JP6997942B2 - Photocurable resin compositions, inks and paints - Google Patents
Photocurable resin compositions, inks and paints Download PDFInfo
- Publication number
- JP6997942B2 JP6997942B2 JP2017144566A JP2017144566A JP6997942B2 JP 6997942 B2 JP6997942 B2 JP 6997942B2 JP 2017144566 A JP2017144566 A JP 2017144566A JP 2017144566 A JP2017144566 A JP 2017144566A JP 6997942 B2 JP6997942 B2 JP 6997942B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- photocurable resin
- oil
- resin composition
- acrylate
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 59
- 239000003973 paint Substances 0.000 title claims description 8
- 239000000976 ink Substances 0.000 title description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 52
- -1 allyl compound Chemical class 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 49
- 229920000642 polymer Polymers 0.000 claims description 35
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 15
- 125000002723 alicyclic group Chemical group 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 239000002966 varnish Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 57
- 239000008158 vegetable oil Substances 0.000 description 54
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000001993 wax Substances 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 239000004641 Diallyl-phthalate Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 244000028419 Styrax benzoin Species 0.000 description 4
- 235000000126 Styrax benzoin Nutrition 0.000 description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 229960002130 benzoin Drugs 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 235000019382 gum benzoic Nutrition 0.000 description 4
- 150000004678 hydrides Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 3
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000019482 Palm oil Nutrition 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000019486 Sunflower oil Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002540 palm oil Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002600 sunflower oil Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical class C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- 235000019485 Safflower oil Nutrition 0.000 description 2
- 241001125048 Sardina Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000019868 cocoa butter Nutrition 0.000 description 2
- 229940110456 cocoa butter Drugs 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 235000005713 safflower oil Nutrition 0.000 description 2
- 239000003813 safflower oil Substances 0.000 description 2
- 235000019512 sardine Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 235000011803 sesame oil Nutrition 0.000 description 2
- 239000008159 sesame oil Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
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- HHCHLHOEAKKCAB-UHFFFAOYSA-N 2-oxaspiro[3.5]nonane-1,3-dione Chemical compound O=C1OC(=O)C11CCCCC1 HHCHLHOEAKKCAB-UHFFFAOYSA-N 0.000 description 1
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- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
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- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000010466 nut oil Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、一般式（１）で表されるアリル化合物を重合して得られるアリル重合体（Ａ）、
エポキシ化植物油（メタ）アクリレート（Ｂ）、
エチレン性不飽和化合物（Ｃ）とを含有することを特徴とする光硬化性樹脂組成物、
並びにその樹脂組成物を含んでなるインキ、塗料に関するものである。
The present invention is an allyl polymer (A) obtained by polymerizing an allyl compound represented by the general formula (1).
Epoxidized vegetable oil (meth) acrylate (B),
A photocurable resin composition comprising an ethylenically unsaturated compound (C),
It also relates to inks and paints containing the resin composition.
従来、光（紫外線等）により硬化させる種々の樹脂組成物が開示されている。そのような樹脂組成物は、インキ、塗料、接着剤、フォトレジストなどに使用されている。
例えば、紫外線硬化タイプの印刷インキは、硬化速度が早く短時間で硬化できること、溶剤を使わないので環境に適合していること、省資源・省エネルギーであること等の点が高く評価され実用化が広がっている。従来から、紫外線により硬化する印刷インキとしては、アクリレート等のエチレン性不飽和化合物、光開始剤、顔料等を含む種々の組み合わせが提案されている。
Conventionally, various resin compositions that are cured by light (ultraviolet rays or the like) have been disclosed. Such resin compositions are used in inks, paints, adhesives, photoresists and the like.
For example, UV-curing type printing inks are highly evaluated for their rapid curing speed and quick curing, environmental friendliness because they do not use solvents, and resource saving and energy saving, and are highly evaluated for practical use. It has spread. Conventionally, various combinations including ethylenically unsaturated compounds such as acrylates, photoinitiators, pigments and the like have been proposed as printing inks that are cured by ultraviolet rays.
しかし、例えば、エチレン性不飽和化合物としてジペンタエリスリトールヘキサアクリレート等を用いたインキ組成物は、添加される光硬化剤等の添加剤の種類にもよるが、インキ組成物自体の保存安定性がよくないことが一般に知られている。そして、保存安定性を改善するために、ジアリルフタレート樹脂を添加することで解決が図られている（特許文献１）。 However, for example, an ink composition using dipentaerythritol hexaacrylate or the like as an ethylenically unsaturated compound has a storage stability of the ink composition itself, although it depends on the type of additive such as a photocuring agent to be added. It is generally known that it is not good. Then, in order to improve the storage stability, a solution is attempted by adding a diallyl phthalate resin (Patent Document 1).
また、例えば、エチレン性不飽和化合物として、ポリエチレングリコールジアクリレートを用いて調製された印刷インキは乾燥皮膜上へのスタンプインキの定着及び固着が良いが、印刷インキ単独では耐湿水性が悪いことが知られている。そして、耐湿水性を改善するために、ジアリルフタレート樹脂を添加することで解決が図られている（特許文献２）。 Further, for example, it is known that a printing ink prepared by using polyethylene glycol diacrylate as an ethylenically unsaturated compound has good fixing and adhesion of the stamp ink on a dry film, but the printing ink alone has poor moisture resistance. Has been printed. Then, in order to improve the moisture resistance, the solution is attempted by adding a diallyl phthalate resin (Patent Document 2).
上記のように、ジアリルフタレート樹脂に代表されるイナート樹脂を添加することによって良好な効果が得られている。しかし、印刷インキ用樹脂組成物の主成分であるエチレン性不飽和化合物の種類によってはイナート樹脂の溶解性が悪く、添加後のインキ組成物は未溶解物のために白濁化し、印刷インキとしての適性が低下する。従来のイナート樹脂は、エチレン性不飽和化合物の種類によっては使用不可能であった。 As described above, a good effect is obtained by adding an inert resin typified by a diallyl phthalate resin. However, depending on the type of ethylenically unsaturated compound that is the main component of the resin composition for printing ink, the solubility of the inert resin is poor, and the ink composition after addition becomes cloudy due to the undissolved material, and is used as a printing ink. The aptitude is reduced. Conventional inert resins cannot be used depending on the type of ethylenically unsaturated compound.
より具体的には、近年、環境保護の観点から、インキ用樹脂組成物中に含まれるエチレン性不飽和化合物として、植物油アクリレート（例えば、エポキシ化大豆油アクリレート等が）頻繁に使用されている。エポキシ化大豆油アクリレートは、植物成分由来のため環境に適している反面、ジアリルフタレート樹脂に対する溶解性が悪いため、樹脂組成物を調製した場合に未溶解物による白濁化が問題点として指摘されている。 More specifically, in recent years, from the viewpoint of environmental protection, vegetable oil acrylates (for example, epoxidized soybean oil acrylates) are frequently used as ethylenically unsaturated compounds contained in resin compositions for inks. Since epoxidized soybean oil acrylate is suitable for the environment because it is derived from a plant component, it has poor solubility in diallyl phthalate resin, and it has been pointed out that white turbidity due to undissolved substances is a problem when preparing a resin composition. There is.
本発明の目的は、広範囲なエチレン性不飽和化合物に用いることのできる式（１）で表されるアリル化合物を重合して得られるアリル重合体（Ａ）を用いた光硬化性樹脂組成物を提供することにあり、より具体的には、エポキシ化植物油（メタ）アクリレートを含有するインキ、及び塗料に対して、アリル重合体（Ａ）を添加しても溶解性（相溶性）に優れる光硬化性樹脂組成物を提供することである。 An object of the present invention is to obtain a photocurable resin composition using an allyl polymer (A) obtained by polymerizing an allyl compound represented by the formula (1), which can be used for a wide range of ethylenically unsaturated compounds. More specifically, light having excellent solubility (compatibility) even when the allyl polymer (A) is added to an ink or a paint containing an epoxidized vegetable oil (meth) acrylate. The present invention is to provide a curable resin composition.
本発明者は、鋭意研究の結果、特定の構造を有するアリル重合体（Ａ）が、エポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン不飽和化合物を組合わせて用いることで、相溶性に優れることを見出し、本発明に完成するに至った。 As a result of diligent research, the present inventor has excellent compatibility with the allyl polymer (A) having a specific structure by using a combination of an epoxidized vegetable oil (meth) acrylate (B) and an ethylene unsaturated compound. We found that and came to complete the present invention.
すなわち、本発明は、以下のとおりである。
項１． 一般式（１）で表されるアリル化合物を重合して得られるアリル重合体（Ａ）と
エポキシ化植物油（メタ）アクリレート（Ｂ）、
エチレン性不飽和化合物（Ｃ）とを含有することを特徴とする光硬化性樹脂組成物。
項２． エポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン性不飽和化合物（Ｃ）の比率が１：９９～９９：１の範囲であることを特徴とする項１に記載の光硬化性樹脂組成物。
項３． 前記式（１）表されるアリル化合物が、式（２）～（９）で表される化合物が、
で表される化合物の何れかである項１または２に記載の光硬化性樹脂組成物。
項４． 更に、光重合開始剤を含有する項１～３のいずれかに記載の光硬化性樹脂組成物。
項５． 項１～４の何れかに記載の光硬化性樹脂組成物を含むことを特徴とするインキ。
項６． 項１～４の何れかに記載の光硬化性樹脂組成物を含むことを特徴とする塗料。
項７． オーバープリントワニスである項６に記載の塗料。
That is, the present invention is as follows.
Item 1. With the allyl polymer (A) obtained by polymerizing the allyl compound represented by the general formula (1)
Epoxidized vegetable oil (meth) acrylate (B),
A photocurable resin composition containing an ethylenically unsaturated compound (C).
Item 2. Item 2. The photocurable resin composition according to Item 1, wherein the ratio of the epoxidized vegetable oil (meth) acrylate (B) to the ethylenically unsaturated compound (C) is in the range of 1:99 to 99: 1.
Item 3. The allyl compound represented by the formula (1) and the compounds represented by the formulas (2) to (9) are
Item 3. The photocurable resin composition according to Item 1 or 2, which is any of the compounds represented by.
Item 4. The photocurable resin composition according to any one of Items 1 to 3, further comprising a photopolymerization initiator.
Item 5. An ink comprising the photocurable resin composition according to any one of Items 1 to 4.
Item 6. A coating material comprising the photocurable resin composition according to any one of Items 1 to 4.
Item 7. Item 6. The paint according to Item 6, which is an overprint varnish.
本発明によれば、インキ、塗料、接着剤及びフォトレジストの成分として使用した場合
に、特定の構造を有するアリル重合体（Ａ）がエポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン不飽和化合物（Ｃ）を組合わせて用いた際に相溶性に優れるため、光硬化性樹脂組成物として、広範囲の割合で、組成の調整が可能となる。とりわけ、プロピレンオキサイド変性アクリレートやエチレンオキサイド変性アクリレートなどのエチレン性不飽和化合物（Ｃ）とエポキシ化植物油（メタ）アクリレート（Ｂ）を併用して用いた場合、ジアリルフタレート樹脂では実現不可能な光硬化性樹脂組成の配合調整が可能となる。
According to the present invention, when used as a component of an ink, a paint, an adhesive and a photoresist, the allyl polymer (A) having a specific structure is an epoxidized vegetable oil (meth) acrylate (B) and an ethylene unsaturated compound. Since the compatibility of (C) is excellent when used in combination, the composition can be adjusted in a wide range as a photocurable resin composition. In particular, when an ethylenically unsaturated compound (C) such as a propylene oxide-modified acrylate or an ethylene oxide-modified acrylate is used in combination with an epoxidized vegetable oil (meth) acrylate (B), photocuring that cannot be achieved with a diallyl phthalate resin is possible. The composition of the sex resin can be adjusted.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
光硬化性樹脂組成物
本発明の光硬化性樹脂組成物は、式（１）で表されるアリル化合物を重合することによって得られるアリル重合体（Ａ）、エポキシ化植物油（メタ）アクリレート（Ｂ）、及びエチレン性不飽和化合物（Ｃ）を含有するものである。エポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン性不飽和化合物（Ｃ）を併用することで、アリル重合体（Ａ）との溶解性が得られる。これは、アリル重合体のＳＰ値とエポキシ化植物油（メタ）アクリレートとエチレン性不飽和化合物の混合物のＳＰ値が近似することによって、溶解性が向上しているものと推測される。
Photocurable Resin Composition The photocurable resin composition of the present invention is an allyl polymer (A) obtained by polymerizing an allyl compound represented by the formula (1), an epoxidized vegetable oil (meth) acrylate (B). ), And the ethylenically unsaturated compound (C). By using the epoxidized vegetable oil (meth) acrylate (B) and the ethylenically unsaturated compound (C) in combination, solubility in the allyl polymer (A) can be obtained. It is presumed that the solubility is improved by approximating the SP value of the allyl polymer with the SP value of the mixture of the epoxidized vegetable oil (meth) acrylate and the ethylenically unsaturated compound.
アリル重合体（Ａ）
本発明の光硬化性樹脂組成物には、式（１）で表されるアリル化合物を重合することによって得られるアリル重合体（Ａ）を用いることができる。
As the photocurable resin composition of the present invention, an allyl polymer (A) obtained by polymerizing an allyl compound represented by the formula (1) can be used.
アリル重合体（Ａ）の重量平均分子量は、２，０００～１５０，０００であることが好ましく、５，０００～１４０，０００であることがより好ましい。なお、明細書において、「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィー（島津製作所製、ＧＰＣシステム）を用いて常温で測定し、標準ポリスチレン検量線を用いて求めることができる。アリル重合体（Ａ）のＳＰ値としては、特に限定されないが、８～１２の範囲であればよい。 The weight average molecular weight of the allyl polymer (A) is preferably 2,000 to 150,000, more preferably 5,000 to 140,000. In the specification, the "weight average molecular weight" can be determined by measuring at room temperature using gel permeation chromatography (manufactured by Shimadzu Corporation, GPC system) and using a standard polystyrene calibration curve. The SP value of the allyl polymer (A) is not particularly limited, but may be in the range of 8 to 12.
式（１）で表されるアリル化合物に基づく単量体単位の含有量は、アリル重合体（Ａ）１００重量％中、２０重量％以上であることが好ましく、５０重量％以上であることがより好ましく、８０重量％以上であることが更に好ましく、９８重量％以上であることが特に好ましく、１００重量％であってもよい。 The content of the monomer unit based on the allyl compound represented by the formula (1) is preferably 20% by weight or more, preferably 50% by weight or more, based on 100% by weight of the allyl polymer (A). More preferably, it is more preferably 80% by weight or more, particularly preferably 98% by weight or more, and it may be 100% by weight.
光硬化性樹脂組成物におけるアリル重合体（Ａ）の含有量は、光硬化性樹脂組成物全量に対して、１～６０重量％であることが好ましく、１～５０重量％であることがより好ましく、５～４５重量％であることが更に好ましい。アリル重合体（Ａ）の含有量が６０重量％を超えると、エポキシ植物油（メタ）アクリレート（Ｂ）の溶解性が悪くなり、粘度も高くなり取扱い性が悪くなることがある。アリル重合体（Ａ）の含有量が１重量％未満であると、光硬化性樹脂組成物に充分な乾燥性が得られないことがある。 The content of the allyl polymer (A) in the photocurable resin composition is preferably 1 to 60% by weight, more preferably 1 to 50% by weight, based on the total amount of the photocurable resin composition. It is preferably 5 to 45% by weight, and more preferably 5 to 45% by weight. If the content of the allyl polymer (A) exceeds 60% by weight, the solubility of the epoxy vegetable oil (meth) acrylate (B) may be deteriorated, the viscosity may be increased, and the handleability may be deteriorated. If the content of the allyl polymer (A) is less than 1% by weight, the photocurable resin composition may not have sufficient drying properties.
（ｉ）ｎ価の脂環式炭化水素基
式（１）中のＺは、ｎ価の脂環式炭化水素基である。この場合、炭素数は３～１８であることが好ましく、４～１２であることがより好ましく、４～１０であることが特に好ましい。
ｎ価の脂環式炭化水素基は、飽和のｎ価の脂環式炭化水素基であってもよく、一部において不飽和結合を有していてもよい。なお、本発明において、脂環式とは、芳香性を有しない環状構造を有する炭化水素基を意味する。
式（１）中のｎ価は、２価又は３価であることが好ましく、２価であることがより好ましい。
(I) n-valent alicyclic hydrocarbon group Z in the formula (1) is an n-valent alicyclic hydrocarbon group. In this case, the number of carbon atoms is preferably 3 to 18, more preferably 4 to 12, and particularly preferably 4 to 10.
The n-valent alicyclic hydrocarbon group may be a saturated n-valent alicyclic hydrocarbon group, or may have an unsaturated bond in a part thereof. In the present invention, the alicyclic type means a hydrocarbon group having a cyclic structure without aromaticity.
The n-valent value in the formula (1) is preferably divalent or trivalent, and more preferably divalent.
また、ｎ価の脂環式炭化水素基はアルキル基を有していてもよい。アルキル基は炭素数１～１０の直鎖又は分岐鎖であればよく、炭素数１～５であることが好ましく、メチル基又はエチル基がより好ましい。アルキル基は、脂環式炭化水素基の置換可能位置に１個又は２個以上存在していてもよい。なお、ｎ価の脂環式炭化水素基は、必ずしもアルキル基を有していなくともよい。 Further, the n-valent alicyclic hydrocarbon group may have an alkyl group. The alkyl group may be a linear or branched chain having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. One or two or more alkyl groups may be present at the substitutable positions of the alicyclic hydrocarbon group. The n-valent alicyclic hydrocarbon group does not necessarily have to have an alkyl group.
式（１）で表される具体的なアリル化合物としては、式（２）～（９）の化合物を例示することができる。 As the specific allyl compound represented by the formula (1), the compounds of the formulas (2) to (9) can be exemplified.
式（２）～（９）、
式（２）～（９）において、環構造内で架橋されていてもよく、環構造内で架橋されたもの例として、アダマンダン、ノルボルナン等を例示することができる。 In the formulas (2) to (9), cross-linking may be performed in the ring structure, and Adamandane, norbornane and the like can be exemplified as examples of the cross-linking in the ring structure.
式（２）～（９）の環上におけるＣＯＯＣＨ２ＣＨ＝ＣＨ２基の置換位置は何れの組み合わせであっても良く、それらの混合物でも良い。特に、２つのＣＯＯＣＨ２ＣＨ＝ＣＨ２基が６員環に結合するときに、２つのＣＯＯＣＨ２ＣＨ＝ＣＨ２基は、オルト配向（１，２位の２置換）、またはメタ配向（１，３位の２置換）、またはパラ配向（１，４位の２置換）のいずれでもよいが、オルト配向（１，２位の２置換）、またはパラ配向（１，４位の２置換）であることが好ましい。 The substitution positions of the COOCH 2 CH = CH 2 groups on the rings of the formulas (2) to (9) may be any combination or a mixture thereof. In particular, when two COOCH 2 CH = CH 2 groups are attached to a 6-membered ring, the two COOCH 2 CH = CH 2 groups are ortho-oriented (two substitutions at positions 1 and 2) or meta-oriented (1,). Either 3-position 2-substitution) or para-orientation (1,4-position 2-substitution), but ortho-orientation (1,2-position 2-substitution) or para-orientation (1,4-position 2-substitution) It is preferable to have.
式（１）中で表される具体的なアリル化合物としては、シクロブタンジカルボン酸ジアリル、シクロペンタンジカルボン酸ジアリル、シクロヘキサンジカルボン酸ジアリル（ヘキサヒドロフタル酸ジアリル）、ノルボルナンジカルボン酸ジアリル、シクロブテンジカルボン酸ジアリル、シクロペンタンジカルボン酸ジアリル、シクロヘキセンジカルボン酸ジアリル（テトラヒドロフタル酸ジアリル）及びノルボルネンジカルボン酸ジアリル等を例示することができる。中でも、１，２‐シクロヘキサンジカルボン酸ジアリル、１，３‐シクロヘキサンジカルボン酸ジアリル、１，４‐シクロヘキサンジカルボン酸ジアリル、ノルボルナンジカルボン酸ジアリルが好ましい。Ｚは、より特に好ましくは、不飽和結合を有しない環状構造であって、炭素数が４～７、更には炭素数が５または６、最も好ましくは炭素数が６である。 Specific examples of the allyl compound represented in the formula (1) include cyclobutanedicarboxylic acid diallyl, cyclopentanedicarboxylic acid diallyl, cyclohexanedicarboxylic acid diallyl (hexahydrophthalate diallyl), norbornandicarboxylic acid diallyl, and cyclobutenedicarboxylic acid diallyl. , Cyclopentanedicarboxylic acid diallyl, cyclohexene dicarboxylic acid diallyl (tetrahydrophthalate diallyl), norbornenedicarboxylic acid diallyl and the like can be exemplified. Of these, diallyl 1,2-cyclohexanedicarboxylic acid, diallyl 1,3-cyclohexanedicarboxylic acid, diallyl 1,4-cyclohexanedicarboxylic acid, and diallyl norbornandicarboxylic acid are preferable. Z is more particularly preferably a cyclic structure having no unsaturated bond, and has 4 to 7 carbon atoms, more preferably 5 or 6 carbon atoms, and most preferably 6 carbon atoms.
（ｉｉｉ）アリル化合物の製造方法
本発明のアリル化合物は、式（１０）で表わされるカルボン酸化合物、又はそれらの酸無水物とハロゲン化アリル又はアリルアルコールとを、必要に応じて、酸性物質、塩基性物質、触媒、溶媒などの存在下、反応させることにより製造できる。式（１０）で表わされるカルボン酸化合物は試薬や工業薬品として入手可能である。
Ｚ-（ＣＯＯＨ）ｎ …（１０）
[式中、ｎ、及びＺに関しては、前記式（１）におけるｎ、及びＺと同じ意味である。]
(Iii) Method for Producing Allyl Compound The allyl compound of the present invention contains a carboxylic acid compound represented by the formula (10), an acid anhydride thereof, and an allyl halide or an allyl alcohol, if necessary. It can be produced by reacting in the presence of a basic substance, a catalyst, a solvent and the like. The carboxylic acid compound represented by the formula (10) is available as a reagent or an industrial chemical.
Z- (COOH) n ... (10)
[In the formula, n and Z have the same meaning as n and Z in the above formula (1). ]
ハロゲン化アリルとしては、例えばアリルクロリド、アリルブロミド、アリルヨージド等が挙げられる。ハロゲン化アリルの使用量に特に制限は無いが、式（１０）で表わされるカルボン酸化合物に対して、通常、２～２０モル当量の範囲であるのが好ましく、反応速度及び容積効率の観点からは、２．３～１０モル当量の範囲であるのがより好ましい。これらのハロゲン化アリル化合物は試薬や工業薬品として入手可能である。 Examples of the allyl halide include allyl chloride, allyl bromide, allyl iodide and the like. The amount of allyl halide used is not particularly limited, but is usually preferably in the range of 2 to 20 molar equivalents with respect to the carboxylic acid compound represented by the formula (10), from the viewpoint of reaction rate and volumetric efficiency. Is more preferably in the range of 2.3 to 10 molar equivalents. These allyl halide compounds are available as reagents and industrial chemicals.
アリルアルコールは試薬や工業薬品として入手可能である。アリルアルコールの使用量に特に制限は無いが、式（１０）で表わされるカルボン酸化合物に対して、通常、２～１０モル当量の範囲であるのが好ましく、２～５モル当量の範囲であるのがより好ましい。 Allyl alcohol is available as a reagent or industrial chemical. The amount of allyl alcohol used is not particularly limited, but is usually preferably in the range of 2 to 10 molar equivalents, preferably in the range of 2 to 5 molar equivalents, with respect to the carboxylic acid compound represented by the formula (10). Is more preferable.
酸性物質としては、ドデシルベンゼンスルホン酸、硫酸が挙げられ、酸性物質の使用量は、式（１０）で表わされるカルボン酸化合物に対して０.００１～０.１モル当量の範囲であるのが好ましく、０.００５～０.０５モル当量の範囲であるのがより好ましい。 Examples of the acidic substance include dodecylbenzene sulfonic acid and sulfuric acid, and the amount of the acidic substance used is in the range of 0.001 to 0.1 molar equivalent with respect to the carboxylic acid compound represented by the formula (10). It is preferably in the range of 0.005 to 0.05 molar equivalents.
塩基性物質としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物；水素化ナトリウム、水素化カリウム等のアルカリ金属の水素化物、炭酸ナトリウム、炭酸カリウム等の炭酸化物、炭酸水素ナトリウム、炭酸水素カリウム等の炭酸水素化物、アルコラート等が一般に用いられるが、アルカリ土類金属の水酸化物、水素化物、炭酸化物、炭酸水素化物や、第４級アンモニウム化合物や脂肪族アミンや芳香族アミンのような有機塩基を用いることも可能である。塩基性物質の使用量は、式（１０）で表わされるカルボン酸化合物に対して０．５～３０モル当量の範囲であるのが好ましく、２～１５モル当量の範囲であるのがより好ましい。 Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydrides of alkali metals such as sodium hydride and potassium hydride, carbon oxides such as sodium carbonate and potassium carbonate, and hydrogen carbonate. Alkaline hydrides such as sodium and potassium hydrogen carbonate, alcoholates and the like are generally used, but alkali earth metal hydroxides, hydrides, carbon oxides, hydrides, quaternary ammonium compounds, aliphatic amines and fragrances. It is also possible to use organic bases such as group amines. The amount of the basic substance used is preferably in the range of 0.5 to 30 molar equivalents with respect to the carboxylic acid compound represented by the formula (10), and more preferably in the range of 2 to 15 molar equivalents.
触媒として、例えば銅、鉄、コバルト、ニッケル、クロム、バナジウム等の遷移金属や遷移金属塩が用いられるが、このうち銅化合物が好適に用いられる。
銅化合物としては特に限定はなく、ほとんどの銅化合物が用いられるが、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅、ヨウ化第一銅等のハロゲン化銅、酸化第一銅、シアン化第一銅、硫酸第一銅、硫酸第二銅、リン酸第二銅、硝酸第一銅、硝酸第二銅等の無機酸の銅塩、水酸化第二銅、炭酸銅、酢酸第一銅、酢酸第二銅等が好ましい。その中でも特に、塩化第一銅、塩化第二銅、臭化第一銅、臭化第二銅、ヨウ化第一銅、硫酸銅、酢酸第二銅は容易に入手可能で安価な点で好適である。
As the catalyst, for example, transition metals such as copper, iron, cobalt, nickel, chromium and vanadium and transition metal salts are used, and among these, copper compounds are preferably used.
The copper compound is not particularly limited, and most copper compounds are used, but cuprous halides such as cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, and cuprous iodide are used. Copper oxide, cuprous cyanide, cuprous sulfate, cupric sulfate, cupric phosphate, cuprous nitrate, cupric nitrate and other inorganic acid copper salts, cupric hydroxide , Copper carbonate, cuprous acetate, cupric acetate and the like are preferable. Among them, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, copper sulfate and cupric acetate are particularly suitable because they are easily available and inexpensive. Is.
反応は、溶媒の存在下又は不存在下にて実施できる。溶媒としては、反応に悪影響を与えない限り特に制限はないが、例えばベンゼン、トルエン、キシレン等の芳香族炭化水素；ヘキサン、ヘプタン、オクタン、シクロヘキサン、メチルシクロヘキサン等の飽和脂肪族炭化水素；ジエチルエーテル、ジエチレングリコールジメチルエーテル、１，４－ジオキサン、テトラヒドロフラン等のエーテル；酢酸エチル、酢酸ブチル等のエステル；塩化メチレン、クロロホルム、四塩化炭素等のハロゲン化炭化水素；ジメチルホルムアミド、Ｎ－メチルピロリドン、スルホラン等が挙げられる。これらは一種を単独で使用してもよいし、二種以上を併用してもよい。溶媒を使用する場合、その使用量に特に制限はないが、式（１０）で表わされるカルボン酸化合物に対して、通常、０．０１～２０倍重量の範囲であるのが好ましく、０．１～１０倍重量の範囲であるのがより好ましい。本反応の場合、溶媒を特に使用しなくてもアリル化合物を効率よく製造できる。 The reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not adversely affect the reaction, but for example, aromatic hydrocarbons such as benzene, toluene and xylene; saturated aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane; diethyl ether. , Diethylene glycol dimethyl ether, ethers such as 1,4-dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; dimethylformamide, N-methylpyrrolidone, sulfolane and the like. Can be mentioned. These may be used alone or in combination of two or more. When a solvent is used, the amount used is not particularly limited, but it is usually preferably in the range of 0.01 to 20 times the weight, preferably 0.1, with respect to the carboxylic acid compound represented by the formula (10). More preferably, it is in the range of ~ 10 times the weight. In the case of this reaction, an allyl compound can be efficiently produced without using a solvent.
特に、塩基性物質を水溶液として反応に用いる場合、反応を促進させるために相間移動触媒を使用するのが好ましい。相間移動触媒に特に制限はないが、例えばトリオクチルメチルアンモニウムクロリド、テトラブチルアンモニウムクロリド、テトラブチルアンモニウムブロミド等の第四級アンモニウム塩；テトラブチルホスホニウムクロリド等のホスホニウム塩；１５‐クラウン‐５，１８‐クラウン‐６等のクラウンエーテル等が挙げられる。相間移動触媒を使用する場合、その使用量は、式（１０）で表わされるカルボン酸化合物に対して、通常、０．００１～１モル当量の範囲であるのが好ましく、０．０１～０．４モル当量の範囲であるのがより好ましい。 In particular, when a basic substance is used as an aqueous solution in the reaction, it is preferable to use a phase transfer catalyst in order to accelerate the reaction. The phase transfer catalyst is not particularly limited, and is, for example, a quaternary ammonium salt such as trioctylmethylammonium chloride, tetrabutylammonium chloride, or tetrabutylammonium bromide; a phosphonium salt such as tetrabutylphosphonium chloride; 15-crown-5,18. -Crown ether such as Crown-6 and the like can be mentioned. When a phase transfer catalyst is used, the amount used is usually preferably in the range of 0.001 to 1 molar equivalent with respect to the carboxylic acid compound represented by the formula (10), and 0.01 to 0. More preferably, it is in the range of 4 molar equivalents.
反応温度は、十分な反応速度を得、かつ副反応を効果的に抑え高収率を得る意味において、通常、－３０～１５０℃の範囲であるのが好ましく、－１０～１３０℃の範囲であるのがより好ましい。また、反応時間は１０分～１５時間の範囲であるのが好ましく、副反応抑制の観点からは１０分～１０時間の範囲であるのが好ましい。 The reaction temperature is usually preferably in the range of −30 to 150 ° C., preferably in the range of −10 to 130 ° C. in the sense that a sufficient reaction rate is obtained and side reactions are effectively suppressed to obtain a high yield. It is more preferable to have it. The reaction time is preferably in the range of 10 minutes to 15 hours, and preferably in the range of 10 minutes to 10 hours from the viewpoint of suppressing side reactions.
反応は、窒素、アルゴンのような不活性ガス雰囲気下で実施するのが好ましい。また、反応は大気圧下でも加圧下でも実施できるが、製造設備面の観点からは、大気圧下で実施するのが好ましい。反応は、例えば攪拌型反応装置に原料を一度に、又は分割して仕込み、上記「００３３」記載の所定温度で所定時間反応させることにより行なうことができる。 The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. Further, although the reaction can be carried out under atmospheric pressure or pressurization, it is preferable to carry out the reaction under atmospheric pressure from the viewpoint of manufacturing equipment. The reaction can be carried out, for example, by charging the raw materials into a stirring reaction device at one time or in portions and reacting them at the predetermined temperature described in "0033" for a predetermined time.
反応終了後、得られた反応混合液を中和した後、必要に応じて水、飽和食塩水等で洗浄してから濃縮し、更に蒸留、カラムクロマトグラフィー等の、有機化合物の精製において通常用いられる精製操作を行なうことによって、純度の高いアリル化合物を取得できる。 After completion of the reaction, the obtained reaction mixture is neutralized, washed with water, saturated saline, etc. as necessary, then concentrated, and further usually used in the purification of organic compounds such as distillation and column chromatography. A highly pure allyl compound can be obtained by carrying out the purification operation.
（ｉｖ）アリル重合体（Ａ）の製造方法
アリル化合物の重合方法は、特に限定されず、通常の重合反応を用いることができる。重合反応には、必要に応じて、適宜重合開始剤を添加してもよい。重合開始剤を用いることで、より高分子量のアリル重合体（Ａ）を短時間に得ることができる。
(Iv) Method for Producing Allyl Polymer (A) The method for polymerizing the allyl compound is not particularly limited, and a normal polymerization reaction can be used. A polymerization initiator may be appropriately added to the polymerization reaction, if necessary. By using the polymerization initiator, a higher molecular weight allyl polymer (A) can be obtained in a short time.
アリル化合物の重合反応に用いる重合開始剤としては、アゾビスイソブチロニトリル、２，２’－アゾビスイソ酪酸ジメチル等のアゾ系重合開始剤、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、ベンゾイルパーオキサイド等の過酸化物系重合開始剤、２－メチル－１－[４－(メチルチオ)フェニル]－２－モルホリノプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン系光重合開始剤、ベンゾイン、ベンゾインエチルエーテル等のベンゾイン系光重合開始剤、ベンゾフェノン等のベンゾフェノン系光重合開始剤、アシルフォスフィンオキサイド等のリン系光重合開始剤などが挙げられる。前記光重合開始剤は、チオキサントン等のイオウ系化合物、ベンジル、９,１０－フェナントレンキノン等のベンジル系化合物など増感剤と併用してもよい。 Examples of the polymerization initiator used in the polymerization reaction of the allyl compound include azobisisobutyronitrile, azo-based polymerization initiators such as dimethyl 2,2'-azobisisobutyrate, ketone peroxides, peroxyketals, hydroperoxides, and dialkylpers. Peroxide-based polymerization initiators such as oxides, diacyl peroxides, peroxydicarbonates, peroxyesters, and benzoyl peroxides, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1- On, acetophenone-based photopolymerization initiators such as 1-hydroxycyclohexylphenylketone, benzoin-based photopolymerization initiators such as benzoin and benzoinethyl ether, benzophenone-based photopolymerization initiators such as benzophenone, and phosphorus-based light such as acylphosphine oxide. Examples thereof include a polymerization initiator. The photopolymerization initiator may be used in combination with a sensitizer such as a sulfur compound such as thioxanthone or a benzyl compound such as benzyl or 9,10-phenanthrenequinone.
重合開始剤の添加量は、アリル化合物１００重量部に対して、１．０重量部以下であることが好ましく、０．２重量部以下であることがより好ましく、０．００１～０．１重量部であることが更に好ましい。 The amount of the polymerization initiator added is preferably 1.0 part by weight or less, more preferably 0.2 part by weight or less, and 0.001 to 0.1 part by weight with respect to 100 parts by weight of the allyl compound. It is more preferably a part.
重合時の反応温度は６０～２４０℃であることが好ましく、８０～２２０℃であることがより好ましい。反応時間は、０．１～１００時間であることが好ましく、１～３０時間であることがより好ましい。 The reaction temperature at the time of polymerization is preferably 60 to 240 ° C, more preferably 80 to 220 ° C. The reaction time is preferably 0.1 to 100 hours, more preferably 1 to 30 hours.
式（１）で表されるアリル化合物を上述の方法等により重合することにより、式（１）で表されるアリル化合物に基づく単量体単位を有するアリル重合体（Ａ）を調製できる。 By polymerizing the allyl compound represented by the formula (1) by the above-mentioned method or the like, an allyl polymer (A) having a monomer unit based on the allyl compound represented by the formula (1) can be prepared.
エポキシ化植物油（メタ）アクリレート（Ｂ）
本発明の光硬化性樹脂組成物には、エポキシ化植物油（メタ）アクリレート（Ｂ）を含有する。エポキシ化植物油（メタ）アクリレート（Ｂ）を含有することで、環境に適応した光硬化性樹脂組成物を提供することができる。
Epoxidized vegetable oil (meth) acrylate (B)
The photocurable resin composition of the present invention contains an epoxidized vegetable oil (meth) acrylate (B). By containing the epoxidized vegetable oil (meth) acrylate (B), it is possible to provide a photocurable resin composition adapted to the environment.
エポキシ化植物油（メタ）アクリレート（Ｂ）は、分子構造中にエポキシ基と（メタ）アクリロイル基を有する化合物である。エポキシ化植物油（メタ）アクリレート（Ｂ）は、エポキシ化植物油が有するエポキシ基に（メタ）アクリル酸を開環付加重合させることで得ることができる。 The epoxidized vegetable oil (meth) acrylate (B) is a compound having an epoxy group and a (meth) acryloyl group in its molecular structure. The epoxidized vegetable oil (meth) acrylate (B) can be obtained by ring-opening addition polymerization of (meth) acrylic acid on the epoxy group of the epoxidized vegetable oil.
このようなエポキシ化植物油（メタ）アクリレート（Ｂ）は、光重合開始剤と併用することにより、紫外線（ＵＶ光）や電子線などのエネルギー線の照射により、速やかに硬化する。特に、エポキシ化植物油（メタ）アクリレート（Ｂ）とラジカル型光重合開始剤とを含む場合、紫外線（ＵＶ光）や電子線などのエネルギー線が照射されると、ラジカル型光重合開始剤が活性化し、ラジカルが発生する。このラジカルとエポキシ化植物油（メタ）アクリレート（Ｂ）の（メタ）アクリロイル基（より具体的には、（メタ）アクリロイル基中のビニル基）が反応することで、エポキシ化植物油（メタ）アクリレート（Ｂ）の硬化反応、重合反応が進行し、硬化する。このようなエポキシ化植物油（メタ）アクリレート（Ｂ）の硬化反応を利用して、基版上に硬化膜を形成する。そして、このようにして形成された硬化膜は、緻密な３次元網目構造を有しているので、耐熱性、耐溶剤性等の耐久性に優れるとともに、硬度にも優れたものとなる。 When such an epoxidized vegetable oil (meth) acrylate (B) is used in combination with a photopolymerization initiator, it is rapidly cured by irradiation with energy rays such as ultraviolet rays (UV light) and electron beams. In particular, when the epoxidized vegetable oil (meth) acrylate (B) and the radical photopolymerization initiator are contained, the radical photopolymerization initiator is activated when irradiated with energy rays such as ultraviolet rays (UV light) and electron beams. Radicals are generated. The reaction between this radical and the (meth) acryloyl group (more specifically, the vinyl group in the (meth) acryloyl group) of the epoxidized vegetable oil (meth) acrylate (B) causes the epoxidized vegetable oil (meth) acrylate (meth) acrylate (. The curing reaction and polymerization reaction of B) proceed and cure. A cured film is formed on the base plate by utilizing the curing reaction of such an epoxidized vegetable oil (meth) acrylate (B). Since the cured film thus formed has a dense three-dimensional network structure, it is excellent in durability such as heat resistance and solvent resistance, and is also excellent in hardness.
また、このようなエポキシ化植物油（メタ）アクリレート（Ｂ）は、硬化するまでの時間が極めて短いものである。そのため、光硬化性樹脂組成物中に添加しても、印刷の生産性への影響はない。 Further, such an epoxidized vegetable oil (meth) acrylate (B) has an extremely short time to cure. Therefore, even if it is added to the photocurable resin composition, it does not affect the printing productivity.
このようなエポキシ化植物油（メタ）アクリレート（Ｂ）の出発原料である植物油は、通常、脂肪酸とグリセリンとの間でのトリエステル（トリグリセリド）である脂肪酸トリグリセリドを主成分とするものであり、脂肪酸成分として不飽和脂肪酸（炭素－炭素二重結合を主鎖中に有する脂肪酸）を含むものである。そして、植物油が有する炭素－炭素二重結合（Ｃ＝Ｃ）の少なくとも一部をエポキシ基に変性（エポキシ変性）することによりエポキシ化植物油が生成する。 The vegetable oil, which is the starting material of such an epoxidized vegetable oil (meth) acrylate (B), is usually composed mainly of a fatty acid triglyceride, which is a triester (triglyceride) between a fatty acid and glycerin, and is a fatty acid. It contains unsaturated fatty acids (fatty acids having a carbon-carbon double bond in the main chain) as a component. Then, an epoxidized vegetable oil is produced by modifying (epoxy-modifying) at least a part of the carbon-carbon double bond (C = C) of the vegetable oil into an epoxy group.
エポキシ化植物油の出発原料である植物油としては、具体的には、アサ実油、エノ油、オイチシカ油、カカオ油、カポック油、カヤ油、カラシ油、キョウニン油、ククイ油、クルミ油、ケシ油、ダイコン種油、大風子油、ツバキ油、ニガー油、ブドウ種子油、ヘントウ油、松種子油、落花生油、米糠油、ごま油、やし油、ひまし油、パーム油、アーモンド油、カシューナッツ油、ヘーゼルナッツ油、松の実油、脱水ひまし油、桐油、亜麻仁油、ひまわり油、ローズヒップ油、荏油、大豆油、菜種油、サフラワー油、綿実油、胡麻油、トウモロコシ油、オリーブ油、ココアバターなどが挙げられる。これらは一種類でも二種類以上の混合物でも構わない。一般的に、植物油はリノール酸、リノレン酸、オレイン酸など不飽和脂肪酸を主成分としている。これら植物油の有する炭素－炭素二重結合（Ｃ＝Ｃ）の少なくとも一部を過酢酸、過安息香酸等でエポキシ化して、エポキシ基に変性（エポキシ変性）することによりエポキシ化植物油が得られる。 Specific examples of vegetable oils that are the starting materials for epoxidized vegetable oils include asa seed oil, eno oil, sardine oil, cacao oil, capoc oil, kaya oil, mustard oil, kyonin oil, kukui oil, walnut oil, and poppy oil. , Daikon seed oil, large wind child oil, camellia oil, niger oil, grape seed oil, gentle oil, pine seed oil, peanut oil, rice bran oil, sesame oil, palm oil, castor oil, palm oil, almond oil, cashew nut oil, hazelnut Examples include oil, pine nut oil, dehydrated sunflower oil, tung oil, flaxseed oil, sunflower oil, rosehip oil, sardine oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, sesame oil, corn oil, olive oil and cocoa butter. These may be one kind or a mixture of two or more kinds. Generally, vegetable oils are mainly composed of unsaturated fatty acids such as linoleic acid, linolenic acid and oleic acid. An epoxidized vegetable oil can be obtained by epoxidizing at least a part of the carbon-carbon double bond (C = C) of these vegetable oils with peracetic acid, perbenzoic acid, or the like and modifying them into epoxy groups (epoxy modification).
上述したような植物油をエポキシ変性したエポキシ化植物油として、特に限定されないが、例えば、エポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化ひまし油、エポキシ化コーン油、エポキシ化菜種油、エポキシ化サフラワー油、エポキシ化ひまわり油、エポキシ化パーム油、エポキシ化綿実油、エポキシ化オリーブ油、エポキシ化ココアバターなどが挙げられる。 The epoxidized vegetable oil obtained by epoxidizing the vegetable oil as described above is not particularly limited, and for example, epoxidized soybean oil, epoxidized flaxseed oil, epoxidized castor oil, epoxidized corn oil, epoxidized rapeseed oil, epoxidized safflower oil, and the like. Examples include epoxidized sunflower oil, epoxidized palm oil, epoxidized cotton seed oil, epoxidized olive oil, and epoxidized cocoa butter.
上述したようなエポキシ化植物油のエポキシ基に（メタ）アクリル酸を開環付加重合させることで、エポキシ化植物油（メタ）アクリレート（Ｂ）が得られる。中でも、エポキシ化大豆油アクリレートが好ましい。大豆油は、出発原料として安定性が高く、また、構造中に比較的多くの炭素－炭素二重結合を有するものである。そのため、大豆油を出発原料としたエポキシ化大豆油（メタ）アクリレートは、ラジカル光重合開始剤から発生したラジカルにより、好適に硬化反応、重合反応を起こす。 An epoxidized vegetable oil (meth) acrylate (B) can be obtained by carrying out ring-opening addition polymerization of (meth) acrylic acid on the epoxy group of the epoxidized vegetable oil as described above. Of these, epoxidized soybean oil acrylate is preferable. Soybean oil is highly stable as a starting material and has a relatively large number of carbon-carbon double bonds in its structure. Therefore, the epoxidized soybean oil (meth) acrylate using soybean oil as a starting material preferably undergoes a curing reaction and a polymerization reaction by the radicals generated from the radical photopolymerization initiator.
このようなエポキシ化植物油（メタ）アクリレート（Ｂ）のＳＰ値は、９～１２範囲であればよい。また、エポキシ化植物油（メタ）アクリレート（Ｂ）は、そのヨウ素価が１５以下であるのが好ましく、１０以下であるのがより好ましい。このようなエポキシ化植物油（メタ）アクリレート（Ｂ）は、その分子構造中に含まれる（メタ）アクリロイ基の含有率が十分に高いものとなり、紫外線照射時において、より短時間で硬化するとともに、硬化後の硬度が十分に高いものとなる。 The SP value of such an epoxidized vegetable oil (meth) acrylate (B) may be in the range of 9 to 12. Further, the epoxidized vegetable oil (meth) acrylate (B) preferably has an iodine value of 15 or less, and more preferably 10 or less. Such an epoxidized vegetable oil (meth) acrylate (B) has a sufficiently high content of (meth) acrylloy groups contained in its molecular structure, and is cured in a shorter time when irradiated with ultraviolet rays. The hardness after curing is sufficiently high.
本発明の光硬化性樹脂組成物に用いるエポキシ化植物油（メタ）アクリレート（Ｂ）の含有量は、光硬化性樹脂組成物中におけるアリル重合体（Ａ）１００重量部に対して、５０～３００重量部であることが好ましく、５０～２５０重量部であることがより好ましく、５０～２００重量部であることがさらに好ましい。 The content of the epoxidized vegetable oil (meth) acrylate (B) used in the photocurable resin composition of the present invention is 50 to 300 with respect to 100 parts by weight of the allyl polymer (A) in the photocurable resin composition. It is preferably parts by weight, more preferably 50 to 250 parts by weight, and even more preferably 50 to 200 parts by weight.
また、光硬化性樹脂組成物に含有されるエポキシ化植物油（メタ）アクリレート（Ｂ）の含有量は、光硬化性樹脂組成物の粘度が１００～３００Ｐａ・ｓ（２５℃）の範囲内になるように添加することが好ましい。 Further, the content of the epoxidized vegetable oil (meth) acrylate (B) contained in the photocurable resin composition is such that the viscosity of the photocurable resin composition is in the range of 100 to 300 Pa · s (25 ° C.). It is preferable to add it as such.
エチレン性不飽和化合物（Ｃ）
本発明の光硬化性樹脂組成物には、上述したエポキシ化植物油（メタ）アクリレート（Ｂ）に加えて、光照射により硬化可能であるエチレン性不飽和化合物（Ｃ）をさらに、含有させる。エチレン性不飽和化合物（Ｃ）としては、炭素‐炭素二重結合を１～２０個有することが好ましく、１～１０個有することがより好ましく、２～６個有することがさらに好ましい。エチレン性不飽和化合物（Ｃ）としては、アクリル酸エステル化合物、（メタ）アリル化合物およびビニル化合物等が挙げられる。また、エチレン性不飽和化合物は２種以上の化合物の混合物を用いることも可能である。なお、本発明におけるエチレン性不飽和化合物（Ｃ）には、上述したエポキシ化植物油（メタ）アクリレート（Ｂ）は含まれないものとする。
Ethylene unsaturated compound (C)
In addition to the above-mentioned epoxidized vegetable oil (meth) acrylate (B), the photocurable resin composition of the present invention further contains an ethylenically unsaturated compound (C) that can be cured by light irradiation. The ethylenically unsaturated compound (C) preferably has 1 to 20 carbon-carbon double bonds, more preferably 1 to 10 carbon-carbon double bonds, and even more preferably 2 to 6 carbon-carbon double bonds. Examples of the ethylenically unsaturated compound (C) include acrylic acid ester compounds, (meth) allyl compounds and vinyl compounds. Further, as the ethylenically unsaturated compound, it is also possible to use a mixture of two or more kinds of compounds. The ethylenically unsaturated compound (C) in the present invention does not contain the above-mentioned epoxidized vegetable oil (meth) acrylate (B).
（メタ）アクリル酸エステル化合物としては、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールプロパン、ジトリメチロールプロパン、ネオペンチルグリコール、１,６－ヘキサンジオール、グリセリン、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類の（メタ）アクリル酸エステル化合物、およびそれらにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加した（メタ）アクリル酸エステル化合物；ビスフェノールＡ、ビスフェノールＦ等のビスフェノール類にエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加したものの（メタ）アクリル酸エステル化合物；エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレート、アルキッド（メタ）アクリレート等の（メタ）アクリル酸エステル化合物を例示することができ、好ましくはペンタエリスリトール、ジペンタエリスリトール、トリメチロールプロパン、ジトリメチロールプロパン、ネオペンチルグリコール、１,６‐ヘキサンジオール、グリセリン、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類の（メタ）アクリル酸エステル化合物、およびそれらにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加した（メタ）アクリル酸エステル化合物であり、より好ましくはペンタエリスリトール、ジペンタエリスリトール、トリメチロールプロパン、ジトリメチロールプロパン等のアルコール類の（メタ）アクリル酸エステル化合物、およびそれらにエチレンオキサイド、プロピレンオキサイド等のアルキレンオキサイドを付加した（メタ）アクリル酸エステル化合物である。 Examples of the (meth) acrylic acid ester compound include alcohols (meth) such as pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin, polyethylene glycol and polypropylene glycol. ) Acrylic acid ester compounds and (meth) acrylic acid ester compounds to which alkylene oxides such as ethylene oxide and propylene oxide are added; alkylene oxides such as ethylene oxide and propylene oxide are added to bisphenols such as bisphenol A and bisphenol F. However, (meth) acrylic acid ester compounds; (meth) acrylic acid ester compounds such as epoxy (meth) acrylate, urethane (meth) acrylate, and alkyd (meth) acrylate can be exemplified, preferably pentaerythritol and dipenta. Alcoholic (meth) acrylic acid ester compounds such as erythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin, polyethylene glycol, polypropylene glycol, and ethylene oxide, propylene oxide, etc. It is a (meth) acrylic acid ester compound to which the alkylene oxide of the above is added, more preferably an alcoholic (meth) acrylic acid ester compound such as pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, and ethylene to them. It is a (meth) acrylic acid ester compound to which an alkylene oxide such as an oxide or a propylene oxide is added.
（メタ）アリル化合物としては、ジ（メタ）アリルフタレート、トリ（メタ）アリルイソシアヌレート等を例示することができる。
ビニル化合物としては、スチレン、ジビニルベンゼン、Ｎ-ビニルピロリドン、酢酸ビニル等を例示することができる。
Examples of the (meth) allyl compound include di (meth) allyl phthalate and tri (meth) allyl isocyanurate.
Examples of the vinyl compound include styrene, divinylbenzene, N-vinylpyrrolidone, vinyl acetate and the like.
なかでも、エチレン性不飽和化合物（Ｃ）のＳＰ値が、８～１２の範囲のものであればよい。具体的には、トリメチロールプロパントリアクリレート（ＳＰ値：９．９）、ジトリメチロールプロパンテトラアクリレート（ＳＰ値：９．８）、ジペンタエリスリトールヘキサアクリレート（ＳＰ値：１０．４）、およびそれらにエチレンオキサイド、またはプロピレンオキサイドを付加したしたものなどを例示できる。 Above all, the SP value of the ethylenically unsaturated compound (C) may be in the range of 8 to 12. Specifically, trimethylolpropane triacrylate (SP value: 9.9), ditrimethylolpropane tetraacrylate (SP value: 9.8), dipentaerythritol hexaacrylate (SP value: 10.4), and the like. Examples thereof include ethylene oxide and those to which propylene oxide is added.
本発明の光硬化性樹脂組成物に含有されるエチレン性不飽和化合物（Ｃ）の含有量は、光硬化性樹脂組成物中におけるアリル重合体（Ａ）１００重量部に対して、５０～７００量部であることが好ましく、５０～６００重量部であることがより好ましく、５０～５００重量部であることがより好ましい。 The content of the ethylenically unsaturated compound (C) contained in the photocurable resin composition of the present invention is 50 to 700 with respect to 100 parts by weight of the allyl polymer (A) in the photocurable resin composition. The amount is preferably parts, more preferably 50 to 600 parts by weight, and even more preferably 50 to 500 parts by weight.
本発明におけるエポキシ化植物油アクリレート（Ｂ）とエチレン性不飽和化合物（Ｃ）の比率は、特に限定されないが、（エポキシ化植物油（メタ）アクリレート（Ｂ）：エチレン性不飽和化合物（Ｃ））の比率が、１：９９～９９：１の範囲であればよく、１０：９０～７０：３０の範囲であることが好ましく、２０：８０～５０：５０の範囲であることがより好ましい。 The ratio of the epoxidized vegetable oil acrylate (B) to the ethylenically unsaturated compound (C) in the present invention is not particularly limited, but is the same as (epoxidized vegetable oil (meth) acrylate (B): ethylenically unsaturated compound (C)). The ratio may be in the range of 1:99 to 99: 1, preferably in the range of 10:90 to 70:30, and more preferably in the range of 20:80 to 50:50.
その他の添加物
本発明の光硬化性樹脂組成物は、重合開始剤を含んでいてもよく、特に光重合開始剤を含有することが好ましい。光硬化性樹脂組成物に含有される光重合開始剤としては、２‐メチル‐１‐[４‐(メチルチオ)フェニル]‐２‐モルホリノプロパン-１、１－ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン系、ベンゾイン、ベンゾインエチルエーテル等のベンゾイン系、ベンゾフェノン等のベンゾフェノン系、アシルフォスフィンオキサイド等のリン系、チオキサントン等のイオウ系、ベンジル、９,１０‐フェナンスレンキノン等のジベンジル系が挙げられる。
Other Additives The photocurable resin composition of the present invention may contain a polymerization initiator, and is particularly preferably containing a photopolymerization initiator. Examples of the photopolymerization initiator contained in the photocurable resin composition include acetophenone-based agents such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 1-hydroxycyclohexylphenylketone, and the like. Examples thereof include benzoin type such as benzoin and benzoin ethyl ether, benzophenone type such as benzophenone, phosphorus type such as acylphosphine oxide, sulfur type such as thioxanthone, and dibenzyl type such as benzyl and 9,10-phenanthlenquinone.
光硬化性樹脂組成物に含有される光重合開始剤の量は、光硬化性樹脂組成物全体に対して、０．１～１５重量％の範囲であることが好ましく、０．５～１２重量％の範囲がより好ましく、１～１０重量％の範囲がさらに好ましい。 The amount of the photopolymerization initiator contained in the photocurable resin composition is preferably in the range of 0.1 to 15% by weight, preferably 0.5 to 12% by weight, based on the entire photocurable resin composition. The range of% is more preferable, and the range of 1 to 10% by weight is further preferable.
光硬化性樹脂組成物には、光開始助剤(例えば、トリエタノールアミン等のアミン系光開始助剤）を併用してもよい。光開始助剤の量は、光硬化性樹脂組成物全体に対して、０．１～５重量％の範囲であることが好ましく、０．５～３重量％の範囲がより好ましい。
また、光硬化性樹脂組成物には、耐摩擦性、ブロッキング防止性、スベリ性、スリキズ防止性を付与するワックスを添加してもよい。ワックスとして、カルナバワックス、木ろう、ラノリン、モンタンワックス、パラフィンワックス、マイクロクリスタリンワックスなどの天然ワックス、フィッシャートロプスワックス、ポリエチレンワックス、ポリプロピレンワックス、ポリテトラフルオロエチレンワックス、ポリアミドワックス、およびシリコーン化合物などの合成ワックス等を例示することができる。ワックスの添加量は、光硬化性樹脂組成物全体に対して、０．１～１０重量％の範囲であることが好ましく、０．５～５重量％の範囲がより好ましい。
A photoinitiator (for example, an amine-based photoinitiator such as triethanolamine) may be used in combination with the photocurable resin composition. The amount of the photoinitiator aid is preferably in the range of 0.1 to 5% by weight, more preferably in the range of 0.5 to 3% by weight, based on the entire photocurable resin composition.
Further, a wax that imparts abrasion resistance, blocking prevention property, slip property, and scratch resistance may be added to the photocurable resin composition. Waxes include natural waxes such as carnauba wax, wood wax, lanolin, montan wax, paraffin wax, microcrystalline wax, Fishertropus wax, polyethylene wax, polypropylene wax, polytetrafluoroethylene wax, polyamide wax, and silicone compounds. Synthetic wax and the like can be exemplified. The amount of wax added is preferably in the range of 0.1 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, based on the entire photocurable resin composition.
本発明の光硬化性樹脂組成物は、種々の添加剤、例示すれば、安定剤（例えば、ハイドロキノン、メトキノン、メチルハイドロキノン等の重合禁止剤）、顔料（例えば、シアニンブルー、ジスアゾエロー、カーミン６ｂ、レーキッドＣ、カーボンブラック、チタンホワイト）等の着色剤、充填剤、粘度調整剤等の各種添加剤を目的に応じて含有することができる。光硬化性樹脂組成物に含有される安定剤の量は、光硬化性樹脂組成物全体に対して、０．０１～２重量％の範囲であることが好ましく、０．１～１重量％の範囲がより好ましい。
着色剤の量は、光硬化性樹脂組成物全体に対して、１～５０重量％の範囲であることが好ましく、１～４５重量％の範囲がより好ましい。
The photocurable resin composition of the present invention comprises various additives, eg, stabilizers (eg, polymerization inhibitors such as hydroquinone, methquinone, methylhydroquinone, etc.), pigments (eg, cyanine blue, disazoero, carmine 6b, etc.). Various additives such as colorants such as rakid C (carbon black, titanium white), fillers, and viscosity modifiers can be contained depending on the purpose. The amount of the stabilizer contained in the photocurable resin composition is preferably in the range of 0.01 to 2% by weight, preferably 0.1 to 1% by weight, based on the entire photocurable resin composition. The range is more preferred.
The amount of the colorant is preferably in the range of 1 to 50% by weight, more preferably in the range of 1 to 45% by weight, based on the entire photocurable resin composition.
本発明の光硬化性樹脂組成物は、アリル重合体（Ａ）、エポキシ化植物油（メタ）アクリレート（Ｂ）、及びエチレン性不飽和化合物（Ｃ）、さらには、着色剤、光重合開始剤、光開始助剤、添加剤（例えば、安定剤）、ワックスを混合することによって製造できる。本発明の光硬化性樹脂組成物は、光を照射することによって硬化する。硬化に用いる光は、一般に紫外線である。 The photocurable resin composition of the present invention comprises an allyl polymer (A), an epoxidized vegetable oil (meth) acrylate (B), an ethylenically unsaturated compound (C), a colorant, a photopolymerization initiator, and the like. It can be produced by mixing a photoinitiator, an additive (eg, a stabilizer), and a wax. The photocurable resin composition of the present invention is cured by irradiating with light. The light used for curing is generally ultraviolet light.
光硬化性樹脂組成物の硬化反応に用いる硬化装置、また、硬化条件は特に限定されず、通常の光硬化反応に用いられる方法であればよい。 The curing device used for the curing reaction of the photocurable resin composition and the curing conditions are not particularly limited, and any method used for a normal photocuring reaction may be used.
本発明の光硬化性樹脂組成物の用途は特に限定されない。インキ（例えば、光硬化性平版用印刷インキ、シルクスクリーンインキ、フレキソインキ等の印刷インキ）等の技術分野において使用できる。 The use of the photocurable resin composition of the present invention is not particularly limited. It can be used in technical fields such as inks (for example, printing inks for photocurable lithographic plates, silk screen inks, printing inks such as flexographic inks) and the like.
例えば、インキの一般的作製方法は次のとおりである。エポキシ化植物油（メタ）アクリレート（Ｂ）、及びエチレン性不飽和化合物（Ｃ）にアリル重合体（Ａ）、及び安定剤等を６０℃～１００℃の温度で攪拌しながら溶解させワニスを作製する。このワニスに、顔料、光重合開始剤、その他添加剤を、バタフライミキサーで撹拌混合後、ビーズミル、ボールミル、サンドミル、アトライター、ロールミル、パールミル、３本ロール等で練肉することでインキが得られる。 For example, a general method for producing ink is as follows. A varnish is prepared by dissolving an allyl polymer (A), a stabilizer and the like in an epoxidized vegetable oil (meth) acrylate (B) and an ethylenically unsaturated compound (C) at a temperature of 60 ° C to 100 ° C with stirring. .. Pigments, photopolymerization initiators, and other additives are mixed with this varnish by stirring with a butterfly mixer, and then kneaded with a bead mill, ball mill, sand mill, attritor, roll mill, pearl mill, three rolls, or the like to obtain ink. ..
（実施例）
以下、実施例を挙げて、本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
(Example)
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
アリル重合体（Ａ）の重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）の測定
重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）はＧＰＣを用いて測定した。Ｍｗ、Ｍｎは標準ポリスチレン換算の重量平均分子量、数平均分子量の値である。
カラム：ＳｈｏｄｅｘＫＦ－８０６Ｌ、ＫＦ－８０４、ＫＦ－８０３、ＫＦ－８０２、ＫＦ－８０１を直列に接続
流速：１．０ｍＬ／ｍｉｎ
温度：４０℃
検出：ＲＩＤ－６Ａ
試料：試料２０ｍｇをテトラヒドロフラン１０ｍＬに溶解させ測定用のサンプルとした。
Measurement of Weight Average Molecular Weight (Mw) and Molecular Weight Distribution ( Mw / Mn) of Allyl Polymer (A) Weight average molecular weight (Mw) and Molecular Weight Distribution (Mw / Mn) were measured using GPC. Mw and Mn are values of weight average molecular weight and number average molecular weight in terms of standard polystyrene.
Column: Shodex KF-806L, KF-804, KF-803, KF-802, KF-801 are connected in series Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detection: RID-6A
Sample: 20 mg of the sample was dissolved in 10 mL of tetrahydrofuran to prepare a sample for measurement.
製造例１ １，２‐シクロヘキサンジカルボン酸ジアリル重合体（アリル重合体Ａ）の合成
１,２‐シクロヘキサンジカルボン酸ジアリルは、シクロヘキサンジカルボン酸無水物とアリルアルコールをエステル化反応させることによって製造した。
３Ｌのセパラブルフラスコに１，２‐シクロヘキサンジカルボン酸ジアリル２４００ｇを加え、６０ｇのベンゾイルパーオキサイドを加えて８０℃で加熱攪拌した。２．５時間反応させた後、３０℃まで冷却した。冷却後、フラスコにメタノールを加え、重合体を沈殿させた。得られた重合体を４０℃で１６時間減圧乾燥した(収量：４０８ｇ、収率：１７％、Ｍｗ＝３２，０００、Ｍｗ／Ｍｎ＝２．８、ＳＰ値 １０．７)。得られた重合体を重合体１とし、実施例１に用いた。
Production Example 1 Synthesis of 1,2-cyclohexanedicarboxylic acid diallyl polymer (allyl polymer A) The 1,2-cyclohexanedicarboxylic acid diallyl was produced by esterifying cyclohexanedicarboxylic acid anhydride with allyl alcohol.
To a 3 L separable flask, 2400 g of diallyl 1,2-cyclohexanedicarboxylate was added, 60 g of benzoyl peroxide was added, and the mixture was heated and stirred at 80 ° C. After reacting for 2.5 hours, the mixture was cooled to 30 ° C. After cooling, methanol was added to the flask to precipitate the polymer. The obtained polymer was dried under reduced pressure at 40 ° C. for 16 hours (yield: 408 g, yield: 17%, Mw = 32,000, Mw / Mn = 2.8, SP value 10.7). The obtained polymer was designated as polymer 1 and used in Example 1.
実施例１～５、比較例１～６
下記表１に記載の各組成の光硬化性樹脂組成物を調製し、光硬化性樹脂組成物の特性を評価した。
Examples 1 to 5, Comparative Examples 1 to 6
The photocurable resin compositions of each composition shown in Table 1 below were prepared, and the characteristics of the photocurable resin compositions were evaluated.
１）光硬化性樹脂組成物の調製
製造例１で得られたアリル重合体（Ａ）、ＤＡＰ樹脂、エポキシ化植物油（メタ）アクリレート（Ｂ）、エチレン性不飽和化合物（Ｃ）、及び重合禁止剤を下記表１、２に記載の各組成量で添加し、９０℃から１２０℃まで加熱混合して光硬化性樹脂組成物を調製した。室温に冷却後、一晩後経過したものの外観が透明であるかで相溶性を確認した。冷却後も外観が透明であったものを○、冷却後室温で白濁したものを×とした。結果は表１、２に示す。
1) Preparation of photocurable resin composition The allyl polymer (A), DAP resin, epoxidized vegetable oil (meth) acrylate (B), ethylenically unsaturated compound (C), and polymerization prohibited obtained in Production Example 1. The agents were added in the respective composition amounts shown in Tables 1 and 2 below, and heated and mixed from 90 ° C. to 120 ° C. to prepare a photocurable resin composition. After cooling to room temperature, the compatibility was confirmed by checking whether the appearance was transparent after one night. Those whose appearance was transparent even after cooling were marked with ◯, and those whose appearance became cloudy at room temperature after cooling were marked with x. The results are shown in Tables 1 and 2.
表１に示した重合体１以外の成分は下記のとおりである。
ＴＭＰＴＡ；トリメチロールプロパントリアクリレート：サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ３５１ＮＳ、ＳＰ値（９．９）
ＤＴＭＰＴＡ；ジトリメチロールプロパンテトラアクリレート：サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ３５５ＮＳ、ＳＰ値（９．８）
３ＥＯ－ＴＭＰＴＡ；３ｍｏｌＥＯ変性トリメチロールプロパントリアクリレート： サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ４５４ＮＳ、ＳＰ値（９．７）
３ＰＯ－ＴＭＰＴＡ；３ｍｏｌＰＯ変性トリメチロールプロパントリアクリレート： サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ４９２ＴＦＮ、ＳＰ値（９．４）
ＤＰＨＡ；ジペンタエリスリトールヘキサアクリレート：東亞合成（株）製 Ｍ-４０４、ＳＰ値（１０．４）
エポキシ化大豆油アクリレート： サートマー（Ｓａｒｔｏｍｅｒ）製 ＣＮ１１１ＵＳ
メチルハイドロキノン：和光純薬工業（株）製
The components other than the polymer 1 shown in Table 1 are as follows.
TMPTA; trimethylolpropane triacrylate: SR351NS manufactured by Sartomer, SP value (9.9)
DTMPTA; Ditrimethylolpropane Tetraacrylate: SR355NS manufactured by Sartomer, SP value (9.8)
3EO-TMPTA; 3 molEO-modified trimethylolpropane triacrylate: SR454NS manufactured by Sartomer, SP value (9.7)
3PO-TMPTA; 3 molPO-modified trimethylolpropane triacrylate: SR492TFN manufactured by Sartomer, SP value (9.4)
DPHA; Dipentaerythritol hexaacrylate: M-404 manufactured by Toagosei Co., Ltd., SP value (10.4)
Epoxidized soybean oil acrylate: CN111US made by Sartomer
Methyl hydroquinone: manufactured by Wako Pure Chemical Industries, Ltd.
表１に示すように、エポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン性不飽和化合物（Ｃ）を併用して用いた場合、重合体１はエポキシ化植物油（メタ）アクリレート（Ｂ）を単独で用いた場合（比較例１）と比べて、相溶性に優れていた。 As shown in Table 1, when the epoxidized vegetable oil (meth) acrylate (B) and the ethylenically unsaturated compound (C) are used in combination, the polymer 1 contains the epoxidized vegetable oil (meth) acrylate (B) alone. Compared with the case used in (Comparative Example 1), the compatibility was excellent.
表２に示した成分は下記のとおりである。
ＤＡＰ樹脂；（株）大阪ソーダ製、ダイソーダップＡ
ＴＭＰＴＡ；トリメチロールプロパントリアクリレート：サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ３５１ＮＳ、ＳＰ値（９．９）
ＤＴＭＰＴＡ；ジトリメチロールプロパンテトラアクリレート：サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ３５５ＮＳ、ＳＰ値（９．８）
３ＥＯ－ＴＭＰＴＡ；３ｍｏｌＥＯ変性トリメチロールプロパントリアクリレート： サートマー（Ｓａｒｔｏｍｅｒ） 製 ＳＲ４５４ＮＳ、ＳＰ値（９．７）
ＤＰＨＡ；ジペンタエリスリトールヘキサアクリレート：東亞合成（株）製 Ｍ-４０４、ＳＰ値（１０．４）
エポキシ化大豆油アクリレート： サートマー（Ｓａｒｔｏｍｅｒ）製 ＣＮ１１１ＵＳ
メチルハイドロキノン：和光純薬工業（株）製
The components shown in Table 2 are as follows.
DAP resin; made by Osaka Soda Co., Ltd., Daiso Dap A
TMPTA; trimethylolpropane triacrylate: SR351NS manufactured by Sartomer, SP value (9.9)
DTMPTA; Ditrimethylolpropane Tetraacrylate: SR355NS manufactured by Sartomer, SP value (9.8)
3EO-TMPTA; 3 molEO-modified trimethylolpropane triacrylate: SR454NS manufactured by Sartomer, SP value (9.7)
DPHA; Dipentaerythritol hexaacrylate: M-404 manufactured by Toagosei Co., Ltd., SP value (10.4)
Epoxidized soybean oil acrylate: CN111US made by Sartomer
Methyl hydroquinone: manufactured by Wako Pure Chemical Industries, Ltd.
表２に示すように、ＤＡＰ樹脂、エポキシ化植物油（メタ）アクリレート（Ｂ）、エチレン性不飽和化合物（Ｃ）の組み合わせにおいては、ＤＡＰ樹脂単独（比較例６）では、エポキシ化植物油（メタ）アクリレート（Ｂ）と溶解せず、エポキシ化植物油（メタ）アクリレート（Ｂ）とエチレン性不飽和化合物（Ｃ）を併用した場合でも相溶しなかった。 As shown in Table 2, in the combination of the DAP resin, the epoxidized vegetable oil (meth) acrylate (B), and the ethylenically unsaturated compound (C), the epoxidized vegetable oil (meth) is used in the DAP resin alone (Comparative Example 6). It did not dissolve in the acrylate (B), and did not dissolve even when the epoxidized vegetable oil (meth) acrylate (B) and the ethylenically unsaturated compound (C) were used in combination.
本発明の光硬化性樹脂組成物は、インキ（例えば、光硬化性平版用印刷インキ、シルクスクリーンインキ、フレキソインキ等の印刷インキ）、塗料の分野において使用可能である。 The photocurable resin composition of the present invention can be used in the fields of inks (for example, printing inks for photocurable slabs, silk screen inks, printing inks such as flexographic inks), and paints.
Claims (6)
エポキシ化大豆油（メタ）アクリレート（Ｂ）と、
ＳＰ値が８～１２のエチレン性不飽和化合物（Ｃ）とを含有することを特徴とする光硬化性樹脂組成物であり、
前記式（１）表されるアリル化合物が、式（２）～（９）で表される化合物である。
Epoxidized soybean oil (meth) acrylate (B) and
A photocurable resin composition comprising an ethylenically unsaturated compound (C) having an SP value of 8 to 12 .
The allyl compound represented by the formula (1) is a compound represented by the formulas (2) to (9).
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