified polymer (A1) or modified polymer (A2). . The modified polymer (A1) is obtained by vinyl polymerization of an ethylenically unsaturated group-containing carboxylic acid (a) with an unsaturated compound (b) other than the ethylenically unsaturated group-containing carboxylic acid (a) added as necessary. The alicyclic epoxy group-containing ethylenically unsaturated compound (c) (hereinafter abbreviated as epoxy group-containing unsaturated compound (c)) is added to the carboxyl group of the acid group-containing resin (p) obtained as described above. It is a modified polymer obtained by the above. The modified copolymer (A2) is an alicyclic epoxy group-containing resin (q1) obtained by vinyl copolymerizing an epoxy group-containing unsaturated compound (c) and an ethylenically unsaturated group-containing carboxylic acid (a), Obtained by vinyl copolymerization with an epoxy group-containing unsaturated compound (c), an ethylenically unsaturated group-containing carboxylic acid (a), and an unsaturated compound (b) other than the ethylenically unsaturated group-containing carboxylic acid (a). An alicyclic epoxy group-containing resin (q2), an alicyclic epoxy group-containing resin (q3) obtained by vinyl polymerization of an epoxy group-containing unsaturated compound (c), or an epoxy group-containing unsaturated compound (c). Alicyclic epoxy group-containing resin (q4) obtained by vinyl copolymerization with unsaturated compound (b) other than ethylenically unsaturated group-containing carboxylic acid (a) (where q1, q2,
When no distinction is required, q3 or q4 is simply referred to as q. ) Is a modified polymer obtained by adding a carboxylic acid (a) containing an ethylenically unsaturated group to the epoxy group of (a).
【０００８】初めに、本発明で使用される原料について
説明する。 （ａ）エチレン性不飽和基含有カルボン酸 上記エチレン性不飽和基含有カルボン酸（ａ）とは、分
子中にエチレン性不飽和基を含有し且つ少なくとも１個
のカルボキシル基を有するビニル重合可能な不飽和カル
ボン酸であって、後述する不飽和化合物（ｂ）と共重合
することができる。具体的には、アクリル酸、メタクリ
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、マレイン
酸、フマール酸、イタコン酸の他、一般式（１）で表せ
る化合物が例示できる。 ＣＨ2＝ＣＲ1ＣＯＯＣＨ2ＣＨ2Ｏ[ＣＯ(ＣＨ2)5Ｏ]ｎＣＯＸＣＯＯＨ （１） （式中、ｎは１〜１０の整数であり、Ｒ1は水素原子ま
たはメチル基を示し、Ｘは炭素数１〜４の（無水）カル
ボン酸残基を示す。） 一般式（１）の化合物は、例えば、ヒドロキシエチル
（メタ）アクリレートにε−カプロラクトンを付加して
得られる化合物に、さらにＸ（ＣＯＯＨ）2またはその
酸無水物を反応させることにより製造することができ
る。First, the raw materials used in the present invention will be described. (A) Ethylenically unsaturated group-containing carboxylic acid The above-mentioned ethylenically unsaturated group-containing carboxylic acid (a) is a vinyl-polymerizable polymer containing an ethylenically unsaturated group in a molecule and having at least one carboxyl group. An unsaturated carboxylic acid, which can be copolymerized with the unsaturated compound (b) described below. Specifically, acrylic acid, methacrylic acid, 2-carboxyethyl (meth) acrylate, 2
-Carboxypropyl (meth) acrylate, maleic acid, fumaric acid, itaconic acid, and compounds represented by the general formula (1) can be exemplified. CH 2 = CR 1 COOCH 2 CH 2 O [CO (CH 2 ) 5 O] nCOXCOOH (1) (wherein, n is an integer of 1 to 10, R 1 represents a hydrogen atom or a methyl group, and X is The compound represented by the general formula (1) is, for example, a compound obtained by adding ε-caprolactone to hydroxyethyl (meth) acrylate, and X ( (COOH) 2 or an acid anhydride thereof.
【０００９】上記で使用される酸または酸無水物として
は、ジカルボン酸、トリカルボン酸、テトラカルボン
酸、ポリカルボン酸、またはそのモノ又はジ無水物が挙
げられるが、好ましくはジカルボン酸無水物である。具
体的には、無水フタル酸、テトラヒドロ無水フタル酸、
無水マレイン酸、無水トリメリット酸、無水ピロメリッ
ト酸、無水コハク酸、無水グルタル酸等が挙げられる。Examples of the acid or acid anhydride used above include dicarboxylic acid, tricarboxylic acid, tetracarboxylic acid, polycarboxylic acid, and mono- or di-anhydride thereof, preferably dicarboxylic anhydride. . Specifically, phthalic anhydride, tetrahydrophthalic anhydride,
Examples include maleic anhydride, trimellitic anhydride, pyromellitic anhydride, succinic anhydride, glutaric anhydride and the like.
【００１０】（ｂ）不飽和カルボン酸以外の不飽和化合
物 エチレン性不飽和基含有カルボン酸（ａ）以外の不飽和
化合物（ｂ）としては、上記エチレン性不飽和基含有カ
ルボン酸（ａ）と共重合可能な化合物であって、メチル
（メタ）アクリレート、ブチル（メタ）アクリレート、
ベンジル（メタ）アクリレート、シクロヘキシル（メ
タ）アクリレート、イソボニル（メタ）アクリレート、
ヒドロキシエチル（メタ）アクリレートの他、下記一般
式（２）で表される化合物のエステル類、スチレン、ヒ
ドロキシスチレンなどのスチレン類、無水マレイン酸、
マレイン酸イミド等が例示できる。 ＣＨ2＝ＣＲ1ＣＯＯＣＨ2ＣＨ2Ｏ[ＣＯ(ＣＨ2)5Ｏ]ｎＨ （２） （式中、ｎは１〜１０の整数であり、Ｒ1は水素原子ま
たはメチル基を示す。） 一般式（２）の化合物は、例えば、ヒドロキシエチル
（メタ）アクリレートにε−カプロラクトンを付加させ
ることにより製造することができる。(B) Unsaturated Compounds Other than Unsaturated Carboxylic Acid The unsaturated compounds (b) other than the ethylenically unsaturated group-containing carboxylic acid (a) include the above-mentioned ethylenically unsaturated group-containing carboxylic acid (a). A copolymerizable compound, comprising methyl (meth) acrylate, butyl (meth) acrylate,
Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate,
In addition to hydroxyethyl (meth) acrylate, esters of compounds represented by the following general formula (2), styrenes such as styrene and hydroxystyrene, maleic anhydride,
Maleic imide and the like can be exemplified. CH 2 = CR 1 COOCH 2 CH 2 O [CO (CH 2) 5 O] nH (2) ( wherein, n is an integer from 1 to 10, R 1 represents a hydrogen atom or a methyl group.) General The compound of the formula (2) can be produced, for example, by adding ε-caprolactone to hydroxyethyl (meth) acrylate.
【００１１】不飽和カルボン酸（ａ）以外の不飽和化合
物（ｂ）としては、使用用途に応じて選択することがで
き、一般的には（メタ）アクリル酸エステルを使用す
る。The unsaturated compound (b) other than the unsaturated carboxylic acid (a) can be selected according to the intended use, and (meth) acrylic acid esters are generally used.
【００１２】（ｐ）酸基含有樹脂 エチレン性不飽和基含有カルボン酸（ａ）単独、又はエ
チレン性不飽和基含有カルボン酸（ａ）と不飽和化合物
（ｂ）とのビニル重合反応は、常法に従って行われて、
酸基含有樹脂（ｐ）を生じる。不飽和基含有カルボン酸
（ａ）と不飽和化合物（ｂ）との構成モル比は、通常、
３：７〜７：３の間で、目的に応じて広く選択すること
ができる。この範囲で耐候性、密着性に優れる樹脂が得
られるからである。上記酸基含有樹脂（ｐ）は、該樹脂
に由来する酸基の一部とエポキシ基含有不飽和化合物
（ｃ）に含まれるエポキシ基とを付加反応させて該樹脂
中に不飽和基を導入することが行なわれるが、該樹脂中
に活性エネルギー線の硬化に必要な不飽和基を導入する
必要があることから、酸基含有樹脂（ｐ）の酸価は１５
以上、好ましくは４０〜５００の範囲である。即ち、高
酸価樹脂である。酸価が１５未満ではアルカリによる未
硬化樹脂組成物の除去が難しく、上記範囲より大きくな
りすぎると硬化被膜の耐湿性、電気特性が劣る場合があ
る。(P) Acid group-containing resin The vinyl polymerization reaction of the ethylenically unsaturated group-containing carboxylic acid (a) alone or the ethylenically unsaturated group-containing carboxylic acid (a) and the unsaturated compound (b) is usually carried out. Done according to law,
This produces an acid-containing resin (p). The constituent molar ratio of the unsaturated group-containing carboxylic acid (a) to the unsaturated compound (b) is usually
It can be widely selected from 3: 7 to 7: 3 depending on the purpose. This is because a resin having excellent weather resistance and adhesion can be obtained in this range. The acid group-containing resin (p) is subjected to an addition reaction between a part of the acid groups derived from the resin and the epoxy group contained in the epoxy group-containing unsaturated compound (c) to introduce an unsaturated group into the resin. However, since it is necessary to introduce an unsaturated group necessary for curing the active energy ray into the resin, the acid value of the acid group-containing resin (p) is 15
As described above, it is preferably in the range of 40 to 500. That is, it is a high acid value resin. If the acid value is less than 15, it is difficult to remove the uncured resin composition with an alkali. If the acid value is too large, the moisture resistance and electrical properties of the cured film may be poor.
【００１３】（ｃ）エポキシ基含有不飽和化合物 上記で得られる酸基含有樹脂（ｐ）の側鎖のカルボキシ
ル基に付加させるエポキシ基含有不飽和化合物（ｃ）と
しては、分子内に少なくとも１種類以上の脂環式骨格を
有する不飽和基含有エポキシ化合物であり、下記一般式
（３）で表される化合物及びそのカプロラクトン変性物
が挙げられる。これらは単独でも２種以上を併用しても
よい。(C) Epoxy group-containing unsaturated compound As the epoxy group-containing unsaturated compound (c) to be added to the carboxyl group in the side chain of the acid group-containing resin (p) obtained above, at least one kind in the molecule is used. The unsaturated group-containing epoxy compound having the alicyclic skeleton described above includes a compound represented by the following general formula (3) and a caprolactone modified product thereof. These may be used alone or in combination of two or more.
【００１４】[0014]
【化１】 Embedded image
【００１５】（各一般式中、Ｒ6は水素原子またはメチ
ル基を示し、Ｒ7は炭素数１〜６の２価の脂肪族飽和炭
化水素基を示し、Ｒ8は炭素数１〜１０の２価の炭化水
素基を示し、ｍは１〜１０の整数を示す。）(In each formula, R 6 represents a hydrogen atom or a methyl group, R 7 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R 8 represents a C 1 to 10 carbon atom. Represents a divalent hydrocarbon group, and m represents an integer of 1 to 10.)
【００１６】エポキシ基含有不飽和化合物（ｃ）を反応
させることにより、組成物の耐水性及び耐酸性が向上す
る。By reacting the epoxy group-containing unsaturated compound (c), the water resistance and acid resistance of the composition are improved.
【００１７】（Ａ１）変性重合体 変性重合体（Ａ１）は、以下の方法により製造すること
ができる。上記不飽和カルボン酸（ａ）のビニル重合反
応、又は不飽和カルボン酸（ａ）と不飽和化合物（ｂ）
とのビニル共重合反応は、常法に従って行い、単独重合
体又は共重合体を製造した後、得られた単独重合体又は
共重合体側鎖のカルボキシル基に脂環式骨格を有するエ
ポキシ基含有不飽和化合物（ｃ）を付加させる。エポキ
シ基含有不飽和化合物（ｃ）の使用量は、変性重合体
（Ａ１）１ｋｇに含まれる二重結合量が、０．５〜４．
０モル、特に１．０〜３．５モルになるように使用する
ことが好ましい。０．５モルより少ない場合には、十分
な硬化性がえられないことがあり、４．０モルより多い
場合には貯蔵安定性に劣る場合がある。付加反応は、温
度１３０℃以下、特に９０〜１３０℃で行われることが
好ましい。９０℃より低いと実用上十分な反応速度が得
られないことがあり、１３０℃より高いと熱によるラジ
カル重合によって二重結合部が架橋し、ゲル化物が生じ
ることがある。(A1) Modified Polymer The modified polymer (A1) can be produced by the following method. Vinyl polymerization reaction of the above unsaturated carboxylic acid (a), or unsaturated carboxylic acid (a) and unsaturated compound (b)
The vinyl copolymerization reaction with is carried out according to a conventional method to produce a homopolymer or a copolymer, and then obtain a homopolymer or a copolymer having an alicyclic skeleton containing an alicyclic skeleton at the carboxyl group of the side chain. The saturated compound (c) is added. The amount of the epoxy group-containing unsaturated compound (c) used is such that the amount of double bonds contained in 1 kg of the modified polymer (A1) is 0.5 to 4.0.
It is preferable to use 0 mol, particularly 1.0 to 3.5 mol. If the amount is less than 0.5 mol, sufficient curability may not be obtained, and if it is more than 4.0 mol, the storage stability may be poor. The addition reaction is preferably performed at a temperature of 130 ° C. or lower, particularly 90 to 130 ° C. If the temperature is lower than 90 ° C., a practically sufficient reaction rate may not be obtained. If the temperature is higher than 130 ° C., the double bond is cross-linked by radical polymerization due to heat, and a gel may be formed.
【００１８】（Ｓ）有機溶剤 付加反応には、有機溶剤（Ｓ）を使用することができ
る。この有機溶剤には特に制限はなく、原料及び生成物
を溶解するものであればよい。例えば、エチレングリコ
ール、プロピレングリコール、ジプロピレングリコール
などのグリコール類；メチルセロソルブ、プロピレング
リコールモノメチルエーテル、ジプロピレングリコール
モノメチルエーテルなどのグリコールエーテル類；エチ
レングリコールジアセテート、プロピレングリコールモ
ノメチルエーテルアセテートなどのグリコールエステル
類；及びこれらの混合溶剤が挙げられる。なかでも低毒
性及び樹脂硬化時の製膜性の良さから、溶剤はグリコー
ルエーテル類が好ましく、特に好ましい溶剤としてプロ
ピレングリコールモノメチルエーテルをあげることがで
きる。(S) Organic Solvent In the addition reaction, an organic solvent (S) can be used. The organic solvent is not particularly limited as long as it can dissolve raw materials and products. For example, glycols such as ethylene glycol, propylene glycol and dipropylene glycol; glycol ethers such as methyl cellosolve, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; glycol esters such as ethylene glycol diacetate and propylene glycol monomethyl ether acetate And mixed solvents thereof. Among them, glycol ethers are preferable as the solvent, and propylene glycol monomethyl ether can be cited as a particularly preferable solvent because of its low toxicity and good film-forming properties when the resin is cured.
【００１９】反応溶剤中の樹脂濃度は、２０〜８０重量
％であることが好ましい。樹脂濃度が２０％重量％より
小さいと十分な反応速度が得られないことがあり、８０
重量％以上であると反応溶液の粘度が高くなりすぎ攪拌
が不十分になる恐れがある。The resin concentration in the reaction solvent is preferably from 20 to 80% by weight. If the resin concentration is less than 20% by weight, a sufficient reaction rate may not be obtained.
If the content is more than 10% by weight, the viscosity of the reaction solution may be too high and stirring may be insufficient.
【００２０】酸基含有樹脂（ｐ）の側鎖のカルボキシル
基にエポキシ基含有不飽和化合物（ｃ）を付加させて変
性重合体（Ａ）を得る反応では、十分な反応速度を得る
ために、触媒を用いて行うのが好ましい。触媒として
は、トリフェニルフォスフィン、トリブチルフォスフィ
ンなどのフォスフィン類；トリエチルアミン、ジメチル
ベンジルアミンなどのアミン類；ジメチルスルフィドな
どのスルフィド類などを用いることができるが、反応速
度面からフォスフィン類が好ましい。これらの触媒の量
はエポキシ基含有不飽和化合物（ｃ）に対して、通常、
０．０１〜１０重量％、好ましくは０．５〜５．０重量
％使用する。触媒量が０．０１％重量％より少ない場合
には十分な反応速度が得られないことがあり、１０重量
％より多く加えると生成した樹脂の諸物性に悪影響を及
ぼす恐れがある。In the reaction of adding the epoxy group-containing unsaturated compound (c) to the carboxyl group on the side chain of the acid group-containing resin (p) to obtain the modified polymer (A), in order to obtain a sufficient reaction rate, It is preferable to use a catalyst. As the catalyst, phosphines such as triphenylphosphine and tributylphosphine; amines such as triethylamine and dimethylbenzylamine; sulfides such as dimethylsulfide and the like can be used, and phosphines are preferred from the viewpoint of reaction rate. The amount of these catalysts is usually based on the amount of the epoxy group-containing unsaturated compound (c).
It is used in an amount of 0.01 to 10% by weight, preferably 0.5 to 5.0% by weight. If the amount of the catalyst is less than 0.01% by weight, a sufficient reaction rate may not be obtained, and if the amount is more than 10% by weight, the physical properties of the produced resin may be adversely affected.
【００２１】付加反応中のゲル物の生成を防止するため
に、本反応はハイドロキノン、ハイドロキノンモノメチ
ルエーテル、フェノチアジンなどの重合禁止剤存在下で
行うことが好ましい。これらの重合禁止剤の量は反応液
全体に対して１〜１０，０００ｐｐｍであることが好ま
しい。重合禁止剤量が反応液全体に対して１ｐｐｍ未満
であると十分な重合禁止効果が得られないことがあり、
１０，０００ｐｐｍを越えると生成した樹脂の諸物性に
悪影響を及ぼす恐れがある。同様の理由から、本付加反
応は分子状酸素含有ガス雰囲気下で行うことが好まし
い。酸素濃度は反応系中に爆発性混合物を形成しないよ
うな濃度であればよいが、通常は１〜７％になるように
調整する。This reaction is preferably carried out in the presence of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether and phenothiazine in order to prevent the formation of a gel during the addition reaction. The amount of these polymerization inhibitors is preferably 1 to 10,000 ppm based on the whole reaction solution. If the amount of the polymerization inhibitor is less than 1 ppm based on the whole reaction solution, a sufficient polymerization inhibitory effect may not be obtained,
If it exceeds 10,000 ppm, the properties of the produced resin may be adversely affected. For the same reason, this addition reaction is preferably performed in an atmosphere of a molecular oxygen-containing gas. The oxygen concentration may be any concentration that does not form an explosive mixture in the reaction system, but is usually adjusted to 1 to 7%.
【００２２】脂環式エポキシ基含有樹脂（ｑ） 脂環式エポキシ基含有樹脂（ｑ）は、前述のように、エ
ポキシ基含有不飽和化合物（ｃ）とエチレン性不飽和基
含有カルボン酸（ａ）をビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ１）、エポキシ基含有不飽和
化合物（ｃ）とエチレン性不飽和基含有カルボン酸
（ａ）とエチレン性不飽和基含有カルボン酸（ａ）以外
の不飽和化合物（ｂ）とビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ２）、エポキシ基含有不飽和
化合物（ｃ）をビニル重合して得られた脂環式エポキシ
基含有樹脂（ｑ３）、又はエポキシ基含有不飽和化合物
（ｃ）とエチレン性不飽和基含有カルボン酸（ａ）以外
の不飽和化合物（ｂ）とビニル共重合して得られた脂環
式エポキシ基含有樹脂（ｑ４）、あるいは、これらの混
合物である。上記において、エポキシ基含有不飽和化合
物（ｃ）、エチレン性不飽和基含有カルボン酸（ａ）、
不飽和化合物（ｂ）は、酸基含有樹脂（ｐ）の項で述べ
たものと同じものが使用できる。得られた脂環式エポキ
シ基含有樹脂（ｑ）のエポキシ当量は２５０〜２，００
０、好ましくは２８０〜１，０００の範囲である。エポ
キシ基含有不飽和化合物（ｃ）とエチレン性不飽和基含
有カルボン酸（ａ）を共重合させる場合には、変性共重
合体（Ａ２）に要求される後述する酸価と前記変性共重
合体（Ａ１）において述べた二重結合の量に合わせて選
択される。Alicyclic epoxy group-containing resin (q) The alicyclic epoxy group-containing resin (q) is, as described above, an epoxy group-containing unsaturated compound (c) and an ethylenically unsaturated group-containing carboxylic acid (a). A) an alicyclic epoxy group-containing resin (q1) obtained by vinyl copolymerization, an epoxy group-containing unsaturated compound (c), an ethylenically unsaturated group-containing carboxylic acid (a), and an ethylenically unsaturated group-containing carboxylic acid. Alicyclic epoxy group-containing resin (q2) obtained by vinyl copolymerization with unsaturated compound (b) other than acid (a), and oil obtained by vinyl polymerization of epoxy group-containing unsaturated compound (c) Fat obtained by vinyl copolymerization with cyclic epoxy group-containing resin (q3) or unsaturated compound (b) other than epoxy group-containing unsaturated compound (c) and ethylenically unsaturated group-containing carboxylic acid (a) Cyclic epoxy group-containing resin (q4) Or a mixture thereof. In the above, an epoxy group-containing unsaturated compound (c), an ethylenically unsaturated group-containing carboxylic acid (a),
As the unsaturated compound (b), the same compounds as described in the section of the acid group-containing resin (p) can be used. The epoxy equivalent of the obtained alicyclic epoxy group-containing resin (q) is from 250 to 2,000.
0, preferably in the range of 280 to 1,000. When the epoxy group-containing unsaturated compound (c) and the ethylenically unsaturated group-containing carboxylic acid (a) are copolymerized, an acid value required for the modified copolymer (A2) described later and the modified copolymer are used. The selection is made according to the amount of the double bond described in (A1).
【００２３】（Ａ２）変性共重合体 変性共重合体（Ａ２）の製造は、上記脂環式エポキシ基
含有樹脂（ｑ）とエチレン性不飽和基含有カルボン酸
（ａ）を付加反応させて、該樹脂中に不飽和基を導入す
ることにより行なわれる。エポキシ基含有不飽和化合物
（ｃ）の使用量は、変性共重合体（Ａ２）１ｋｇに含ま
れる二重結合量が、０．５〜４．０モル、特に１．０〜
３．５モルになるように使用することが好ましい。０．
５モルより少ない場合には、十分な硬化性がえられない
ことがあり、４．０モルより多い場合には貯蔵安定性に
劣る場合がある。(A2) Modified copolymer The modified copolymer (A2) is produced by subjecting the alicyclic epoxy group-containing resin (q) and the carboxylic acid (a) containing an ethylenically unsaturated group to an addition reaction. This is carried out by introducing an unsaturated group into the resin. The amount of the epoxy group-containing unsaturated compound (c) used is such that the amount of double bonds contained in 1 kg of the modified copolymer (A2) is 0.5 to 4.0 mol, particularly 1.0 to 4.0 mol.
It is preferable to use 3.5 mol. 0.
If the amount is less than 5 mol, sufficient curability may not be obtained, and if it is more than 4.0 mol, the storage stability may be poor.
【００２４】付加反応の条件、触媒、溶剤、重合禁止剤
等は、変性共重合体（Ａ１）の製造の場合と同一であ
る。The conditions of the addition reaction, the catalyst, the solvent, the polymerization inhibitor and the like are the same as those for the production of the modified copolymer (A1).
【００２５】（Ｂ）重合性ビニルモノマー（反応性希釈
剤） 本発明の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、１個以上
の（メタ）アクリル基を有する反応性希釈剤としての重
合性ビニルモノマー（Ｂ）を配合する。（Ｂ）成分は、
（Ａ）成分１００重量部に対して１〜１５０重量部の割
合で配合される。重合性ビニルモノマー（Ｂ）として
は、変性共重合体（Ａ）を溶解し得るものであれば特に
制限はなく、例えば、イソボニル（メタ）アクリレー
ト、シクロヘキシル（メタ）アクリレート、オクチル
（メタ）アクリレート等のアルキルあるいはシクロアル
キル（メタ）アクリレート；２−ヒドロキシエチル（メ
タ）アクリレート、３−ヒドロキシプロピル（メタ）ア
クリレート等のヒドロキシアルキル（メタ）アクリレー
ト；エチレングリコールのモノまたはジ（メタ）アクリ
レート、メトキシエチレングリコールの（メタ）アクリ
レート、テトラエチレングリコールのモノまたはジ（メ
タ）アクリレート、トリプロピレングリコールのモノま
たはジ（メタ）アクリレート等のグリコールのモノまた
はジ（メタ）アクリレート；３，４−エポキシシクロヘ
キシルメチル（メタ）アクリレート、グリシジル（メ
タ）アクリレート等のエポキシ基含有（メタ）アクリレ
ート；グリセリンジ（メタ）アクリレートトリメチロー
ルプロパントリ（メタ）アクリレート、ペンタエリスリ
トールのトリまたはテトラ（メタ）アクリレート、ジペ
ンタエリスリトールヘキサアクリレート等のポリオール
またはそのアルキレンオキサイドの（メタ）アクリレー
ト等が例示できる。これらのうち、引火点が１００℃以
上であるものが製造工程における安全性確保の面から好
ましい。(B) Polymerizable vinyl monomer (reactive diluent) The active energy ray-curable unsaturated resin composition of the present invention may contain one or more (V) A polymerizable vinyl monomer (B) as a reactive diluent having a (meth) acryl group is blended. The component (B)
It is blended in a ratio of 1 to 150 parts by weight based on 100 parts by weight of the component (A). The polymerizable vinyl monomer (B) is not particularly limited as long as it can dissolve the modified copolymer (A). Examples thereof include isobonyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate. Alkyl or cycloalkyl (meth) acrylate; hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; ethylene glycol mono- or di (meth) acrylate, methoxyethylene glycol Mono- or di- (meth) acrylates of glycol, such as mono- or di- (meth) acrylate of tetraethylene glycol, mono- or di- (meth) acrylate of tripropylene glycol; 3,4-epoxy Epoxy group-containing (meth) acrylates such as cyclohexylmethyl (meth) acrylate and glycidyl (meth) acrylate; glycerin di (meth) acrylate trimethylolpropane tri (meth) acrylate, tri or tetra (meth) acrylate of pentaerythritol, Examples thereof include polyols such as pentaerythritol hexaacrylate and (meth) acrylates of alkylene oxides thereof. Among them, those having a flash point of 100 ° C. or higher are preferable from the viewpoint of ensuring safety in the manufacturing process.
【００２６】（Ｃ）重合開始剤 本発明の活性エネルギー線硬化型不飽和樹脂組成物に
は、紫外線硬化のために使用される重合開始剤（Ｃ）を
添加してもよい。使用する重合開始剤（Ｃ）としては、
特に制限はなく、ベンゾイン類、アセトフェノン類、ケ
タール類、ベンゾフェノン類、キサントン類、パーオキ
サイド類等の公知慣用のものを用いることができる。重
合開始剤は、硬化型不飽和樹脂組成物中に１〜１０重量
％の割合で配合することが好ましい。(C) Polymerization Initiator The active energy ray-curable unsaturated resin composition of the present invention may contain a polymerization initiator (C) used for ultraviolet curing. As the polymerization initiator (C) to be used,
There is no particular limitation, and known and commonly used substances such as benzoins, acetophenones, ketals, benzophenones, xanthones, peroxides and the like can be used. The polymerization initiator is preferably blended in the curable unsaturated resin composition at a ratio of 1 to 10% by weight.
【００２７】他の添加物 本発明の硬化型不飽和樹脂組成物には、必要に応じてエ
ポキシ樹脂等の反応性樹脂；硫酸バリウム、酸化珪素、
タルク、クレー及び炭酸カルシウム等の充填剤；フタロ
シアニングリーン、クリスタルバイオレット、酸化チタ
ン及びカーボンブラック等の着色用顔料；密着性付与剤
及びレベリング剤等の各種添加剤、並びにハイドロキノ
ン、ハイドロキノンモノメチルエーテル、フェノチアジ
ン等の重合禁止剤等を配合することができる。Other Additives The curable unsaturated resin composition of the present invention may contain, if necessary, a reactive resin such as an epoxy resin; barium sulfate, silicon oxide,
Fillers such as talc, clay and calcium carbonate; coloring pigments such as phthalocyanine green, crystal violet, titanium oxide and carbon black; various additives such as adhesion promoters and leveling agents; hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like Can be blended.
【００２８】本発明の組成物は、特に脂環式エポキシ基
含有エチレン性不飽和化合物（ｃ）に由来する脂環式エ
ポキシ基とエチレン性不飽和基含有カルボン酸（ａ）に
由来する酸基との付加反応及び脂環式エポキシ基含有樹
脂に由来する脂環式エポキシ基と酸基含有不飽和化合物
に由来する酸基との開環付加反応の反応性が高いために
容易に反応して、樹脂中に活性エネルギー線硬化可能な
不飽和基を導入することができる。本発明の活性エネル
ギー線硬化型不飽和樹脂組成物は、塗料、インキ、接着
剤、レジスト樹脂等の構成成分として有用である。The composition of the present invention is particularly useful in an alicyclic epoxy group-containing ethylenically unsaturated compound (c) and an alicyclic epoxy group and an acid group derived from an ethylenically unsaturated group-containing carboxylic acid (a). And the ring-opening addition reaction between the alicyclic epoxy group derived from the alicyclic epoxy group-containing resin and the acid group derived from the acid group-containing unsaturated compound has a high reactivity. An active energy ray-curable unsaturated group can be introduced into the resin. The active energy ray-curable unsaturated resin composition of the present invention is useful as a constituent component of paints, inks, adhesives, resist resins and the like.
【００２９】[0029]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明はこれらに限定されるものではない。な
お、「％」は、特に示す場合を除くほか「重量％」を示
す。 （評価項目） （１）密着性：ＪＩＳ Ｋ５４００「碁盤目試験」に従
い評価した。 （２）耐水性：沸騰水中に１時間浸漬し、塗膜表面を目
視観察した。 （３）耐酸性：３０℃の２０％塩酸中に１時間浸漬し、
塗膜表面を目視観察した。EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Note that “%” indicates “% by weight” unless otherwise specified. (Evaluation items) (1) Adhesion: Evaluated in accordance with JIS K5400 "Cross-cut test". (2) Water resistance: The coating film surface was immersed in boiling water for 1 hour, and the coating film surface was visually observed. (3) Acid resistance: immersed in 20% hydrochloric acid at 30 ° C for 1 hour,
The coating film surface was visually observed.
【００３０】（製造例１）攪拌機、温度計、還流冷却
管、滴下ロート及び窒素導入管を備えた内容積５リット
ルのセパラブルフラスコにプロピレングリコールモノメ
チルエーテル６００ｇ及びｔ−ブチルパーオキシ−２−
エチルヘキサノエート１０ｇを仕込み、９０℃に昇温
後、メタクリル酸２００ｇ、メタクリル酸ベンジル２５
０ｇ、プロピレングリコールモノメチルエーテル３００
ｇ及びアゾビスジメチルバレロニトリル１０ｇの混合液
を３時間かけて滴下し、さらに６時間熟成することによ
り、カルボキシル基含有アクリル系樹脂溶液を得た。反
応は窒素気流下で行った。続いて、３，４−エポキシシ
クロヘキシルメチルアクリレート（ダイセル化学工業
（株）製「サイクロマーＡ２００」）４２５ｇ、トリフ
ェニルフォスフィン４５ｇ及びハイドロキノンモノメチ
ルエーテル１．８ｇを加え、１００℃で２０時間反応さ
せることにより、変性共重合体（Ａ１）の溶液を得た。
反応は酸素７容量％、窒素９３％容量の混合気流下で行
った。(Production Example 1) 600 g of propylene glycol monomethyl ether and t-butylperoxy-2- were placed in a 5-liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet tube.
After charging 10 g of ethyl hexanoate and heating to 90 ° C., 200 g of methacrylic acid and 25 g of benzyl methacrylate were added.
0 g, propylene glycol monomethyl ether 300
g and 10 g of azobisdimethylvaleronitrile were added dropwise over 3 hours, and the mixture was aged for 6 hours to obtain a carboxyl group-containing acrylic resin solution. The reaction was performed under a nitrogen stream. Subsequently, 425 g of 3,4-epoxycyclohexylmethyl acrylate (“Cyclomer A200” manufactured by Daicel Chemical Industries, Ltd.), 45 g of triphenylphosphine, and 1.8 g of hydroquinone monomethyl ether were added, and reacted at 100 ° C. for 20 hours. As a result, a solution of the modified copolymer (A1) was obtained.
The reaction was performed under a mixed gas flow of 7% by volume of oxygen and 93% by volume of nitrogen.
【００３１】（比較製造例１）製造例１と同様のフラス
コにプロピレングリコールモノメチルエーテル６００ｇ
及びｔ−ブチルパーオキシ−２−エチルヘキサノエート
１０ｇを仕込み、９０℃に昇温後、メタクリル酸２００
ｇ、メタクリル酸ベンジル２５０ｇ、プロピレングリコ
ールモノメチルエーテル３００ｇ及びアゾビスジメチル
バレリニトリル１０ｇの混合溶液を３時間かけて滴下
し、さらに６時間熟成することにより、カルボキシル基
含有アクリル系樹脂溶液を得た。反応は窒素気流下で行
った。続いて、グリシジルメタクリレート３３０ｇ、ト
リフェニルフォスフィン４５ｇ及びハイドロキノンモノ
メチルエーテル１．８ｇを加え、１００℃で３０時間反
応させることにより、硬化性樹脂（Ｂ１）の溶液を得
た。反応は酸素７容量％、窒素９３容量％の混合気流下
で行った。Comparative Example 1 600 g of propylene glycol monomethyl ether was placed in the same flask as in Example 1.
And 10 g of t-butylperoxy-2-ethylhexanoate, heated to 90 ° C.,
g, benzyl methacrylate 250 g, propylene glycol monomethyl ether 300 g and a mixed solution of azobisdimethyl valerinitrile 10 g were added dropwise over 3 hours, and the mixture was aged for 6 hours to obtain a carboxyl group-containing acrylic resin solution. The reaction was performed under a nitrogen stream. Subsequently, 330 g of glycidyl methacrylate, 45 g of triphenylphosphine and 1.8 g of hydroquinone monomethyl ether were added, and reacted at 100 ° C. for 30 hours to obtain a solution of the curable resin (B1). The reaction was performed under a mixed gas flow of 7% by volume of oxygen and 93% by volume of nitrogen.
【００３２】（実施例１）実施例１として、製造例１で
製造した変性共重合体（Ａ１）の溶液（Ａ１の乾燥重量
に換算して５０重量部）に、トリメチロールプロパント
リアクリレート５０重量部、開始剤としてチバガイギー
製「イルガキュア９０７」２重量部を配合して硬化性樹
脂組成物を調製した。硬化性樹脂組成物をボンデライト
鋼板ＰＢ−１４４（日本テストパネル（株）製）に膜厚
１０ミクロンで塗布し、高圧水銀灯（露光量１，０００
ｍＪ／ｃｍ2）で露光後、１５０℃で２０分間加熱処理
した。得られた塗膜について密着性、耐水性、耐酸性を
評価した。結果を表１に表す。Example 1 As Example 1, 50 parts by weight of trimethylolpropane triacrylate was added to a solution of the modified copolymer (A1) produced in Production Example 1 (50 parts by weight in terms of the dry weight of A1). And 2 parts by weight of "Irgacure 907" manufactured by Ciba Geigy as an initiator to prepare a curable resin composition. The curable resin composition was applied to a bonderite steel sheet PB-144 (manufactured by Nippon Test Panel Co., Ltd.) at a film thickness of 10 microns, and a high-pressure mercury lamp (exposure:
(mJ / cm 2 ) and heat-treated at 150 ° C. for 20 minutes. The obtained coating film was evaluated for adhesion, water resistance, and acid resistance. The results are shown in Table 1.
【００３３】（比較例１）製造例１で製造した変性共重
合体の代わりに比較製造例１で製造した変性共重合体
（Ｂ１）の溶液を使用し、実施例１と同様に操作して塗
膜について評価を行った。Comparative Example 1 The procedure of Example 1 was repeated, except that the solution of the modified copolymer (B1) produced in Comparative Production Example 1 was used instead of the modified copolymer produced in Production Example 1. The coating film was evaluated.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】本発明の活性エネルギー線硬化型不飽和
樹脂組成物から形成される被膜はエチレン性不飽和基含
有カルボン酸に由来する酸基と脂環式エポキシ基含有エ
チレン性不飽和化合物のエポキシ基との化学反応によっ
て生じた分子骨格が比較的立体障害の大きな構造である
ため加水分解促進物質（例えば水、海水等）に対して化
学的に安定であり、耐水性等の耐久性に優れた顕著な硬
化を奏すると共に密着性に優れる。また、溶剤が低毒性
であるために、製造及び使用時に特別な設備を必要とし
ない。The film formed from the active energy ray-curable unsaturated resin composition of the present invention comprises an acid group derived from an ethylenically unsaturated group-containing carboxylic acid and an alicyclic epoxy group-containing ethylenically unsaturated compound. Since the molecular skeleton generated by the chemical reaction with the epoxy group has a structure with relatively large steric hindrance, it is chemically stable to hydrolysis promoting substances (eg, water, seawater, etc.), and has durability such as water resistance. Excellent remarkable curing and excellent adhesion. In addition, since the solvent has low toxicity, no special equipment is required for production and use.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J011 QA03 QA13 QA23 QA24 QB02 QB03 SA01 SA02 SA21 SA22 SA31 SA32 SA61 SA62 SA76 UA01 WA01 WA02 WA05 WA06 4J027 AA02 AA08 BA07 BA08 BA20 BA21 BA26 BA28 CA11 CA14 CA16 CA18 CB10 4J100 AB02Q AB07Q AJ02P AJ08P AJ09P AK32Q AL03Q AL08P AL08Q AL09Q AM21Q AM43Q BA02Q BA03Q BA15Q BA16P BA21P BA21Q BA38Q BC03Q BC04Q BC07Q BC43Q BC54Q BC58Q CA01 CA04 CA31 HA62 JA01 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 QA03 QA13 QA23 QA24 QB02 QB03 SA01 SA02 SA21 SA22 SA31 SA32 SA61 SA62 SA76 UA01 WA01 WA02 WA05 WA06 4J027 AA02 AA08 BA07 BA08 BA20 BA21 BA26 BA28 CA11 CA14 CA16 CA18CB10 AB10Q AJ02P AJ08P AJ09P AK32Q AL03Q AL08P AL08Q AL09Q AM21Q AM43Q BA02Q BA03Q BA15Q BA16P BA21P BA21Q BA38Q BC03Q BC04Q BC07Q BC43Q BC54Q BC58Q CA01 CA04 CA31 HA62 JA01
Claims (7)
（ａ）を重合して得られた酸基含有樹脂（ｐ）と脂環式
エポキシ基含有エチレン性不飽和化合物（ｃ）との変性
重合体（Ａ１）に、有機溶剤（Ｓ）又は有機溶剤（Ｓ）
と重合性ビニルモノマー（Ｂ）を配合してなる活性エネ
ルギー線硬化型不飽和樹脂組成物。1. A modified polymer of an acid group-containing resin (p) obtained by polymerizing an ethylenically unsaturated group-containing carboxylic acid (a) and an alicyclic epoxy group-containing ethylenically unsaturated compound (c). (A1) an organic solvent (S) or an organic solvent (S)
And an active energy ray-curable unsaturated resin composition comprising a polymerizable vinyl monomer (B).
基含有カルボン酸（ａ）とエチレン性不飽和基含有カル
ボン酸（ａ）以外の不飽和化合物（ｂ）を重合して得ら
れたものである請求項１に記載の活性エネルギー線硬化
型不飽和樹脂組成物。2. An acid group-containing resin (p) obtained by polymerizing an ethylenically unsaturated group-containing carboxylic acid (a) and an unsaturated compound (b) other than the ethylenically unsaturated group-containing carboxylic acid (a). The active energy ray-curable unsaturated resin composition according to claim 1, wherein
化合物（ｃ）とエチレン性不飽和基含有カルボン酸
（ａ）を共重合して得られた脂環式エポキシ基含有樹脂
（ｑ）とエチレン性不飽和基含有カルボン酸（ａ）との
変性共重合体（Ａ２）に、有機溶剤（Ｓ）又は有機溶剤
（Ｓ）と重合性ビニルモノマー（Ｂ）を配合してなる活
性エネルギー線硬化型不飽和樹脂組成物。3. An alicyclic epoxy group-containing resin (q) obtained by copolymerizing an alicyclic epoxy group-containing ethylenically unsaturated compound (c) and an ethylenically unsaturated group-containing carboxylic acid (a). Active energy ray curing obtained by blending an organic solvent (S) or an organic solvent (S) and a polymerizable vinyl monomer (B) with a modified copolymer (A2) with an ethylenically unsaturated group-containing carboxylic acid (a). Type unsaturated resin composition.
式エポキシ基含有エチレン性不飽和化合物（ｃ）とエチ
レン性不飽和基含有カルボン酸（ａ）とエチレン性不飽
和基含有カルボン酸（ａ）以外の不飽和化合物（ｂ）を
共重合して得られたものである請求項３に記載の活性エ
ネルギー線硬化型不飽和樹脂組成物。4. An alicyclic epoxy group-containing resin (q) comprising an alicyclic epoxy group-containing ethylenically unsaturated compound (c), an ethylenically unsaturated group-containing carboxylic acid (a) and an ethylenically unsaturated group-containing carboxylic acid. The active energy ray-curable unsaturated resin composition according to claim 3, which is obtained by copolymerizing an unsaturated compound (b) other than the acid (a).
ル類を用いることを特徴とする請求項１または請求項３
に記載の活性エネルギー線硬化型不飽和樹脂組成物。5. The method according to claim 1, wherein propylene glycol ethers are used as the organic solvent.
The active energy ray-curable unsaturated resin composition according to the above item.
ピレングリコールモノメチルエーテルであることを特徴
とする請求項５に記載の活性エネルギー線硬化型不飽和
樹脂組成物。6. The active energy ray-curable unsaturated resin composition according to claim 5, wherein the propylene glycol ether is propylene glycol monomethyl ether.
る請求項１〜６のいずれかに記載の活性エネルギー線硬
化型不飽和樹脂組成物。7. The active energy ray-curable unsaturated resin composition according to claim 1, further comprising a polymerization initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11064387A JP2000256429A (en) | 1999-03-11 | 1999-03-11 | Active energy ray-curable unsaturated resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11064387A JP2000256429A (en) | 1999-03-11 | 1999-03-11 | Active energy ray-curable unsaturated resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000256429A true JP2000256429A (en) | 2000-09-19 |
Family
ID=13256870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11064387A Pending JP2000256429A (en) | 1999-03-11 | 1999-03-11 | Active energy ray-curable unsaturated resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP2000256429A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100024893A (en) * | 2008-08-26 | 2010-03-08 | 타무라 카켄 코포레이션 | Photopolymer composition, solder resist composition for print circuit boards and print circuit boards |
| JP2012233168A (en) * | 2011-04-22 | 2012-11-29 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition and application using the same |
-
1999
- 1999-03-11 JP JP11064387A patent/JP2000256429A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100024893A (en) * | 2008-08-26 | 2010-03-08 | 타무라 카켄 코포레이션 | Photopolymer composition, solder resist composition for print circuit boards and print circuit boards |
| KR101727101B1 (en) * | 2008-08-26 | 2017-04-14 | 타무라 카켄 코포레이션 | Photopolymer composition, solder resist composition for print circuit boards and print circuit boards |
| JP2012233168A (en) * | 2011-04-22 | 2012-11-29 | Nippon Synthetic Chem Ind Co Ltd:The | Acrylic resin composition and application using the same |
| JP2016191070A (en) * | 2011-04-22 | 2016-11-10 | 日本合成化学工業株式会社 | Acrylic resin composition and applications using the same |
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