KR101993738B1 - Polyfuntional thio(meth)acrylate resin, active-energy-ray curable hard coating resin composition containing the same, cured film obtained by curing the composition, plastic film laminated the cured film, injection molded article using the plastic film and processed products - Google Patents
Polyfuntional thio(meth)acrylate resin, active-energy-ray curable hard coating resin composition containing the same, cured film obtained by curing the composition, plastic film laminated the cured film, injection molded article using the plastic film and processed products Download PDFInfo
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- KR101993738B1 KR101993738B1 KR1020130022987A KR20130022987A KR101993738B1 KR 101993738 B1 KR101993738 B1 KR 101993738B1 KR 1020130022987 A KR1020130022987 A KR 1020130022987A KR 20130022987 A KR20130022987 A KR 20130022987A KR 101993738 B1 KR101993738 B1 KR 101993738B1
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- South Korea
- Prior art keywords
- meth
- acrylate
- formula
- group
- cured film
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- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 125000000446 sulfanediyl group Chemical group *S* 0.000 title claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 19
- 239000011342 resin composition Substances 0.000 title claims description 32
- 239000002985 plastic film Substances 0.000 title claims description 19
- 229920006255 plastic film Polymers 0.000 title claims description 19
- 238000002347 injection Methods 0.000 title claims description 8
- 239000007924 injection Substances 0.000 title claims description 8
- 239000000203 mixture Substances 0.000 title description 15
- -1 thiol compound Chemical class 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 16
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 65
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 21
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- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 5
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 16
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
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- 239000003960 organic solvent Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
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- 238000011156 evaluation Methods 0.000 description 5
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- 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 4
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZODNDDPVCIAZIQ-UHFFFAOYSA-N (2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C ZODNDDPVCIAZIQ-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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- 238000001746 injection moulding Methods 0.000 description 3
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- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical group C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- BXYWKXBAMJYTKP-UHFFFAOYSA-N 2-[2-[2-[2-(3-sulfanylpropanoyloxy)ethoxy]ethoxy]ethoxy]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOCCOCCOCCOC(=O)CCS BXYWKXBAMJYTKP-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 2
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
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- 150000002148 esters Chemical class 0.000 description 2
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
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- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- CZZVAVMGKRNEAT-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)CO.OCC(C)(C)C(O)=O CZZVAVMGKRNEAT-UHFFFAOYSA-N 0.000 description 1
- ICGDKKACLISIAM-UHFFFAOYSA-N 2,3,5,6-tetramethylpiperazine Chemical compound CC1NC(C)C(C)NC1C ICGDKKACLISIAM-UHFFFAOYSA-N 0.000 description 1
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- ZKFHQUZUPMYLAB-UHFFFAOYSA-N 2,3-dihydroxy-4-octoxy-4-oxobutanoic acid Chemical compound CCCCCCCCOC(=O)C(O)C(O)C(O)=O ZKFHQUZUPMYLAB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- NWJAYEGLJQMTJV-UHFFFAOYSA-N 5-methyl-6,7,8,8a-tetrahydro-3h-pyrimido[5,4-d]pyrimidine Chemical compound N1C=NC=C2N(C)CNCC21 NWJAYEGLJQMTJV-UHFFFAOYSA-N 0.000 description 1
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- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
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- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
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- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
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- HZHWZZXJPIFIPG-UHFFFAOYSA-N benzene;butyl acetate Chemical compound C1=CC=CC=C1.CCCCOC(C)=O HZHWZZXJPIFIPG-UHFFFAOYSA-N 0.000 description 1
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
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- 125000004386 diacrylate group Chemical group 0.000 description 1
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- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001692 polycarbonate urethane Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
Abstract
(목적) 본 발명은, 높은 경도와 내찰상성을 구비하고, 하드코팅성이 우수하고, 또한 높은 신장도와 굴곡성을 구비하는 유연성이 높은 경화막을 형성할 수 있는 다관능 티오(메타)아크릴레이트 수지를 제공하는 것을 목적으로 한다.
(해결수단) (식1)에 의하여 산출되는 ｘ가 100이상, 200이하인 다관능 티올 화합물(A)의 티올 말단과, 2관능의 (메타)아크릴레이트 화합물(B)의 적어도 일방의 말단에 구비하는 (메타)아크릴로일기가 엔-티올 반응하여 이루어지고, 일반식(1)으로 표현되는 말단구조를 2이상 구비하는 다관능 티오(메타)아크릴레이트 수지를 사용한다.
[수1]
[화학식 1]
(식 중에서, X는 다관능 티올 화합물(A)의 말단 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상 또는 분기상의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)
(1), at least one terminal of the thiol terminal of the polyfunctional thiol compound (A) having x of not less than 100 and not more than 200 and the bifunctional (meth) acrylate compound (B) A multi-functional thio (meth) acrylate resin having two or more terminal structures represented by the general formula (1) is used.
[Number 1]
[Chemical Formula 1]
(Wherein X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A), R 1 and R 3 each represent hydrogen or a methyl group, R 2 represents O or -O-R 9 -O-. R 9 is an alkylene group linear or branched C1~20, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, -CH 2 CH 2 OP═O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - and at least the structure selected from the structures represented by the following formulas (1-1) to M, p and q are positive integers, and p + q = 2 to 6.)
Description
본 발명은, 다관능 티오(메타)아크릴레이트 수지(多官能thio(meth)acylate樹脂), 이것을 함유하는 활성 에너지선 경화형 하드코팅 수지조성물(活性 energy線 硬化型 hard coating 樹脂組成物)과 그 경화막(硬化膜), 경화막이 적층된 플라스틱 필름(plastic film), 플라스틱 필름을 사용한 플라스틱 사출 성형품(plastic 射出 成型品) 및 가공제품(加功製品)에 관한 것이다.
The present invention relates to a multi-functional thio (meth) acylate resin (multifunctional thio (meth) acylate resin), an active energy ray curable hard coating resin composition (active energy ray curable hard coating resin composition) (Plastic film) laminated with a cured film, a plastic injection molded product (plastic injection molded product) using a plastic film, and a processed product (cured product).
플라스틱 제품의 표면에 무늬나 촉감 등의 장식이나 내찰상성의 부여를 실시하는 제조공법으로서, (1)ＰＥＴ(폴리에틸렌테레프탈레이트) 등의 플라스틱 필름에 접착층이나 무늬층, 하드코팅층을 적층한 장식용 하드코팅 필름을 금형(金型)내에 삽입하고 사출 성형과 동시에 플라스틱 성형품에 부착하는 인 몰드 성형공법(Ｆｉｌｍ Ｉｎｓｅｒｔ Ｍｏｕｌｄｉｎｇ, Ｉｎ-Ｍｏｌｄ Ｄｅｃｏｒａｔｉｎｇ, Ｉｎ-Ｍｏｌｄ Ｌａｍｉｎａｔｉｎｇ 등이라고 한다)이나, (2)사출 성형한 플라스틱 제품 표면 및 강판(鋼板), 건재(建材)에 장식용 하드코팅 필름을 접합시키는 필름 부착 장식공법이 주목받고 있다.(1) a hard coating for decorative use in which an adhesive layer, a pattern layer and a hard coat layer are laminated on a plastic film such as PET (polyethylene terephthalate) or the like; In-mold decorating, or in-mold laminating (hereinafter referred to as "In-Mold Decorating") in which a film is inserted into a mold and adhered to a plastic molded article at the same time of injection molding, Attention has been paid to a decorative method with a film adhering a decorative hard coating film to the surface of a product, a steel plate, and a building material.
상기 공법에서는, 장식용 하드코팅 필름이 금형 내면(內面) 또는 성형품의 제품형상을 따르도록 신장(伸張)된다. 그러나 일반적으로 하드코팅성을 우선할수록 딱딱해져 깨지기 쉬운 성상이 되기 때문에, 상기 공법에 사용되는 장식용 하드코팅 필름은, 신장시의 응력으로 크랙이 발생하기 쉬워 가공성이 저하해버린다. 구체적으로는, 곡면이 심한 가공이나 상자형의 가공(딥 드로잉 가공(deep drawing 加工)이라고 한다)으로 크랙이 발생하기 쉬워, 하드코팅성을 저하시키는 대신에 유연성을 부여시켜 가공성을 향상시키거나 또는 디자인성이 제한되는 것이었다.In the above method, the decorative hard coating film is stretched so as to conform to the inner surface of the mold or the product shape of the molded product. However, in general, hard coatability becomes harder and fragile as the hard coat property is preferentially used. Therefore, the decorative hard coat film used in the above method tends to be cracked due to stress during elongation, resulting in deterioration of processability. Concretely, cracks are likely to occur due to a severe curved surface or box type (deep drawing), so that flexibility is imparted instead of lowering hard coatability to improve workability, or The design was limited.
최근, 제품의 차별화를 꾀하기 위해서 디자인의 복잡화나 표면의 내찰상성이 요구되고 있어, 하드코팅 필름에 있어서의 유연성과 하드코팅성의 양립은 필수불가결하다. 이에 대하여는 다양한 방법이 제안되어 있다. 예를 들면, 3관능 이상의 (메타)아크릴올리고머와 1∼2관능 (메타)아크릴모노머의 배합 조성에 의한 가교밀도(架橋密度)를 컨트롤하는 방법을 들 수 있다(특허문헌1 참조). 이 방법에 의하면, 높은 표면 경도와 성형시의 변형에 추종할 수 있는 유연성을 겸비한 하드코팅 필름이 얻어지지만, 표면 경도와 유연성이 트레이드 오프(trade-off)의 관계가 되고 있어, 어느 정도의 균형으로 타협하지 않을 수 없다고 하는 문제가 있었다.In recent years, in order to differentiate products, design complexity and surface scratch resistance are required, and it is indispensable to have both flexibility and hard coatability in a hard coating film. Various methods have been proposed for this. For example, a method of controlling the crosslinking density (crosslinking density) by the blending composition of the trifunctional or more (meth) acryl oligomer and the (meth) acrylic monomer is disclosed (see Patent Document 1). According to this method, a hard coat film having high surface hardness and flexibility capable of following deformation at the time of molding can be obtained, but surface hardness and flexibility have a trade-off relationship, There is a problem that it can not be compromised.
또한 다른 예로서, 분자량이 5,000∼50,000의 (메타)아크릴로일 당량(當量)이 200g/ｅｑ 이상 800g/ｅｑ 이하의 폴리머 (메타)아크릴레이트와, 분자량 1,000∼10,000의 (메타)아크릴로일 당량 100g/ｅｑ 이상 200g/ｅｑ 미만의 다관능 우레탄(메타)아크릴레이트를 배합하는 방법이 제안되어 있다(특허문헌2 참조). 그러나 이것에 있어서도, 하드코팅성과 유연성의 트레이드 오프의 균형을 (메타)아크릴로일 당량으로 규정한 것으로서, 어느 정도의 균형으로 타협하지 않을 수 없다.As another example, a polymer (meth) acrylate having a (meth) acryloyl equivalent weight of 5,000 to 50,000 and a molecular weight of 200 g / eq or more and 800 g / eq or less and a (meth) A polyfunctional urethane (meth) acrylate having an equivalent weight of at least 100 g / eq and less than 200 g / eq has been proposed (see Patent Document 2). However, also in this case, the balance of the trade-off between the hard coating and the flexibility is defined as the (meth) acryloyl equivalent, and it is compromised to some degree.
또한 라디컬 중합성 이중결합을 구비하지 않는 비반응성 수지를 (메타)아크릴모노머에 배합함으로써 가공성을 부여하는 방법도 제안되어 있다(특허문헌3 참조). 그러나 이러한 비반응성 수지나 가소성 수지를 배합하는 경우에는, 유연해지는 가공성은 향상되지만, 최근 요구되는 높은 하드코팅성에 도달하기에는 곤란했다.
A process for imparting processability by blending a non-reactive resin having no radically polymerizable double bond in a (meth) acrylic monomer has also been proposed (see Patent Document 3). However, when such a nonreactive resin or a plastic resin is blended, the processability to be softened is improved, but it has been difficult to attain the high hard coating property required recently.
일본국 공개특허 특개2011-148964호 공보Japanese Unexamined Patent Application Publication No. 2011-148964
일본국 공개특허 특개2004-123780호 공보Japanese Patent Application Laid-Open No. 2004-123780
일본국 공개특허 특개2008-208154호 공보
Japanese Patent Application Laid-Open No. 2008-208154
본 발명은, 하드코팅성이 있고 또한 유연성이 높아 가공성이 우수한 경화막을 형성할 수 있는 다관능 티오(메타)아크릴레이트 수지를 제공하는 것을 목적으로 한다.
An object of the present invention is to provide a multifunctional thio (meth) acrylate resin capable of forming a cured film having hard coatability and high flexibility and having excellent processability.
즉, 본 발명1은, (식1)에 의하여 산출되는 ｘ가 100∼200인 다관능 티올 화합물(A)(이하, (A)성분이라고도 한다)의 티올 말단과, 2관능의 (메타)아크릴레이트 화합물(B)(이하, (B)성분이라고도 한다)의 적어도 일방의 말단에 구비하는 (메타)아크릴로일기가 엔-티올 반응하여 이루어지고, 일반식(1)으로 표현되는 말단구조를 2이상 구비하는 다관능 티오(메타)아크릴레이트 수지이다. That is, the present invention 1 is a method for preparing a polyfunctional thiol compound (A) (hereinafter also referred to as a component (A)) having x of 100 to 200 and a bifunctional (meth) acrylic (Meth) acryloyl group in at least one end of the compound (B) (hereinafter, also referred to as component (B)) is subjected to an endothiol reaction, and the terminal structure represented by the general formula (1) Functional thio (meth) acrylate resin.
[수1][Number 1]
[화학식 1][Chemical Formula 1]
(식 중에서, X는 다관능 티올 화합물(A)의 말단 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상(直鎖狀) 또는 분기상(分岐狀)의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)(Wherein X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A), R 1 and R 3 each represent hydrogen or a methyl group, R 2 represents O or -O-R 9 -O-. R 9 represents a linear or branched alkylene group having 1 to 20 carbon atoms, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3 ) O ) mCH 2 CH (CH 3) -, -CH 2 CH 2 OP = O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - , and the following formulas (1-1) to (1- 3), m, p and q are positive integers, and p + q = 2 to 6.)
본 발명2는, (A)성분의 티올 말단과, (B)성분의 적어도 일방의 말단에 구비하는 (메타)아크릴로일기가 엔-티올 반응하여 결합한, 하기 일반식(2)으로 표현되는 말단구조를 구비하는 다관능 티오(메타)아크릴레이트 수지이다.(2), wherein the thiol end of the component (A) is bound to the (meth) acryloyl group at least at one end of the component (B) by an endothiol reaction and the end represented by the following general formula Functional thio (meth) acrylate resin.
[화학식 2](2)
(식 중에서, X는 다관능 티올 화합물(A)의 말단 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상 또는 분기상의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)(Wherein X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A), R 1 and R 3 each represent hydrogen or a methyl group, R 2 represents O or -O-R 9 -O-. R 9 is an alkylene group linear or branched C1~20, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, -CH 2 CH 2 OP═O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - and at least the structure selected from the structures represented by the following formulas (1-1) to M, p and q are positive integers, and p + q = 2 to 6.)
본 발명3은, 본 발명1 또는 2에 있어서, (A)성분이, 하기 일반식(3)∼(7)으로 표현되는 다관능 티올 화합물 중의 어느 하나인 다관능 티오(메타)아크릴레이트 수지이다.The present invention 3 is the polyfunctional thio (meth) acrylate resin according to the first or second aspect of the present invention, wherein the component (A) is any one of the polyfunctional thiol compounds represented by the following general formulas (3) to (7) .
[화학식 3](3)
(식 중에서, R4는 수소 또는 메틸기, n은 1∼12의 정수를 나타낸다.)(Wherein R 4 represents hydrogen or a methyl group, and n represents an integer of 1 to 12).
[화학식 4][Chemical Formula 4]
(식 중에서, R5는 수소 또는 메틸기를 나타낸다.)(In the formula, R 5 represents hydrogen or a methyl group.)
[화학식 5][Chemical Formula 5]
(식 중에서, R6은 수소 또는 메틸기를 나타낸다.)(In the formula, R 6 represents hydrogen or a methyl group.)
[화학식 6][Chemical Formula 6]
(식 중에서, R7은 수소 또는 메틸기를 나타낸다.)(In the formula, R 7 represents hydrogen or a methyl group.)
[화학식 7](7)
(식 중에서, R8은, 수소 또는 메틸기를 나타낸다.)(In the formula, R 8 represents hydrogen or a methyl group.)
본 발명4는, 본 발명1∼3중의 어느 하나의 다관능 티오(메타)아크릴레이트 수지, (메타)아크릴로일기를 3개 이상 구비하는 다관능 (메타)아크릴레이트 및 광중합개시제를 함유하는 활성 에너지선 경화형 하드코팅 수지조성물이다.The present invention 4 is characterized in that the polyfunctional thio (meth) acrylate resin of any one of the inventions 1 to 3, the polyfunctional (meth) acrylate having three or more (meth) acryloyl groups, Energy ray curable hard coating resin composition.
본 발명5는, 본 발명4의 활성 에너지선 경화형 하드코팅 수지조성물에 활성 에너지선을 조사함으로써 경화시켜서 얻어지는 경화막이다.The present invention 5 is a cured film obtained by curing an active energy ray-curable hard-coating resin composition of the present invention 4 by irradiating an active energy ray.
본 발명6은, 본 발명5의 경화막이 적층된 플라스틱 필름이다.The sixth invention is a plastic film laminated with the cured film of the fifth invention.
본 발명7은, 본 발명6의 플라스틱 필름을 사용한 플라스틱 사출 성형품이다.The present invention 7 is a plastic injection molded article using the plastic film of the sixth aspect of the present invention.
본 발명8은, 본 발명6의 플라스틱 필름을 적층한 가공제품이다.
The present invention 8 is a processed product obtained by laminating the plastic film of the sixth invention.
본 발명의 티오에테르 결합(thioether結合) 함유의 다관능 티오(메타)아크릴레이트 수지를 사용하면, 유연성과, 높은 연필경도와 내찰상성을 구비하는 우수한 하드코팅성(우수한 표면 찰상형성 곤란성)을 양립한 경화막을 형성할 수 있다. 이에 따라 종래의 기술로는 곤란했던, 가공성이 높을 뿐만 아니라 경화막 표면의 내찰상성을 부여할 수 있는 하드코팅 필름을 형성할 수 있다.
The use of the thioether bond-containing polyfunctional thio (meth) acrylate resin of the present invention makes it possible to achieve excellent hard coatability (difficulty in forming excellent surface scratches) having flexibility, high pencil hardness and scratch resistance, A cured film can be formed. As a result, it is possible to form a hard coating film that is not only difficult with conventional techniques, but also has high processability and can impart scratch resistance to the surface of the cured film.
본 발명에 있어서의 (A)성분은, 단관능 티올 화합물이 아니라, 반응성 관능기로서 티올기(-ＳＨ)를 말단에 2개 이상 구비하는 다관능 티올 화합물이면 특별하게 한정되지 않는다. (A)성분을 다관능 티올 화합물로 함으로써, 본 발명의 수지는 말단에 (메타)아크릴로일기를 2개 이상 구비한 다관능 티오(메타)아크릴레이트 수지로 할 수 있고, 활성 에너지선을 조사해서 얻어지는 경화물은 조밀한 3차원 가교구조를 취하기 쉬워지기 때문에, 우수한 하드코팅성을 구비하는 것으로 할 수 있다. 본 명세서에 있어서의 다관능 티오(메타)아크릴레이트 수지란, 2개 이상의 티오에테르 결합을 함유하는 다관능 (메타)아크릴레이트를 의미한다.The component (A) in the present invention is not particularly limited as long as it is not a monofunctional thiol compound, but a multifunctional thiol compound having two or more thiol groups (-SH) as reactive functional groups. When the component (A) is a polyfunctional thiol compound, the resin of the present invention can be a polyfunctional thio (meth) acrylate resin having at least two (meth) acryloyl groups at the ends, The resulting cured product is easy to take a dense three-dimensional cross-linking structure, and thus can have excellent hard coatability. The polyfunctional thio (meth) acrylate resin in the present specification means a polyfunctional (meth) acrylate containing two or more thioether bonds.
또한 상기 (A)성분은, (식1)에 의하여 산출되는 ｘ가 100∼200인 것이, 우수한 하드코팅성을 구비하는 경화막을 형성하는 다관능 티오(메타)아크릴레이트 수지를 구비하는 것으로 할 수 있는 점에서 바람직하다. x가 100∼200이면, 조밀한 3차원 가교구조가 얻어질 수 있어 보다 우수한 하드코팅성을 부여할 수 있다. 구체적인 예로서는, 일반식(3)∼(7)으로 표현되는 테트라에틸렌글리콜비스(3-메르캅토프로피오네이트), 트리메틸올프로판트리스(3-메르캅토프로피오네이트), 트리스-[(3-메르캅토프로피오닐옥시)-에틸]-이소시아누레이트, 펜타에리스리톨테트라키스-3-메르캅토프로피오네이트, 디펜타에리스리톨헥사키스(3-메르캅토프로피오네이트) 등의 다관능 티올 화합물을 들 수 있고, 이들은 1종 또는 2종 이상을 혼합해서 사용할 수 있다. 입수 용이성의 점으로부터, 일반식(3)∼(7)으로 표현되는 다관능 티올 화합물이 더 바람직하다.The component (A) may comprise a multifunctional thio (meth) acrylate resin which forms a cured film having excellent hard coatability, wherein x calculated from (Formula 1) is 100 to 200 . When x is 100 to 200, a dense three-dimensional cross-linking structure can be obtained and better hard coatability can be imparted. Specific examples include tetraethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), tris- [(3-mercaptopropionate) Polyfunctional thiol compounds such as pentaerythritol tetrakis-3-mercaptopropionate and dipentaerythritol hexakis (3-mercaptopropionate) can be used These may be used alone or in combination of two or more. From the viewpoint of availability, the polyfunctional thiol compounds represented by the general formulas (3) to (7) are more preferable.
[수1][Number 1]
상기 (B)성분은, 적어도 일방의 말단에 (메타)아크릴로일기를 구비하는 2관능의 (메타)아크릴레이트이면 특별하게 한정되지 않는다. 3관능 혹은 그 이상의 다관능 (메타)아크릴레이트 화합물을 사용한 경우에는, 다관능 티올 화합물과의 엔-티올 반응(ene-thiol 反應)으로 분자끼리의 가교구조가 과도하게 형성되기 쉬워지는 결과, 겔화가 발생하기 쉽고, 반응 제어가 곤란해진다. 구체적인 예로서는, 에틸렌글리콜디(메타)아크릴레이트, 디에틸렌글리콜디(메타)아크릴레이트, 트리에틸렌글리콜디(메타)아크릴레이트, 폴리에틸렌글리콜디(메타)아크릴레이트, 프로필렌글리콜디(메타)아크릴레이트, 디프로필렌글리콜디(메타)아크릴레이트, 트리프로필렌글리콜디(메타)아크릴레이트, 폴리프로필렌디(메타)아크릴레이트, 1,3-부탄디올(메타)아크릴레이트, 1,4-부탄디올디(메타)아크릴레이트, 네오펜틸글리콜디(메타)아크릴레이트, 2-(메타)아크릴로일옥시에틸애시드포스페이트, 3-메틸-1.5-펜탄디올디(메타)아크릴레이트, 1.6-헥산디올디(메타)아크릴레이트, 2-부틸-2-에틸-1.3-프로판디올디(메타)아크릴레이트, 1.9-노난디올디(메타)아크릴레이트, 디메틸올트리시클로데칸디(메타)아크릴레이트, ＥＯ 또는 ＰＯ변성 비스페놀A디(메타)아크릴레이트 화합물, 히드록시피발산네오펜틸글리콜디(메타)아크릴레이트, 2-히드록시-3-아크릴로일옥시프로필메타크릴레이트, 디(메타)아크릴산무수물 등을 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용해서 배합하여도 좋다. 더 바람직하게는, 용이하게 입수할 수 있는 점에서, 트리프로필렌글리콜디(메타)아크릴레이트, 디메틸올트리시클로데칸디(메타)아크릴레이트, 2-히드록시-3-아크릴로일옥시프로필메타크릴레이트, 디(메타)아크릴산무수물이다. 2종 이상 사용하는 경우에 각 2관능 (메타)아크릴레이트 성분의 사용 비율은, 특히 제한되지 않는다.The component (B) is not particularly limited as long as it is a bifunctional (meth) acrylate having at its one end a (meth) acryloyl group. When a trifunctional or higher polyfunctional (meth) acrylate compound is used, the cross-linking structure between the molecules is likely to be excessively formed due to the ene-thiol reaction with the polyfunctional thiol compound. As a result, And the reaction control becomes difficult. Specific examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di Butanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, EO or PO-modified bisphenol (meth) acrylate, (Meth) acrylate compound, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, di (meth) acrylic acid anhydride and the like . These may be used alone or in combination of two or more. (Meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate Di (meth) acrylic acid anhydride. In the case of using two or more kinds of them, the use ratio of each bifunctional (meth) acrylate component is not particularly limited.
상기 엔-티올 반응이란, 본 발명에서는, (메타)아크릴로일 화합물의 반응성 불포화기와 티올 화합물의 티올기와의 부가반응을 말한다. 본 발명의 다관능 티오(메타)아크릴레이트는, 상기 (A)성분과 (B)성분의 라디컬 공중합반응에 의한 라디컬 공중합체는 포함되지 않는다. 라디컬 공중합체라고 하면, 본 발명이 구비하는 일반식(1)의 구조가 포함되지 않고, (B)성분만의 장쇄중합물이 (A)성분의 티올 말단과 결합한 구조가 되고, 하드코팅성은 향상하지만 가공성이 저하하는 경향이 된다.The above-mentioned ene-thiol reaction refers to an addition reaction between a reactive unsaturated group of a (meth) acryloyl compound and a thiol group of a thiol compound in the present invention. The multifunctional thio (meth) acrylate of the present invention does not include the radical copolymer by the radical copolymerization reaction of the component (A) and the component (B). Radical copolymer does not include the structure of the general formula (1) of the present invention, and the long chain polymer only of the component (B) is bonded to the thiol end of the component (A), and the hard coatability is improved However, the workability tends to decrease.
본 발명의 다관능 티오(메타)아크릴레이트 수지는, 상기 (A)성분의 말단 티올기(-ＳＨ)와, (B)성분의 적어도 일방의 말단에 구비하는 (메타)아크릴로일기가, 엔-티올 반응해서 얻어진 생성물이며, 일반식(1)으로 표현되는 말단구조를 2이상 구비하는 것이다. 본 발명의 다관능 티오(메타)아크릴레이트 수지에 있어서의 (B)성분의 사용 비율은, (A)성분의 티올기 1개에 대하여 (B)성분의 2관능 (메타)아크릴레이트 화합물이 1∼3분자가 되는 비율이 바람직하다. (B)성분의 비율을 이 비율로 함으로써, 미반응의 (B)성분의 증가를 억제하고 하드코팅성을 더 우수한 것으로 할 수 있을 뿐만 아니라, (B)성분의 양쪽 말단이 티올기와 반응하는 확률을 낮추고, 분자량의 증대를 방지하고 고점도화를 방지하고 유기용제 등에 대한 양호한 상용성을 구비하게 하며, 또한 겔화하기 어려워진다. 경화물의 가공성과 하드코팅성의 양립을 우수하게 하는 점에서, 더 바람직하게는 (B)성분의 사용 비율은, 1∼2분자이다.In the polyfunctional thio (meth) acrylate resin of the present invention, the (meth) acryloyl group at the terminal of at least one of the terminal thiol group (-SH) and the component (B) -Thiol, and has two or more end structures represented by the general formula (1). The proportion of the component (B) in the polyfunctional thio (meth) acrylate resin of the present invention is such that the bifunctional (meth) acrylate compound of the component (B) is 1 To 3 molecules is preferable. (B) component at this ratio can suppress the increase of the unreacted component (B) and improve the hard coatability. In addition, the probability of reacting both ends of the component (B) with the thiol group To prevent the increase of the molecular weight, to prevent the increase of the viscosity, to have the good compatibility with the organic solvents, etc., and it becomes difficult to gel. More preferably, the use ratio of the component (B) is 1 to 2 molecules in order to make the processability and hard coatability of the cured product excellent.
엔-티올 반응은 반응성이 높아 무촉매에서도 반응이 진행하지만, 산 또는 아민 촉매를 사용하는 것이 바람직하다. 구체적으로는, 예를 들면 산촉매로서는, 옥틸산제1주석, 디부틸주석디라우레이트 등을 들 수 있는 주석화합물, 아민 촉매로서는, 트리에틸아민, 이미다졸리딘(imidazolidine), 프롤린(proline), 키나알칼로이드(cinchona alkaloid), 트리아자비시클로데센, 디아자비시클로운데센, 헥사히드로메틸피리미도피리미딘, 디아자비시클로노난, 테트라메틸구아니딘, 디아자비시클로옥탄, 디이소프로필에틸아민, 테트라메틸피페리딘을 들 수 있다. 이들은 1종을 단독으로 사용하여도 좋고, 2종 이상을 혼합해서 사용해도 좋다. 또 상기 촉매의 사용량은, 전중합성분 100중량부에 대하여, 0.001∼0.01중량부 정도로 하는 것이 바람직하다.The en-thiol reaction is highly reactive and proceeds even in the absence of a catalyst, but it is preferable to use an acid or an amine catalyst. Specific examples of the acid catalyst include tin compounds such as octyl tartrate and dibutyl tin dilaurate, and examples of the amine catalyst include triethylamine, imidazolidine, proline, But are not limited to, cinchona alkaloid, triazabicyclo decene, diazabicyclo undecene, hexahydromethylpyrimidopyrimidine, diazabicyclo noonane, tetramethylguanidine, diazabicyclooctane, diisopropylethylamine, tetramethylpiperazine Peridin. These may be used singly or as a mixture of two or more kinds. The amount of the catalyst to be used is preferably about 0.001 to 0.01 part by weight based on 100 parts by weight of the total polymerization component.
또 상기 엔-티올 반응에 있어서는, 메토퀴논, 하이드로퀴논, 트리메틸하이드로퀴논, N-니트로소페닐히드록실아민 등의 중합금지제를 사용할 수 있다. 중합금지제의 사용량은 특별하게 한정되지 않지만, 얻어지는 수지의 반응 경화성에 악영향을 끼치는 일이 없도록 하기 위해서 생성물의 합계 중량 100중량부에 대하여, 보통 1중량부 정도 이하로 하는 것이 바람직하다. 또한 중합을 방지하기 위해서, 반응계중에 공기를 흡입시키는 등을 하여도 좋다.In the above-mentioned ene-thiol reaction, polymerization inhibitors such as methoquinone, hydroquinone, trimethylhydroquinone, N-nitrosophenylhydroxylamine and the like can be used. The amount of the polymerization inhibitor to be used is not particularly limited, but it is preferably about 1 part by weight or less based on 100 parts by weight of the total weight of the products so as not to adversely affect the reaction curability of the resulting resin. Further, in order to prevent polymerization, air may be sucked into the reaction system.
상기 엔-티올 반응에서는, 유기용제를 사용하지 않고 무용제로 생성물을 얻을 수 있다. 또한 각 성분이 용해 가능한 유기용제를 사용해 용제중에서의 합성도 가능하고, 그 경우에 유기용제의 희석 효과에 의해 생성물을 저점도로 얻을 수 있는 장점이 있다. 바람직한 유기용제로서는, 메틸에틸케톤이나 메틸이소부틸케톤 등을 들 수 있는 케톤류 이외의 유기용제이면, 특별하게 한정되지 않고 공지의 것을 사용할 수 있다. 케톤류를 사용하였을 경우에는, (A)성분의 티올기와 (B)성분의 (메타)아크릴로일기와의 엔-티올 반응이 저해되어버린다. 적합한 유기용제로서, 구체적으로는, 프로판올, 부탄올 등의 알코올류; 톨루엔, 벤젠 등의 방향족 탄화수소류; 아세트산부틸, 아세트산에틸 등을 들 수 있다, 이들은 1종을 단독으로 사용하여도 좋고, 2종 이상을 혼합해서 사용해도 좋다. 각 반응공정에 있어서, 반응 온도를 높게 설정하면 반응을 효율적으로 단시간에 진행시킬 수 있기 때문에 비등점이 높은 것이 바람직하지만, 활성 에너지선 경화형 하드코팅제로서는 건조성이 좋은 것이 바람직한 점을 고려하면, 아세트산에틸, 아세트산부틸, 톨루엔이 바람직하다.In the above-mentioned ene-thiol reaction, the product can be obtained as a solvent without using an organic solvent. In addition, it is possible to synthesize an organic solvent in which each component is soluble in a solvent. In this case, the product can be obtained at a low point by the dilution effect of the organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent other than ketones such as methyl ethyl ketone and methyl isobutyl ketone, and known solvents can be used. When a ketone is used, the enol reaction of the thiol group of the component (A) with the (meth) acryloyl group of the component (B) is inhibited. Specific examples of suitable organic solvents include alcohols such as propanol and butanol; Aromatic hydrocarbons such as toluene and benzene; Butyl acetate, and ethyl acetate. These may be used singly or in combination of two or more kinds. In view of the fact that a high boiling point can be obtained because the reaction can be efficiently progressed in a short time in each of the reaction steps, it is preferable that the active energy ray-curable hard coating agent has good dryability. , Butyl acetate, and toluene are preferable.
본 발명은 또한 (A)성분의 티올 말단과 (B)성분의 적어도 일방의 (메타)아크릴로일기가 엔-티올 반응하여 결합한 하기 일반식(2)으로 표현되는 말단구조를 구비하는 티오에테르 결합을 함유하는 다관능 티오(메타)아크릴레이트 수지이기도 한다.The present invention also provides a thioether linkage having a terminal structure represented by the following general formula (2) in which at least one (meth) acryloyl group of the thiol end of the component (A) and the component (B) (Meth) acrylate resin containing a polyfunctional thio (meth) acrylate.
[화학식 2](2)
(식 중에서, X는 다관능 티올 화합물(A)의 말단 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상 또는 분기상의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)(Wherein X represents a structure excluding the terminal thiol group of the polyfunctional thiol compound (A), R 1 and R 3 each represent hydrogen or a methyl group, R 2 represents O or -O-R 9 -O-. R 9 is an alkylene group linear or branched C1~20, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, -CH 2 CH 2 OP═O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - and at least the structure selected from the structures represented by the following formulas (1-1) to M, p and q are positive integers, and p + q = 2 to 6.)
본 발명의 다관능 티오(메타)아크릴레이트 수지는, 일반식(2)으로 표현되는 것과 같이, 1분자중에 2∼6의 괄호내의 말단구조를 구비한다. 괄호내에서 나타내는 구조가 하나뿐이면, 경화막의 하드코팅성이 저하한다. 괄호내에서 나타내는 구조가 2∼6이면, 조밀한 3차원 가교구조를 구축하기 때문에 하드코팅성이 향상한다. 괄호내에서 나타내는 구조가 6을 넘으면, 엔-티올 반응의 제어가 곤란해져 겔화하기 쉬워진다.The multifunctional thio (meth) acrylate resin of the present invention has a terminal structure in parentheses of 2 to 6 in one molecule, as represented by the general formula (2). If there is only one structure shown in parentheses, the hard coatability of the cured film deteriorates. When the structure represented by the parentheses is 2 to 6, hard coatability is improved because a dense three-dimensional crosslinked structure is formed. When the structure represented by the parentheses exceeds 6, control of the ene-thiol reaction becomes difficult, and gelation tends to occur.
본 발명의 다관능 티오(메타)아크릴레이트 수지에 있어서의 (A)성분과 (B)성분, 이들의 비율, 제조방법은 상기한 바와 같다.The component (A) and the component (B) in the polyfunctional thio (meth) acrylate resin of the present invention, their ratio, and the production method are as described above.
상기 다관능 티오(메타)아크릴레이트 수지, (메타)아크릴로일기를 3개 이상 구비하는 다관능 (메타)아크릴레이트 및 광중합개시제를 함유하는 활성 에너지선 경화형 하드코팅 수지조성물도 또한 본 발명의 하나이다. 본 발명의 활성 에너지선 경화형 하드코팅 수지조성물의 경화물은, 가교밀도가 높기 때문에 하드코팅성이 우수하고, 또한 유연성이 우수하다. 그 때문에 종래 검토되고 있었던 가교밀도의 조정이나 미반응 수지 등의 배합 등의 방법으로는 곤란했던, 경화막의 하드코팅성과 유연성의 양립을 달성할 수 있어, 장식용 하드코팅 필름용의 부재에 적합하게 사용할 수 있다.An active energy ray-curable hardcoat resin composition containing the polyfunctional thio (meth) acrylate resin, polyfunctional (meth) acrylate having three or more (meth) acryloyl groups and a photopolymerization initiator is also one of the present invention . The cured product of the active energy ray-curable hard coat resin composition of the present invention has excellent hard coatability and excellent flexibility because of high crosslinking density. Therefore, it is possible to achieve both the hard coating and the flexibility of the cured film, which has been difficult to attain by the method of adjusting the crosslinking density or the blending of unreacted resin, which has been conventionally examined, and can be suitably used for members for decorative hard- .
상기 (메타)아크릴로일기를 3개 이상 구비하는 다관능 (메타)아크릴레이트는, 1분자중에 (메타)아크릴로일기의 말단을 3개 이상 구비하는 (메타)아크릴레이트이면 특별하게 한정되지 않고, 구체적으로는, 트리메틸올프로판트리(메타)아크릴레이트, 트리메틸올프로판에톡시트리(메타)아크릴레이트, 글리세린에톡시트리(메타)아크릴레이트, 글리세린프로폭시트리(메타)아크릴레이트, 에톡시화 이소시아누르산트리(메타)아크릴레이트, ε-카프로락톤 변성 트리스-(2-(메타)아크릴로옥시에틸)이소시아누레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트, 펜타에리스리톨에톡시트리/테트라(메타)아크릴레이트, 펜타에리스리톨프로폭시트리/테트라(메타)아크릴레이트, 디트리메틸올프로판테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, ε-카프로락톤 변성 디펜타에리스리톨헥사(메타)아크릴레이트, 우레탄(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트를 들 수 있다. 이들은 각각을 단독으로 또는 2종 이상을 병용해서 배합하여도 좋다. 하드코팅성 및 경화성의 점으로부터 바람직하게는, 펜타에리스리톨트리/테트라(메타)아크릴레이트, 디펜타에리스리톨헥사(메타)아크릴레이트, 글리세린프로폭시트리(메타)아크릴레이트, ε-카프로락톤 변성 트리스-(2-(메타)아크릴로옥시에틸)이소시아누레이트, 우레탄(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트이다. 더 바람직하게는, 우레탄(메타)아크릴레이트, 펜타에리스리톨트리/테트라(메타)아크릴레이트, 폴리에스테르(메타)아크릴레이트이다. 2종 이상 사용하는 경우에 각 다관능 (메타)아크릴레이트 성분의 사용 비율은, 특히 제한되지 않는다.The polyfunctional (meth) acrylate having three or more (meth) acryloyl groups is not particularly limited as long as it is a (meth) acrylate having three or more terminals of the (meth) acryloyl group in one molecule (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy tri (meth) acrylate, glycerine ethoxy tri (meth) acrylate, glycerin propoxy tri Tetra (meth) acrylate, pentaerythritol ethoxytri / pentaerythritol tri (meth) acrylate,? -Caprolactone modified tris- (2- (meth) acryloxyethyl) isocyanurate, Tetra (meth) acrylate, pentaerythritol propoxytri / tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, lactone-ε- caprolactone-modified dipentaerythritol hexa (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate. These may be used alone or in combination of two or more. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin propoxytri (meth) acrylate, epsilon -caprolactone-modified tris (meth) acrylate or the like, from the viewpoint of hard coatability and curability. (Meth) acryloyloxyethyl isocyanurate, urethane (meth) acrylate, and polyester (meth) acrylate. More preferred are urethane (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate and polyester (meth) acrylate. When two or more of them are used, the use ratio of each polyfunctional (meth) acrylate component is not particularly limited.
상기 우레탄(메타)아크릴레이트로서는, 다가(多價)의 이소시아네이트 화합물과 2개 이상의 수산기 함유 화합물을 반응시켜서 얻어지는 말단 이소시아네이트기 함유 화합물에 수산기 함유 (메타)아크릴레이트를 반응시켜서 얻어지는, 분자내에 3개 이상의 (메타)아크릴로일기를 구비하는 우레탄(메타)아크릴레이트, 및 다가 이소시아네이트 화합물과 1개의 수산기를 함유하는 (메타)아크릴레이트 화합물을 반응시켜서 얻어지는, 분자중에 3개 이상의 (메타)아크릴로일기를 구비하는 우레탄(메타)아크릴레이트 등을 들 수 있다.As the urethane (meth) acrylate, there can be used a compound obtained by reacting a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound with two or more hydroxyl group-containing compounds to react with a hydroxyl group-containing (meth) (Meth) acryloyl group in the molecule, which is obtained by reacting a urethane (meth) acrylate having a (meth) acryloyl group and a (meth) acryloyl group and a (Meth) acrylate having a carboxyl group and a carboxyl group.
폴리에스테르(메타)아크릴레이트로서는, 분자중에 에폭시기를 3개 이상 함유하는 화합물에 (메타)아크릴산을 반응시켜서 얻어지는, (메타)아크릴로일기를 3개 이상 구비하는 에폭시(메타)아크릴레이트 등을 들 수 있다.Examples of the polyester (meth) acrylate include epoxy (meth) acrylates having three or more (meth) acryloyl groups obtained by reacting (meth) acrylic acid with a compound containing three or more epoxy groups in the molecule .
상기 광중합개시제로서는, 자외선에 의해 분해되어 라디컬을 발생시켜 중합을 시작시킬 수 있는 것이면, 특별하게 한정되지 않고 공지의 것을 사용할 수 있다. 구체적으로는, 예를 들면 2,2-디메톡시-1,2-디페닐에탄-1-온, 1-시클로헥실페닐케톤, 2-히드록시-2-메틸-1-페닐-프로판-1-온, 1-[4-(2-히드록시에톡시)-페닐]-2-히드록시-2-메틸-1-프로판-1-온, 2-메틸-1-[4-(메틸티오)페닐]-2-몰포리노프로판-1-온, 2-벤질-2-디메틸아미노-1-(4-몰포리노페닐)-부타논-1, 비스(2,4,6-트리메틸벤조일)-페닐포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐-포스핀옥사이드, 4-메틸벤조페논 등을 들 수 있고, ＢＡＳＦ사 등으로부터 용이하게 입수할 수 있다. 이들은 1종을 단독으로 혹은 2종 이상을 조합하여 사용할 수 있다. 광중합개시제의 사용량은, 활성 에너지선 경화형 수지조성물 100중량부에 대하여, 0.1∼10중량부 정도로 하는 것이 바람직하다.The photopolymerization initiator is not particularly limited as long as it can decompose by ultraviolet rays to generate radicals to initiate polymerization, and known ones can be used. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy- Methyl-1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- ] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, and the like, and they are readily available from BASF. These may be used singly or in combination of two or more. The photopolymerization initiator is preferably used in an amount of about 0.1 to 10 parts by weight based on 100 parts by weight of the active energy ray curable resin composition.
본 발명의 활성 에너지선 경화형 하드코팅 수지조성물은, 내마모성 향상이나 블록킹성 향상을 목적으로 무기 필러와 배합하여도 좋다. 무기 필러로서는, 실리카나 금속산화물 미립자 등의 공지의 것을 한정 없이 사용할 수 있다. 예를 들면 산화티탄, 산화알루미늄, 산화안티몬, 산화주석, 산화지르코늄, 산화아연, 산화세륨, 산화인듐 등을 들 수 있다. 이들은 1종을 단독으로 또는 2종 이상을 조합시켜서 사용할 수 있다. 이들 중에서, 상업적으로 제품군이 충실하고 입수 용이하며 염가이기 때문에, 실리카, 산화티탄, 산화알루미늄, 산화지르코늄 및 산화아연이 바람직하다.The active energy ray-curable hard coat resin composition of the present invention may be blended with an inorganic filler for the purpose of improving abrasion resistance and improving blocking property. As the inorganic filler, known materials such as silica and metal oxide fine particles can be used without limitation. For example, titanium oxide, aluminum oxide, antimony oxide, tin oxide, zirconium oxide, zinc oxide, cerium oxide, and indium oxide. These may be used singly or in combination of two or more. Of these, silica, titanium oxide, aluminum oxide, zirconium oxide and zinc oxide are preferable because they are commercially available, are easy to obtain, and are inexpensive.
상기 무기 필러의 평균입자지름이 200ｎｍ(레이저 회절·산란법에 의한다) 이하로 제어된 것을 사용하는 것이 바람직하다. 평균입자지름이 200ｎｍ을 넘으면 경화막에 백화(白化)가 발생하기 쉬워 헤이즈나 투과 효율 등의 광학특성을 손상시킬 우려가 있다.It is preferable to use an inorganic filler whose average particle size is controlled to 200 nm or less (by laser diffraction / scattering method). If the average particle diameter exceeds 200 nm, whitening may occur in the cured film, which may deteriorate optical properties such as haze and transmission efficiency.
본 발명의 활성 에너지선 경화형 하드코팅 수지조성물은, 필요에 따라 첨가제를 더 배합할 수도 있다. 상기 첨가제로서는, 산화방지제, 자외선흡수제, 광안정제, 소포제, 표면조정제, 오염방지제, 안료, 대전방지제, 금속산화물 미립자 분산체를 들 수 있다.The active energy ray-curable hard coat resin composition of the present invention may further contain additives as required. Examples of the additives include antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifouling agents, pigments, antistatic agents and metal oxide fine particle dispersions.
또한 상기 활성 에너지선 경화형 하드코팅제에 활성 에너지선을 조사함으로써 경화시켜서 얻어지는 경화막도 본 발명의 하나이다. 본 발명의 경화막을 사용하면, 가공성과 하드코팅성이 양립하는 장식 하드코팅 필름으로써 사용할 수 있다.Further, a cured film obtained by curing the active energy ray-curable hard coating agent by irradiating an active energy ray is also one of the present invention. When the cured film of the present invention is used, it can be used as a decorative hard coating film in which both workability and hard coatability are compatible.
상기 활성 에너지선으로서는, 광(光)(자외선 등의 광선), 전자선, X선, α선, β선, γ선, 중성자선 등을 들 수 있다. 일반적으로 널리 보급되어 있다고 하는 점에서, 광과 전자선이 바람직하다.Examples of the active energy ray include light (rays such as ultraviolet rays), electron rays, X rays,? Rays,? Rays,? Rays, neutron rays and the like. Light and an electron beam are preferable because they are generally widely used.
상기 경화막이 적층된 플라스틱 필름도 본 발명의 하나이다. 지금까지 하드코팅층의 크랙 때문에 적용할 수 없었던 것 같은 곡면이 심한 가공이나 딥 드로잉 가공에 있어서도 대응할 수 있고, 종래와 동등한 찰상에 강한 하드코팅성을 성형품의 표면에 부여할 수 있다. 구체적으로는, ＩＭＬ공법이나 필름 접합 장식에 적합하게 사용할 수 있다.The plastic film laminated with the cured film is also one of the present invention. It is possible to cope with severe curved surfaces and deep drawing processes which have not been applicable because of the cracks of the hard coat layer so far, and it is possible to impart hard coatability to the surface of the molded article which is comparable to the conventional scratch resistance. Specifically, it can be suitably used for an IML method or a film joint decoration.
상기 플라스틱 필름의 기재(基材)로서는, 특히 제한은 없고, 예를 들면 플라스틱(폴리카보네이트, 폴리메틸메타크릴레이트, 폴리스티렌, 폴리에스테르, 폴리올레핀, 에폭시 수지, 멜라민 수지, 트리아세틸셀룰로오스 수지, ＡＢＳ수지, ＡＳ수지, 노보넨계 수지(norbornene系 樹脂) 등)을 들 수 있다.The base material of the plastic film is not particularly limited and examples thereof include plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin , AS resin, norbornene resin (norbornene resin), etc.).
상기 플라스틱 필름에 경화막을 적층시키는 방법으로서는, 공지의 방법으로, 활성 에너지선 경화형 하드코팅 수지조성물을 도포해서 건조시킨 후에, 활성 에너지선을 조사해서 경화시킴으로써 한다. 수지조성물의 도포 방법으로서는, 예를 들면 바 코터 도포, 메이어 바 도포(meyer bar 塗布), 에어나이프 도포, 그라비아 도포, 리버스 그라비아 도포(reverse gravure 塗布), 오프셋 인쇄(offset 印刷), 플렉소그래픽 인쇄(flexographic 印刷), 스크린 인쇄법 등을 들 수 있다. 또 도포량은 특별하게 한정되지 않지만, 보통은 건조후의 중량이 0.1∼20g/m2, 바람직하게는 0.5∼10g/m2이 되는 범위이다.As a method for laminating a cured film on the plastic film, an active energy ray-curable hard-coating resin composition is coated and dried by a known method, and then cured by irradiation with active energy rays. Examples of the application method of the resin composition include a bar coater application, a Meyer bar application, an air knife application, a gravure application, a reverse gravure application, an offset printing, a flexographic printing (flexographic printing), and a screen printing method. Also the coating amount is not particularly limited, and usually it is the weight after drying 0.1~20g / m 2, preferably in the range in which the 0.5~10g / m 2.
본 발명은 또한 상기 플라스틱 필름을 사용한 플라스틱 사출 성형품이기도 한다. 종래에는 하드코팅층의 크랙의 문제로부터, 플라스틱 사출 성형품의 하드코팅성에 타협을 강요하거나 또는 디자인성에 제한이 있었지만, 본 발명의 플라스틱 필름을 사용하면, 복잡한 디자인성에 대응하고, 또한 표면의 상처에 강한 플라스틱 사출 성형품을 얻을 수 있고, 휴대전화 단말이나 PC라고 하는 전기기기의 프레임이나, 차내 내장 트림이나 외장 커버의 일부에 사용 가능하다.The present invention is also a plastic injection molded product using the plastic film. Conventionally, from the viewpoint of the cracking of the hard coating layer, the hard coating property of the plastic injection molded article is forced to compromise or the design property is limited. However, when the plastic film of the present invention is used, And can be used for a frame of an electric device such as a cellular phone terminal or a PC, a part of a built-in trim or an outer cover of a vehicle.
본 발명은 또한 상기 플라스틱 필름을 적층한 가공제품이기도 한다. 플라스틱 필름의 적층방법은, 금형내에 삽입해 사출 성형과 동시에 플라스틱 성형품에 부착하는 공법과는 달리, 열가소성 수지를 사출 성형 또는 압출성형한 플라스틱 가공품의 표면에 플라스틱 필름을 접합하는 것이다. 또한 가공제품으로서는, 휴대전화 단말이나 PC라고 하는 전기기기의 프레임이나, 차내 내장 트림이나 외장 커버의 일부, 플라스틱 용기에 사용 가능하다.The present invention is also a processed product obtained by laminating the plastic film. Unlike a method of inserting a plastic film into a mold and attaching it to a plastic molded article at the same time of injection molding, a plastic film is bonded to the surface of a plastic processed article obtained by injection molding or extrusion molding of a thermoplastic resin. Further, the processed product can be used for a frame of an electric device such as a cellular phone terminal or a PC, a part of a built-in trim or an outer cover of a vehicle, and a plastic container.
이하에, 실시예 및 비교예를 들어서 본 발명을 구체적으로 설명하지만, 본 발명은 이들 각 예에 한정되는 것은 아니다. 또 각 예중에서, 부 및 ％은 특기하지 않는 한 전부 중량기준이다.Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Further, in each of the examples, parts and percentages are by weight unless otherwise specified.
<합성예1>≪ Synthesis Example 1 &
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기(dropping funnel)를 부착한 4구 플라스크에, 톨루엔 31.0부, (B)성분으로서 디메틸올트리시클로데칸디아크릴레이트(이하, ＤＣＰ-Ａ) 31.0부, 트리에틸아민(이하, ＴＥＡ) 0.01부, 메토퀴논 0.2부를 넣어 교반하면서 60도까지 가열하고, 미리 준비해 둔 (A)성분으로서 테트라에틸렌글리콜비스(3-메르캅토프로피오네이트)(이하, ＥＧ-ＭＰ, 상기 일반식(3)에 상당; (식1)이 산출한 ｘ=186) 19.0부, 톨루엔 19.0부의 혼합 용액을, 적하 깔때기로부터 2시간에 걸쳐서 전량을 적하했다. 그 후에 60도로 5시간 보온하고, 일반식(1)의 말단구조를 구비하는 티오에테르 결합 함유의 2관능 아크릴레이트(수지1)를 얻었다.A flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel was charged with 31.0 parts of toluene, 31.0 parts of dimethyloltricyclodecane diacrylate (hereinafter referred to as DCP-A) , 0.01 part of triethylamine (hereinafter referred to as TEA) and 0.2 part of methoquinone were charged and heated to 60 ° C. with stirring. Then, tetraethylene glycol bis (3-mercaptopropionate) (hereinafter referred to as EG -MP, a mixture of 19.0 parts of x = 186 and 19.0 parts of toluene, calculated according to the formula (3), x = 186 calculated in (formula 1), was added dropwise over 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 degrees for 5 hours to obtain a bifunctional acrylate (resin 1) containing a thioether bond and having a terminal structure of the general formula (1).
<합성예2>≪ Synthesis Example 2 &
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 아세트산부틸 30.8부, (B)성분으로서 2-히드록시-3-아크릴로일옥시프로필메타크릴레이트(상품명 「ＮＫ에스테르701Ａ」신나카무라화학공업주식회사) 30.8부, ＴＥＡ 0.01부, 메토퀴논 0.2부를 넣어 교반하면서 60도까지 가열하고, 미리 준비해 둔 (A)성분으로서 트리메틸올프로판트리스(3-메르캅토프로피오네이트)(이하, ＴＭ-ＭＰ, 상기 일반식(4)에 상당; x=133) 19.2부, 아세트산부틸 19.2부의 혼합 용액을, 적하 깔때기로부터 2시간에 걸쳐서 전량을 적하했다. 그 후에 60도로 5시간 보온하고, 일반식(1)의 말단구조를 구비하는 티오에테르 결합 함유의 3관능 메타크릴레이트(수지2)를 얻었다.To a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel, 30.8 parts of butyl acetate and 2 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: NK ester (Manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.01 part of TEA and 0.2 part of methoquinone were placed and heated to 60 ° C with stirring, and trimethylolpropane tris (3-mercaptopropionate) 19.2 parts of TM-MP, corresponding to the general formula (4); x = 133) and 19.2 parts of butyl acetate was added dropwise over a period of 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a trifunctional methacrylate (resin 2) containing a thioether bond and having a terminal structure of the general formula (1).
<합성예3>≪ Synthesis Example 3 &
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 아세트산부틸 31.9부, (B)성분으로서 테트라에틸렌글리콜디아크릴레이트(이하, 4ＥＧＡ) 31.9부, ＴＥＡ 0.01부, 메토퀴논 0.2부를 넣어 교반하면서 60도까지 가열하고, 미리 준비해 둔 (A)성분으로서 트리스-[(3-메르캅토프로피오닐옥시)-에틸]-이소시아누레이트(이하, ＴＩ-ＭＰ, 상기 일반식(5)에 상당; x=176) 18.1부, 아세트산부틸 18.1부의 혼합 용액을, 적하 깔때기로부터 2시간에 걸쳐서 전량을 적하했다. 그 후에 60도로 5시간 보온하고, 일반식(1)의 말단구조를 구비하는 티오에테르 결합 함유의 3관능 아크릴레이트(수지3)를 얻었다.To a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet, and a dropping funnel were added 31.9 parts of butyl acetate, 31.9 parts of tetraethylene glycol diacrylate (hereinafter referred to as 4EGA), 0.01 part of TEA, (Hereinafter, referred to as TI-MP, the above-mentioned general formula ((A)) as the component (A) 5); x = 176) and 18.1 parts of butyl acetate was added dropwise over a period of 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 ° C for 5 hours to obtain a trifunctional acrylate (resin 3) containing thioether bond having the terminal structure of the general formula (1).
<합성예4>≪ Synthesis Example 4 &
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 톨루엔 39.8부, (B)성분으로서 트리프로필렌글리콜디아크릴레이트(이하, ＴＰＧＤＡ) 39.8부, ＴＥＡ 0.01부, 메토퀴논 0.2부를 넣어 교반하면서 60도까지 가열하고, 미리 준비해 둔 (A)성분으로서 펜타에리스리톨테트라키스(3-메르캅토프로피오네이트)(이하, ＰＴ-ＭＰ, 상기 일반식(6)에 상당; x=123) 10.7부, 톨루엔 10.7부의 혼합 용액을, 적하 깔때기로부터 2시간에 걸쳐서 전량를 적하했다. 그 후에 60도로 5시간 보온하고, 일반식(1)의 말단구조를 구비하는 티오에테르 결합 함유의 4관능 아크릴레이트(수지4)를 얻었다.39.8 parts of toluene, 39.8 parts of tripropylene glycol diacrylate (hereinafter referred to as TPGDA) as a component (B), 0.01 part of TEA, 0.2 part of methoquinone 0.2 (Hereinafter referred to as PT-MP, corresponding to the above general formula (6); x = 123 (3)) as the component (A) ) And 10.7 parts of toluene was added dropwise over 2 hours from the dropping funnel. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a tetrafunctional acrylate (resin 4) containing a thioether bond and having the terminal structure of the formula (1).
<합성예5>≪ Synthesis Example 5 &
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 아세트산부틸 35.6부, (B)성분으로서 ＮＫ에스테르701Ａ 35.6부, ＴＥＡ 0.01부, 메토퀴논 0.2부를 넣어 교반하면서 60도까지 가열하고, 미리 준비해 둔 (A)성분으로서 디펜타에리스리톨헥사키스(3-메르캅토프로피오네이트)(이하, ＤＰ-ＭＰ, 상기 일반식(7)에 상당; x=131) 14.4부, 아세트산부틸 14.4부의 혼합 용액을, 적하 깔때기로부터 2시간에 걸쳐서 전량을 적하했다. 그 후에 60도로 5시간 보온하고, 일반식(1)의 말단구조를 구비하는 티오에테르 결합 함유의 6관능 메타크릴레이트(수지5)를 얻었다.35.6 parts of butyl acetate, 35.6 parts of NK ester 701A, 0.01 part of TEA and 0.2 part of methoquinone were placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, 14.4 parts of dipentaerythritol hexaquis (3-mercaptopropionate) (hereinafter referred to as DP-MP, corresponding to the general formula (7); x = 131) as the component (A) 14.4 parts of the mixed solution was dropped from the dropping funnel over 2 hours. Thereafter, the mixture was kept at 60 ° C. for 5 hours to obtain a 6-functional methacrylate (resin 5) containing a thioether bond and having a terminal structure represented by the general formula (1).
<실시예1>≪ Example 1 >
합성예1에 의해 얻어진 티오에테르 결합 함유의 2관능 아크릴레이트(수지1) 100부에 대하여, 펜타에리스리톨트리아크릴레이트(이하, ＰＥ3Ａ) 50부, 광중합개시제(상품명 「이르가큐어184」ＢＡＳＦ사) 5부, 메틸에틸케톤(이하, ＭＥＫ) 95부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.50 parts of pentaerythritol triacrylate (hereinafter, referred to as PE3A), 50 parts of a photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF), 100 parts of a bifunctional acrylate (resin 1) containing thioether bond obtained in Synthesis Example 1, , And 95 parts of methyl ethyl ketone (hereinafter referred to as MEK) were blended to obtain an active energy ray-curable hard coating resin composition having a solid content of 40%.
<실시예2>≪ Example 2 >
합성예2에 의해 얻어진 티오에테르 결합 함유의 3관능 메타크릴레이트(수지2) 100부에 대하여, ＰＥ3Ａ 116.7부, 이르가큐어184 8.3부, ＭＥＫ 191.7부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.116.7 parts of PE3A, 8.3 parts of Irgacure 184 and 191.7 parts of MEK were blended with 100 parts of the trifunctional methacrylate (resin 2) containing thioether linkage obtained in Synthesis Example 2 to obtain an active energy ray curing type Hard-coating resin composition.
<실시예3>≪ Example 3 >
합성예2에 의해 얻어진 티오에테르 결합 함유의 3관능 메타크릴레이트(수지2) 100부에 대하여, 6관능 우레탄아크릴레이트(상품명 「ＵＡ-306Ｈ」;교에이샤화학주식회사) 50부, 이르가큐어184 5부, ＭＥＫ 95부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.50 parts of hexafunctional urethane acrylate (trade name " UA-306H ", manufactured by Kyoeisha Chemical Co., Ltd.) was added to 100 parts of trifunctional methacrylate (Resin 2) containing thioether bond obtained in Synthesis Example 2, 184, and 95 parts of MEK were blended to obtain an active energy ray-curable hard coating resin composition having a solid content of 40%.
<실시예4><Example 4>
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 메틸이소부틸케톤 39.5부를 넣고, 질소기류하에서 110도까지 승온시킨 후, 글리시딜메타크릴레이트(이하, ＧＭＡ) 26.0부, 아조비스이소부티로니트릴 1.2부의 혼합액을 넣은 적하 깔때기로부터 2시간에 걸쳐서 전량 적하하고, 5시간 반응시킴으로써 ＧＭＡ공중합체를 얻었다. 그 후에 상온까지 냉각한 후, 아크릴산을 13.2부, 트리페닐포스핀 0.3부, 메토퀴논 0.1부를 넣고, 적하 깔때기를 빼고 질소유입구를 에어 버블링 장치(air bubbling裝置)로 교환해서 공기를 버블링 하면서 교반하고, 110도로 6시간 반응시켜 중량평균분자량 17,000의 폴리에스테르아크릴레이트를 얻었다. 이 폴리에스테르아크릴레이트 125부에 대하여, 합성예2에 의해 얻어진 티오에테르 결합 함유의 3관능 메타크릴레이트(수지2)를 100부, 이르가큐어184 5부, ＭＥＫ 20부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.39.5 parts of methyl isobutyl ketone was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, and the mixture was heated to 110 DEG C in a nitrogen stream, glycidyl methacrylate (GMA) , And 1.2 parts of azobisisobutyronitrile was added dropwise over a period of 2 hours from the dropping funnel, and the mixture was reacted for 5 hours to obtain a GMA copolymer. After cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine and 0.1 part of methoquinone were charged, the dropping funnel was removed, the nitrogen inlet was replaced with an air bubbling device, and air was bubbled And reacted at 110 DEG C for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. 100 parts of trifunctional methacrylate (Resin 2) containing thioether bond, 5 parts of Irgacure 184 and 20 parts of MEK obtained in Synthesis Example 2 were blended with 125 parts of this polyester acrylate to obtain a solid content of 40% Of active energy ray-curable hard coating resin composition.
<실시예5>≪ Example 5 >
합성예3에 의해 얻어진 티오에테르 결합 함유의 3관능 아크릴레이트(수지3) 100부에 대하여, ＰＥ3Ａ 116.7부, 이르가큐어184 8.3부, ＭＥＫ 191.7부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.116.7 parts of PE3A, 8.3 parts of Irgacure 184 and 191.7 parts of MEK were added to 100 parts of trifunctional acrylate (resin 3) containing thioether bond obtained in Synthesis Example 3 to obtain an active energy ray hardening type hardener To prepare a coating resin composition.
<실시예6>≪ Example 6 >
합성예4에 의해 얻어진 티오에테르 결합 함유의 4관능 아크릴레이트(수지4) 100부에 대하여, 글리세린트리아크릴레이트(상품명 「데나콜ＤＡ-314」; 나가세화성공업주식회사) 50부, 이르가큐어184 5부, ＭＥＫ 95부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.50 parts of glycerin triacrylate (trade name " Denacol DA-314 ", manufactured by Nagase Kasei Kogyo Co., Ltd.), 100 parts of Irgacure 184 , And 95 parts of MEK were blended to obtain an active energy ray-curable hard coating resin composition having a solid content of 40%.
<실시예7>≪ Example 7 >
합성예5에 의해 얻어진 티오에테르 결합 함유의 6관능 메타크릴레이트(수지5) 100부에 대하여, ε-카프로락톤 변성 트리스-(2-(메타)아크릴로옥시에틸)이소시아누레이트(상품명 「ＮＫ에스테르Ａ-9300-1ＣＬ」; 신나카무라화학공업주식회사) 50부, 이르가큐어184 5부, ＭＥＫ 95부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.Caprolactone-modified tris- (2- (meth) acryloxyethyl) isocyanurate (trade name: " Tetraethyleneglycol) " was added to 100 parts of 6-functional methacrylate (Resin 5) 50 parts of NK Ester A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts of Irgacure 184 and 95 parts of MEK were mixed to obtain an active energy ray-curable hard coating resin composition having a solid content of 40%.
<비교예1>≪ Comparative Example 1 &
일반적인 하드코팅제의 구성 성분으로서 알려진 펜타에리스리톨트리아크릴레이트(ＰＥ3Ａ)를 비교로서 사용하였다. ＰＥ3Ａ로서 시판품 중에서 상품명 「아로닉스Ｍ305」(동아합성주식회사 제품)를 100부, 이르가큐어184 5.0부, ＭＥＫ 145부를 혼합한 것을, 고형분 40%의 범용 하드코팅제로 하여 비교예1로 하였다.Pentaerythritol triacrylate (PE3A), known as a component of a common hard coating, was used as a comparison. As the PE3A, 100 parts of Aronix M305 (product of Dong-A Synthetic Co., Ltd.), 5.0 parts of Irgacure 184 and 145 parts of MEK were mixed in a commercially available product to obtain a general hard coating having a solid content of 40%.
<비교예2>≪ Comparative Example 2 &
가교밀도 감소에 의한 유연성 부여를 목적으로 하여, 비교예1의 수지조성의 일부를, 단관능 아크릴모노머; 이소보닐아크릴레이트로 치환했다. 아로닉스Ｍ305 25.0부, 이소보닐아크릴레이트 75.0부, 이르가큐어184 5.0부, ＭＥＫ 145부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.For the purpose of imparting flexibility by decreasing the crosslinking density, a part of the resin composition of Comparative Example 1 was replaced with a monofunctional acrylic monomer; Substituted with isobornyl acrylate. 25.0 parts of Aronix M305, 75.0 parts of isobornyl acrylate, 5.0 parts of Irgacure 184 and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예3>≪ Comparative Example 3 &
유연성 부여의 목적으로부터, 비교예1의 수지조성에 라디컬 중합성기를 구비하지 않는 미반응 수지를 배합했다. 아로닉스Ｍ305 80부, 포화 폴리에스테르 수지 상품명 「ＫＡ-2056」(아라카와화학공업주식회사) 33.3부, 이르가큐어184 5부, ＭＥＫ 131.7부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.For the purpose of imparting flexibility, an unreacted resin having no radically polymerizable group was blended into the resin composition of Comparative Example 1. 80 parts of Aronix M305, 33.3 parts of a saturated polyester resin "KA-2056" (Arakawa Chemical Industries, Ltd.), 5 parts of Irgacure 184 and 131.7 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예4>≪ Comparative Example 4 &
ＵＡ-306Ｈ 100부, 이르가큐어184 5부, ＭＥＫ 145부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.100 parts of UA-306H, 5 parts of Irgacure 184 and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예5>≪ Comparative Example 5 &
데나콜ＤＡ-314 100부, 이르가큐어184 5부, ＭＥＫ 145부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.100 parts of Denacol DA-314, 5 parts of Irgacure 184 and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예6>≪ Comparative Example 6 >
교반기, 온도계, 환류냉각기, 질소유입구 및 적하 깔때기를 부착한 4구 플라스크에, 메틸이소부틸케톤 39.5부를 넣고, 질소기류하에서 110도까지 승온시킨 후, 글리시딜메타크릴레이트(이하, ＧＭＡ) 26.0부, 아조비스이소부티로니트릴 1.2부의 혼합액을 넣은 적하 깔때기로부터 2시간에 걸쳐서 전량 적하하고, 5시간 반응시킴으로써 ＧＭＡ공중합체를 얻었다. 그 후에 상온까지 냉각한 후, 아크릴산을 13.2부, 트리페닐포스핀 0.3부, 메토퀴논 0.1부를 넣고, 적하 깔때기를 빼고 질소유입구를 에어 버블링 장치로 교환해서 공기를 버블링 하면서 교반하고, 110도로 6시간 반응시켜 중량평균분자량 17,000의 폴리에스테르아크릴레이트를 얻었다. 이 폴리에스테르아크릴레이트 100부에 대하여, 이르가큐어184 2부를 배합하여, 고형분 40%의 활성 에너지선 경화형 하드코팅 수지조성물로 하였다.39.5 parts of methyl isobutyl ketone was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet and a dropping funnel, and the mixture was heated to 110 DEG C in a nitrogen stream, glycidyl methacrylate (GMA) , And 1.2 parts of azobisisobutyronitrile was added dropwise over a period of 2 hours from the dropping funnel, and the mixture was reacted for 5 hours to obtain a GMA copolymer. After cooling to room temperature, 13.2 parts of acrylic acid, 0.3 part of triphenylphosphine, and 0.1 part of methoquinone were added. The dropping funnel was removed, the nitrogen inlet was replaced with an air bubbling device, the air was stirred while bubbling, And reacted for 6 hours to obtain a polyester acrylate having a weight average molecular weight of 17,000. Two parts of Irgacure 184 were blended with 100 parts of the polyester acrylate to obtain an active energy ray-curable hard coating resin composition having a solid content of 40%.
<비교예7>≪ Comparative Example 7 &
ＮＫ에스테르Ａ-9300-1ＣＬ 100부, 이르가큐어184 5부, ＭＥＫ 145부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.100 parts of NK Ester A-9300-1CL, 5 parts of Irgacure 184 and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예8>≪ Comparative Example 8 >
유연성을 구비하는 다관능 아크릴레이트로서, ε-카프로락톤 변성 디펜타에리스리톨헥사아크릴레이트; 상품명 「ＤＰＣＡ-120」(니혼카야쿠주식회사)을 100부, 이르가큐어184 5부, ＭＥＫ 145부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.As polyfunctional acrylates having flexibility,? -Caprolactone-modified dipentaerythritol hexaacrylate; 100 parts of DPCA-120 (Nippon Kayaku Co., Ltd.), 5 parts of Irgacure 184 and 145 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
<비교예9>≪ Comparative Example 9 &
교반기, 온도계, 환류냉각기, 질소유입구를 부착한 4구 플라스크에, 이소포론디이소시아네이트 15.9부, 폴리카보네이트디올(수평균분자량 1000, 상품명 「듀라놀Ｔ6001」아사히화성케미컬즈) 35.8부, 메틸이소부틸케톤 40부를 넣고, 교반하면서 60도까지 가온해 1시간 보온한 후, 디부틸주석디아세테이트 0.05부 첨가하고 80도로 2시간 반응시켜, 폴리카보네이트디올의 ＯＨ기 양쪽 말단에 각각 이소포론디이소시아네이트를 부가시켜, 폴리카보네이트의 양쪽 말단에 이소시아네이트기를 유입했다. 그 후에 40도까지 냉각하고, 2-히드록시에틸아크릴레이트 8.3부와 디부틸주석디아세테이트 0.05부를 넣고, 80도까지 가온해 5시간 반응시켜, 이소시아네이트 말단에 2-히드록시에틸아크릴레이트의 ＯＨ기를 부가시켜, 폴리카보네이트우레탄디아크릴레이트(수지6)가 얻어졌다. 실온까지 냉각시킨 뒤, 이르가큐어184를 5부, ＭＥＫ 47부를 혼합하여, 고형분 40%의 활성 에너지선 수지조성물로 하였다.A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet was charged with 15.9 parts of isophorone diisocyanate, 35.8 parts of a polycarbonate diol (number average molecular weight 1000, trade name "DYRANOL T6001" by Asahi Kasei Chemicals) 40 parts of ketone were added and the mixture was heated to 60 DEG C with stirring and maintained at that temperature for 1 hour. Then, 0.05 part of dibutyltin diacetate was added and reacted at 80 DEG C for 2 hours to add isophorone diisocyanate to both ends of the OH group of the polycarbonate diol And an isocyanate group was introduced into both ends of the polycarbonate. After cooling to 40 ° C, 8.3 parts of 2-hydroxyethyl acrylate and 0.05 part of dibutyltin diacetate were added and the mixture was warmed to 80 ° C. and reacted for 5 hours to obtain an OH group of 2-hydroxyethyl acrylate at the end of the isocyanate To give a polycarbonate urethane diacrylate (Resin 6). After cooling to room temperature, 5 parts of Irgacure 184 and 47 parts of MEK were mixed to obtain an active energy ray resin composition having a solid content of 40%.
각 실시예 및 비교예의 하드코팅제를, 두께 188μm의 일면 접착용이 처리 폴리에틸렌테레프탈레이트 필름(상품명 「코스모샤인Ａ4100」 도요방적주식회사)의 접착용이면에 바 코터 Ｎｏ．12로 도포하고, 80도로 1분간 건조시킨 후, 자외선광을 300ｍＪ/ｃｍ2 조사하여, 막 두께 5μm의 경화막을 얻었다.The hard coating agents of each of the examples and comparative examples were coated with Bar Coater No. 12 on the back surface of a polyethylene terephthalate film (trade name " Cosmo Shine A4100 " manufactured by Toyo Bunsha Co., Ltd.) having a thickness of 188 mu m, After drying, ultraviolet light was irradiated at 300 mJ / cm 2 to obtain a cured film having a thickness of 5 탆.
각 실시예 및 비교예의 하드코팅제를 사용해 작성된 경화막은, 하드코팅성의 평가로서, 연필경도 시험과 내찰상성 시험으로 평가했다. 가공성의 평가는, 경화필름을 일방향으로 신장시키는 인장시험에 의하여 산출되는 신장도, 굴곡성으로 평가했다. 이들의 평가결과는 표2, 3에 나타낸다.The cured films prepared using the hard coating agents of the examples and comparative examples were evaluated by pencil hardness test and scratch resistance test as evaluation of hard coatability. The evaluation of the workability was made by evaluating the elongation and flexural strength calculated by a tensile test in which the cured film was stretched in one direction. The evaluation results are shown in Tables 2 and 3.
(연필경도 시험)(Pencil hardness test)
ＪＩＳ-K-5600에 준거하여, 연필경도를 평가했다. 연필경도 Ｆ이상의 것을 우수한 경도로서 하드코팅성을 충분하게 충족시키는 것으로 하고, 연필경도 Ｂ이하의 것은 하드코팅성이 떨어지는 것으로 평가했다.The pencil hardness was evaluated in accordance with JIS-K-5600. The pencil hardness of F or higher was considered to be an excellent hardness sufficiently satisfying the hard coating property and the pencil hardness B or lower was evaluated to be poor in hard coating property.
(내찰상성의 평가)(Evaluation of scratch resistance)
#0000스틸 울(steel wool)을 사용하고, 100g/ｃｍ2 하중을 걸어 경화막 표면을 10왕복 찰상하고, 육안으로 상처의 유무를 확인했다. 상처가 없으면 우수한 하드코팅성을 구비하고, 상처가 수 개이면 하드코팅제로서 사용 가능하고, 상처가 다수이면 하드코팅제로서 적당하지 않은 결과라고 평가했다.# 0000 Steel wool was used and the surface of the cured film was scratched 10 times by applying a load of 100 g / cm 2 , and the presence or absence of scratches was visually observed. Without scratches, it has excellent hard coatability. If scratches are few, it can be used as a hard coating agent, and if scratches are many, it is not suitable as a hard coating agent.
(신장도)(Elongation degree)
신장도는, 경화막을 길이 100mm, 폭 7mm의 직사각형 모양으로 잘라낸 시험편을 인장시험기(형식번호 「ＲＴＣ-1250Ａ」 주식회사 오리엔테크)에 척간 거리 50mm로 세트하고, 실온 25도, 습도 45% ＲＨ의 환경 아래, 인장속도 10mm/ｍｉｎ으로 실시하고, 척간 거리를 각각 60mm(신장도 20%), 65mm(신장도 30%), 70mm(신장도 40%)가 된 점에서 정지하고, 경화막의 크랙의 유무를 육안으로 관찰하였다. 크랙이 없으면 ○, 크랙이 발생하고 있으면 ×라고 평가했다. 경화막의 신장도의 측정에 의하여 경화막의 유연성을 평가할 수 있다. 신장도가 크면 유연한 경화막이라고 할 수 있고, 예를 들면, 도포 필름의 성형가공공정에 있어서 신장의 응력에 대하여 유연하게 추종할 수 있기 때문에, 경화막의 크랙을 억제할 수 있어 가공성에 기여할 수 있다.The elongation was measured by setting a test piece cut out into a rectangular shape having a length of 100 mm and a width of 7 mm at a chuck distance of 50 mm on a tensile tester (Model No. RTC-1250A, Orientec Co., Ltd.) (Elongation: 20%), 65 mm (elongation: 30%), and 70 mm (elongation: 40%), and the presence or absence of cracks in the cured film Were visually observed. &Amp; cir & was evaluated as & cir & The flexibility of the cured film can be evaluated by measuring the elongation of the cured film. When the elongation degree is large, it can be said to be a flexible cured film. For example, it is possible to flexibly follow the stress of elongation in the molding process of the coating film, so that cracking of the cured film can be suppressed, .
(굴곡성의 평가)(Evaluation of flexibility)
경화막 표면을 밖으로 향하게 하고, φ 2mm의 원기둥으로 감아, 크랙의 유무를 육안으로 확인했다. 크랙이 없으면 ○라고 하고 크랙이 있으면 ×라고 했다.The surface of the cured film was faced out, and the film was wound with a cylinder of 2 mm in diameter to visually confirm the presence of cracks. When there is no crack, it is said ○, and when there is crack, it was called x.
Claims (8)
[수1]
[화학식 1]
(식 중에서, X는 다관능 티올 화합물(A)의 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상(直鎖狀) 또는 분기상(分岐狀)의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다.)
[화학식 7]
(식 중에서, R5는 수소 또는 메틸기를 나타낸다.)
[화학식 8]
(식 중에서, R6은 수소 또는 메틸기를 나타낸다.)
[화학식 9]
(식 중에서, R7은 수소 또는 메틸기를 나타낸다.)
[화학식 10]
(식 중에서, R8은, 수소 또는 메틸기를 나타낸다.)
The thiol group of the polyfunctional thiol compound (A) containing at least one of the compounds represented by the following general formulas (4) to (7) and having x of 100 or more and 200 or less calculated by the formula (1) At least one (meth) acryloyl group of the (meth) acrylate compound (B) is ene-thiol reacted with the (meth) acrylate compound represented by the general formula (Meth) acrylate resin (multifunctional thio (meth) acylate resin) having at least two (meth) acryloyl groups, and polyfunctional (meth) acrylate having at least two An active energy ray-curable hard coating resin composition (active energy ray-curable hard coating resin composition) containing a photopolymerization initiator.
[Number 1]
[Chemical Formula 1]
(Wherein X represents a structure excluding the thiol group of the polyfunctional thiol compound (A), R 1 and R 3 are each hydrogen or a methyl group, R 2 is O or -O-R 9 -O-, R 9 represents a straight chain or branched alkylene group having 1 to 20 carbon atoms, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3 ) O) mCH 2 CH (CH 3 ) -, -CH 2 CH 2 OP═O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - M, p and q are positive integers, and p + q = 2 to 6.)
(7)
(In the formula, R 5 represents hydrogen or a methyl group.)
[Chemical Formula 8]
(In the formula, R 6 represents hydrogen or a methyl group.)
[Chemical Formula 9]
(In the formula, R 7 represents hydrogen or a methyl group.)
[Chemical formula 10]
(In the formula, R 8 represents hydrogen or a methyl group.)
[수1]
[화학식 5]
(식 중에서, X는 다관능 티올 화합물(A)의 티올기를 제외하는 구조를 나타낸다. R1 및 R3은 각각 수소 또는 메틸기, R2는 Ｏ 또는 -Ｏ-R9-Ｏ-를 나타낸다. R9는, Ｃ1∼20의 직쇄상 또는 분기상의 알킬렌기, -(ＣＨ2ＣＨ2Ｏ)ｍＣＨ2ＣＨ2-, -(ＣＨ2ＣＨ(ＣＨ3)Ｏ)ｍＣＨ2ＣＨ(ＣＨ3)-, -ＣＨ2ＣＨ2ＯＰ=Ｏ(ＯＨ)ＯＣＨ2ＣＨ2-, -ＣＨ2ＣＨ(ＯＨ)ＣＨ2- 및 하기 일반식(1-1)∼(1-3)으로 표현되는 구조로부터 선택되는 적어도 일종이다. m, p 및 q는 양의 정수, p + q = 2∼6을 나타낸다. n은 2∼6을 나타낸다.)
[화학식 2]
[화학식 3]
[화학식 4]
[화학식 7]
(식 중에서, R5는 수소 또는 메틸기를 나타낸다.)
[화학식 8]
(식 중에서, R6은 수소 또는 메틸기를 나타낸다.)
[화학식 9]
(식 중에서, R7은 수소 또는 메틸기를 나타낸다.)
[화학식 10]
(식 중에서, R8은, 수소 또는 메틸기를 나타낸다.)
The thiol group of the polyfunctional thiol compound (A) containing at least one of the compounds represented by the following general formulas (4) to (7) and having x of 100 or more and 200 or less calculated by the formula (1) (Meth) acrylate compound having a structure represented by the following general formula (2) wherein at least one (meth) acryloyl group of the (meth) acrylate compound (B) , A polyfunctional (meth) acrylate having at least three (meth) acryloyl groups, and a photopolymerization initiator.
[Number 1]
[Chemical Formula 5]
(Wherein X represents a structure excluding the thiol group of the polyfunctional thiol compound (A), R 1 and R 3 are each hydrogen or a methyl group, R 2 is O or -O-R 9 -O-, R 9 is an alkylene group linear or branched C1~20, - (CH 2 CH 2 O) mCH 2 CH 2 -, - (CH 2 CH (CH 3) O) mCH 2 CH (CH 3) -, - CH 2 CH 2 OP - O (OH) OCH 2 CH 2 -, -CH 2 CH (OH) CH 2 - and at least one kind selected from the structures represented by the following general formulas (1-1) M, p and q are positive integers, and p + q = 2 to 6. n represents 2 to 6.)
(2)
(3)
[Chemical Formula 4]
(7)
(In the formula, R 5 represents hydrogen or a methyl group.)
[Chemical Formula 8]
(In the formula, R 6 represents hydrogen or a methyl group.)
[Chemical Formula 9]
(In the formula, R 7 represents hydrogen or a methyl group.)
[Chemical formula 10]
(In the formula, R 8 represents hydrogen or a methyl group.)
A cured film (cured film) obtained by curing an active energy ray-curable hard-coating resin composition according to claim 1 or 2 by irradiating with an active energy ray.
A plastic film laminated with the cured film of claim 3.
A plastic injection molded article (plastic injection molded article) using the plastic film of claim 4.
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| JPJP-P-2012-049408 | 2012-03-06 | ||
| JP2012049408 | 2012-03-06 |
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| KR (1) | KR101993738B1 (en) |
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| JP6609993B2 (en) * | 2015-05-22 | 2019-11-27 | 日油株式会社 | Curable resin composition |
| CN109922959B (en) * | 2016-09-14 | 2021-01-12 | 理研科技株式会社 | Hard coat laminated film |
| CN110770025B (en) * | 2017-05-10 | 2022-05-31 | 理研科技株式会社 | Hard coat laminated film |
| TW201936814A (en) * | 2018-01-12 | 2019-09-16 | 日商日油股份有限公司 | Film for insert molding, resin molded product, and image display device |
| KR20200124672A (en) * | 2018-02-22 | 2020-11-03 | 리껭테크노스 가부시키가이샤 | Anti-glare hard coat multilayer film |
| CN112533963B (en) * | 2018-08-21 | 2023-07-25 | 三井化学株式会社 | (meth) acrylate, monomer composition for dental material, molded article, composition for dental material, and method for producing (meth) acrylate |
| CN110016311B (en) * | 2019-04-09 | 2021-04-16 | 湘潭大学 | Fast-curing epoxy resin adhesive and preparation method thereof |
| JP2021127426A (en) * | 2020-02-17 | 2021-09-02 | 三井化学株式会社 | (meth)acrylate, monomer composition, molding, dental material composition and dental material |
| KR102641709B1 (en) * | 2023-05-22 | 2024-02-29 | 단국대학교 천안캠퍼스 산학협력단 | Self-healing cross-linker compound and hydrogel for lenses or for lens restoration comprising the same |
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| JP2002500700A (en) | 1998-04-03 | 2002-01-08 | エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック | Polymerizable composition for producing optical lens having high refractive index and high Abbe number, and lens obtained therefrom |
| JP2004536934A (en) | 2001-07-25 | 2004-12-09 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | High refractive index optical resin composition |
| JP4872671B2 (en) * | 2004-12-20 | 2012-02-08 | 株式会社ニコン | Adhesive multilayer diffractive optical element |
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| US5057567A (en) * | 1990-01-22 | 1991-10-15 | Witco Corporation | Mixed 3-alkylthiopropionic acid esters with pentaerythritol |
| JP3429393B2 (en) * | 1995-06-14 | 2003-07-22 | Ｈｏｙａ株式会社 | Flexible intraocular lens |
| JP2004123780A (en) | 2002-09-30 | 2004-04-22 | Dainippon Ink & Chem Inc | Active energy ray-curable resin composition |
| EP1477511A1 (en) * | 2003-05-15 | 2004-11-17 | DSM IP Assets B.V. | Radiation curable thiol-ene composition |
| JP3884758B2 (en) * | 2005-03-11 | 2007-02-21 | 積水化学工業株式会社 | Base proliferating agent and base-reactive curable composition |
| JP5151179B2 (en) | 2007-02-23 | 2013-02-27 | 東洋インキＳｃホールディングス株式会社 | Active energy ray-curable composition, printed matter using the composition, and molded decorative sheet molded product |
| JP2011148964A (en) | 2009-12-22 | 2011-08-04 | Toyobo Co Ltd | Hardcoat film for molding |
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| JP2002500700A (en) | 1998-04-03 | 2002-01-08 | エシロール アテルナジオナール カンパニー ジェネラーレ デ オプティック | Polymerizable composition for producing optical lens having high refractive index and high Abbe number, and lens obtained therefrom |
| JP2004536934A (en) | 2001-07-25 | 2004-12-09 | ピーピージー インダストリーズ オハイオ， インコーポレイテッド | High refractive index optical resin composition |
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| TW201343681A (en) | 2013-11-01 |
| TWI572624B (en) | 2017-03-01 |
| JP6103477B2 (en) | 2017-03-29 |
| CN103304455B (en) | 2016-12-28 |
| CN103304455A (en) | 2013-09-18 |
| JP2013213200A (en) | 2013-10-17 |
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