JP2000063459A - Photocurable resin composition and formation of uneven pattern - Google Patents
Photocurable resin composition and formation of uneven patternInfo
- Publication number
- JP2000063459A JP2000063459A JP10239746A JP23974698A JP2000063459A JP 2000063459 A JP2000063459 A JP 2000063459A JP 10239746 A JP10239746 A JP 10239746A JP 23974698 A JP23974698 A JP 23974698A JP 2000063459 A JP2000063459 A JP 2000063459A
- Authority
- JP
- Japan
- Prior art keywords
- photocurable resin
- resin composition
- film
- resin
- layer
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims description 37
- 230000015572 biosynthetic process Effects 0.000 title description 5
- 239000011347 resin Substances 0.000 claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 25
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 238000010894 electron beam technology Methods 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 21
- 229920002545 silicone oil Polymers 0.000 claims description 21
- 238000004049 embossing Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006082 mold release agent Substances 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 2
- 239000004615 ingredient Substances 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 78
- 239000010408 film Substances 0.000 description 65
- 239000010410 layer Substances 0.000 description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 23
- 238000012546 transfer Methods 0.000 description 18
- -1 methylol group Chemical group 0.000 description 17
- 239000000463 material Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 11
- 239000003504 photosensitizing agent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229920001296 polysiloxane Polymers 0.000 description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000002950 deficient Effects 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 102100026735 Coagulation factor VIII Human genes 0.000 description 5
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000193 polymethacrylate Polymers 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 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 3
- 229920000298 Cellophane Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- 239000003522 acrylic cement Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 230000003362 replicative effect Effects 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WVFBDVFCOCLEFM-UHFFFAOYSA-N 1,1,2,4,4-pentachlorobuta-1,3-diene Chemical compound ClC(Cl)=CC(Cl)=C(Cl)Cl WVFBDVFCOCLEFM-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- XMWGTKZEDLCVIG-UHFFFAOYSA-N 1-(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1 XMWGTKZEDLCVIG-UHFFFAOYSA-N 0.000 description 1
- MVWPVABZQQJTPL-UHFFFAOYSA-N 2,3-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 MVWPVABZQQJTPL-UHFFFAOYSA-N 0.000 description 1
- RKYJPYDJNQXILT-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCCOC(=O)C=C RKYJPYDJNQXILT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-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
- 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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- CKKQLOUBFINSIB-UHFFFAOYSA-N 2-hydroxy-1,2,2-triphenylethanone Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C(=O)C1=CC=CC=C1 CKKQLOUBFINSIB-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- VHFGGWSXGDWGOY-UHFFFAOYSA-N 2-isocyanatoethyl 2-methylprop-2-enoate 5-isocyanato-2-methylpent-2-enoic acid Chemical compound N(=C=O)CCC=C(C(=O)O)C.C(C(=C)C)(=O)OCCN=C=O VHFGGWSXGDWGOY-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- UZDMJPAQQFSMMV-UHFFFAOYSA-N 4-oxo-4-(2-prop-2-enoyloxyethoxy)butanoic acid Chemical compound OC(=O)CCC(=O)OCCOC(=O)C=C UZDMJPAQQFSMMV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
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- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
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- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 102100023401 Dual specificity mitogen-activated protein kinase kinase 6 Human genes 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000624426 Homo sapiens Dual specificity mitogen-activated protein kinase kinase 6 Proteins 0.000 description 1
- 101001024616 Homo sapiens Neuroblastoma breakpoint family member 9 Proteins 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-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
- 102100037013 Neuroblastoma breakpoint family member 9 Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Chemical class 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/0276—Replicating a master hologram without interference recording
- G03H1/028—Replicating a master hologram without interference recording by embossing
Landscapes
- Diffracting Gratings Or Hologram Optical Elements (AREA)
- Holo Graphy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は、光硬化性樹脂組成
物及び凹凸パターンの形成方法に関し、更に詳しくは耐
熱性及び柔軟性等を同時に有する被膜形成が可能である
ウレタン変性アクリル系樹脂を主たる被膜形成成分とす
る光硬化性樹脂組成物及び回折格子又はレリーフホログ
ラム等の凹凸パターンの形成方法に関する。TECHNICAL FIELD The present invention relates to a photocurable resin composition and a method for forming a concavo-convex pattern, and more particularly to a urethane-modified acrylic resin capable of forming a coating having heat resistance and flexibility at the same time. The present invention relates to a photocurable resin composition as a film-forming component and a method for forming an uneven pattern such as a diffraction grating or a relief hologram.
【0002】[0002]
【従来の技術】従来、光硬化性樹脂組成物(塗料)を、
例えば、ポリエステルフイルム等の基材上に塗工して光
硬化性樹脂層を形成し、この光硬化性樹脂層に各種凹凸
パターンを付与した後、紫外線や電子線を露光し、該樹
脂層を硬化させ、その後形成された凹凸パターン面に金
属蒸着や屈折率の異なる層を積層し、回折格子やレリー
フホログラム等とする方法が行なわれている。2. Description of the Related Art Conventionally, a photocurable resin composition (paint) is
For example, a photocurable resin layer is formed by coating on a substrate such as a polyester film, various concave and convex patterns are applied to the photocurable resin layer, and then the resin layer is exposed to ultraviolet rays or electron beams. A method is used in which a metal is vapor-deposited or a layer having a different refractive index is laminated on the surface of a concave-convex pattern formed after curing to form a diffraction grating or a relief hologram.
【0003】上記の凹凸パターンの付与方法としては、
例えば、レリーフホログラムを形成する場合には、所望
の凹凸パターンが形成されているマスターホログラムか
ら作製したプレススタンパー(以下単にプレススタンパ
ーという)を用意しておき、このプレススタンパーを上
記光硬化性樹脂層に重ねて加圧(エンボス)し、プレス
スタンパーの凹凸パターンを樹脂層に転写させ、その状
態で露光して樹脂層を硬化させ凹凸パターンを固定して
いる。このようにして多数のレリーフホログラムを形成
する場合には、1個のプレススタンパーで多数のエンボ
ス加工を行なっている。As a method of applying the above-mentioned uneven pattern,
For example, in the case of forming a relief hologram, a press stamper (hereinafter simply referred to as a press stamper) prepared from a master hologram on which a desired concavo-convex pattern is formed is prepared, and this press stamper is used as the photocurable resin layer. Then, pressure is applied (embossing) to transfer the embossed pattern of the press stamper to the resin layer, and the resin layer is cured by exposing in that state to fix the embossed pattern. When a large number of relief holograms are formed in this way, a large number of embossing processes are performed with a single press stamper.
【0004】[0004]
【発明が解決しようとしている課題】上記従来の光硬化
性塗料は多くの場合に液状であるために、塗料の保存安
定性が劣り、得られるホログラム等の凹凸パターンの品
質安定性に不安がある。又、従来の光硬化性塗料を用い
た場合には、該塗料中に多くの添加剤が配合されている
ために、多数回のエンボス処理を繰り返し行なうと、プ
レススタンパーに塗料中の成分が付着し、プレススタン
パーの微細な凹凸パターンが損われ、同様に得られるホ
ログラム等の品質が不安定となる。Since the above-mentioned conventional photo-curable paints are liquid in many cases, the storage stability of the paints is poor, and there is concern about the quality stability of the resulting concave-convex pattern such as holograms. . In addition, when a conventional photo-curable paint is used, many additives are mixed in the paint, so if the embossing process is repeated many times, the components in the paint adhere to the press stamper. However, the fine concavo-convex pattern of the press stamper is damaged, and the quality of similarly obtained holograms becomes unstable.
【0005】更に回折格子やレリーフホログラムは従
来、各種のカードや証券等の装飾や偽造防止の目的に使
用されているが、その用途の拡大とともに更に優れた強
度、耐熱性、耐擦傷性、耐水性、耐薬品性、基材に対す
る密着性が要求されるとともに、被貼着物の屈曲性や伸
縮に対する追随性が要求されるようになった。特に従来
の光硬化性塗料からなる回折格子やレリーフホログラム
の場合には、使用している樹脂が光硬化によって柔軟性
を失い、その結果として被貼着物の屈曲や伸縮によって
回折格子やレリーフホログラムとしての機能を喪失する
ものであった。Diffraction gratings and relief holograms have been conventionally used for the purpose of decorating various cards and securities and for the purpose of preventing forgery, but with the expansion of their applications, they are further excellent in strength, heat resistance, scratch resistance, and water resistance. Properties, chemical resistance, and adhesion to a base material are required, and flexibility to the adherend and conformability to expansion and contraction are required. Particularly in the case of a diffraction grating or relief hologram made of conventional photo-curable paint, the resin used loses flexibility due to photo-curing, and as a result, bending or stretching of the adherend results in a diffraction grating or relief hologram. Was lost.
【0006】本出願人の発明者は、これらの問題点を解
決するために、特開昭61−156273号公報や特公
平5−54502号公報に開示したような材料系を用い
て、優れた強度、耐熱性、耐擦傷性、耐水性、耐薬品
性、基材に対する密着性を有する被膜が形成可能で、且
つ被貼着物の屈曲性や伸縮に対する追随性をも有する回
折格子やレリーフホログラム等を形成することができる
光硬化性樹脂組成物を提供することに成功した。In order to solve these problems, the inventor of the present applicant has been excellent in using the material system as disclosed in JP-A-61-156273 and JP-B-5-54502. Diffraction gratings and relief holograms that can form coatings with strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to base materials, and also have flexibility with respect to the flexibility and expansion and contraction of the adherend It has succeeded in providing a photocurable resin composition capable of forming a resin.
【0007】しかしながら、上記特開昭61−1562
73号公報に記載の反応性樹脂は、主鎖にヒドロキシエ
チルメタクリレート単位を有する樹脂に、ジイソシアネ
ートを介して、再度ヒドロキシエチルメタクリレートを
付加結合させて、樹脂に2重結合を導入する方式である
ため、樹脂に2重結合を設計通りに導入することは困難
で、又、系中の微量な水分に影響されて樹脂がゲル化し
易い等の問題点があった。又、特公平5−54502号
公報に記載の反応性樹脂は、メラミン骨格を有するた
め、耐水性という点で若干劣り、又、メチロール基があ
る場合は加水分解によりホルムアルデヒドが発生する等
の問題点を有していた。従って、本発明の目的は、優れ
た強度、耐熱性、耐擦傷性、耐水性、耐薬品性、基材に
対する密着性を有する被膜が形成可能で、且つ被貼着物
の屈曲性や伸縮に対する追随性をも有する回折格子やレ
リーフホログラム等を形成することができる光硬化性樹
脂組成物を提供することである。However, the above-mentioned JP-A-61-1562 is used.
The reactive resin described in Japanese Patent Publication No. 73 is a system in which hydroxyethyl methacrylate is added to a resin having a hydroxyethyl methacrylate unit in its main chain via diisocyanate again to introduce a double bond into the resin. However, it is difficult to introduce a double bond into the resin as designed, and there is a problem that the resin tends to gel due to the influence of a trace amount of water in the system. Further, the reactive resin described in JP-B-5-54502 has a melamine skeleton and thus is slightly inferior in water resistance. Further, when there is a methylol group, formaldehyde is generated by hydrolysis. Had. Therefore, the object of the present invention is to form a coating having excellent strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to a substrate, and to follow the flexibility and expansion / contraction of an adherend. It is an object of the present invention to provide a photocurable resin composition capable of forming a diffraction grating, a relief hologram, and the like which also have properties.
【0008】[0008]
【課題を解決するための手段】上記目的は以下の本発明
によって達成される。即ち、本発明は、下記構造式で表
されるウレタン変性アクリル系樹脂と離型剤とを必須成
分として含有することを特徴とする光硬化性樹脂組成物
である。
(式中、Zは嵩高い環状構造の基を表わし、6個のR1
は夫々互いに独立して水素原子又はメチル基を表わし、
R2はC1〜C16の炭化水素基を表わし、X及びYは直
鎖状又は分岐鎖状のアルキレン基を表わす。l(エル)
とmとnとo(オー)とpの合計を100とした場合
に、lは20〜90、mは5〜80、nは0〜50、o
+pは10〜80、pは0〜40の整数である。)The above object can be achieved by the present invention described below. That is, the present invention is a photocurable resin composition containing a urethane-modified acrylic resin represented by the following structural formula and a release agent as essential components. (In the formula, Z represents a group having a bulky cyclic structure, and 6 R 1
Are each independently a hydrogen atom or a methyl group,
R 2 represents a C 1 to C 16 hydrocarbon group, and X and Y represent a linear or branched alkylene group. l
, M, n, o (o), and p are 100, 1 is 20 to 90, m is 5 to 80, n is 0 to 50, o
+ P is an integer of 10 to 80 and p is an integer of 0 to 40. )
【0009】本発明によれば、光硬化性樹脂組成物の主
被膜形成成分として特定のウレタン変性アクリル系樹脂
を使用することによって、優れた強度、耐熱性、耐擦傷
性、耐水性、耐薬品性、基材に対する密着性を有する被
膜が形成可能で、且つ被貼着物の屈曲性や伸縮に対する
追随性をも有する回折格子やレリーフホログラム等を形
成することができる光硬化性樹脂組成物を提供すること
ができる。According to the present invention, by using a specific urethane-modified acrylic resin as a main film forming component of a photocurable resin composition, excellent strength, heat resistance, scratch resistance, water resistance and chemical resistance can be obtained. PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of forming a film having adhesiveness and adhesion to a substrate, and capable of forming a diffraction grating, a relief hologram and the like having flexibility and flexibility of an adherend. can do.
【0010】[0010]
【発明の実施の形態】次に好ましい実施の形態を挙げて
本発明を更に詳しく説明する。本発明で使用するウレタ
ン変性アクリル系樹脂は、例えば、好ましい1例とし
て、メタクリル酸メチル20〜90モルと、嵩高い基を
有するビニルモノマー5〜80モルとメタクリル酸0〜
50モルと2−ヒドロキシエチルメタクリレート10〜
80モルとを共重合して得られるアクリル共重合体であ
って、該共重合体中に存在している水酸基にメタクリロ
イルオキシエチルイソシアネート(2−イソシアネート
エチルメタクリレート)を反応させて得られる樹脂であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The urethane-modified acrylic resin used in the present invention is, for example, as a preferred example, 20 to 90 mol of methyl methacrylate, 5 to 80 mol of vinyl monomer having a bulky group, and 0 to methacrylic acid.
50 moles and 2-hydroxyethyl methacrylate 10-
It is an acrylic copolymer obtained by copolymerizing with 80 mol, and is a resin obtained by reacting methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate) with the hydroxyl groups present in the copolymer. .
【0011】従って、上記メタクリロイルオキシエチル
イソシアネートが共重合体中に存在している全ての水酸
基に反応している必要はなく、共重合体中の2−ヒドロ
キシエチルメタクリレート単位の水酸基の少なくとも1
0モル%以上、好ましくは50モル%以上がメタクリロ
イルオキシエチルイソシアネートと反応していればよ
い。上記の2−ヒドロキシエチルメタクリレートに代え
て又は併用して、N−メチロールアクリルアミド、N−
メチロールメタクリルアミド、2−ヒドロキシエチルア
クリレート、2−ヒドロキシエチルメタクリレート、2
−ヒドロキシプロピルアクリレート、2−ヒドロキシプ
ロピルメタクリレート、4−ヒドロキシブチルアクリレ
ート、4−ヒドロキシブチルメタクリレート等の水酸基
を有するモノマーも使用することができる。Therefore, it is not necessary for the methacryloyloxyethyl isocyanate to react with all the hydroxyl groups present in the copolymer, and at least one of the hydroxyl groups of the 2-hydroxyethyl methacrylate unit in the copolymer should be at least one.
It is sufficient that 0 mol% or more, preferably 50 mol% or more, react with methacryloyloxyethyl isocyanate. Instead of or in combination with the above 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-
Methylol methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
A monomer having a hydroxyl group such as -hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate can also be used.
【0012】以上の如く、水酸基含有アクリル系樹脂中
に存在している水酸基を利用して、分子中に多数のメタ
クリロイル基を導入したウレタン変性アクリル系樹脂を
主成分とする樹脂組成物によって、例えば、回折格子等
を形成する場合には、硬化手段として紫外線や電子線等
の電離放射線が使用でき、しかも高架橋密度でありなが
ら柔軟性及び耐熱性等に優れた回折格子等を形成するこ
とができる。As described above, by utilizing a hydroxyl group existing in a hydroxyl group-containing acrylic resin, a resin composition containing a urethane-modified acrylic resin as a main component, in which a large number of methacryloyl groups are introduced into the molecule, can be used, for example. When forming a diffraction grating or the like, ionizing radiation such as ultraviolet rays or electron beams can be used as a curing means, and it is possible to form a diffraction grating or the like which has a high crosslink density but is excellent in flexibility and heat resistance. .
【0013】上記のウレタン変性アクリル系樹脂は、前
記共重合体を溶解可能な溶剤、例えば、トルエン、ケト
ン、セロソルブアセテート、ジメチルスルフォキサイド
等の溶媒に溶解させ、この溶液を撹拌しながら、メタク
リロイルオキシエチルイソシアネートを滴下及び反応さ
せることにより、イソシアネート基がアクリル系樹脂の
水酸基と反応してウレタン結合を生じ、該ウレタン結合
を介して樹脂中にメタクリロイル基を導入することがで
きる。この際使用するメタクリロイルオキシエチルイソ
シアネートの使用量は、アクリル系樹脂の水酸基とイソ
シアネート基との比率で水酸基1モル当たりイソシアネ
ート基0.1〜5モル、好ましくは0.5〜3モルの範
囲になる量である。尚、上記樹脂中の水酸基よりも当量
以上のメタクリロイルオキシエチルイソシアネートを使
用する場合には、該メタクリロイルオキシエチルイソシ
アネートは樹脂中のカルボキシル基とも反応して−CO
NH−CH 2CH 2−の連結を生じることもあり得る。The above urethane-modified acrylic resin is
Solvent capable of dissolving the copolymer, for example, toluene, keto
, Cellosolve acetate, dimethyl sulfoxide
Dissolve in a solvent such as
Liloyloxyethyl isocyanate is added dropwise and reacted.
The isocyanate group of the acrylic resin
Reacts with a hydroxyl group to form a urethane bond, and the urethane bond
It is possible to introduce a methacryloyl group into the resin via
Wear. Methacryloyloxyethyliso used at this time
The amount of cyanate used depends on the hydroxyl group of the acrylic resin and the isocyanate.
Isocyanate per mole of hydroxyl group in proportion to cyanate group
Group of 0.1 to 5 mol, preferably 0.5 to 3 mol.
It is the amount to be enclosed. The equivalent of the hydroxyl group in the resin
Use the above methacryloyloxyethyl isocyanate
When used, the methacryloyloxyethyl isocyanate
Anates also react with the carboxyl groups in the resin to produce --CO
NH-CH 2CH 2It is also possible that a-linkage occurs.
【0014】以上の例は、前記構造式において、全ての
R1及びR2がメチル基であり、X及びYがエチレン基で
ある場合であるが、本発明は、これらに限定されず、6
個のR1は夫々独立して水素原子又はメチル基であって
もよく、更にR2の具体例としては、例えば、メチル
基、エチル基、n−又はiso−プロピル基、n−、i
so−又はtert−ブチル基、置換又は未置換のフェ
ニル基、置換又は未置換のベンジル基等が挙げられ、X
及びYの具体例としては、エチレン基、プロピレン基、
ジエチレン基、ジプロピレン基等が挙げられる。このよ
うにして得られる本発明で使用するウレタン変性アクリ
ル系樹脂は全体の分子量としては、ポリスチレン換算分
子量で1万〜20万、更に2〜4万であることがより好
ましい。尚、上記の嵩高い基を有するモノマーとして
は、例えば、イソボニル(メタ)アクリレート、シクロ
ヘキシル(メタ)アクリレート、ジシクロペンタニル
(メタ)アクリレート、ジシクロペンテニル(メタ)ア
クリレート、EO変性ジシクロペンテニル(メタ)アク
リレート等の如く、5員環、6員環或はそれ以上の嵩高
い基を有するモノマーであることが好ましい。The above examples are the cases where all R 1 and R 2 in the above structural formula are methyl groups and X and Y are ethylene groups, but the present invention is not limited to these.
Each R 1 may independently be a hydrogen atom or a methyl group, and specific examples of R 2 include, for example, a methyl group, an ethyl group, n- or iso-propyl group, n-, i.
Examples thereof include a so- or tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and the like, X
Specific examples of Y and Y include ethylene group, propylene group,
Examples thereof include a diethylene group and a dipropylene group. The urethane-modified acrylic resin used in the present invention thus obtained has a total molecular weight of 10,000 to 200,000, more preferably 20,000 to 40,000 in terms of polystyrene. Examples of the monomer having a bulky group include, for example, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and EO-modified dicyclopentenyl ( A monomer having a 5-membered ring, a 6-membered ring, or a bulky group such as a meth) acrylate is preferable.
【0015】次に本発明で使用するウレタン変性アクリ
ル系樹脂の製造例を示す。
製造例1
冷却器、滴下ロート及び温度計付きの2リットルの四つ
口フラスコに、トルエン40g及びメチルエチルケトン
(MEK)40gをアゾ系の開始剤とともに仕込み、2
−ヒドロキシエチルメタクリレート(HEMA)22.
4g、メチルメタクリレート(MMA)53.4g、メ
タクリル酸(MAA)7.4g、イソボニルメタクリレ
ート(IBM)13.9g、トルエン30g及びMEK
20gの混合液を滴下ロートを経て、約2時間かけて滴
下させながら100〜110℃の温度下で8時間反応さ
せた後、室温まで冷却した。これに、2−イソシアネー
トエチルメタクリレート(昭和電工製、カレンズMO
I)27.8g、プロピレングリコールモノメチルエー
テルアセテート20g及びMEK20gの混合液を加え
て、ラウリン酸ジブチル錫を触媒として付加反応させ
た。反応生成物のIR分析により2200cm-1の吸収
ピークの消失を確認し反応を終了した。Next, a production example of the urethane-modified acrylic resin used in the present invention will be shown. Production Example 1 To a 2-liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 40 g of toluene and 40 g of methyl ethyl ketone (MEK) were charged together with an azo-based initiator.
-Hydroxyethyl methacrylate (HEMA) 22.
4 g, methyl methacrylate (MMA) 53.4 g, methacrylic acid (MAA) 7.4 g, isobornyl methacrylate (IBM) 13.9 g, toluene 30 g and MEK.
20 g of the mixed solution was allowed to react through a dropping funnel for about 2 hours while reacting at a temperature of 100 to 110 ° C. for 8 hours, and then cooled to room temperature. In addition to this, 2-isocyanate ethyl methacrylate (Showa Denko, Karens MO
I) A mixed solution of 27.8 g, propylene glycol monomethyl ether acetate 20 g and MEK 20 g was added to carry out an addition reaction using dibutyltin laurate as a catalyst. The reaction was terminated after confirming the disappearance of the absorption peak at 2200 cm -1 by IR analysis of the reaction product.
【0016】製造例2
冷却器、滴下ロート及び温度計付きの2リットルの四つ
口フラスコに、トルエン60g及びMEK60gをアゾ
系の開始剤とともに仕込み、HEMA22.4g、MM
A44.5g、MAA7.4g、IBM44.4g、ト
ルエン50g及びMEK50gの混合液を滴下ロートを
経て、約2時間かけて滴下させながら100〜110℃
の温度下で8時間反応させた後、室温まで冷却した。こ
れに、2−イソシアネートエチルメタクリレート(昭和
電工製、カレンズMOI)27.8g、プロピレングリ
コールモノメチルエーテルアセテート40g及びMEK
40gの混合液を加えて、ラウリン酸ジブチル錫を触媒
として付加反応させた。反応生成物のIR分析により2
200cm-1の吸収ピークの消失を確認し反応を終了し
た。Production Example 2 To a 2-liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 60 g of toluene and 60 g of MEK were charged together with an azo-based initiator, and HEMA was 22.4 g and MM.
A mixture of A44.5g, MAA7.4g, IBM44.4g, toluene 50g and MEK50g is passed through a dropping funnel, and is added dropwise over about 2 hours at 100 to 110 ° C.
After reacting at the temperature of 8 hours, it was cooled to room temperature. To this, 27.8 g of 2-isocyanate ethyl methacrylate (Showa Denko, Karenz MOI), 40 g of propylene glycol monomethyl ether acetate and MEK.
40 g of the mixed solution was added, and an addition reaction was performed using dibutyltin laurate as a catalyst. 2 by IR analysis of the reaction product
After confirming the disappearance of the absorption peak at 200 cm -1, the reaction was terminated.
【0017】製造例3
冷却器、滴下ロート及び温度計付きの2リットルの四つ
口フラスコに、トルエン40g及びMEK40gをアゾ
系の開始剤とともに仕込み、HEMA22.4g、MM
A44.5g、MAA7.4g、ジシクロペンタニルメ
タクリレート(DSPM)22.0g、トルエン30g
及びMEK30gの混合液を滴下ロートを経て、約2時
間かけて滴下させながら100〜110℃の温度下で8
時間反応させた後、室温まで冷却した。これに、2−イ
ソシアネートエチルメタクリレート(昭和電工製、カレ
ンズMOI)27.8g、プロピレングリコールモノメ
チルエーテルアセテート30g及びMEK30gの混合
液を加えて、ラウリン酸ジブチル錫を触媒として付加反
応させた。反応生成物のIR分析により2200cm-1
の吸収ピークの消失を確認し反応を終了した。Production Example 3 In a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 40 g of toluene and 40 g of MEK were charged together with an azo-based initiator, and HEMA was 22.4 g and MM.
A 44.5 g, MAA 7.4 g, dicyclopentanyl methacrylate (DSPM) 22.0 g, toluene 30 g
And a mixed solution of 30 g of MEK through a dropping funnel, while being dropped for about 2 hours at a temperature of 100 to 110 ° C.
After reacting for a time, it was cooled to room temperature. To this, a mixed solution of 27.8 g of 2-isocyanatoethyl methacrylate (Karenz MOI manufactured by Showa Denko), 30 g of propylene glycol monomethyl ether acetate and 30 g of MEK was added, and dibutyltin laurate as a catalyst was subjected to an addition reaction. 2200 cm -1 by IR analysis of the reaction product
The disappearance of the absorption peak of was confirmed and the reaction was terminated.
【0018】製造例4
冷却器、滴下ロート及び温度計付きの2リットルの四つ
口フラスコに、プロピレングリコールモノメチルエーテ
ルアセテート60g及びMEK60gをアゾ系の開始剤
とともに仕込み、HEMA22.4g、MMA44.5
g、MAA7.4g、DSPM44.4g、プロピレン
グリコールモノメチルエーテルアセテート50g及びM
EK50gの混合液を滴下ロートを経て、約2時間かけ
て滴下させながら100〜110℃の温度下で8時間反
応させた後、室温まで冷却した。これに、2−イソシア
ネートエチルメタクリレート(昭和電工製、カレンズM
OI)27.8g、プロピレングリコールモノメチルエ
ーテルアセテート40g及びMEK40gの混合液を加
えて、ラウリン酸ジブチル錫を触媒として付加反応させ
た。反応生成物のIR分析により2200cm-1の吸収
ピークの消失を確認し反応を終了した。Production Example 4 60 g of propylene glycol monomethyl ether acetate and 60 g of MEK were charged together with an azo-based initiator in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, and 22.4 g of HEMA and 44.5 of MMA.
g, MAA 7.4 g, DSPM 44.4 g, propylene glycol monomethyl ether acetate 50 g and M
The mixture of 50 g of EK was added dropwise through a dropping funnel for about 2 hours to react for 8 hours at a temperature of 100 to 110 ° C., and then cooled to room temperature. To this, 2-isocyanate ethyl methacrylate (Showa Denko, Karenz M
A mixed solution of 27.8 g of OI), 40 g of propylene glycol monomethyl ether acetate and 40 g of MEK was added to carry out an addition reaction using dibutyltin laurate as a catalyst. The reaction was terminated after confirming the disappearance of the absorption peak at 2200 cm -1 by IR analysis of the reaction product.
【0019】製造例5
冷却器、滴下ロート及び温度計付きの2リットルの四つ
口フラスコに、プロピレングリコールモノメチルエーテ
ルアセテート80g及びMEK80gをアゾ系の開始剤
とともに仕込み、HEMA22.4g、MAA7.4
g、シクロヘキシルメタクリレート(CHM)117.
6g、プロピレングリコールモノメチルエーテルアセテ
ート60g及びMEK60gの混合液を滴下ロートを経
て、約2時間かけて滴下させながら100〜110℃の
温度下で8時間反応させた後、室温まで冷却した。これ
に、2−イソシアネートエチルメタクリレート(昭和電
工製、カレンズMOI)41.7g、プロピレングリコ
ールモノメチルエーテルアセテート60g及びMEK6
0gの混合液を加えて、ラウリン酸ジブチル錫を触媒と
して付加反応させた。反応生成物のIR分析により22
00cm−1の吸収ピークの消失を確認し反応を終了し
た。以上で得られた本発明で使用するウレタン変性アク
リル系樹脂の製造に使用した原料組成と得られた樹脂の
物性値を下記表1に示す。Production Example 5 80 g of propylene glycol monomethyl ether acetate and 80 g of MEK were charged together with an azo-based initiator in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, and HEMA 22.4 g and MAA 7.4.
g, cyclohexyl methacrylate (CHM) 117.
A mixed solution of 6 g, 60 g of propylene glycol monomethyl ether acetate and 60 g of MEK was allowed to react for 8 hours at a temperature of 100 to 110 ° C. while being dropped for about 2 hours through a dropping funnel, and then cooled to room temperature. To this, 41.7 g of 2-isocyanate ethyl methacrylate (Showa Denko, Karenz MOI), 60 g of propylene glycol monomethyl ether acetate and MEK6.
0 g of the mixed solution was added to carry out an addition reaction with dibutyltin laurate as a catalyst. 22 by IR analysis of the reaction product
The disappearance of the absorption peak at 00 cm -1 was confirmed and the reaction was terminated. The raw material composition used in the production of the urethane-modified acrylic resin used in the present invention obtained above and the physical properties of the obtained resin are shown in Table 1 below.
【0020】表1
表中の「C=C量」はポリマー1分子中の二重結合の平
均個数である。表中の分子量は、ポリスチレン換算分子
量である。分子量測定はゲルパーミエーションクロマト
グラフィー(GPC)でテトラヒドロフラン(THF)
を溶媒として行った。Table 1 "C = C amount" in the table is the average number of double bonds in one molecule of the polymer. The molecular weights in the table are polystyrene-equivalent molecular weights. Molecular weight is measured by gel permeation chromatography (GPC) with tetrahydrofuran (THF).
Was used as a solvent.
【0021】本発明の光硬化性樹脂組成物は、上記のウ
レタン変性アクリル系樹脂を被膜形成成分の主成分とし
て、離型剤とともに適当な有機溶剤に溶解してなること
を特徴とする。使用する有機溶剤としては、上記したよ
うなウレタン変性アクリル系樹脂を溶解する有機溶剤で
あれば何れでもよいが、塗工性や乾燥性を考慮すると、
トルエン、キシレン等の芳香族系溶剤、アセトン、メチ
ルエチルケトン(MEK)、メチルイソブチルケトン、
シクロヘキサノン等のケトン系溶剤、メチルセロソル
ブ、エチルセロソルブ等のセロソルブ系有機溶剤等が挙
げられ、特にこれらの溶剤からなる混合系溶剤が好まし
く使用される。上記組成物における前記ウレタン変性ア
クリル系樹脂の固形分濃度は特に限定されないが、一般
的には重量基準で約1〜50重量%の範囲が好ましい。The photocurable resin composition of the present invention is characterized in that the above urethane-modified acrylic resin is dissolved in an appropriate organic solvent together with a release agent as a main component of the film-forming component. The organic solvent used may be any organic solvent that dissolves the urethane-modified acrylic resin as described above, but in consideration of coatability and drying property,
Aromatic solvents such as toluene and xylene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone,
Examples thereof include ketone solvents such as cyclohexanone, and cellosolve organic solvents such as methyl cellosolve and ethyl cellosolve. In particular, a mixed solvent composed of these solvents is preferably used. The solid content concentration of the urethane-modified acrylic resin in the composition is not particularly limited, but is generally preferably in the range of about 1 to 50% by weight on a weight basis.
【0022】本発明の光硬化性樹脂組成物は、上記ウレ
タン変性アクリル系樹脂に加えて、離型剤を含有する。
本発明で用いられる離型剤としては従来公知の離型剤、
例えば、ポリエチレンワックス、アミドワックス、テフ
ロンパウダー等の固形ワックス、弗素系、リン酸エステ
ル系の界面活性剤、シリコーン等が何れも使用可能であ
る。特に好ましい離型剤は変性シリコーンであり、具体
的には、
1)変性シリコーンオイル側鎖型、
2)変性シリコーンオイル両末端型、
3)変性シリコーンオイル片末端型、
4)変性シリコーンオイル側鎖両末端型、
5)トリメチルシロキシケイ酸を含有するメチルポリシ
ロキサン(シリコーンレジンと呼ぶ)、
6)シリコーングラフトアクリル樹脂、及び
7)メチルフェニルシリコーンオイル等が挙げられる。The photocurable resin composition of the present invention contains a release agent in addition to the urethane modified acrylic resin.
As the release agent used in the present invention, a conventionally known release agent,
For example, polyethylene wax, amide wax, solid wax such as Teflon powder, fluorine-based or phosphoric acid ester-based surfactants, and silicone can all be used. A particularly preferable releasing agent is a modified silicone, and specifically, 1) modified silicone oil side chain type, 2) modified silicone oil both ends type, 3) modified silicone oil one end type, 4) modified silicone oil side chain Examples thereof include both-end type, 5) methylpolysiloxane containing trimethylsiloxysilicic acid (referred to as silicone resin), 6) silicone graft acrylic resin, and 7) methylphenyl silicone oil.
【0023】変性シリコーンオイルは、反応性シリコー
ンオイルと非反応性シリコーンオイルとに分けられる。
反応性シリコーンオイルとしては、アミノ変性、エポキ
シ変性、カルボキシル変性、カルビノール変性、メタク
リル変性、メルカプト変性、フェノール変性、片末端反
応性、異種官能基変性等が挙げられる。非反応性シリコ
ーンオイルとしては、ポリエーテル変性、メチルスチリ
ル変性、アルキル変性、高級脂肪エステル変性、親水性
特殊変性、高級アルコキシ変性、高級脂肪酸変性、フッ
素変性等が挙げられる。The modified silicone oil is divided into reactive silicone oil and non-reactive silicone oil.
Examples of the reactive silicone oil include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, one-end-reactive, and different functional group-modified. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
【0024】上記シリコーンオイルの中でも、被膜形成
成分と反応性である基を有する種類の反応性シリコーン
オイルは、樹脂層の硬化とともに樹脂に反応して結合す
るので、後に凹凸パターンが形成された樹脂層の表面に
ブリードアウトすることがなく、特徴的な性能を付与す
ることができる。特に、蒸着工程での蒸着層との密着性
向上には有効である。Among the above silicone oils, a reactive silicone oil of a type having a group reactive with a film-forming component reacts with the resin as the resin layer cures and binds to the resin. Characteristic performance can be imparted without bleeding out on the surface of the layer. In particular, it is effective in improving the adhesion to the vapor deposition layer in the vapor deposition step.
【0025】本発明では、本発明の光硬化性樹脂組成物
(塗料)を、例えば、ポリエステルフイルム等の基材上
に塗工して光硬化性樹脂層を形成し、この光硬化性樹脂
層に各種凹凸パターンを付与した後、紫外線や電子線を
露光し、該樹脂層を硬化させ、その後形成された凹凸パ
ターン面に金属蒸着や屈折率の異なる層を積層し、回折
格子やレリーフホログラム等とすることができる。In the present invention, the photocurable resin composition (paint) of the present invention is applied onto a substrate such as a polyester film to form a photocurable resin layer, and the photocurable resin layer is formed. After applying various concavo-convex patterns to the surface, the resin layer is cured by exposing it to ultraviolet rays or electron beams, and then a metal deposition or a layer with a different refractive index is laminated on the concavo-convex pattern surface formed, such as a diffraction grating or a relief hologram. Can be
【0026】従って、組成物のフイルムへのコーティン
グ(塗工及び乾燥)工程と、ホログラム等の複製工程を
別工程で実施する場合には、コーティングして形成され
た塗膜表面にタックがあると、この塗膜を有するフイル
ムをロール状に直接巻き取る場合にブロッキングを生じ
て不都合である。塗布及び乾燥時に塗布層の表面側に局
在するような溶剤系を用いて塗布及び乾燥することが上
記のブロッキング防止には有効であり、又、複製時の反
復エンボス性を高めるためにも有効である。又、塗膜の
表面にタックがある場合は、離型性フイルムを塗膜表面
にラミネートしてからフイルムを巻き取る方法を選択す
ることができる。連続工程で組成物のフイルムへのコー
ティング(塗工及び乾燥)工程と、ホログラム等の複製
工程とを行う場合は、上記の制約条件が緩和される。Therefore, when the step of coating the composition with the film (coating and drying) and the step of replicating the hologram and the like are carried out in separate steps, there is tack on the surface of the coating film formed by coating. However, when the film having this coating film is directly wound into a roll, blocking occurs, which is inconvenient. Coating and drying using a solvent system that is localized on the surface side of the coating layer during coating and drying is effective in preventing the above blocking, and also effective in increasing the repetitive embossing property during replication. Is. When the surface of the coating film has tack, a method of laminating the releasable film on the surface of the coating film and then winding the film can be selected. When the steps of coating the composition on the film (coating and drying) and the step of replicating a hologram or the like are performed in a continuous process, the above constraint conditions are relaxed.
【0027】本発明では、上記の如き離型剤(特にシリ
コーン)を樹脂組成物に含有させることによって、例え
ば、回折格子等をエンボス加工で作製する場合に、回折
格子のプレススタンパーと光硬化した樹脂層の剥離性を
良好にし、プレススタンパーの汚染を防止し、プレスス
タンパーを長期間連続して使用することができるように
なる(これを反復エンボス性と名づける)。上記離型剤
の使用量は、前記ウレタン変性アクリル系樹脂100重
量部当たり約0.1〜50重量部の範囲、好ましくは約
0.5〜10重量部の範囲で使用する。離型剤の使用量
が上記範囲未満では、プレススタンパーと光硬化樹脂層
との剥離が不十分であり、プレススタンパーの汚染を防
止することが困難である。一方、離型剤の使用量が上記
範囲を超えると組成物の塗工時のはじきによる塗膜面の
面荒れの問題が生じたり、製品において基材自身及び近
接する層、例えば、蒸着層の密着性を阻害したり、転写
時に皮膜破壊等(膜強度が弱くなりすぎる)を引き起こ
す等の点で好ましくない。In the present invention, the release agent (particularly silicone) as described above is contained in the resin composition so that, for example, when a diffraction grating or the like is produced by embossing, it is photocured with the press stamper of the diffraction grating. The release property of the resin layer is improved, the press stamper is prevented from being contaminated, and the press stamper can be used continuously for a long period of time (this is called repetitive embossing property). The release agent is used in an amount of about 0.1 to 50 parts by weight, preferably about 0.5 to 10 parts by weight, based on 100 parts by weight of the urethane-modified acrylic resin. When the amount of the release agent used is less than the above range, the release of the press stamper and the photocurable resin layer is insufficient, and it is difficult to prevent the press stamper from being contaminated. On the other hand, if the amount of the release agent used exceeds the above range, a problem of surface roughness of the coating film due to cissing at the time of coating the composition may occur, or the substrate itself and the adjacent layer in the product, for example, a vapor deposition layer It is not preferable in that the adhesiveness is hindered, or the film is broken at the time of transfer (the film strength becomes too weak).
【0028】更に硬化後に得られる樹脂層の柔軟性や架
橋密度を調整するために、本発明の光硬化性樹脂組成物
に、通常の熱可塑性樹脂やアクリル系、その他の単官能
又は多官能のモノマー、オリゴマー等を包含させること
ができる。例えば、単官能ではテトラヒドロフルフリル
(メタ)アクリレート、ヒドロキシエチル(メタ)アク
リレート、ビニルピロリドン、(メタ)アクリロイルオ
キシエチルサクシネート、(メタ)アクリロイルオキシ
エチルフタレート等のモノ(メタ)アクリレート、2官
能以上では、骨格構造で分類するとポリオール(メタ)
アクリレート(エポキシ変性ポリオール(メタ)アクリ
レート、ラクトン変性ポリオール(メタ)アクリレート
等)、ポリエステル(メタ)アクリレート、エポキシ
(メタ)アクリレート、ウレタン(メタ)アクリレー
ト、その他ポリブタジエン系、イソシアヌール酸系、ヒ
ダントイン系、メラミン系、リン酸系、イミド系、フォ
スファゼン系等の骨格を有するポリ(メタ)アクリレー
トであり、紫外線、電子線硬化性である様々なモノマ
ー、オリゴマー、ポリマーが利用できる。Further, in order to adjust the flexibility and crosslink density of the resin layer obtained after curing, the photocurable resin composition of the present invention may be added with a conventional thermoplastic resin, acrylic resin, or other monofunctional or polyfunctional resin. Monomers, oligomers and the like can be included. For example, in the case of monofunctional, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, and other mono (meth) acrylates, and bifunctional or higher. Then, when classified by the skeleton structure, polyol (meta)
Acrylate (epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate, etc.), polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, other polybutadiene-based, isocyanuric acid-based, hydantoin-based, It is a poly (meth) acrylate having a skeleton such as a melamine-based, phosphoric acid-based, imide-based, or phosphazene-based skeleton, and various monomers, oligomers, and polymers curable with ultraviolet rays and electron beams can be used.
【0029】更に詳しく述べると、2官能のモノマー、
オリゴマーとしてはポリエチレングリコールジ(メタ)
アクリレート、ポリプロピレングリコールジ(メタ)ア
クリレート、ネオペンチルグリコールジ(メタ)アクリ
レート、1,6−ヘキサンジオールジ(メタ)アクリレ
ート等、3官能のモノマー、オリゴマー、ポリマーとし
てはトリメチロールプロパントリ(メタ)アクリレー
ト、ペンタエリスリトールトリ(メタ)アクリレート、
脂肪族トリ(メタ)アクリレート等、4官能のモノマ
ー、オリゴマーとしてはペンタエリスリトールテトラ
(メタ)アクリレート、ジトリメチロールプロパンテト
ラ(メタ)アクリレート、脂肪族テトラ(メタ)アクリ
レート等が挙げられ、5官能以上のモノマー、オリゴマ
ーとしてはジペンタエリスリトールペンタ(メタ)アク
リレート、ジペンタエリスリトールヘキサ(メタ)アク
リレート等の他、ポリエステル骨格、ウレタン骨格、フ
ォスファゼン骨格を有する(メタ)アクリレート等が挙
げられる。官能基数は特に限定されるものではないが、
官能基数が3より小さいと耐熱性が低下する傾向があ
り、又、20以上では柔軟性が低下する傾向があるた
め、特に3〜20官能のものが好ましい。More specifically, a bifunctional monomer,
Polyethylene glycol di (meth) as oligomer
Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and other trifunctional monomers, oligomers and polymers as trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate,
Examples of tetrafunctional monomers and oligomers such as aliphatic tri (meth) acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate. Examples of the monomer and oligomer include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and (meth) acrylate having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton. The number of functional groups is not particularly limited,
When the number of functional groups is less than 3, the heat resistance tends to decrease, and when it is 20 or more, the flexibility tends to decrease, so that those having 3 to 20 functional groups are particularly preferable.
【0030】上記モノマー或いはオリゴマーの使用量
は、前記ウレタン変性アクリル系樹脂100重量部当た
り約5〜40重量部の範囲、好ましくは約10〜30重
量部の範囲で使用する。モノマー或いはオリゴマーの使
用量が上記範囲未満では、得られる硬化樹脂層の強度、
耐熱性、耐擦傷性、耐水性、耐薬品性、基材に対する密
着性が十分とはいえず、一方、モノマー或いはオリゴマ
ーの使用量が上記範囲を超えると表面のタックが高くな
り、ブロッキングを引き起こしたり、ホログラム等の複
製時に版(プレススタンパー)に材料が一部残る(版取
られ)ことにより反復エンボス性が低下する等の点で好
ましくない。The amount of the above monomer or oligomer used is in the range of about 5 to 40 parts by weight, preferably about 10 to 30 parts by weight, per 100 parts by weight of the urethane-modified acrylic resin. When the amount of the monomer or oligomer used is less than the above range, the strength of the obtained cured resin layer,
Heat resistance, scratch resistance, water resistance, chemical resistance, adhesion to the substrate is not sufficient, on the other hand, if the amount of the monomer or oligomer used exceeds the above range, the tack of the surface becomes high, causing blocking. In addition, when the hologram or the like is duplicated, a part of the material remains on the printing plate (press stamper) (printing is performed), so that the repetitive embossing property is deteriorated.
【0031】本発明において、光硬化性樹脂組成物を紫
外線によって硬化させる場合には、該組成物に光増感剤
を添加することが必要であり、一方、電子線によって硬
化を行なう場合には光増感剤は不要である。光増感剤と
しては、従来の紫外線硬化型塗料の光増感剤として用い
られている各種の光増感剤、例えば、ベンゾイン、ベン
ゾインメチルエーテル、ベンゾインエチルエーテル、ベ
ンゾインイソプロピルエーテル、α−メチルベンゾイ
ン、α−フェニルベンゾイン等のベンゾイン系化合物;
アントラキノン、メチルアントラキノン等のアントラキ
ノン系化合物;ベンジル:ジアセチル;アセトフェノ
ン、ベンゾフェノン等のフェニルケトン化合物;ジフェ
ニルジスルフィド、テトラメチルチウラムスルフィド等
のスルフィド化合物;α−クロルメチルナフタリン;ア
ントラセン及びヘキサクロロブタジエン、ペンタクロロ
ブタジエン等のハロゲン化炭化水素等が挙げられる。こ
のような光増感剤は前記ウレタン変性アクリル系樹脂1
00重量部当たり約0.5〜10重量部の範囲で使用す
ることが好ましい。In the present invention, when the photocurable resin composition is cured by ultraviolet rays, it is necessary to add a photosensitizer to the composition, while when it is cured by electron beam. No photosensitizer is required. As the photosensitizer, various photosensitizers used as photosensitizers for conventional UV-curable coating materials, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin. , Benzoin compounds such as α-phenylbenzoin;
Anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl: diacetyl; phenylketone compounds such as acetophenone and benzophenone; sulfide compounds such as diphenyldisulfide and tetramethylthiuram sulfide; α-chloromethylnaphthalene; anthracene and hexachlorobutadiene, pentachlorobutadiene and the like And the like. Such a photosensitizer is the urethane-modified acrylic resin 1 described above.
It is preferably used in the range of about 0.5 to 10 parts by weight per 00 parts by weight.
【0032】本発明の光硬化性樹脂組成物は、上記の各
成分に加えて、ハイドロキノン、t−ブチルハイドロキ
ノン、カテコール、ハイドロキノンモノメチルエーテル
等のフェノール類;ベンゾキノン、ジフェニルベンゾキ
ノン等のキノン類;フェノチアジン類:銅類等の重合防
止剤を配合すると貯蔵安定性が向上する。更に、必要に
応じて、促進剤、粘度調節剤、界面活性剤、消泡剤、シ
ランカップリング剤等の各種助剤を配合してもよい。
又、スチレン・ブタジエンラバー等の高分子体を配合す
ることも可能である。The photocurable resin composition of the present invention comprises, in addition to the above components, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines. : Storage stability is improved by adding a polymerization inhibitor such as copper. Further, if necessary, various auxiliaries such as an accelerator, a viscosity modifier, a surfactant, an antifoaming agent and a silane coupling agent may be added.
It is also possible to blend a polymer such as styrene / butadiene rubber.
【0033】次に上記本発明の光硬化性樹脂組成物の用
途について幾つかの例を挙げて説明する。前記光硬化性
組成物を、金属板、紙、ポリエチレンテレフタレート等
の基材に塗布又は含浸し、次いで組成物中に含まれてい
る有機溶剤が飛散する温度、例えば、l00〜165℃
に設定した加熱炉内に0.1〜1分間程度導いて乾燥さ
せて光硬化性樹脂層を基材上に形成する。そして、この
光硬化性樹脂層に、例えば、プレススタンパーを用いて
所望のホログラムレリーフのパターニング(エンボス加
工)行ない、次いで紫外線、電子線等を照射して樹脂層
を光硬化させる。得られるホログラムは一般的には透過
型であるため、反射層を設ける必要がある。反射層とし
ては、光を反射する金属薄膜を用いると不透明タイプの
ホログラムとなり、透明な物質でホログラム層と屈折率
差がある場合は透明タイプとなるがいずれも本発明に使
用できる。反射層は、昇華、真空蒸着、スパッタリン
グ、反応性スパッタリング、イオンプレーティング、電
気メッキ等の公知の方法で形成可能である。Next, the use of the photocurable resin composition of the present invention will be described with reference to some examples. A temperature at which the photocurable composition is applied or impregnated on a substrate such as a metal plate, paper, or polyethylene terephthalate, and then the organic solvent contained in the composition is scattered, for example, 100 to 165 ° C.
The photocurable resin layer is formed on the base material by introducing the film into the heating furnace set for 1 to about 0.1 to 1 minute and drying it. Then, for example, a desired hologram relief patterning (embossing) is performed on the photocurable resin layer using a press stamper, and then the resin layer is photocured by irradiation with ultraviolet rays, electron beams, or the like. Since the obtained hologram is generally a transmission type, it is necessary to provide a reflection layer. If a metal thin film that reflects light is used as the reflective layer, it becomes an opaque type hologram, and if it is a transparent substance and has a refractive index difference from that of the hologram layer, it becomes a transparent type, but both can be used in the present invention. The reflective layer can be formed by a known method such as sublimation, vacuum deposition, sputtering, reactive sputtering, ion plating, electroplating and the like.
【0034】不透明タイプのホログラムを形成する金属
薄膜としては、例えば、Cr、Ti、Fe、Co、N
i、Cu、Ag、Au、Ge、Al、Mg、Sb、P
b、Pd、Cd、Bi、Sn、Se、In、Ga、Rb
等の金属及びその酸化物、窒化物等を単独若しくは2種
類以上組み合わせて形成される薄膜である。上記金属薄
膜の中でもAl、Cr、Ni、Ag、Au等が特に好ま
しく、その膜厚は1〜10,000nm、望ましくは2
0〜200nmの範囲である。The metal thin film forming the opaque type hologram is, for example, Cr, Ti, Fe, Co, N.
i, Cu, Ag, Au, Ge, Al, Mg, Sb, P
b, Pd, Cd, Bi, Sn, Se, In, Ga, Rb
It is a thin film formed of a single metal or a combination of two or more of such metals and oxides and nitrides thereof. Among the above metal thin films, Al, Cr, Ni, Ag, Au and the like are particularly preferable, and the film thickness thereof is 1 to 10,000 nm, preferably 2
It is in the range of 0 to 200 nm.
【0035】透明タイプのホログラムを形成する薄膜
は、ホログラム効果を発現できる光透過性のものであれ
ば、いかなる材質のものも使用できる。例えば、ホログ
ラム形成層(光硬化樹脂層)の樹脂と屈折率の異なる透
明材料がある。この場合の屈折率はホログラム形成層の
樹脂の屈折率より大きくても、小さくてもよいが、屈折
率の差は0.1以上が好ましく、より好ましくは0.5
以上であり、1.0以上が最適である。又、上記以外で
は20nm以下の金属性反射膜がある。好適に使用され
る透明タイプ反射層としては、酸価チタン(Ti
O2)、硫化亜鉛(ZnS)、Cu・Al複合金属酸化
物等が挙げられる。The thin film forming the transparent type hologram may be made of any material as long as it is light transmissive and capable of exhibiting the hologram effect. For example, there is a transparent material having a refractive index different from that of the resin of the hologram forming layer (photocurable resin layer). The refractive index in this case may be higher or lower than the refractive index of the resin of the hologram forming layer, but the difference in refractive index is preferably 0.1 or more, more preferably 0.5.
It is above, and 1.0 or more is optimal. In addition to the above, there is a metallic reflective film having a thickness of 20 nm or less. As a transparent type reflective layer that is preferably used, acid value titanium (Ti
O 2 ), zinc sulfide (ZnS), Cu / Al mixed metal oxide, and the like.
【0036】更に具体的には、ホログラムパターンのエ
ンボス加工は、例えば、プレススタンパーを周面に装着
した金属ロ−ルとペーパーロールよりなる1対のエンボ
スロールを使用して通常の方法で、例えば、50〜15
0℃、10〜50kg/cm2の圧力で行う。エンボス
加工は片面エンボスで十分であるが、両面エンボスでも
よい。エンボスに当たっては、エンボスロールの温度設
定が重要であり、エンボス形状を再現する観点からは比
較的高温で、比較的高い圧力でエンボスする方が良く、
エンボス版への付着を防止するためには全く逆の関係と
なる。又、有効に作用する熱容量から考えた場合は、複
製するフイルムの搬送速度も重要である。樹脂組成物の
エンボスロールへの付着を低減するためには、上述した
離型剤の選定も重要である。More specifically, the hologram pattern is embossed by a usual method using, for example, a pair of embossing rolls consisting of a metal roll having a press stamper mounted on the peripheral surface and a paper roll. , 50-15
It is carried out at 0 ° C. and a pressure of 10 to 50 kg / cm 2 . One-sided embossing is sufficient for embossing, but double-sided embossing is also possible. When embossing, it is important to set the temperature of the embossing roll, and from the viewpoint of reproducing the embossed shape, it is better to emboss at a relatively high temperature and a relatively high pressure.
In order to prevent sticking to the embossed plate, the relationship is completely opposite. In consideration of the effective heat capacity, the transfer speed of the film to be reproduced is also important. In order to reduce the adhesion of the resin composition to the embossing roll, selection of the above-mentioned mold release agent is also important.
【0037】又、本発明の光硬化性樹脂組成物を用いる
ことにより、予めオフセット印刷した基材の表面に光硬
化性樹脂組成物を塗布し、乾燥後、光硬化性樹脂をエン
ボス加工した後に光硬化させてレリーフを形成させて立
体的な地図やポスターを製造することができる。更に、
ポリエチレンテレフタレート製の剥離フイルム等の第1
の基材上に光硬化性樹脂組成物を塗布し、乾燥後、光硬
化性樹脂層上に絵柄を印刷し、次いで印刷面上にホット
スタンプ剤を塗布した後、合板、ABSシート、亜鉛板
等の第2の基材をホットスタンプ剤面に貼合し、熱転写
ロール等により第2の基材上に印刷された樹脂層を転写
させ、剥離フイルムを除去し、露呈した光硬化性樹脂層
を光硬化させることにより、絵柄を基材に転写したフイ
ルムや金属板等が製造できる。Further, by using the photocurable resin composition of the present invention, the photocurable resin composition is applied to the surface of a substrate which has been offset-printed in advance, and after drying, the photocurable resin is embossed. It can be photocured to form a relief to produce a three-dimensional map or poster. Furthermore,
First release film made of polyethylene terephthalate
After coating the photocurable resin composition on the base material of No. 1, dried, printing a pattern on the photocurable resin layer, then applying a hot stamping agent on the printed surface, plywood, ABS sheet, zinc plate A second base material such as the above is attached to the hot stamping agent surface, the resin layer printed on the second base material is transferred by a heat transfer roll or the like, the release film is removed, and the exposed photocurable resin layer is exposed. By photocuring the film, a film, a metal plate or the like having a pattern transferred to a substrate can be manufactured.
【0038】本発明の光硬化性樹脂組成物の硬化に用い
る光としては、高エネルギー電離性放射線及び紫外線が
挙げられる。高エネルギー電離性放射線源としては、例
えば、コッククロフト型加速器、ハンデグラーフ型加速
器、リニヤーアクセレーター、ベータトロン、サイクロ
トロン等の加速器によって加速された電子線が工業的に
最も便利且つ経済的に使用されるが、その他に放射性同
位元素や原子炉等から放射されるγ線、X線、α線、中
性子線、陽子線等の放射線も使用できる。紫外線源とし
ては、例えば、紫外線螢光灯、低圧水銀灯、高圧水銀
灯、超高圧水銀灯、キセノン灯、炭素アーク灯、太陽灯
等が挙げられる。Light used for curing the photocurable resin composition of the present invention includes high energy ionizing radiation and ultraviolet rays. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as Cockcroft accelerator, Handegraaf accelerator, linear accelerator, betatron, cyclotron is industrially most convenient and economically used. However, radiation such as γ-rays, X-rays, α-rays, neutron rays, and proton rays emitted from radioactive isotopes and nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp.
【0039】[0039]
【実施例】次に実施例及び比較例を挙げて本発明を更に
具体的にに説明する。尚、例中の部又は%は特に断りの
ない限り重量基準である。
実施例1
前記製造例1〜5で得た樹脂溶液を用いて下記5種の本
発明の光硬化性樹脂組成物A〜Eを調製した。組成物A
:
製造例1の樹脂溶液(固形分基準) 100部
シリコーン:トリメチルシロキシケイ酸含有メチルポリシロキサン(商品名
KF−7312、信越化学工業社製) 1部
多官能モノマー(商品名SR−399、サートマー社製) 20部
光増感剤(商品名イルガキュア907、チバスペシャルティケミカルズ社製)
5部
メチルエチルケトン(MEK)で希釈して組成物の固形
分を50%に調整した。EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, parts or% in the examples are based on weight unless otherwise specified. Example 1 The following 5 kinds of photocurable resin compositions A to E of the present invention were prepared using the resin solutions obtained in the above Production Examples 1 to 5. Composition A : Resin solution of Production Example 1 (based on solid content) 100 parts Silicone: trimethylsiloxysilicic acid-containing methylpolysiloxane (trade name KF-7312, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Polyfunctional monomer (trade name SR- 399, manufactured by Sartomer) 20 parts Photosensitizer (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%.
【0040】組成物B
:
製造例2の樹脂溶液(固形分基準) 100部
シリコーン:アミノ変性反応性シリコーンオイル(両末端型)(商品名KF−
8012、信越化学工業社製) 1部
多官能モノマー(商品名SR−399、サートマー社製) 20部
光増感剤(商品名イルガキュア651、チバスペシャルティケミカルズ社製)
5部
メチルエチルケトン(MEK)で希釈して組成物の固形
分を50%に調整した。 Composition B : Resin solution of Production Example 2 (based on solid content) 100 parts Silicone: Amino-modified reactive silicone oil (both ends type) (trade name KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Polyfunctional Monomer (trade name SR-399, manufactured by Sartomer) 20 parts Photosensitizer (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%. did.
【0041】組成物C
:
製造例3の樹脂溶液(固形分基準) 100部
シリコーンオイル:アミノ変性反応性シリコーンオイル(側鎖型)(商品名
KF−860、信越化学工業社製) 1部
多官能モノマー(商品名NKオリゴU−15HA、新中村化学工業社製)
20部
光増感剤(商品名イルガキュア907、チバスペシャルティケミカルズ社製)
5部
メチルエチルケトン(MEK)で希釈して組成物の固形
分を50%に調整した。 Composition C : Resin solution of Production Example 3 (based on solid content) 100 parts Silicone oil: Amino-modified reactive silicone oil (side chain type) (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Many Functional monomer (brand name NK oligo U-15HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts Photosensitizer (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts Solid composition diluted with methyl ethyl ketone (MEK) The minutes were adjusted to 50%.
【0042】組成物D
:
製造例4の樹脂溶液(固形分基準) 100部
シリコーンオイル:アミノ変性反応性シリコーンオイル(片末端型)(商品名
KF−8012、信越化学工業社製) 1部
多官能モノマー(商品名SR−399、サートマー社製) 20部
光増感剤(商品名イルガキュア907、チバスペシャルティケミカルズ社製)
5部
メチルエチルケトン(MEK)で希釈して組成物の固形
分を50%に調整した。 Composition D : Resin solution of Production Example 4 (based on solid content) 100 parts Silicone oil: Amino-modified reactive silicone oil (one end type) (trade name KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Many Functional monomer (brand name SR-399, manufactured by Sartomer) 20 parts Photosensitizer (brand name Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) to make the solid content of the composition 50%. It was adjusted.
【0043】組成物E
:
製造例5の樹脂溶液(固形分基準) 100部
シリコーン:メタクリル変性シリコーンオイル(商品名X−22−164B、
信越化学工業社製) 3部
多官能モノマー(商品名SR−399、サートマー社製) 20部
光増感剤(商品名イルガキュア651、チバスペシャルティケミカルズ社製)
5部
メチルエチルケトン(MEK)で希釈して組成物の固形
分を50%に調整した。 Composition E : Resin solution of Production Example 5 (based on solid content) 100 parts Silicone: Methacryl modified silicone oil (trade name X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Polyfunctional monomer (trade name SR) -399, manufactured by Sartomer) 20 parts Photosensitizer (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%.
【0044】(1)ホログラムの複製
ホログラムの複製は、特開昭61−156273号公報
に記載の図1に示した連続複製装置によって行った。
実施例2〜6
前記5種の本発明の光硬化性樹脂組成物のそれぞれを5
0μmの片面易接着処理ポリエチレンテレフタレートフ
イルム(ダイアホイルT−600E、ダイヤホイルヘキ
スト社製)の易接着処理面上に20m/min.の速度
でロールコーターで塗工し、100℃で乾燥して溶剤を
揮散させた後、乾燥膜厚で2g/m2の複製用感光性フ
イルムを得た。得られたフイルムはいずれも常温ではべ
とつかず、巻き取り状態で保管できるものであった。(1) Hologram duplication The hologram duplication was performed by the continuous duplication device shown in FIG. 1 described in JP-A-61-156273. Examples 2 to 6 Each of the five photocurable resin compositions of the present invention was used.
20 m / min. On the easy-adhesion-treated surface of a polyethylene terephthalate film (Diafoil T-600E, manufactured by Diafoil Hoechst Co., Ltd.) having a single-sided easy adhesion treatment of 0 μm. After coating with a roll coater at 100 ° C. and drying at 100 ° C. to volatilize the solvent, a photosensitive film for duplication having a dry film thickness of 2 g / m 2 was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.
【0045】複製装置のエンボスローラーには、レーザ
ー光を用いて作ったマスターホログラムから引続き作成
したプレススタンパーが設置されている。尚、樹脂製版
にマスターホログラムから複製ホログラムを作製し、こ
れをシリンダー上に貼り付けたものも使用できる。上記
で作製した複製用感光性フイルムを給紙側に仕掛け、1
50℃で加熱プレスして微細な凹凸パターンを形成させ
た。引き続き、水銀灯より発生した紫外線を照射して光
硬化させた。引き続き真空蒸着法によりアルミニウム層
をこの上に蒸着して反射型のレリーフホログラムを形成
した。The embossing roller of the copying apparatus is provided with a press stamper which is subsequently created from a master hologram created by using a laser beam. A replica hologram prepared from a master hologram on a resin plate and attached on a cylinder can also be used. Mount the photopolymer film for reproduction prepared above on the paper feed side, and
A hot press was applied at 50 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type relief hologram.
【0046】この表面に、接着剤層(ニッセツPE−1
18+CK101、日本カーバイド製)をロールコート
で塗工し、100℃で乾燥して溶剤を揮散させた後、剥
離フイルムとしてシリコーン処理PETフイルム(SP
O5、東京セロファン紙社製)をラミネートし、乾燥膜
厚で25g/m2の接着剤層を得た。これは、ラベル形
態となっており、立体像を写し出す印刷物やディスプレ
イ等に用いることができる。On this surface, an adhesive layer (Nissetsu PE-1
18 + CK101, manufactured by Nippon Carbide Co., Ltd., is applied by a roll coat, dried at 100 ° C. to evaporate the solvent, and then a silicone-treated PET film (SP) is used as a release film.
O5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m 2 . This is in the form of a label and can be used for a printed matter, a display, or the like that displays a stereoscopic image.
【0047】(2)回折格子の形成
複製装置はホログラム複製で利用した図1(特開昭61
−156273号公報)に示したものと同一のものであ
る。
実施例7〜11
前記5種の本発明の光硬化性樹脂組成物のそれぞれを5
0μmの片面易接着処理ポリエチレンテレフタレートフ
イルム(ダイアホイルT−600E、ダイヤホイルヘキ
スト社製)の易接着処理面上に20m/min.の速度
でロールコーターで塗工し、100℃で乾燥して溶剤を
揮散させた後、乾燥膜厚で2g/m2の複製用感光性フ
イルムを得た。得られたフイルムはいずれも常温ではべ
とつかず、巻き取り状態で保管できるものであった。(2) Forming Diffraction Grating The duplicating apparatus shown in FIG.
No. 156273). Examples 7 to 11 Each of the five photocurable resin compositions of the present invention was used.
20 m / min. On the easy-adhesion-treated surface of a polyethylene terephthalate film (Diafoil T-600E, manufactured by Diafoil Hoechst Co., Ltd.) having a single-sided easy adhesion treatment of 0 μm. After coating with a roll coater at 100 ° C. and drying at 100 ° C. to volatilize the solvent, a photosensitive film for duplication having a dry film thickness of 2 g / m 2 was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.
【0048】複製装置のエンボスローラーには、電子線
を用いて描画したマスター回折格子から引続き作成した
プレススタンパーが設置されている。尚、樹脂製版にマ
スター回折格子から複製回折格子を作製し、これをシリ
ンダー上に貼り付けたものも使用できる。上記で作製し
た複製用感光性フイルムを給紙側に仕掛け、150℃で
加熱プレスして微細な凹凸パターンを形成させた。引き
続き、水銀灯より発生した紫外線を照射して光硬化させ
た。引き続き真空蒸着法によりアルミニウム層をこの上
に蒸着して反射型の回折格子を形成した。The embossing roller of the copying apparatus is provided with a press stamper which is subsequently created from a master diffraction grating drawn by using an electron beam. It is also possible to use a resin plate in which a duplicated diffraction grating is prepared from the master diffraction grating and is stuck on a cylinder. The duplicating photosensitive film prepared above was set on the paper feed side and heated and pressed at 150 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type diffraction grating.
【0049】この表面に、接着剤層(ニッセツPE−1
18+CK101、日本カーバイド製)をロールコート
で塗工し、100℃で乾燥して溶剤を揮散させた後、剥
離フイルムとしてシリコーン処理PETフイルム(SP
O5、東京セロファン紙社製)をラミネートし乾燥膜厚
で25g/m2の接着剤層を得た。これは、ラベル形態
となっており、立体像を写し出す印刷物やディスプレイ
等に用いることができる。On this surface, an adhesive layer (Nissetsu PE-1
18 + CK101, manufactured by Nippon Carbide Co., Ltd., is applied by a roll coat, dried at 100 ° C. to evaporate the solvent, and then a silicone-treated PET film (SP) is used as a release film.
O5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m 2 . This is in the form of a label and can be used for a printed matter, a display, or the like that displays a stereoscopic image.
【0050】(3)転写方式によるホログラム形成
実施例12〜16
25μmのポリエチレンテレフタレートフイルム(ルミ
ラーT60、東レ社製)に20m/min.の速度で剥
離層をグラビアコートで塗工し、100℃で乾燥して溶
剤を揮散させた後、乾燥膜厚で1g/m2の剥離層/P
ETの層構成からなるフイルムを得た。(3) Hologram formation by transfer method Examples 12 to 16 25 μm polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) at 20 m / min. The peeling layer is coated with a gravure coat at a speed of 1 and dried at 100 ° C. to volatilize the solvent, and then the peeled layer / P of the dried film thickness is 1 g / m 2.
A film having a layer structure of ET was obtained.
【0051】尚、上記における剥離層は、転写箔を転写
した後に被転写体の表面に転移して最表面になる層であ
り、転写層の剥離性や箔切れ性等を向上させる目的で設
けられ、基材フイルムの種類に応じて既知の各種の材料
が利用できる。剥離層の材質としては、例えば、ポリメ
タクリル酸エステル樹脂、ポリ塩化ビニル樹脂、セルロ
ース樹脂、シリコーン樹脂、塩化ゴム、カゼイン、各種
界面活性剤、金属酸化物等の中、1種若しくは2種以上
を混合したものが用いられる。特に、剥離層は基材フイ
ルムと転写層との間の剥離力が1〜5g/インチ(90
°剥離)になるように、その材質等を適宜選択して形成
するのが好ましい。この剥離層はインキ化し、塗布等の
公知の方法によって基材フイルムの表面に形成すること
ができ、その厚みは剥離力、箔切れ等を考慮すると0.
1〜2μmの範囲が好ましい。The peeling layer in the above is a layer which is transferred to the surface of the transferred material and becomes the outermost surface after the transfer foil is transferred, and is provided for the purpose of improving the peeling property and foil cutting property of the transfer layer. However, various known materials can be used depending on the type of the base film. Examples of the material of the release layer include one or more of polymethacrylic acid ester resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, and the like. A mixture is used. In particular, the peeling layer has a peeling force between the base film and the transfer layer of 1 to 5 g / inch (90
It is preferable that the material and the like be appropriately selected so as to form (peeling). This release layer can be formed into an ink and formed on the surface of the base film by a known method such as coating, and its thickness is 0.
The range of 1 to 2 μm is preferable.
【0052】前記5種の本発明の光硬化性樹脂組成物の
それぞれを剥離層/PETの層構成からなるフイルムの
剥離層上にロールコーターで塗工し、100℃で乾燥し
て溶剤を揮散させた後、乾燥膜厚で2g/m2の複製用
感光性フイルムを得た。得られたフイルムはいずれも常
温ではべとつかず、巻き取り状態で保管できるものであ
った。Each of the five photocurable resin compositions of the present invention was coated on a release layer of a film having a layer structure of release layer / PET with a roll coater and dried at 100 ° C. to evaporate the solvent. After that, a photosensitive film for duplication having a dry film thickness of 2 g / m 2 was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.
【0053】複製装置のエンボスローラーには、レーザ
ー光を用いて作ったマスターホログラムから引続き作成
したプレススタンパーが設置されている。尚、樹脂製版
にマスターホログラムから複製ホログラムを作製し、こ
れをシリンダー上に貼り付けたものも使用できる。上記
で作製した複製用感光性フイルムを給紙側に仕掛け、1
50℃で加熱プレスして微細な凹凸パターンを形成させ
た。引き続き、水銀灯より発生した紫外線を照射して光
硬化させた。引き続き真空蒸着法によりアルミニウム層
をこの上に蒸着して反射型のレリーフホログラムを形成
した。この表面に、接着剤層をグラビアコートで塗工
し、100℃で乾燥して溶剤を揮散させた後、乾燥膜厚
で1g/m2の接着剤層を得た。The embossing roller of the copying apparatus is provided with a press stamper which is continuously created from a master hologram created by using a laser beam. A replica hologram prepared from a master hologram on a resin plate and attached on a cylinder can also be used. Mount the photopolymer film for reproduction prepared above on the paper feed side, and
A hot press was applied at 50 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type relief hologram. An adhesive layer was applied to this surface by gravure coating, dried at 100 ° C. to volatilize the solvent, and an adhesive layer having a dry film thickness of 1 g / m 2 was obtained.
【0054】尚、上記における接着層としては、感熱性
接着性樹脂としては公知のものが使用できる。例えば、
ポリイソプレンゴム、ポリイソブチレンゴム、スチレン
ブタジエンゴム等のゴム系、ポリ(メタ)アクリル酸メ
チル、ポリ(メタ)アクリル酸エチル、ポリ(メタ)ア
クリル酸プロピル、ポリ(メタ)アクリル酸ブチル、ポ
リ(メタ)アクリル酸2エチルヘキシル等の(メタ)ア
クリル酸エステル系、ポリイソブチルエーテル等のポリ
ビニルエーテル系、ポリ酢酸ビニル、塩化ビニル−酢酸
ビニル共重合体等のポリ塩化ビニル系、ポリアクリルア
ミド、ポリメチロールアクリルアミド等のポリアミド
系、ポリ塩化ビニル等の塩化ビニル系、ポリスチレン、
ポリエステル、ポリ塩化オレフィン、ポリビニルブチラ
ール、又、その他、酢酸ビニル/アクリル酸オクチル、
酢酸ビニル/アクリル酸ブチル、塩化ビニリデン/アク
リル酸ブチル等が挙げられる。As the above-mentioned adhesive layer, a known heat-sensitive adhesive resin can be used. For example,
Rubber-based materials such as polyisoprene rubber, polyisobutylene rubber, and styrene-butadiene rubber, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, poly ( (Meth) acrylic ester such as 2-ethylhexyl acrylate, polyvinyl ether such as polyisobutyl ether, polyvinyl acetate such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyacrylamide, polymethylolacrylamide Polyamide series such as, polyvinyl chloride series such as polyvinyl chloride, polystyrene,
Polyester, polychlorinated olefins, polyvinyl butyral, and others, vinyl acetate / octyl acrylate,
Examples thereof include vinyl acetate / butyl acrylate and vinylidene chloride / butyl acrylate.
【0055】又、塗工するフイルムとしては、転写性と
剥離性を有するものであればよく、例えば、2軸延伸さ
れたポリエチレンテレフタレート(PET)フイルムが
寸法安定性、耐熱性、強靭性等の点から最も好ましい。
これ以外に、ポリ塩化ビニルフイルム、ポリプロピレン
フイルム、ポリエチレンフイルム、ポリカーボネートフ
イルム、セロファン、ポリビニルアルコールフイルム、
アセテートフイルム、ナイロンフイルム、ポリアミドフ
イルム、ポリアミドイミドフイルム、エチレン/ビニル
アルコール共重合体フイルム、フッ素含有フイルム、各
種共押出しフイルム等が使用できる。厚みとしては5μ
m〜200μm、好ましくは10μm〜50μmが良
い。The film to be applied may be one having transferability and releasability. For example, a biaxially stretched polyethylene terephthalate (PET) film has dimensional stability, heat resistance and toughness. Most preferred from the point.
In addition to this, polyvinyl chloride film, polypropylene film, polyethylene film, polycarbonate film, cellophane, polyvinyl alcohol film,
Acetate film, nylon film, polyamide film, polyamideimide film, ethylene / vinyl alcohol copolymer film, fluorine-containing film, various coextrusion films and the like can be used. 5μ as thickness
m to 200 μm, preferably 10 μm to 50 μm.
【0056】合板の上に前記アクリル系接着剤面を下に
してフイルム面側から熱ロールにて熱転写を行なった。
次いで、剥離フイルムを剥し、水銀灯より発生した紫外
線を照射して、表層の樹脂を硬化させた。これは、転写
箔の形態になっており、立体像を写し出す印刷物やディ
スプレイ等に用いることができる。転写機で塩化ビニル
カード上への熱転写を行ったところ、箔切れは良好で密
着性も優れるものであった。以上の実施例2〜16の加
工品の物性を表2に示す。Thermal transfer was carried out on the plywood from the film side with the acrylic adhesive side facing down by a heat roll.
Then, the peeling film was peeled off, and ultraviolet rays generated from a mercury lamp were irradiated to cure the resin on the surface layer. This is in the form of a transfer foil, and can be used for a printed matter, a display, or the like showing a stereoscopic image. When thermal transfer was performed on a vinyl chloride card with a transfer machine, the foil was cut well and the adhesion was excellent. Table 2 shows the physical properties of the processed products of Examples 2 to 16 above.
【0057】比較例1
実施例1における組成物Aの樹脂に代えて同量の樹脂
(メタクリル酸−アクリル酸共重合樹脂BR−77、三
菱レーヨン社製)を用い、シリコーオイルを使用しない
他は組成物Aと同一組成の組成物Fを調製し、該組成物
Fを用いて前記と同様にホログラムの複製、回折格子の
複製及び転写方式によるホログラム形成を行なった。こ
れら加工品の物性を表2に示す。Comparative Example 1 The same amount of resin (methacrylic acid-acrylic acid copolymer resin BR-77, manufactured by Mitsubishi Rayon Co., Ltd.) was used in place of the resin of the composition A in Example 1, and no silicone oil was used. A composition F having the same composition as the composition A was prepared, and the composition F was used to perform hologram duplication, diffraction grating duplication, and hologram formation by a transfer method in the same manner as described above. Table 2 shows the physical properties of these processed products.
【0058】尚、物性の評価法は次の通りである。剥離性(プレススタンパーからの剥離性)
:塗工フイル
ムを図1(特開昭61−156273号公報)の複製装
置で1000m連続複製を行い、プレススタンパー上に
樹脂の残りがないかを確認することにより行った。
○・・・残りがない。×・・・残りがある。耐薬品性
:加工品の硬化表面をメチルエチルケトンをし
み込ませたガーゼで100回往復させて擦ったとき、表
面に異常がなかったものを良好とし、表面に異常を生じ
たものを不良とした。
○・・・良好。×・・・不良。The evaluation method of the physical properties is as follows. Peelability (Peelability from press stamper) : The coating film is continuously duplicated for 1000 m by the duplicating apparatus shown in FIG. 1 (JP-A 61-156273), and it is confirmed whether or not the resin remains on the press stamper. I went by. ○: There is no remaining. ×: There is a rest. Chemical resistance : When the cured surface of the processed product was rubbed 100 times with a gauze impregnated with methyl ethyl ketone and rubbed, there was no abnormality on the surface, and those with an abnormality on the surface were regarded as defective. ○: Good. X: defective.
【0059】耐熱性:加工品の硬化表面を熱ロールで2
00℃に加熱し、3分間保持した後の変色や変形等を見
た。異常のなかったものを良好とし、黄変若しくは変形
や剥離を生じたものを不良とした。
○・・・良好。×・・・不良。耐擦傷性
:#0000のスチールウールで加工品の硬化
表面を10回擦ったとき、表面に何の変化もなかったも
のを良好とし、表面が傷つき、白化したものを不良とし
た。
○・・・良好。×・・・不良。 Heat resistance : The hardened surface of the processed product is heated with a hot roll.
Discoloration and deformation were observed after heating to 00 ° C. and holding for 3 minutes. Those with no abnormality were regarded as good, and those with yellowing or deformation or peeling were regarded as defective. ○: Good. X: defective. Scratch resistance : When the cured surface of the processed product was rubbed 10 times with # 0000 steel wool, the surface without any change was regarded as good, and the surface scratched and whitened was regarded as poor. ○: Good. X: defective.
【0060】蒸着適性:ホログラム又は回折格子形成面
に、真空蒸着法によりアルミニウム層を蒸着した後、密
着性をセロテープ碁盤目試験で評価した。
○・・・蒸着性良好。×・・・蒸着性不良。転写箔適性
:ホログラム又は回折格子形成面に、真空蒸
着法によりアルミニウム層を蒸着した後、更にヒートシ
ール用のアクリル系接着剤(ホットスタンプ剤)を塗工
して得たものを、転写機を用いてポリ塩化ビニルカード
上へ転写し、転写箔の箔切れ性及び密着性を評価した。
○・・・良好。×・・・不良。 Deposition suitability : An aluminum layer was deposited on the hologram or diffraction grating formation surface by a vacuum deposition method, and the adhesion was evaluated by a cellotape cross-cut test. Good: Good vapor deposition property. X: Poor vapor deposition property. Transfer foil suitability : An aluminum layer is vapor-deposited on the hologram or diffraction grating formation surface by a vacuum vapor deposition method, and then an acrylic adhesive (hot stamping agent) for heat sealing is applied to obtain a transfer machine. It was used to transfer onto a polyvinyl chloride card and the foil breakability and adhesion of the transfer foil were evaluated. ○: Good. X: defective.
【0061】耐屈曲性:ポリ塩化ビニルカード上へ転写
した転写箔にエンボス文字加工をして、エンボス文字に
割れ等が生じてないかを確認した。
○・・・変化なし。×・・・割れがある。 Bending resistance : The transfer foil transferred onto a polyvinyl chloride card was subjected to embossed character processing to check whether the embossed character had cracks or the like. ○: No change. X: There is a crack.
【0062】表2:評価結果 Table 2: Evaluation results
【0063】[0063]
【発明の効果】本発明によれば、光硬化性樹脂組成物の
主被膜形成成分として特定のウレタン変性アクリル系樹
脂を使用することによって、優れた強度、耐熱性、耐擦
傷性、耐水性、耐薬品性、基材に対する密着性を有する
被膜が形成可能で、且つ被貼着物の屈曲性や伸縮に対す
る追随性をも有する回折格子やレリーフホログラムを形
成することができる光硬化性樹脂組成物を提供すること
ができる。According to the present invention, by using a specific urethane-modified acrylic resin as a main film forming component of a photocurable resin composition, excellent strength, heat resistance, scratch resistance, water resistance, A photocurable resin composition capable of forming a coating film having chemical resistance and adhesion to a substrate, and capable of forming a diffraction grating or a relief hologram having flexibility and flexibility of an adherend. Can be provided.
【図1】 本発明で使用した凹凸形状の付与方法を説明
する図FIG. 1 is a diagram for explaining a method of giving an uneven shape used in the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) G03H 1/20 G03H 1/20 // G03F 7/033 G03F 7/033 (C08L 33/04 83:04) Fターム(参考) 2H025 AA00 AA06 AA07 AA08 AA10 AA13 AA14 AB20 AC01 AC06 AD01 BC42 BC53 BC83 BC92 CC20 FA01 FA03 2H049 AA13 AA40 AA43 AA48 CA15 CA30 2K008 AA00 AA13 DD14 FF13 FF14 GG05 4J002 BB032 BD122 BG011 BG041 BG051 BG071 BG081 BL013 BN122 CD203 CF203 CF273 CH053 CK021 CK023 CL002 CP032 CQ013 EB027 EB147 EB157 EE027 EE057 EH076 EL066 EU016 EU026 EU186 EU196 EV047 EW046 FD100 FD162 FD200 FD330 GH01 HA05 4J027 AA01 AA04 AC03 AC04 AC06 AE01 AE04 AF05 AJ01 AJ02 AJ08 BA01 BA02 BA12 BA13 BA15 BA16 BA19 BA23 BA24 BA26 BA27 BA28 BA29 CA03 CA04 CA07 CA10 CA23 CA27 CA28 CB10 CC05 CC06 CD08─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) G03H 1/20 G03H 1/20 // G03F 7/033 G03F 7/033 (C08L 33/04 83:04) F-term (reference) 2H025 AA00 AA06 AA07 AA08 AA10 AA13 AA14 AB20 AC01 AC06 AD01 BC42 BC53 BC83 BC92 CC20 FA01 FA03 2H049 AA13 AA40 AA43 AA48 CA15 CA30 2K008 AA00 AA13 DD14 FF13 FF1 BB105101141 CF273 CH053 CK021 CK023 CL002 CP032 CQ013 EB027 EB147 EB157 EE027 EE057 EH076 EL066 EU016 EU026 EU186 EU196 EV047 EW046 FD100 FD162 FD200 FD330 GH01 HA05 4J027 AA01 AA04 AC03 AC04 AC06 AE01 AE04 AF05 AJ01 AJ02 AJ08 BA01 BA02 BA12 BA13 BA15 BA16 BA19 BA23 BA24 BA26 BA27 BA28 BA29 CA03 CA04 CA07 CA10 CA23 CA27 CA28 CB10 CC05 CC06 CD08
Claims (9)
リル系樹脂と離型剤とを必須成分として含有することを
特徴とする光硬化性樹脂組成物。 (式中、Zは嵩高い環状構造の基を表わし、6個のR1
は夫々互いに独立して水素原子又はメチル基を表わし、
R2はC1〜C16の炭化水素基を表わし、X及びYは直鎖
状又は分岐鎖状のアルキレン基を表わす。l(エル)と
mとnとo(オー)とpの合計を100とした場合に、
lは20〜90、mは5〜80、nは0〜50、o+p
は10〜80、pは0〜40の整数である。)1. A photocurable resin composition comprising a urethane-modified acrylic resin represented by the following structural formula and a release agent as essential components. (In the formula, Z represents a group having a bulky cyclic structure, and 6 R 1
Are each independently a hydrogen atom or a methyl group,
R 2 represents a C 1 to C 16 hydrocarbon group, and X and Y represent a linear or branched alkylene group. When the total of l (el), m, n, o (oh) and p is 100,
l is 20 to 90, m is 5 to 80, n is 0 to 50, o + p
Is an integer of 10 to 80 and p is an integer of 0 to 40. )
〜50重量部の割合で含有されている請求項1に記載の
光硬化性樹脂組成物。2. The release agent is 0.1 per 100 parts by weight of the resin.
The photocurable resin composition according to claim 1, wherein the photocurable resin composition is contained in a proportion of ˜50 parts by weight.
求項1又は2に記載の光硬化性樹脂組成物。3. The photocurable resin composition according to claim 1, wherein the release agent is a modified silicone oil.
ンオイルである請求項3に記載の光硬化性樹脂組成物。4. The photocurable resin composition according to claim 3, wherein the modified silicone oil is a reactive silicone oil.
で1万〜20万である請求項1〜4の何れか1項に記載
の光硬化性樹脂組成物。5. The photocurable resin composition according to claim 1, wherein the resin has a molecular weight in terms of polystyrene of 10,000 to 200,000.
含む請求項1〜5の何れか1項に記載の光硬化性樹脂組
成物。6. The photocurable resin composition according to claim 1, which contains a polyfunctional monomer or a polyfunctional oligomer.
化性樹脂組成物を、基材の少なくとも一方の面に塗布及
び乾燥して光硬化性樹脂層を形成し、該光硬化性樹脂層
の表面をエンボス加工した後、該樹脂層に露光して樹脂
層を硬化させることを特徴とする凹凸パターンの形成方
法。7. The photocurable resin composition according to claim 1 is applied and dried on at least one surface of a substrate to form a photocurable resin layer, A method for forming a concavo-convex pattern, comprising embossing the surface of a curable resin layer and then exposing the resin layer to cure the resin layer.
7に記載の凹凸パターンの形成方法。8. The method for forming a concavo-convex pattern according to claim 7, wherein the exposure is performed with ultraviolet rays or electron beams.
ログラムである請求項7又は8に記載の凹凸パターンの
形成方法。9. The method for forming an uneven pattern according to claim 7, wherein the uneven pattern is a diffraction grating or a relief hologram.
Priority Applications (2)
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JP23974698A JP3355308B2 (en) | 1998-08-26 | 1998-08-26 | Photocurable resin composition and method for forming uneven pattern |
US09/362,726 US6344495B1 (en) | 1998-07-31 | 1999-07-29 | Photo-curable resin composition and method for forming concave-convex pattern |
Applications Claiming Priority (1)
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---|---|---|---|
JP23974698A JP3355308B2 (en) | 1998-08-26 | 1998-08-26 | Photocurable resin composition and method for forming uneven pattern |
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JP2000063459A true JP2000063459A (en) | 2000-02-29 |
JP3355308B2 JP3355308B2 (en) | 2002-12-09 |
Family
ID=17049322
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JP23974698A Expired - Lifetime JP3355308B2 (en) | 1998-07-31 | 1998-08-26 | Photocurable resin composition and method for forming uneven pattern |
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US7420005B2 (en) | 2001-06-28 | 2008-09-02 | Dai Nippon Printing Co., Ltd. | Photocurable resin composition, finely embossed pattern-forming sheet, finely embossed transfer sheet, optical article, stamper and method of forming finely embossed pattern |
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