JP5517112B2 - Photocurable resin composition and its use - Google Patents
Photocurable resin composition and its use Download PDFInfo
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- JP5517112B2 JP5517112B2 JP2011002694A JP2011002694A JP5517112B2 JP 5517112 B2 JP5517112 B2 JP 5517112B2 JP 2011002694 A JP2011002694 A JP 2011002694A JP 2011002694 A JP2011002694 A JP 2011002694A JP 5517112 B2 JP5517112 B2 JP 5517112B2
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- JP
- Japan
- Prior art keywords
- resin composition
- photocurable resin
- resin
- diallyl phthalate
- acrylate monomer
- 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 55
- 239000011347 resin Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 43
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 34
- 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 claims description 33
- 239000000178 monomer Substances 0.000 claims description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 29
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 claims description 20
- 239000003973 paint Substances 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002966 varnish Substances 0.000 claims description 4
- FRDVGLLSCPBABZ-UHFFFAOYSA-N 1,6-dimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1C=CC=CC1(C)C=O FRDVGLLSCPBABZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- -1 polypropylene Polymers 0.000 description 33
- 239000000976 ink Substances 0.000 description 19
- 229920003023 plastic Polymers 0.000 description 14
- 239000004033 plastic Substances 0.000 description 14
- 239000004743 Polypropylene Substances 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- 229920001155 polypropylene Polymers 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000001723 curing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 3
- 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
- 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 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 210000003811 finger Anatomy 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- RSROEZYGRKHVMN-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;oxirane Chemical compound C1CO1.CCC(CO)(CO)CO RSROEZYGRKHVMN-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 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
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- 208000023514 Barrett esophagus Diseases 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bisphenol F Natural products C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines 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
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 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 1
- 235000008429 bread Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 235000012730 carminic acid Nutrition 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 210000003813 thumb Anatomy 0.000 description 1
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- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Description
本発明は、アクリレートモノマー、ジアリルフタレート樹脂、キシレンホルムアルデヒド樹脂を含有する光硬化可能な樹脂組成物、及びそれを含んでなるインキ、塗料に関する。さらに詳しくは、ポリプロピレン（ＰＰ）あるいはポリエチレンテレフタレート（ＰＥＴ）等のプラスチックとの密着性に優れた光硬化性樹脂組成物に関する。 The present invention relates to a photocurable resin composition containing an acrylate monomer, a diallyl phthalate resin, and a xylene formaldehyde resin, and an ink and a paint comprising the same. More specifically, the present invention relates to a photocurable resin composition having excellent adhesion to plastics such as polypropylene (PP) or polyethylene terephthalate (PET).
従来、光（例えば、紫外線）により硬化させる種々の樹脂組成物は、インキ、塗料、接着剤、フォトレジスト等に使用されている。例えば、紫外線硬化タイプの印刷インキは、硬化速度が速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。 Conventionally, various resin compositions that are cured by light (for example, ultraviolet rays) are used in inks, paints, adhesives, photoresists, and the like. For example, UV-curing type printing inks are highly evaluated and have been put to practical use because of their fast curing speed, which can be cured in a short time, compatibility with the environment because they do not use solvents, and resource and energy savings. It has spread.
そのような樹脂組成物の中で、ジアリルフタレート（ジアリルオルソフタレート、ジアリルイソフタレート、ジアリルテレフタレート等）から誘導されたジアリルフタレート樹脂を含有する樹脂組成物は、紙用のＵＶオフセットインキとして採用されている。 Among such resin compositions, a resin composition containing a diallyl phthalate resin derived from diallyl phthalate (diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, etc.) is employed as a UV offset ink for paper. Yes.
しかしながら、プラスチック用のオフセットインキとして用いる際に、ジアリルフタレート樹脂を配合するとプラスチックの印刷基材とインキの密着性に問題が発生するため採用されていない。今日、ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン（ＰＰ）といった様々な種類のプラスチック製品が市販されており、ジアリルフタレート樹脂の欠点であるプラスチックとの密着性の向上が要求されている。 However, when used as an offset ink for plastics, if a diallyl phthalate resin is blended, a problem arises in the adhesion between the printing substrate of the plastic and the ink, which is not adopted. Today, various types of plastic products such as polyethylene terephthalate (PET) and polypropylene (PP) are commercially available, and improvement in adhesion to plastic, which is a drawback of diallyl phthalate resin, is required.
特許文献１には、３個以上のエチレン性不飽和二重結合を有するモノマーおよび（イソ）ジアリルフタレートポリマー、塩素化ポリエチレンから選ばれるイソシアネート基と反応する官能基を有しない非ラジカル反応性樹脂を主成分とする組成物に対し、イソシアネート化合物を配合することによって、ポリプロピレン（ＰＰ）、ポリエチレンテレフタレート（ＰＥＴ）等へのフィルム及びシートへの密着性が改善することが記載されているが、イソシアネート化合物を配合しているため、水の存在下ではイソシアネート化合物が反応してしまい、プラスチックとの密着性が損なわれてしまう。また、保存安定性が悪く、使用もドライオフセットや水無しオフセット印刷といった水を用いない印刷のみに使用が制限されるといった問題点がある。そのため、より広い汎用性を有しプラスチック基材との密着性に優れる光硬化性樹脂組成物の開発が切望されている。 Patent Document 1 discloses a non-radical reactive resin having no functional group that reacts with an isocyanate group selected from a monomer having three or more ethylenically unsaturated double bonds, an (iso) diallyl phthalate polymer, and a chlorinated polyethylene. It is described that the adhesion to films and sheets on polypropylene (PP), polyethylene terephthalate (PET), etc. is improved by adding an isocyanate compound to the main component composition. Therefore, the isocyanate compound reacts in the presence of water, and adhesion with the plastic is impaired. In addition, storage stability is poor, and use is limited to printing that does not use water such as dry offset and waterless offset printing. Therefore, development of the photocurable resin composition which has wider versatility and is excellent in adhesiveness with a plastic base material is earnestly desired.
本発明の目的は、ポリプロピレン（ＰＰ）又はポリエチレンテレフタレート（ＰＥＴ）等のプラスチック基材との密着性に優れたアクリレートモノマー、ジアリルフタレート樹脂、及びキシレンホルムアルデヒド樹脂を含有する光硬化性樹脂組成物を提供することを課題とする。 An object of the present invention is to provide a photocurable resin composition containing an acrylate monomer, a diallyl phthalate resin, and a xylene formaldehyde resin having excellent adhesion to a plastic substrate such as polypropylene (PP) or polyethylene terephthalate (PET). The task is to do.
本発明者は、上記課題を解決するために鋭意研究した結果、アクリレートモノマー、ジアリルフタレート樹脂を含有する光硬化性組成物において、キシレンホルムアルデヒド樹脂を含有させることで、光硬化性樹脂組成物が、ポリポロピレン（ＰＰ）あるいはポリエチレンテレフタレート（ＰＥＴ）等のフィルムに対する密着性に優れていることを見出し、本発明を完成するに至った。本発明はこれらの知見に基づき完成されたものであり、プラスチック基材との密着性に優れた光硬化性樹脂組成物、並びにその樹脂組成物を含有するインキ、塗料である。 As a result of diligent research to solve the above problems, the present inventor, in a photocurable composition containing an acrylate monomer and a diallyl phthalate resin, contains a xylene formaldehyde resin, It has been found that the film has excellent adhesion to a film such as polypropylene (PP) or polyethylene terephthalate (PET), and the present invention has been completed. The present invention has been completed based on these findings, and is a photocurable resin composition excellent in adhesiveness to a plastic substrate, and an ink and a paint containing the resin composition.
本発明はすなわち、
（ａ）アクリレートモノマー
（ｂ）ジアリルフタレート樹脂
（ｃ）キシレンホルムアルデヒド樹脂
を含有することを特徴とする光硬化性樹脂組成物を提供する。さらに、本発明は、その光硬化性樹脂組成物を含有するインキ及び塗料も提供する。
The present invention is
(A) Acrylate monomer
(B) Diallyl phthalate resin (c) A photocurable resin composition comprising a xylene formaldehyde resin is provided. Furthermore, this invention also provides the ink and coating material containing the photocurable resin composition.
項１. （ａ）アクリレートモノマー
（ｂ）ジアリルフタレート樹脂
（ｃ）キシレンホルムアルデヒド樹脂
を含有することを特徴とする光照射により硬化可能な光硬化性樹脂組成物。
項２. 重量平均分子量が１００〜２０００の範囲である（ｃ）キシレンホルムアルデヒド樹脂を含有する項１に記載の光硬化性樹脂組成物。
項３. 水酸基価が５〜４００ｍｇＫＯＨ／ｇの範囲である（ｃ）キシレンホルムアルデヒド樹脂を含有する項１に記載の光硬化性樹脂組成物。
項４. （ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、（ｃ）キシレンアルデヒド樹脂が１〜３０重量部含有する項１〜３のいずれかに記載の光硬化性樹脂組成物。
項５. 更に、光重合開始剤を含有する項１〜４のいずれかに記載の光硬化性樹脂組成物。
項６. 項１〜５のいずれかに記載の光硬化性樹脂組成物を含有するインキ。
項７. 項１〜５のいずれかに記載の光硬化性樹脂組成物を含有する塗料。
項８. オーバープリントワニスである項７に記載の塗料。
Item 1. A photocurable resin composition curable by light irradiation, comprising (a) an acrylate monomer, (b) a diallyl phthalate resin, and (c) a xylene formaldehyde resin.
Item 2. The photocurable resin composition according to Item 1, comprising a (c) xylene formaldehyde resin having a weight average molecular weight in the range of 100 to 2,000.
Item 3. The photocurable resin composition according to Item 1, comprising a (c) xylene formaldehyde resin having a hydroxyl value in the range of 5 to 400 mgKOH / g.
Item 4. The photocuring according to any one of Items 1 to 3, wherein 1 to 30 parts by weight of (c) xylene aldehyde resin is contained with respect to 100 parts by weight of the total of (a) acrylate monomer and (b) diallyl phthalate resin Resin composition.
Item 5. The photocurable resin composition according to any one of Items 1 to 4, further comprising a photopolymerization initiator.
Item 6. An ink containing the photocurable resin composition according to any one of Items 1 to 5.
Item 7. A paint containing the photocurable resin composition according to any one of Items 1 to 5.
Item 8. The paint according to Item 7, which is an overprint varnish.
本発明によれば、インキ、塗料、接着剤およびフォトレジストが、合成高分子の基材、特にプラスチック基材に対して密着性に優れる光硬化性樹脂組成物が得られる。また、本発明の光硬化性樹脂組成物は、光照射時の硬化速度にも優れる。 According to the present invention, a photocurable resin composition in which ink, paint, adhesive, and photoresist are excellent in adhesion to a synthetic polymer substrate, particularly a plastic substrate, can be obtained. Moreover, the photocurable resin composition of this invention is excellent also in the cure rate at the time of light irradiation.
光硬化性樹脂組成物
以下、本発明の光硬化性樹脂組成物について詳細に説明する。本発明の光硬化性樹脂組成物は、硬化前の樹脂組成物であり、少なくとも（ａ）アクリレートモノマー、（ｂ）ジアリルフタレート樹脂、および（ｃ）キシレンホルムアルデヒド樹脂を含有することを特徴とする光硬化性樹脂組成物である。
Photocurable resin composition Hereinafter, the photocurable resin composition of the present invention will be described in detail. The photocurable resin composition of the present invention is a resin composition before curing, and contains at least (a) an acrylate monomer, (b) a diallyl phthalate resin, and (c) a xylene formaldehyde resin. It is a curable resin composition.
本発明の光硬化性樹脂組成物中に用いられる（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂との配合比（（ａ）アクリレートモノマー：（ｂ）ジアリルフタレート樹脂）は、１０：９０〜９０：１０の範囲内で適宜選択することができ、中でも樹脂組成物の取扱い易さ、また硬化速度の点で、５０：５０〜８０：２０の範囲が好ましく、５０：５０〜７０：３０の範囲がより好ましい。上記範囲であれば、光硬化を行う際に十分な硬化速度が得られる。 The blending ratio of (a) acrylate monomer and (b) diallyl phthalate resin ((a) acrylate monomer: (b) diallyl phthalate resin) used in the photocurable resin composition of the present invention is 10:90 to 90. : The range of 10 can be suitably selected, and the range of 50:50 to 80:20 is preferable and the range of 50:50 to 70:30 is preferable in terms of the ease of handling of the resin composition and the curing rate. Is more preferable. If it is the said range, sufficient hardening rate will be obtained when performing photocuring.
アクリレートモノマー
本発明で用いられる（ａ）アクリレートモノマーは、単官能または多官能の（メタ）アクリレート化合物をいい、具体的には、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、およびそれらを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で付加した（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）アクリレート等のアクリル酸エステル化合物；エポキシ化大豆油アクリレート等のアクリル酸エステル化合物を例示することができ、中でも、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、およびそれらを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で付加した（メタ）アクリル酸エステル化合物が好ましく、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に、およびそれらを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で付加した（メタ）アクリル酸エステル化合物がより好ましい。
Acrylate monomer The (a) acrylate monomer used in the present invention refers to a monofunctional or polyfunctional (meth) acrylate compound, specifically, pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl. (Meth) acrylic acid ester compounds of alcohols such as glycol, 1,6-hexanediol, glycerin, polyethylene glycol and polypropylene glycol, and (meth) acrylic acid esters obtained by adding them with alkylene oxides such as ethylene oxide and propylene oxide Compound: (meth) acrylic acid ester obtained by adding alkylene oxide such as ethylene oxide and propylene oxide to bisphenol such as bisphenol A and bisphenol F Tellurium compounds; acrylic ester compounds such as epoxy (meth) acrylate, urethane (meth) acrylate, alkyd (meth) acrylate; acrylic ester compounds such as epoxidized soybean oil acrylate, among others, pentaerythritol, (Meth) acrylic acid ester compounds of alcohols such as dipentaerythritol, trimethylolpropane, ditrimethylolpropane, neopentyl glycol, 1,6-hexanediol, glycerin, polyethylene glycol, polypropylene glycol, and the like, and ethylene oxide, propylene (Meth) acrylic acid ester compounds added with alkylene oxides such as oxides are preferred, pentaerythritol, dipentaerythritol, trimethylol pro More preferred are (meth) acrylic acid ester compounds in which they are added to (meth) acrylic acid ester compounds of alcohols such as bread and ditrimethylolpropane, and alkylene oxides such as ethylene oxide and propylene oxide.
ジアリルフタレート樹脂
本発明で用いられる（ｂ）ジアリルフタレート樹脂とは、ジアリルオルソフタレートプレポリマー、ジアリルイソフタレートプレポリマー、ジアリルテレフタレートプレポリマー等のジアリルフタレート樹脂に代表され、これらの単独、あるいは二種以上の混合物であってよい。また、当該樹脂はジアリルオルソフタレートモノマー、ジアリルイソフタレートモノマー、ジアリルテレフタレートモノマー等の２種以上のいわゆるジアリルモノマーの共重合体からなるプレポリマーであってもよい。この場合、ベンゼン環上の水素原子が塩素、臭素等のハロゲン原子で置換されていてもよく、また分子内に存在する不飽和結合が全部または一部において水添されたプレポリマーもここに含まれるものとする。
Diallyl phthalate resin (b) The diallyl phthalate resin used in the present invention is typified by diallyl phthalate resins such as diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, diallyl terephthalate prepolymer, and the like alone or in combination of two or more. It may be a mixture of The resin may be a prepolymer made of a copolymer of two or more so-called diallyl monomers such as diallyl orthophthalate monomer, diallyl isophthalate monomer, and diallyl terephthalate monomer. In this case, hydrogen atoms on the benzene ring may be substituted with halogen atoms such as chlorine and bromine, and prepolymers in which unsaturated bonds existing in the molecule are all or partly hydrogenated are also included here. Shall be.
本発明のジアリルフタレート樹脂の分子量は特に限定されないが、溶媒への溶解性、硬化性が向上する点で、重量平均分子量が１０，０００〜２００，０００であることが好ましく、重量平均分子量が２０，０００〜６０，０００であることがより好ましい。尚、重量平均分子量はＧＰＣにより測定され、標準ポリスチレン換算で表されるものである。 The molecular weight of the diallyl phthalate resin of the present invention is not particularly limited, but the weight average molecular weight is preferably 10,000 to 200,000, and the weight average molecular weight is 20 in terms of improving solubility in a solvent and curability. More preferably, it is 000-60,000. In addition, a weight average molecular weight is measured by GPC, and is represented by standard polystyrene conversion.
キシレンホルムアルデヒド樹脂
本発明で用いられる（ｃ）キシレンホルムアルデヒド樹脂は、市販品からの入手、またはキシレン（好ましくは、メタキシレン）とホルムアルデヒドの付加縮合により容易に合成可能な樹脂である。
本発明で用いられる（ｃ）キシレンホルムアルデヒド樹脂は、重量平均分子量１００〜２０００の範囲であり、２００〜１７００の範囲が好ましく、２００〜１５００の範囲がより好ましい。または、（ｃ）キシレンホルムアルデヒド樹脂のＯＨ価（水酸基価）は、５〜４００ｍｇＫＯＨ／ｇの範囲であり、１０〜３００ｍｇＫＯＨ／ｇの範囲が好ましく、１０〜２００ｍｇＫＯＨ／ｇの範囲がより好ましい。上記範囲の物性を有する（ｃ）キシレンホルムアルデヒド樹脂を光硬化性樹脂組成物に含有することで十分に本発明の効果が得られる。
Xylene Formaldehyde Resin (c) The xylene formaldehyde resin used in the present invention is a resin that can be obtained from a commercial product or easily synthesized by addition condensation of xylene (preferably metaxylene) and formaldehyde.
The (c) xylene formaldehyde resin used in the present invention has a weight average molecular weight of 100 to 2000, preferably 200 to 1700, and more preferably 200 to 1500. Alternatively, (c) the xylene formaldehyde resin has an OH value (hydroxyl value) in the range of 5 to 400 mgKOH / g, preferably in the range of 10 to 300 mgKOH / g, and more preferably in the range of 10 to 200 mgKOH / g. The effect of the present invention can be sufficiently obtained by including (c) xylene formaldehyde resin having physical properties in the above range in the photocurable resin composition.
市販品としては、例えば、フドー（株）製のニカノールＧ、ニカノールＨ、ニカノールＨＨ、ニカノールＹ１０００、ニカノールＬ、ニカノールＬＬ、ニカノールＬＬＬ、ニカノールＹ-５０、ニカノールＨＰ-７０、ニカノールＨＰ−１００、ニカノールＨＰ−１２０、ニカノールＨＰ-１５０、ニカノールＨＰ-２１０等を例示することができ、これらを単独または２種以上を混合して使用してもよい。 Commercially available products include, for example, Nikanol G, Nikanol H, Nikanol HH, Nikanol Y1000, Nikanol L, Nikanol LL, Nikanol LLL, Nikanol Y-50, Nikanol HP-70, Nikanol HP-100, Nikanol manufactured by Fudou Co., Ltd. Examples thereof include HP-120, Nikanol HP-150, Nikanol HP-210 and the like, and these may be used alone or in admixture of two or more.
本発明の光硬化性樹脂組成物中への（ｃ）キシレンホルムアルデヒド樹脂の配合量は、（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、（ｃ）キシレンアルデヒド樹脂が１〜３０重量部の範囲内であり、１〜２０重量部の範囲が好ましく、１〜１５重量部の範囲がより好ましい。
また、本発明の光硬化性樹脂組成物へ、（ｃ）キシレンホルムアルデヒド樹脂を配合することによって、光硬化する際の硬化速度が改善させる。
The compounding amount of (c) xylene formaldehyde resin in the photocurable resin composition of the present invention is as follows: (c) xylene aldehyde resin with respect to 100 parts by weight of the total of (a) acrylate monomer and (b) diallyl phthalate resin Is in the range of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 1 to 15 parts by weight.
Moreover, the cure rate at the time of photocuring improves by mix | blending (c) xylene formaldehyde resin with the photocurable resin composition of this invention.
その他添加剤
本発明の光硬化性樹脂組成物には、アクリレート化合物以外の光照射により硬化可能であるエチレン性不飽和化合物をさらに含有させてもよい。エチレン性不飽和化合物は、１〜２０、例えば１〜１０、特に２〜５の炭素-炭素二重結合を有する化合物を例示することができる。具体的なエチレン性不飽和化合物としては、（メタ）アリル化合物およびビニル化合物が挙げられる。また、上記エチレン性不飽和化合物を２種以上組合せて混合物として用いてもよい。
Other Additives The photocurable resin composition of the present invention may further contain an ethylenically unsaturated compound that can be cured by light irradiation other than the acrylate compound. Examples of the ethylenically unsaturated compound include compounds having 1 to 20, for example, 1 to 10, particularly 2 to 5 carbon-carbon double bonds. Specific ethylenically unsaturated compounds include (meth) allyl compounds and vinyl compounds. Two or more of the above ethylenically unsaturated compounds may be used in combination as a mixture.
（メタ）アリル化合物の例としては、トリメチロールプロパンジ（メタ）アリルエーテル、ペンタエリスリトールトリ（メタ）アリルエーテル、グリセリンモノ（メタ）アリルエーテル等の（メタ）アリルエーテル化合物やアクリル酸（メタ）アリル、マレイン酸ジ（メタ）アリル、フマル酸ジ（メタ）アリル等の（メタ）アリルエステル化合物、ジアリルフタレート、トリアリルイソシアヌレート等を例示することができる。ビニル化合物のとして例は、スチレン、またはα-メチルスチレン、α-エチルスチレン、α-クロルスチレン等のα置換スチレン、フルオロスチレン、クロロスチレン、ブロモスチレン、クロロメチルスチレン、メトキシスチレン等の核置換スチレン、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 (meth) allyl compounds include (meth) allyl ether compounds such as trimethylolpropane di (meth) allyl ether, pentaerythritol tri (meth) allyl ether, glycerin mono (meth) allyl ether, and acrylic acid (meth). Examples thereof include (meth) allyl ester compounds such as allyl, di (meth) allyl maleate, and di (meth) allyl fumarate, diallyl phthalate, triallyl isocyanurate, and the like. Examples of vinyl compounds include styrene or α-substituted styrene such as α-methyl styrene, α-ethyl styrene, α-chloro styrene, etc., and nucleus-substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethyl styrene, and methoxy styrene. , Divinylbenzene, N-vinylpyrrolidone, vinyl acetate and the like.
本発明の光硬化性樹脂組成物には、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を例示することができる。
光硬化性樹脂組成物に含有される光重合開始剤の量は、（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、２０重量部以下、例えば０．５〜１５重量部の範囲であればよい。
The photocurable resin composition of the present invention may contain a polymerization initiator, and particularly preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator contained in the photocurable resin composition include acetophenone series such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 1-hydroxycyclohexyl phenyl ketone, Examples include benzoin such as benzoin and benzoin ethyl ether, benzophenone such as benzophenone, phosphorus such as acylphosphine oxide, sulfur such as thioxanthone, and dibenzyl such as benzyl and 9,10-phenanthrenequinone. it can.
The amount of the photopolymerization initiator contained in the photocurable resin composition is 20 parts by weight or less, for example, 0.5 to 15 with respect to 100 parts by weight in total of (a) acrylate monomer and (b) diallyl phthalate resin. It may be in the range of parts by weight.
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）を併用できる。光開始助剤の量は、（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、２０重量部以下、例えば０．５〜１０重量部であってよい。 A photoinitiator (for example, an amine photoinitiator such as triethanolamine) can be used in combination with the photocurable resin composition. The amount of the photoinitiating aid may be 20 parts by weight or less, for example, 0.5 to 10 parts by weight with respect to a total of 100 parts by weight of (a) acrylate monomer and (b) diallyl phthalate resin.
本発明の光硬化性樹脂組成物には、種々の添加剤、例示すれば、安定剤（例えば、ハイドロキノン、メトキノン等の重合禁止剤）、着色剤（例えば、シアニンブルー、ジスアゾイエロー、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顔料）、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、（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、１重量部以下、例えば０．００１〜０．５重量部であってよい。光硬化性樹脂組成物に含有される着色剤の量は、（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、１００重量部以下、例えば５〜８０重量部であることが好ましい。 In the photocurable resin composition of the present invention, various additives, for example, stabilizers (for example, polymerization inhibitors such as hydroquinone and methoquinone), colorants (for example, cyanine blue, disazo yellow, carmine 6b, Various additives such as a pigment such as Raked C, carbon black, and titanium white), a filler, and a viscosity modifier may be contained depending on the purpose. The amount of the stabilizer contained in the photocurable resin composition is 1 part by weight or less, for example, 0.001 to 0.5 with respect to 100 parts by weight in total of (a) acrylate monomer and (b) diallyl phthalate resin. It may be part by weight. The amount of the colorant contained in the photocurable resin composition is 100 parts by weight or less, for example, 5 to 80 parts by weight with respect to 100 parts by weight in total of the (a) acrylate monomer and (b) diallyl phthalate resin. It is preferable.
本発明の光硬化性樹脂組成物は、（ａ）アクリレートモノマー、（ｂ）ジアリルフタレート樹脂、（ｃ）キシレンホルムアルデヒド樹脂を含有し、必要に応じて、光重合開始剤、光開始助剤、添加剤（例えば、安定剤、顔料）を混合することによって製造することができる。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。光は、一般に紫外線である。 The photocurable resin composition of the present invention contains (a) an acrylate monomer, (b) a diallyl phthalate resin, and (c) a xylene formaldehyde resin, and if necessary, a photopolymerization initiator, a photoinitiator aid, and addition It can manufacture by mixing an agent (for example, stabilizer, pigment). The photocurable resin composition of the present invention is cured by irradiating light. The light 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、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。なお、硬化反応時のコンベア速度は、硬化後のコート面を指で触り、コート面に指紋が付かないコンベアスピード[「タックフリーコンベアスピード」という。（硬化性が良いほど、タックフリーコンベアスピードの値は大きくなる）]で硬化させることが好ましい。 The curing apparatus and curing conditions used for the curing reaction of the photocurable resin composition are not particularly limited as long as it is a method used for a normal photocuring reaction. The conveyor speed during the curing reaction is a conveyor speed at which the coated surface after curing is touched with a finger and no fingerprint is attached to the coated surface [referred to as “tack-free conveyor speed”. (The better the curability, the higher the tack-free conveyor speed value)].
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、グラビアインキ等の印刷インキ）、塗料（例えば、紙用、プラスチック用、金属用、木工用等の塗料、例示すれば、オーバープリントワニス）、接着剤、フォトレジスト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. Inks (for example, printing inks for photo-curable lithographic printing plates, silk screen inks, gravure inks, etc.), paints (for example, paints for paper, plastics, metals, woodworking, for example, overprint varnishes) ), Adhesives, photoresists, and other technical fields.
例えば、インキの一般的作成方法は次のとおりである。（ａ）アクリレートモノマーに（ｂ）ジアリルフタレート樹脂および（ｃ）キシレンホルムアルデヒド樹脂を４０℃〜１００℃の温度で攪拌しながら溶解させた後、必要に応じて、安定剤（特に、ハイドロキノン、メトキノン等の重合禁止剤）および／または光重合開始剤を添加して混合物を得る。この混合物に顔料を添加することにより、インキが得られる。また、オーバープリントワニスの作成は、顔料を使用しない以外は、インキと同様の手順により行える。 For example, a general method for producing ink is as follows. (A) After the (b) diallyl phthalate resin and (c) xylene formaldehyde resin are dissolved in the acrylate monomer while stirring at a temperature of 40 ° C. to 100 ° C., a stabilizer (especially hydroquinone, methoquinone, etc. A polymerization inhibitor) and / or a photoinitiator to obtain a mixture. An ink can be obtained by adding a pigment to the mixture. The overprint varnish can be prepared by the same procedure as that for ink except that no pigment is used.
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、但し、本発明はその要旨を逸脱しない限り、以下の実施例に限定されるものではない。
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof.
１）光硬化性樹脂組成物1) Photocurable resin composition
以下に実施例および比較例で用いた配合剤を示す。
＊１樹脂１；フドー（株）製ニカノールH（重量平均分子量480、水酸基価20mgKOH/g）
＊２樹脂２；フドー（株）製ニカノールHP100（重量平均分子量1200、水酸基価160mgKOH/g）
＊３樹脂３；フドー（株）製ニカノールLLL（重量平均分子量340、水酸基価25mgKOH/g）
＊４樹脂４；フドー（株）製ニカノールY1000（重量平均分子量330、水酸基価20mgKOH/g）
＊５樹脂５；ヤスハラケミカル（株）製テルペンフェノール樹脂YSポリスターTH130
＊６ＤＡＰ樹脂；ダイソー（株）製ジアリルフタレート樹脂
＊７アクリレートモノマー；トリメチロールプロパンエチレンオキサイド付加トリアクリレート
＊８光重合開始剤；BASFジャパン（株）製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（ＩＲＧＡＣＵＲＥ９０７）
＊９重合禁止剤；BASFジャパン（株）製オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート（ＩＲＧＡＮＯＸ１０７６）
The compounding agents used in Examples and Comparative Examples are shown below.
* 1 Resin 1; Nikanol H manufactured by Fudo Co., Ltd. (weight average molecular weight 480, hydroxyl value 20 mgKOH / g)
* 2 Resin 2; Nikanol HP100 manufactured by Fudou Co., Ltd. (weight average molecular weight 1200, hydroxyl value 160 mgKOH / g)
* 3 Resin 3; Nikanol LLL manufactured by Fudo Co., Ltd. (weight average molecular weight 340, hydroxyl value 25 mgKOH / g)
* 4 Resin 4; Nikanol Y1000 (Fudo Co., Ltd.) (weight average molecular weight 330, hydroxyl value 20 mgKOH / g)
* 5 Resin 5; Terpene phenol resin YS Polystar TH130 manufactured by Yasuhara Chemical Co., Ltd.
* 6 DAP resin; diallyl phthalate resin from Daiso Corp. * 7 acrylate monomer; trimethylolpropane ethylene oxide addition triacrylate * 8 photopolymerization initiator; 2-methyl-1- [4- (methylthio) from BASF Japan Ltd. ) Phenyl] -2-morpholinopropane-1 (IRGACURE907)
* 9 Polymerization inhibitor: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX1076) manufactured by BASF Japan
下記表１に示す配合により、各光硬化性樹脂組成物をアクリレートモノマー７０部にジアリルフタレート樹脂を３０部、樹脂１〜５を１０部、重合禁止剤を０．３部加え、６０℃に加熱しながら固体が完全に溶解するまで撹拌した。続いて、光重合開始剤を１０部加え、完全に溶解させることで調整した。 According to the formulation shown in Table 1 below, each photocurable resin composition was heated to 60 ° C. by adding 30 parts of diallyl phthalate resin to 10 parts of acrylate monomer, 10 parts of resins 1 to 5 and 0.3 part of a polymerization inhibitor. While stirring, the solid was completely dissolved. Then, it adjusted by adding 10 parts of photoinitiators and making it melt | dissolve completely.
２）評価基材
ＰＥＴ基材：東洋紡績株式会社製 二軸延伸ポリエチレンテレフタレートフィルム（ＢＯＰＥＴフィルム） 東洋紡エステル（登録商標）フィルム 品名はＥ５１０２ 片面コロナ処理 厚み２５μｍ
ＰＰ基材：東洋紡績株式会社製 二軸延伸ポリプロピレンフィルム(ＢＯＰＰフィルム） パイレン(登録商標)フィルム−ＯＴ 品名はＰ２１６１ 片面コロナ処理 厚み５０μｍ
2) Evaluation base material PET base material: Biaxially stretched polyethylene terephthalate film (BOPET film) manufactured by Toyobo Co., Ltd.
PP base material: manufactured by Toyobo Co., Ltd. Biaxially stretched polypropylene film (BOPP film) Pyrene (registered trademark) film-OT Product name is P2161 Single-sided corona treatment Thickness 50 μm
３）硬化皮膜の作成
表１に示される組成物をプラスチックフィルムにバーコーター（＃３）でコートして、コンベア型紫外線硬化装置（アイグラフィックス（株）製、条件：ランプ出力６０Ｗ／ｃｍ、照射距離１０ｃｍ、コンベア速度５０〜６０ｍ／ｍｉｎ）を用いて、硬化皮膜を作成した。ＵＶ硬化性は、硬化後コート面を指で触り、コート面に指紋が付かない状態であるタックフリー状態になる最も速いコンベアスピードで各評価を実施した。このコンベア速度を「タックフリーコンベアスピード」とする（硬化性が良いほど、タックフリーコンベアスピードの値は大きくなる）。
3) Preparation of cured film The composition shown in Table 1 was coated on a plastic film with a bar coater (# 3), and a conveyor type ultraviolet curing device (manufactured by Eye Graphics Co., Ltd., conditions: lamp output 60 W / cm, A cured film was prepared using an irradiation distance of 10 cm and a conveyor speed of 50 to 60 m / min. Each UV curing property was evaluated at the fastest conveyor speed at which the coated surface was touched with a finger after curing and the coated surface was in a tack-free state where no fingerprint was attached. This conveyor speed is referred to as “tack-free conveyor speed” (the higher the curability, the larger the value of the tack-free conveyor speed).
４）密着性評価方法
プラスチックフィルムにコートした硬化皮膜に、ニチバン製１８ｍｍ幅のセロテープ（登録商標）（品番：ＬＰ−１８、粘着力：４．０１Ｎ／１０ｍｍ）を貼り付け、親指で５回強く擦った後、セロハンテープを引き離して硬化皮膜の剥離の程度を評価した。評価基準は下記の通りとした。
○：剥離しないもの
△：５０％程度の剥離するもの
×：剥離するもの
4) Adhesiveness evaluation method Nichiban 18 mm wide cello tape (registered trademark) (Part No .: LP-18, adhesive strength: 4.01 N / 10 mm) is affixed to the cured film coated on the plastic film, and 5 times strong with the thumb. After rubbing, the cellophane tape was pulled away to evaluate the degree of peeling of the cured film. The evaluation criteria were as follows.
○: not peeled Δ: about 50% peeled ×: peeled
実施例１〜４及び比較例１、２ プラスチック基材との密着性の評価
上述した方法を用いて各樹脂組成物とプラスチック基材の密着性試験を行った。密着性評価の結果を下表２に示す。
Examples 1 to 4 and Comparative Examples 1 and 2 Evaluation of Adhesion with Plastic Substrate The adhesion test between each resin composition and the plastic substrate was performed using the method described above. The results of adhesion evaluation are shown in Table 2 below.
アクリレートモノマー、ジアリルフタレート樹脂を含有する光硬化性樹脂組成物にキシレンホルムアルデヒド樹脂を添加することで、プラスチック基材との密着性が優れた光硬化性樹脂組成物が得られる。 By adding a xylene formaldehyde resin to a photocurable resin composition containing an acrylate monomer and a diallyl phthalate resin, a photocurable resin composition having excellent adhesion to a plastic substrate can be obtained.
本発明の光硬化性樹脂組成物は、インキ（例えば、オフセットインキ）、塗料、接着剤、フォトレジスト等に使用できる。
The photocurable resin composition of the present invention can be used for ink (for example, offset ink), paint, adhesive, photoresist and the like.
Claims (6)
（ｂ）ジアリルフタレート樹脂
（ｃ）キシレンホルムアルデヒド樹脂
を含有することを特徴とする光照射により硬化可能な光硬化性樹脂組成物であって、
（Ｃ）キシレンホルムアルデヒド樹脂の重量平均分子量が１００〜２０００、及び水酸基価が５〜４００ｍｇＫＯＨ/ｇの範囲であり、
（ａ）アクリレートモノマーと（ｂ）ジアリルフタレート樹脂の合計１００重量部に対して、（ｃ）キシレンアルデヒド樹脂が１〜３０重量部含有するものである。 (A) an acrylate monomer (b) a diallyl phthalate resin (c) a xylene formaldehyde resin, a photocurable resin composition curable by light irradiation ,
(C) The xylene formaldehyde resin has a weight average molecular weight of 100 to 2000 and a hydroxyl value of 5 to 400 mgKOH / g,
(C) xylene aldehyde resin contains 1 to 30 parts by weight with respect to a total of 100 parts by weight of (a) acrylate monomer and (b) diallyl phthalate resin.
The paint according to claim 5 , which is an overprint varnish.
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