JP2944164B2 - Liquid photosensitive resin composition for flexographic printing plates - Google Patents
Liquid photosensitive resin composition for flexographic printing platesInfo
- Publication number
- JP2944164B2 JP2944164B2 JP2207975A JP20797590A JP2944164B2 JP 2944164 B2 JP2944164 B2 JP 2944164B2 JP 2207975 A JP2207975 A JP 2207975A JP 20797590 A JP20797590 A JP 20797590A JP 2944164 B2 JP2944164 B2 JP 2944164B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- weight
- glycol
- average molecular
- photosensitive resin
- 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.)
- Expired - Lifetime
Links
- 238000007639 printing Methods 0.000 title claims description 23
- 239000011342 resin composition Substances 0.000 title claims description 9
- 239000007788 liquid Substances 0.000 title description 10
- 150000002009 diols Chemical class 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 24
- 229920000728 polyester Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 7
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 150000003077 polyols Chemical group 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005336 cracking Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000005442 diisocyanate group Chemical group 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- VGHCVSPDKSEROA-UHFFFAOYSA-N 2-methyl-1,4-dioxecane-5,10-dione Chemical compound CC1COC(=O)CCCCC(=O)O1 VGHCVSPDKSEROA-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 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
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-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
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 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
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-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
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BGGMVFKOJRFRCF-UHFFFAOYSA-N C(O)C(C(C(O)CO)(C(O)CO)C(O)CO)O Chemical compound C(O)C(C(C(O)CO)(C(O)CO)C(O)CO)O BGGMVFKOJRFRCF-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-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
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- CNPHCSFIDKZQAK-UHFFFAOYSA-N n-prop-2-enylprop-2-enamide Chemical compound C=CCNC(=O)C=C CNPHCSFIDKZQAK-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- WZESLRDFSNLECD-UHFFFAOYSA-N phenyl prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1 WZESLRDFSNLECD-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Printing Plates And Materials Therefor (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は光照射前の状態が液状であるフレキソ印刷用
感光性樹脂組成物に関する。本発明の組成物は、特に段
ボールシート、重袋の印刷といった版厚とレリーフ深度
がともに大きい印刷版に好適なフレキソ印刷版に用いら
れる。The present invention relates to a photosensitive resin composition for flexographic printing, which is in a liquid state before light irradiation. The composition of the present invention is used in a flexographic printing plate suitable for a printing plate having a large plate thickness and a large relief depth, particularly for printing on a corrugated cardboard sheet or a heavy bag.
段ボール印刷、フィルム印刷といったフレキソ印刷に
おいて、ゴム版の代わりに感光性樹脂版が使用されるよ
うになって久しい。そして段ボール印刷のように彫りの
深いレリーフを有する版が使用される用途においては、
レリーフにならない非画像領域の未硬化感光性樹脂の再
使用が可能なため、経済的メリットが大きいこと、リレ
ーフ形状がシャープであること、さらには洗い出しが水
系の洗浄液でできるため、作業環境が優れているといっ
た理由により、光硬化前に液状の感光性樹脂が多用され
ている。In flexographic printing such as cardboard printing and film printing, photosensitive resin plates have been used for a long time instead of rubber plates. And in applications where a plate with a deep relief is used, such as cardboard printing,
Excellent work environment because the uncured photosensitive resin in the non-image area that does not become relief can be reused, which has great economical advantages, sharp relief shape, and can be washed out with an aqueous cleaning solution. For this reason, liquid photosensitive resins are frequently used before photocuring.
これらの液状の感光性樹脂組成物に関する先行技術は
例えば特公昭54−41202号公報、同55−13017号公報、同
55−13018号公報、同55−48293号公報、同52−7761号公
報、同52−36444号公報、同55−34413号公報、同53−35
481号公報、同59−50971号公報、同60−28291号公報等
に開示されている。Prior art relating to these liquid photosensitive resin compositions is disclosed, for example, in JP-B-54-41202, JP-B-55-13017, and JP-B-55-13017.
No. 55-13018, No. 55-48293, No. 52-7761, No. 52-36444, No. 55-34413, No. 53-35
Nos. 481, 59-50971 and 60-28291.
しかし、従来上記の用途に使用されている液状感光性
樹脂から製版された印刷版については、印刷中や版拭き
中にレリーフが欠けたり、版をトリミングするためにナ
イフ等で断裁する際に、版が割れたりするといった問題
点があり、その改良が望まれていた。ちなみに上記した
公知技術に於ても、硬化物の引張強伸度及び引裂強度を
改良することによって当該問題を解決することが指摘さ
れているが、本発明者の研究による該物性項目を改良す
るだけでは必ずしも問題の解決にならないことが分かっ
てきた。即ち、同じレベルの引張強伸度及び、引裂強度
物性を示す版材でも版欠けの発生する程度は大きく異な
る場合があることが判明したのである。However, for a printing plate made from a liquid photosensitive resin conventionally used for the above applications, the relief is missing during printing or wiping the plate, or when cutting with a knife or the like to trim the plate, There was a problem that the plate was cracked, and improvement was desired. Incidentally, it is pointed out that in the above-mentioned known technology, the problem can be solved by improving the tensile strength and elongation and the tear strength of the cured product. It turns out that alone does not always solve the problem. That is, it has been found that even plate materials exhibiting the same level of tensile strength and elongation and tear strength physical properties may have significantly different degrees of plate chipping.
本発明はかかる状況下において、上記した従来技術の
問題点を解決し液状感光性樹脂の特長を発揮しながら、
当該問題点を解消した実用上の物性バランスの取れた液
状感光性樹脂組成物を提供することを課題とするもので
ある。この目的のため、鋭意研究した結果、今まで対象
としていなかったある特定の力学的物性即ち、硬化物と
したときの耐ノッチ亀裂性が、従来から取り上げられて
いた引張物性に加えて重要であることが分かった。そし
て本発明によって明らかにされたこの力学的物性が必要
なレベルになるための液状感光性樹脂組成物を鋭意研究
することにより、本発明の特定の組成が、該物性レベル
を満足するために必要であることがわかり、本発明を完
成するに至った。Under such circumstances, the present invention solves the above-mentioned problems of the prior art and demonstrates the features of the liquid photosensitive resin,
It is an object of the present invention to provide a liquid photosensitive resin composition having a practical balance of physical properties that has solved the above problems. For this purpose, as a result of diligent research, certain mechanical properties that have not been targeted so far, namely the notch crack resistance when cured, are important in addition to the tensile properties that have been conventionally taken up. I found it. And, by intensively studying a liquid photosensitive resin composition for bringing the mechanical properties to the required level revealed by the present invention, the specific composition of the present invention is required to satisfy the physical property level. Thus, the present invention has been completed.
すなわち、本発明は 重量平均分子量が、それぞれ1.0×1033以上のポリ
エーテルジオールとポリエステルジオールをセグメント
し、該両ジオールのモル比が1/2〜2/1の範囲にあり、且
つその両末端が(メタ)アクリル化されていて、重量平
均分子量が2.3×104〜5.0×104であるプレポリマー100
重量部と、 下記一般式Iで示される単官能モノマー45〜95重量
%と一般式IIで示される多官能モノマー5〜15重量%を
含有するエチレン付加重合性モノマー20〜60重量部と、 一般式I… H2C=C(R1)−COO−R2 一般式II… (H2C=C(R1)−COOnX 〔両式中のR1はH又はCH3、R2は分子量2.0×102〜1.0×
103のアルコール残基、Xは分子量60〜5.0×102のポリ
オール残基を表わす。n=2〜6である。但し、上記分
子量は分子量分布を有さない化合物の場合は分子量を、
又分子量分布を有する化合物の場合は数平均分子量を意
味する。〕 光重合開始剤を上記+の全量に対し0.1〜5.0重
量%と、 熱重合禁止剤を上記+の全量に対し0.01〜1.0
重量%とを必須成分とする感光性樹脂組成物であって、 該組成物の硬化物の耐ノッチ亀裂性が20秒以上であ
ることを特徴とするフレキソ印刷版用液状感光性樹脂組
成物 を提供するものである。That is, the present invention has a weight average molecular weight, and segments, respectively 1.0 × 10 3 3 or more polyether diols and polyester diols, the molar ratio of the both diol is in the range of 1 / 2-2 / 1, and the two Prepolymer 100 whose terminal is (meth) acrylated and has a weight average molecular weight of 2.3 × 10 4 to 5.0 × 10 4
Parts by weight; 20 to 60 parts by weight of an ethylene addition polymerizable monomer containing 45 to 95% by weight of a monofunctional monomer represented by the following general formula I and 5 to 15% by weight of a polyfunctional monomer represented by the following general formula II; formula I ... H 2 C = C ( R 1) -COO-R 2 formula II ... (H 2 C = C (R 1) -COO n X [R 1 in both formulas are H or CH 3, R 2 Is the molecular weight of 2.0 × 10 2 to 1.0 ×
Alcohol residue of 10 3, X represents a polyol residue having a molecular weight 60 to 5.0 × 10 2. n = 2-6. However, the molecular weight is the molecular weight in the case of a compound having no molecular weight distribution,
In the case of a compound having a molecular weight distribution, it means a number average molecular weight. 0.1 to 5.0% by weight of the photopolymerization initiator with respect to the total amount of +, and 0.01 to 1.0% by weight of the thermal polymerization inhibitor with respect to the total amount of +.
% By weight of a photosensitive resin composition for flexographic printing plates, wherein the cured product of the composition has notch crack resistance of 20 seconds or more. To provide.
なお、本発明における重量平均分子量若しくは数平均
分子量とは、GPC法を用いたポリスチレン換算平均分子
量であって、後述される条件下で測定されたものであ
る。The weight average molecular weight or number average molecular weight in the present invention is an average molecular weight in terms of polystyrene using a GPC method, and is measured under the conditions described later.
本発明で用いるプレポリマーの重量平均分子量は、2.
3×104〜5.0×104である。重量平均分子量が2.3×104を
下回ると、段ボール印刷に必要なshore A硬度で40度前
後の柔らかく、かつ引張強伸度の高い値版が得にくいう
え、耐ノッチ亀裂性の優れた版が得られない。又、耐ノ
ッチ亀裂性を良好なレベルに保とうとすると、エチレン
付加重合性モノマーの配合比に制限があるため、得られ
たレンジ粘度が、100ポイズ前後と低くなり、本発明の
主たる用途である版厚4〜8mmといった厚い版の成形が
装置上でコントロールできないという問題も生じる。一
方、重量平均分子量が5.0×104を上回るとエチレン付加
重合性モノマーの配合比に制限があるため、レンジ粘度
が高くなりすぎ、レンジ製造や製版時のレンジ取り扱い
が困難になり、且つ特別の加湿並びに取り扱い手段が必
要になるため、実用的な液状感光性樹脂を調整すること
ができない。The weight average molecular weight of the prepolymer used in the present invention is 2.
It is 3 × 10 4 to 5.0 × 10 4 . If the weight-average molecular weight is less than 2.3 × 10 4 , it is difficult to obtain a soft, high tensile strength and elongation plate with a shore A hardness required for corrugated cardboard printing of around 40 degrees, and a plate with excellent notch crack resistance is obtained. I can't get it. Also, if the notch cracking resistance is to be kept at a favorable level, the range of the obtained range viscosity is as low as about 100 poise because there is a limitation on the blending ratio of the ethylene addition polymerizable monomer, which is the main use of the present invention. There is also a problem that molding of a thick plate having a plate thickness of 4 to 8 mm cannot be controlled on the apparatus. On the other hand, if the weight average molecular weight exceeds 5.0 × 10 4 , there is a limitation on the blending ratio of the ethylene addition polymerizable monomer, so that the range viscosity becomes too high, and it becomes difficult to handle the range during range production and plate making, and special Since humidification and handling means are required, a practical liquid photosensitive resin cannot be prepared.
なお、レンジの諸物性バランスのとりやすさから云え
ば、2.5×104〜4.0×104の範囲にあるのがより好まし
い。In addition, from the standpoint of easy balance of various physical properties of the range, it is more preferable that the range be 2.5 × 10 4 to 4.0 × 10 4 .
本発明で用いるプレポリマーのセグメントとして用い
られるポリエーテルジオール、ポリエステルジオールは
公知のものが使用できる。これらのジオールとしては主
鎖が飽和結合で成っているものが、柔軟で強靭な版を得
るために好ましい。Known polyether diols and polyester diols used as segments of the prepolymer used in the present invention can be used. As these diols, those having a main chain composed of saturated bonds are preferable in order to obtain a flexible and tough plate.
即ちそのようなポリエーテルジオールとしては、例え
ばポリオキシエチレングリコール(PEG)、ポリオキシ
プロピレングリコール(PPG)、ポリオキシエチレン−
プロピレングリコールランダム又はブロック共重合体、
ポリオキシテトラエチレングリコール(PTMG)、ポリオ
キシエチレン−テトラエチレングリコールランダム又は
ブロック共重合体、ポリオキシプロピレン−テトラエチ
レングリコールランダム又はブロック共重合体などが挙
げられる。That is, examples of such polyether diols include polyoxyethylene glycol (PEG), polyoxypropylene glycol (PPG), and polyoxyethylene glycol.
Propylene glycol random or block copolymer,
Examples thereof include polyoxytetraethylene glycol (PTMG), polyoxyethylene-tetraethylene glycol random or block copolymer, and polyoxypropylene-tetraethylene glycol random or block copolymer.
一方、ポリエステルジオールとしては、飽和ジカルボ
ン酸とアルキレングリコール又はオキシアルキレングリ
コールとを縮合したポリエステルジオール、例えばポリ
エチレンアジペートジオール、ポリジエチレングリコー
ルアジペートジオール、ポリブチレンアジペートジオー
ル、ポリ−1,6−ヘキサングリコールアジペートジオー
ル、ポリネオペンチルグリコールアジペートジオール、
ポリプロピレンアジペートジオールなどが挙げられる。
また、例えばβ−プロピオラクトン及びその置換体、δ
−バレロラクトン及びその置換体、ε−カプロラクトン
及びその置換体などの五員環、六員環、七員環あるいは
それ以上のラクトンを開環重合したラクトン系ポリエス
テルジオールも用いることができるが、そのラクトン系
ポリステルジオールの中では、入手しやすさの点からε
−カプロラクトンから得られたカプロラクトンポリエス
テルジオールが好適である。On the other hand, as the polyester diol, a polyester diol obtained by condensing a saturated dicarboxylic acid and an alkylene glycol or an oxyalkylene glycol, for example, polyethylene adipate diol, polydiethylene glycol adipate diol, polybutylene adipate diol, poly-1,6-hexane glycol adipate diol, Polyneopentyl glycol adipate diol,
And polypropylene adipate diol.
Further, for example, β-propiolactone and its substituted product, δ
-Valerolactone and a substituted product thereof, a lactone-based polyester diol obtained by ring-opening polymerization of a 5-membered ring, a 6-membered ring, a 7-membered ring or a more lactone such as ε-caprolactone and a substituted product thereof can also be used. Among lactone-based polyester diols, ε is preferred from the viewpoint of availability.
-Caprolactone polyesterdiol obtained from caprolactone is preferred.
本発明に用いられる上記のジオールの分子量は重量平
均分子量で1.0×103以上のものがよく、好ましくは、1.
5×103以上である。1.0×103未満だとウレタン結合濃度
が高くなり、柔軟な版を得るのが困難になる。上限は、
プレポリマー分子量の1/2以下であればよい。The molecular weight of the diol used in the present invention is preferably not less than 1.0 × 10 3 in weight average molecular weight, and is preferably 1.
5 × 10 3 or more. When it is less than 1.0 × 10 3 , the urethane bond concentration becomes high, and it becomes difficult to obtain a flexible plate. The upper limit is
It suffices if it is 1/2 or less of the prepolymer molecular weight.
なお、分子量は数平均分子量ではなく、重量平均分子
量で規定した上記の範囲のものを使用することが重要で
ある。その理由は確認されてはいないが、耐ノッチ亀裂
性を左右するのはポリマー中の高分子量物の分布が影響
しているためと思われる。It is important that the molecular weight is not in the number average molecular weight but in the above range defined by the weight average molecular weight. Although the reason has not been confirmed, it is considered that the notch cracking resistance is affected by the distribution of high molecular weight substances in the polymer.
又、ポリエーテルジオールとポリエステルジオールの
モル比は1/2〜2/1の範囲である。この比率が1/2より小
さくなると組成物にしたとき、その硬化物のゴム的な反
発弾性特性が低下し、特に高速のフレキソ印刷には不向
きになる。またこの比率が2/1より大きくなれば本発明
の目的である耐ノッチ亀裂性が低下し実用上問題となる
ケースが発生する。The molar ratio between the polyether diol and the polyester diol is in the range of 1/2 to 2/1. When this ratio is less than 1/2, when the composition is made into a composition, the rubbery rebound resilience of the cured product is reduced, which makes the composition unsuitable especially for high-speed flexographic printing. If the ratio is more than 2/1, the notch cracking resistance, which is the object of the present invention, may be reduced, which may cause a practical problem.
次にジオールの鎖延長剤として使用されるジイソシア
ナートは公知のものが使用される。具体的には、以下に
例示する化合物が使用できるが、版の黄変化を避けたい
場合は非芳香族系のジイソシアナートを使用することが
好ましい。Next, known diisocyanates used as chain extenders for diols are used. Specifically, the following compounds can be used, but when it is desired to avoid yellowing of the plate, it is preferable to use a non-aromatic diisocyanate.
即ち、本発明で用いられるジイソシアナートとして
は、例えばトリレンジイソシアナート(2,4−TDI、2,6
−TDI、2,4−TDI/2,6−TDI混合品)、メチレンビスジイ
ソシアナート(MDI)、1,5−ナフタレンジイソシアナー
ト(NDI)、トリジンジイソシアナート(TODI)及びこ
れらの水素添加タイプ、ヘキサメイレンジイソシアナー
ト(HMDI)、イソホロンジイソシアナート(IPDI)、p
−フェニレンジイソシアナート、トランスシクロヘキサ
ンジイソシアナート、キシレンジイソシアナート、トリ
メチルヘキサメチレンジイソシアナート(TMDI)などが
挙げられる。これらのジイソシアナートの中で、入手の
容易さやコストの点から、通常TDI,MDI,HMDI及びIPDIが
好ましく用いられる。また、形成されるレリーフ体の黄
変を嫌う場合には、例えばHMDI,IPDI,水素化TDI,水素化
MDIなどを用いることが好ましい。That is, as the diisocyanate used in the present invention, for example, tolylene diisocyanate (2,4-TDI, 2,6
-TDI, 2,4-TDI / 2,6-TDI mixture), methylenebisdiisocyanate (MDI), 1,5-naphthalenediisocyanate (NDI), tolidine diisocyanate (TODI) and hydrogens thereof Addition type, hexamylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), p
-Phenylene diisocyanate, transcyclohexane diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI) and the like. Among these diisocyanates, TDI, MDI, HMDI and IPDI are usually preferably used from the viewpoint of availability and cost. In addition, when discoloration of the formed relief body is disliked, for example, HMDI, IPDI, hydrogenated TDI, hydrogenated
It is preferable to use MDI or the like.
プレポリマーの両末端に(メタ)アクリル基を導入す
るのも公知の方法で容易に行なうことができる。例え
ば、イソシアナート末端のウレタン化物に水酸基を有す
る(メタ)アクリレート化合物を付加させる方法、或い
は、水酸基末端のウレタン化物とカルボン酸又はその酸
無水物もしくはその酸塩化物を有する(メタ)アクリレ
ート若しくは(メタ)アクリル酸を反応させる方法、或
いは特公昭55−13017号に開示されているような(メ
タ)アクリル基含有イソシアナート化合物とを反応させ
る方法が例示できる。なお、これらの反応に使用される
(メタ)アクリレート化合物も公知のものを使用すれば
よい。Introduction of (meth) acrylic groups at both ends of the prepolymer can be easily performed by a known method. For example, a method of adding a (meth) acrylate compound having a hydroxyl group to a urethane compound at an isocyanate terminal, or a (meth) acrylate having a urethane compound at a hydroxyl group and a carboxylic acid or an acid anhydride or an acid chloride thereof or ( Examples thereof include a method of reacting (meth) acrylic acid and a method of reacting with a (meth) acrylic group-containing isocyanate compound as disclosed in JP-B-55-13017. In addition, what is necessary is just to use a well-known thing also as a (meth) acrylate compound used for these reactions.
即ち、例えばヒドロキシル基などの活性水素をもつ官
能基を含有し、かつエチレン型付加重合性不飽和基を有
する(メタ)アクリレート化合物としては、2−ヒドロ
キシエチル(メタ)アクリレート、2−ヒドロキシプロ
ピル(メタ)アクリレート、ポリオキシプロピレングリ
コールモノ(メタ)アクリレート(n300〜1000)、ポ
リオキシエチレングリコールモノ(メタ)アクリレート
(n300〜1000)等があげられる。That is, examples of (meth) acrylate compounds containing a functional group having active hydrogen such as a hydroxyl group and having an ethylene-type addition-polymerizable unsaturated group include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl ( (Meth) acrylate, polyoxypropylene glycol mono (meth) acrylate (n300 to 1000), polyoxyethylene glycol mono (meth) acrylate (n300 to 1000) and the like.
本発明において使用されるエチレン付加重合性モノマ
ーの内、下記一般式I及びIIで特定されたモノマーは、
本発明に於て耐ノッチ亀裂性向上と柔軟な特性の双方を
満足させるのに必須の成分である。Among the ethylene addition polymerizable monomers used in the present invention, the monomers specified by the following general formulas I and II are:
In the present invention, it is an essential component for satisfying both the improvement of notch crack resistance and the soft property.
一般式I… H2C=C(R1)−COO−R2 一般式II… (H2C=C(R1)−COOnX 〔両式中のR1はH又はCH3、R2は分子量2.0×102〜1.0×
103のアルコール残基、Xは分子量60〜5.0×102のポリ
オール残基を表わす。n=2〜6である。但し、上記分
子量は分子量分布を有さない化合物の場合は分子量を、
又分子量分布を有する化合物の場合は数平均分子量を意
味する。〕 一般式Iで示されるR2の具体例としてはPEG,PPG,PTMG
といったポリオキシアルキレングリコールから片末端の
水酸基を除いた残基、これらのモノアルキル(炭素数10
以内)若しくはモノアリル(炭素数10以内)エーテルか
ら片末端の水酸基を除いた残基、ステアリル、といった
長鎖アルコールから水酸基を除いた残基を例示できる。
この中でも、前二者のR2を有するモノマーが一般式Iの
モノマー全量の1/2以上配合されているのが、耐ノッチ
亀裂性向上の点から好ましい。R2の分子量が上記下限よ
り下回ると版の柔軟性付与が難しくなるので好ましく、
また上記上限を上回ると組成物の粘度が高くなり好まし
くない。General formula I ... H 2 C = C ( R 1) -COO-R 2 formula II ... (H 2 C = C (R 1) -COO n X [R 1 in both formulas are H or CH 3, R 2 is a molecular weight of 2.0 × 10 2 to 1.0 ×
Alcohol residue of 10 3, X represents a polyol residue having a molecular weight 60 to 5.0 × 10 2. n = 2-6. However, the molecular weight is the molecular weight in the case of a compound having no molecular weight distribution,
In the case of a compound having a molecular weight distribution, it means a number average molecular weight. Specific examples of R 2 represented by the general formula I include PEG, PPG, PTMG
Monooxy (residues having 10 carbon atoms), such as polyoxyalkylene glycols, in which the hydroxyl groups at one end have been removed.
) Or monoallyl (within 10 carbon atoms) ether and a residue obtained by removing a hydroxyl group from a long-chain alcohol such as stearyl.
Among these, it is preferable that the former two monomers having R 2 are mixed in at least 1/2 of the total amount of the monomers of the general formula I from the viewpoint of improving notch cracking resistance. When the molecular weight of R 2 is lower than the lower limit, it is difficult to impart flexibility to the plate, which is preferable.
On the other hand, if it exceeds the above upper limit, the viscosity of the composition becomes undesirably high.
一般式IIに示される多官能モノマーのXの具体例とし
ては、次に示すポリオールから2つ以上の水酸基を除い
た残基が例示できる。1,3−ブチレングリコール、1,4−
ブチレングリコール、1,6−ヘキサンジオール、ネオペ
ンチルグリコール、ジエチレングリコール、トリエチレ
ングリコール、テトラエチレングリコール、数平均分子
量5.0×102以下のポリオキシエチレングリコール、ポリ
オキシプロピレングリコール、2,2−ビス〔4−(ヒド
ロキシエトキシ)フェニル〕プロパン、2,2−ビス〔4
−(ヒドロキシジエトキシ)フェニル〕プロパン、数平
均分子量5.0×102以下の2,2−ビス〔4−(ヒドロキシ
ポリエトキシ)フェニル〕プロパン、トリメチロールプ
ロパン、テトラメチロール、ペンタエリスリトール、ビ
スンフェノールAとエチレングリコール若しくはプロピ
レングリコールとの共重合体(数平均分子量5.0×102以
下)、トリス(ヒドロキシエチル)イソシアヌレート、
ネオペンチルグリコール変性トリメチロールプロパン等
である。Xの分子量が上記下限より下回ると耐ノッチ亀
裂性が却って低下する傾向にあり、好ましくない。また
上記上限を上回るとやはり耐ノッチ亀裂性が低下しはじ
め、さらに版の引張強度を高く保つのが難しくなり好ま
しくない。この中でもnの数が3〜4程度の多官能モノ
マーを単独若しくはnが2のモノマーと併用するのが耐
ノッチ亀裂性の向上の点においてより好ましい。Specific examples of X of the polyfunctional monomer represented by the general formula II include a residue obtained by removing two or more hydroxyl groups from the following polyol. 1,3-butylene glycol, 1,4-
Butylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyoxyethylene glycol having a number average molecular weight of 5.0 × 10 2 or less, polyoxypropylene glycol, 2,2-bis [4 -(Hydroxyethoxy) phenyl] propane, 2,2-bis [4
-(Hydroxydiethoxy) phenyl] propane, 2,2-bis [4- (hydroxypolyethoxy) phenyl] propane having a number average molecular weight of 5.0 × 10 2 or less, trimethylolpropane, tetramethylol, pentaerythritol, bisphenol A With ethylene glycol or propylene glycol (number average molecular weight 5.0 × 10 2 or less), tris (hydroxyethyl) isocyanurate,
And neopentyl glycol-modified trimethylolpropane. If the molecular weight of X is less than the above lower limit, the notch crack resistance tends to decrease rather, which is not preferable. If the upper limit is exceeded, the notch cracking resistance starts to decrease, and it is difficult to maintain a high tensile strength of the plate, which is not preferable. Among them, it is more preferable to use a polyfunctional monomer having n of about 3 to 4 alone or in combination with a monomer having n of 2 from the viewpoint of improving notch cracking resistance.
一般式I,IIとともに用いられる他のエチレン付加重合
性モノマーとしては公知の各種モノマーを使用すること
ができる。これらの具体例は従来技術の項で記した公知
文献の他、例えば、山下晋三他編,「架橋剤ハンドブッ
ク」大成社(1981),井本稔他著,「UV・EB硬化技術」
総合技術センター(1982),下等清視著「紫外線硬化シ
ステム」総合技術センター(1989)等の成書に記載され
ている。As the other ethylene addition polymerizable monomer used together with the general formulas I and II, various known monomers can be used. Examples of these are known literature described in the section of the prior art, for example, Shinzo Yamashita et al., "Crosslinking Agent Handbook" Taiseisha (1981), Minoru Imoto et al., "UV / EB curing technology"
It is described in such books as the General Technology Center (1982) and Kiyomi Shimogami's "Ultraviolet Curing System" General Technology Center (1989).
例えば、アクリル酸やメタクリル酸などの不飽和カル
ボン酸又はそのエステル、倒えばアルキル−、シクロア
ルキル−、ハロゲン化アルキル−、アルコキシアルキル
−、ヒドロキシアルキル−、ジアルキルアミノアルキル
−、テトラヒドロフルフリル−、アリル−、グリシジル
−、ベンジル−、フェノキシ−アクリレート及びメアク
リレート、アルキレングリコール、ポリオキシアルキレ
ングリコールのモノ又はジアクリレート及びメタクリレ
ート、トリメチロールプロパントリアクリレート及びメ
タクリレート、ペンタエリトリットテトラアクリレート
及びメタクリレートなど、アクリルアミド、メタクリル
アミド又はその誘導体、例えばアルキル基やヒドロキシ
アルキル基でN−置換又はN,N′−置換したアクリルア
ミド及びメタクリルアミド、ジアセトンアクリルアミド
及びメタクリルアミド、N,N′−アルキレンビスアクリ
ルアミド及びメタクリルアミドなど、アリル化合物、例
えばアリルアルコール、アリルイソシアネート、ジアリ
ルフタレート、トリアリルシアヌレートなど、マレイン
酸、無水マレイン酸、フマル酸又はそのエステル、例え
ばアルキル、ハロゲン化アルキル、アルコキシアルキル
のモノ又はジマルエート及びフマレートなど、その他の
不飽和化合物、例えばスチレン、ビニルトルエン、ジビ
ニルベンゼン、N−ビニルカルバゾール、N−ビニルピ
ロリドンなどが用いられる。For example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid or esters thereof, in other words, alkyl-, cycloalkyl-, halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, dialkylaminoalkyl-, tetrahydrofurfuryl-, allyl Acrylamide, methacrylic acid, such as-, glycidyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylene glycol, polyoxyalkylene glycol mono- or diacrylate and methacrylate, trimethylolpropane triacrylate and methacrylate, pentaerythritol tetraacrylate and methacrylate Amides or derivatives thereof, for example, acrylamide and methacrylyl N-substituted or N, N'-substituted with an alkyl group or a hydroxyalkyl group , Diacetone acrylamide and methacrylamide, N, N'-alkylenebisacrylamide and methacrylamide, allyl compounds such as allyl alcohol, allyl isocyanate, diallyl phthalate, triallyl cyanurate and the like, maleic acid, maleic anhydride, fumaric acid Alternatively, other unsaturated compounds such as mono- or dimalate and fumarate of alkyl, alkyl halide, alkoxyalkyl and the like, for example, styrene, vinyltoluene, divinylbenzene, N-vinylcarbazole, N-vinylpyrrolidone and the like are used.
また、レリーフ体の硬化収縮を問題にする場合には、
エチレン型付加重合性モノマーとして、例えばイソボニ
ルアクリレート又はメタクリレート、ノルボルニルアク
リレート又はメタクリレート、ジシクロペンテノキシエ
チルアクリレート又はメタクリレート、ジシクロペンテ
ノキシプロピルアクリレート又はメタクリレートなど、
ジエチレングリコールジシクロペンテニルモノエーテル
のアクリル酸エステル又はメタクリル酸エステル、ポリ
オキシエチレン若しくはポリプロピレングリコールジシ
クロペンテニルモノエーテルのアクリル酸エステル又は
メタクリル酸エステルなど、ジシクロペンテニルシンナ
メート、ジシクロペンテノキシエチルシンナメート等が
例示できる。In addition, when curing shrinkage of the relief body is a problem,
As the ethylene type addition polymerizable monomer, for example, isobornyl acrylate or methacrylate, norbornyl acrylate or methacrylate, dicyclopentenoxyethyl acrylate or methacrylate, dicyclopentenoxypropyl acrylate or methacrylate,
Dicyclopentenyl cinnamate, dicyclopentenyloxycinnamate, such as acrylate or methacrylate of diethylene glycol dicyclopentenyl monoether, acrylate or methacrylate of polyoxyethylene or polypropylene glycol dicyclopentenyl monoether Etc. can be exemplified.
プレポリマー100重量部に対し、それらのエチレン付
加重合性モノマーは20〜60重量部の範囲で使用されねば
ならない。20重量部を下回ると、組成物粘度が著しく高
くなり且つ強度物性が得にくくなる。一方、60重量部を
上回るとゴム弾性に乏しい物性になり、さらに耐ノッチ
亀裂性が低下することがあり、いずれも好ましくない。For 100 parts by weight of prepolymer, these ethylene addition polymerizable monomers must be used in the range of 20 to 60 parts by weight. If the amount is less than 20 parts by weight, the viscosity of the composition becomes extremely high, and it becomes difficult to obtain the strength physical properties. On the other hand, if it exceeds 60 parts by weight, the rubber elasticity becomes poor, and the notch cracking resistance may be further reduced.
エチレン付加重合性モノマーの選択にあたっては、光
硬化したときに硬化物が10℃以上の温度に置かれて実質
的に透明であることが必要である。硬化物が白濁すると
耐ノッチ亀裂性が急激に低下することがあるからであ
る。なお、この透明の程度は硬化物が着色剤や増感剤等
の添加物による可視光吸収を持たない波長領域で厚さ1m
mの試料片の透過率が80%以上であればよい。In selecting the ethylene addition-polymerizable monomer, it is necessary that the cured product be substantially transparent at a temperature of 10 ° C. or higher when photocured. This is because if the cured product becomes cloudy, the notch crack resistance may rapidly decrease. The degree of transparency is 1 m in the wavelength region where the cured product does not have visible light absorption due to additives such as colorants and sensitizers.
It suffices that the transmittance of the sample piece of m is 80% or more.
エチレン付加重合性モノマー中の一般式I,IIで示され
る特定のモノマーの使用比率は硬化物の柔軟性とゴム弾
性そして耐ノッチ亀裂性の点から前者は45〜95重量%で
あり、後者は5〜15重量%である。そのいずれが外れて
も本発明の目的を満足させることができない。特に一般
式IIの多官能モノマーは上限数値より多くなってはいけ
ない。なお、そのモノマーの特に好ましい使用範囲は、
5〜10wt%である。From the viewpoint of the flexibility, rubber elasticity and notch cracking resistance of the cured product, the former is 45 to 95% by weight, and the latter is 5 to 15% by weight. If any of them is off, the object of the present invention cannot be satisfied. In particular, the polyfunctional monomer of the general formula II must not exceed the upper limit. Incidentally, a particularly preferred use range of the monomer is,
5 to 10% by weight.
本発明で用いられる光重合開始剤としては、従来公知
の化合物の中から任意のものを選択して用いることがで
きる。このような光重合開始剤としては、例えばベンゾ
インやベンゾインエチルエーテル、ベンゾイン−n−プ
ロピルエーテル、ベンゾイン−イソプロピルエーテル、
ベンゾインイソブチル−エーテルなどのベンゾインアル
キルエーテル類、2,2−ジメトキシ−2−フェニルアセ
トフェノン、ベンゾフェノン、ベンジル、ジアセチル、
ジフェニルスルフィド、エオシン、チオニン、9,10−ア
ントラキノン、2−エチル−9,10−アントラキノンなど
が挙げられる。As the photopolymerization initiator used in the present invention, any one of conventionally known compounds can be selected and used. Examples of such a photopolymerization initiator include benzoin, benzoin ethyl ether, benzoin-n-propyl ether, benzoin-isopropyl ether,
Benzoin alkyl ethers such as benzoin isobutyl-ether, 2,2-dimethoxy-2-phenylacetophenone, benzophenone, benzyl, diacetyl,
Examples include diphenyl sulfide, eosin, thionine, 9,10-anthraquinone, and 2-ethyl-9,10-anthraquinone.
これらの光重合開始剤は、それぞれ単独で用いてもよ
いし、2種以上を組み合わせて用いてもよい。その含有
量は、前記プレポリマーとモノマーの全量に対し0.1〜
5重量%の範囲である。These photopolymerization initiators may be used alone or in combination of two or more. Its content is 0.1 to the total amount of the prepolymer and the monomer.
It is in the range of 5% by weight.
次に、本発明で用いられる熱重合禁止剤としては、特
に制限はなく、従来液状感光剤樹脂組成物で常用されて
いるものの中から任意に選択して用いることができる。
そのようなものとしては、例えばヒドロキノン、モノ第
三ブチルヒドロキノン、ベンゾキノン、2,5−ジフェニ
ル−p−ベンゾキノン、ピクリン酸、ジ−p−フルオロ
フェニルアミン、ジ−p−メトキシフェノール、2,6−
ジ第三ブチル−p−クレゾールなどを挙げることができ
る。これらの熱重合禁止剤は熱重合反応(暗反応)を防
止するためのものであり、従って該熱重合禁止剤の含有
量は、プレポリマーとモノマーとの全量に対し0.01〜1.
0重量%の範囲で選ばれる。Next, the thermal polymerization inhibitor used in the present invention is not particularly limited, and may be arbitrarily selected from those conventionally used in liquid photosensitive resin compositions.
Such include, for example, hydroquinone, mono-tert-butylhydroquinone, benzoquinone, 2,5-diphenyl-p-benzoquinone, picric acid, di-p-fluorophenylamine, di-p-methoxyphenol, 2,6-
Ditertiary butyl-p-cresol and the like can be mentioned. These thermal polymerization inhibitors are for preventing a thermal polymerization reaction (dark reaction), and therefore, the content of the thermal polymerization inhibitor is 0.01 to 1.1 with respect to the total amount of the prepolymer and the monomer.
It is selected in the range of 0% by weight.
本発明に於て分子量を規定するのに用いられるGPC法
によるポリスチレン換算平均分子量の測定条件は次の通
りである。The conditions for measuring the average molecular weight in terms of polystyrene by the GPC method used for defining the molecular weight in the present invention are as follows.
カラム:次のポリエチレンゲル カラムを使用し
た。TSK GEL GMHXL(7.8mm×300mm)2本。溶媒:TH
F(水の少量添加を行なわない)。流量:1.0ml/min
(補正を行なうこと)。試料濃度:0.5%以下。検量
線作成:濃度は試料濃度の約1/2程度。有効数字:二
桁で表示。GPC装置:高速GPC HLC−8020(東ソー株
式会社製)。検出器:RI,UV(254nm)。標準ポリス
チレン:分子量範囲は5.00×102〜1.26×106。Column: The following polyethylene gel column was used. Two TSK GEL GMHXL (7.8mm x 300mm). Solvent: TH
F (no small addition of water). Flow rate: 1.0ml / min
(Perform correction). Sample concentration: 0.5% or less. Calibration curve preparation: The concentration is about 1/2 of the sample concentration. Significant digits: Displayed in two digits. GPC device: High-speed GPC HLC-8020 (manufactured by Tosoh Corporation). Detector: RI, UV (254 nm). Standard polystyrene: The molecular weight range is 5.00 × 10 2 to 1.26 × 10 6 .
本発明の目的を達成するための必須の要件である耐ノ
ッチ亀裂性の測定方法は以下の通りである。The method for measuring notch crack resistance, which is an essential requirement for achieving the object of the present invention, is as follows.
第1図に示した構成で厚さ0.1mmのポリエステル基
材の支持体上に、試験に供する感光性樹脂を延展し支持
体込みの厚さを7mmに設定する。A photosensitive resin to be subjected to a test is extended on a polyester base support having a thickness of 0.1 mm in the configuration shown in FIG. 1 and the thickness including the support is set to 7 mm.
上下ガラスを介して両面から順次、ケミカルランプ
により所定の露光量に対するまで照射する。支持体側か
らは、ガラス越しの光源強度が約1mW/cm2で350mJ/cm2照
射し、他面からは、ガラス越しの光源強度が約1.5mW/cm
2で250mJ/cm2照射する。次にカバーフィルムをとり、さ
らにレリーフ側から約1200mJ/cm2ケミカルランプで照射
する。光源強度はオーク製作所製、UVメーター:UV−M01
を用い測定した(ケミカルランプの強度にはセンサーUV
−35を、殺菌線ランプにはセンサーUV−25を使用し
た)。Irradiation is sequentially performed from both sides through a glass upper and lower glass to a predetermined exposure amount by a chemical lamp. From the support side, the light source intensity through the glass was irradiated 350 mJ / cm 2 to about 1 mW / cm 2, from the other surface, the light source intensity through the glass of about 1.5 mW / cm
2 at 250 mJ / cm 2 irradiation. Next, the cover film is removed, and further irradiated from the relief side with a chemical lamp of about 1200 mJ / cm 2 . Light source intensity is manufactured by Oak Works, UV meter: UV-M01
(The intensity of the chemical lamp is measured by the sensor UV
−35, and a sterilization line lamp using a sensor UV-25).
こうして得られた7mm厚のベタ版を第2図に示した
サイズに切り取る。The solid plate having a thickness of 7 mm thus obtained is cut into the size shown in FIG.
第2図に示した寸法の線に沿ってナイフで深さ1+
/−0.3mmの切り筋を入れる。Knife depth 1+ along the line of dimensions shown in FIG.
/ Insert a 0.3 mm cut streak.
該切筋が外側になるように持ち、素早く第3図のよ
うに折り曲げ、生じた亀裂が支持体に到達するまでの時
間を秒単位で測定する。その測定を三回繰り返し、平均
値を求める(小数点以下四捨五入し、整数で表示)。The scissors are held outward and bent quickly as shown in FIG. 3, and the time until the resulting crack reaches the support is measured in seconds. The measurement is repeated three times, and the average value is obtained (rounded off to the nearest whole number and displayed as an integer).
こうして求められた亀裂成長に要する時間を試料の
耐ノッチ亀裂性として表わす。The time required for crack growth thus determined is expressed as the notch crack resistance of the sample.
以下、本発明を合成例、実施例、比較例で具体的に説
明する。Hereinafter, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples.
合成例−1 ポリエーテルジオールとしてPEG−PPG−PEG型のブロ
ックエーテルジオール(Mw<重量平均分子量を表わす、
以下同じ>=3.3×103、PPG/PEGモル比率=8/2)1モル
とポリエステルジオールとしてポリ(プロピレンアジペ
ート)エステルジオール(Mw=7.2×103)1モルと触媒
としてBTL 0.5grを反応容器に入れてよく混合した。そ
こにトリレンジイソシアネート(以下TDIと略記する、
2,4−体/2,6−体モル比率=4/1)2.4モル添加し、良く
撹拌してから外温を40度から80度に昇温し、イソシアネ
ート基の反応率が計算値に対し100%を少し越えたとこ
ろで、2−ヒドロキシプロピルメタクリレートとポリ
(オキシプロピレン)グリコールモノメタクリレート
(Mn<数平均分子量を表わす、以下同じ>=4.8×102)
とを各1モルずつ添加し良く撹拌した。赤外スペクトル
上でイソシアナートの特性吸収が認められなくなったと
ころで冷却を開始し、約40度付近になった時点で撹拌を
とめ、内容物を取り出した。このなかの過剰のビニル化
剤を除いたポリマー分をプレポリマーAとした。Synthesis Example-1 As a polyether diol, a block ether diol of PEG-PPG-PEG type (Mw <indicating a weight average molecular weight,
The same applies hereinafter> = 3.3 × 10 3 , 1 mol of PPG / PEG molar ratio = 8/2), 1 mol of poly (propylene adipate) ester diol (Mw = 7.2 × 10 3 ) as polyester diol and 0.5 gr of BTL as catalyst Mix well in a container. There is tolylene diisocyanate (hereinafter abbreviated as TDI,
2,4-form / 2,6-form molar ratio = 4/1) 2.4 mol was added, and the mixture was stirred well and the external temperature was raised from 40 ° C to 80 ° C. On the other hand, when it exceeds a little over 100%, 2-hydroxypropyl methacrylate and poly (oxypropylene) glycol monomethacrylate (Mn <representing the number average molecular weight; the same applies hereinafter) = 4.8 × 10 2 )
And 1 mol of each were added and stirred well. Cooling was started when the characteristic absorption of the isocyanate was no longer observed on the infrared spectrum, and when the temperature reached about 40 ° C., stirring was stopped and the contents were taken out. The polymer content from which the excess vinylating agent was removed was designated as prepolymer A.
ポリマー分を分取してそのMwを測定したところ3.2×1
04であった。このポリマー成分を化学分解したところポ
リエステルとポリエーテルとがポリマーセグメントとし
て所定の比率で一分子中にはいっていることがわかっ
た。When the polymer component was separated and its Mw was measured, it was 3.2 × 1
0 was 4 . When the polymer component was chemically decomposed, it was found that polyester and polyether were included in one molecule as a polymer segment at a predetermined ratio.
合成例−2 ポリエーテルジオールとしてポリ(オキシプロピレ
ン)グリコール(Mw=4.0×103)1モルとポリエステル
ジオールとしてポリ(プロピレンアジペート)エステル
ジオール(Mw=4.2×103)1モルと触媒としてBTL 0.5g
rとを反応容器に入れよく混合した。そこにTDI(2,4−
体/2,6−体モル比率=4/1)2.3モル添加し良く撹拌して
から、外温を40度から80度に昇温し、イソシアナート基
の反応率が計算値に対し100%を少し越えたところで、
2−ヒドロキシプロピルメタクリレートを2モル添加し
良く撹拌した。赤外スペクトル上でイソシアネートの特
性吸収が認められなくなったところで冷却を開始し、約
40度付近になった時点で撹拌をとめ内容物を取り出し
た。このなかの過剰のビニル化剤を除いたポリマー分を
プレポリマーB1とした。ポリマー分を分取してそのMwを
測定したところ、3.7×104であった。Synthesis Example-2 1 mol of poly (oxypropylene) glycol (Mw = 4.0 × 10 3 ) as polyether diol, 1 mol of poly (propylene adipate) ester diol (Mw = 4.2 × 10 3 ) as polyester diol, and BTL 0.5 as catalyst g
was placed in a reaction vessel and mixed well. There TDI (2,4-
(Formula / 2,6-form molar ratio = 4/1) 2.3 mol was added and stirred well, then the external temperature was raised from 40 ° C to 80 ° C, and the conversion of the isocyanate group was 100% of the calculated value. A little beyond
Two moles of 2-hydroxypropyl methacrylate were added and stirred well. Cooling was started when the characteristic absorption of isocyanate was no longer observed on the infrared spectrum,
When the temperature reached about 40 degrees, the stirring was stopped and the contents were taken out. The polymer content from which the excess vinylating agent was removed was designated as prepolymer B1. The polymer component was separated and its Mw was measured to be 3.7 × 10 4 .
合成例−3 ポリエーテルジオールとしてポリ(オキシプロピレ
ン)グリコール(Mw=4.0×103)0.7モルとポリエステ
ルジオールとしてポリ(プロピレンアジペート)エステ
ルジオール(Mw=4.2×103)1.3モルと触媒としてBTL
0.5grとを反応容器に入れよく混合した。そこにTDI(2,
4−体/2,6−体モル比率=4/1)2.3モル添加し、良く撹
拌してから外温を40度から80度に昇温し、イソシアナー
ト基の反応率が計算値に対し100%を少し越えたところ
で、2−ヒドロキシプロピルメタクリレートを2モル添
加し良く撹拌した。赤外スペクトル上でイソシアナート
の特性吸収が認められなくなったところで冷却をICし、
約40度付近になった時点で撹拌をとめ内容物を取り出し
た。このほかの過剰のビニル化剤を除いたポリマー分を
プレポリマーB2とした。ポリマー分を分取してそのMwを
測定したところ3.6×104であった。Synthesis Example-3 0.7 mol of poly (oxypropylene) glycol (Mw = 4.0 × 10 3 ) as polyether diol, 1.3 mol of poly (propylene adipate) ester diol (Mw = 4.2 × 10 3 ) as polyester diol, and BTL as catalyst
0.5 gr was put into a reaction vessel and mixed well. There TDI (2,
4-mol / 2,6-mol ratio = 4/1) 2.3 mol was added, and the mixture was stirred well and the external temperature was raised from 40 ° to 80 °, and the reaction rate of the isocyanate group was calculated with respect to the calculated value. At a little over 100%, 2 mol of 2-hydroxypropyl methacrylate was added and stirred well. When the characteristic absorption of isocyanate is no longer recognized on the infrared spectrum, cooling IC is performed,
When the temperature reached about 40 degrees, the stirring was stopped and the contents were taken out. The polymer content excluding the other excess vinylating agent was designated as prepolymer B2. The polymer component was separated and its Mw was measured to be 3.6 × 10 4 .
合成例−4 合成例−3において、ポリエーテルジオールとポリエ
ステルジオールの仕込みモルを1.3モルと0.7モルに変更
する以外は合成例−3と同様に合成してプレポリマーB3
を得た。ポリマー分を分取しそのMwを求めたところ、Mw
=3.9×104であった。Synthesis Example-4 A prepolymer B3 was synthesized in the same manner as in Synthesis Example-3 except that the charged moles of the polyether diol and the polyester diol were changed to 1.3 mol and 0.7 mol.
I got When the polymer component was collected and its Mw was determined, Mw was obtained.
= 3.9 × 10 4 .
比較合成例−1 合成例−3において、ポリエーテルジオールを0.4モ
ル、ポリエステルジオールを1.6モル仕込んだ他は合成
例−3と同様に反応させ、プレポリマーCを得た。ポリ
マー分のMwは3.8×104であった。Comparative Synthesis Example-1 Prepolymer C was obtained in the same manner as in Synthesis Example-3 except that 0.4 mol of the polyether diol and 1.6 mol of the polyester diol were used. Mw of the polymer component was 3.8 × 10 4 .
比較合成例−2 合成例−3において、ポリエーテルジオールを1.6モ
ル、ポリエステルジオールを0.4モル仕込んだ他は合成
例−3と同様に反応させ、プレポリマーDを得た。ポリ
マー分のMwは3.7×104であった。Comparative Synthesis Example-2 A prepolymer D was obtained in the same manner as in Synthesis Example-3 except that 1.6 mol of the polyether diol and 0.4 mol of the polyester diol were used. Mw of the polymer component was 3.7 × 10 4 .
合成例−5 ポリ(オキシエチレン)グリコール(Mw=3.0×103)
1モルと合成例−1で用いたポリエステルジオール1モ
ルとを仕込み、さらにBTL 0.4grを滴下し良く混合撹拌
した。次いで、ヘキサメチレンジイソシアナート(HMDI
と略記する)2.2モルを撹拌しながら一度に仕込んだ。
熱媒温度を50度から80度に昇温し、7時間反応させた。
次いで反応容器の中に、ポリ(オキシプロピレン)グリ
コールモノメタクリレート(Mn=6.0×102)を0.5モル
仕込み、赤外スペクトル上にλNCOの吸収が認められな
くなるまで反応させ、プレポリマーEを得た。ポリマー
分のMwは4.7×104であった。Synthesis Example-5 Poly (oxyethylene) glycol (Mw = 3.0 × 10 3 )
1 mol and 1 mol of the polyester diol used in Synthesis Example 1 were charged, and 0.4 g of BTL was added dropwise, followed by thorough mixing and stirring. Then, hexamethylene diisocyanate (HMDI
2.2 mol) were charged all at once with stirring.
The temperature of the heating medium was raised from 50 degrees to 80 degrees, and the reaction was performed for 7 hours.
Then, 0.5 mol of poly (oxypropylene) glycol monomethacrylate (Mn = 6.0 × 10 2 ) was charged into the reaction vessel, and reacted until absorption of λ NCO was not recognized on the infrared spectrum to obtain prepolymer E. Was. Mw of the polymer component was 4.7 × 10 4 .
比較合成例−3 合成例−1で用いたポリエーテルジオール2モルに対
し、TDI4モルを加え両末端がイソシアナートのアダクト
を合成した。次いでこの中に、合成例−1で用いたポリ
エステルジオール1モルを仕込み、4時間反応させエス
テル・エーテルブロックポリウレタンを合成した。次い
で、ポリ(オキシプロピレン)グリコールモノメタクリ
レート(Mn=6.0×102)とBTL 0.3grとを添加し、熱媒
温度70度から80度に昇温し、赤外スペクトル上でイソシ
アナート基の特性吸収が見られなくなるまで反応させ、
プレポリマーFを得た。このポリマーのMwは1.7×104で
あった。Comparative Synthesis Example-3 To 2 mol of the polyether diol used in Synthesis Example-1, 4 mol of TDI was added to synthesize an adduct having both ends isocyanate. Next, 1 mol of the polyester diol used in Synthesis Example 1 was charged therein and reacted for 4 hours to synthesize an ester / ether block polyurethane. Next, poly (oxypropylene) glycol monomethacrylate (Mn = 6.0 × 10 2 ) and BTL 0.3 gr were added, and the temperature of the heating medium was increased from 70 ° C. to 80 ° C., and the characteristics of the isocyanate group on the infrared spectrum were measured. React until no absorption is seen,
Prepolymer F was obtained. The Mw of this polymer was 1.7 × 10 4 .
実施例、比較例 上記合成例、比較合成例で合成したプレポリマーを用
い表−1に示す感光性組成物を調製した。Examples and Comparative Examples Using the prepolymers synthesized in the above Synthesis Examples and Comparative Synthesis Examples, photosensitive compositions shown in Table 1 were prepared.
得られた組成物の評価は次のようにて行なった。な
お、断りのない限り測定は20度で行なった。The obtained composition was evaluated as follows. In addition, the measurement was performed at 20 degrees unless otherwise noted.
粘度測定:B型回転粘度計使用。 Viscosity measurement: B type rotational viscometer used.
硬度、剛球落下式反発弾性測定:厚さが6mmのベタ
版を両面からの紫外線照射によって作成した(照射両:
片面1400mJ/cm2を両サイドから行なった。光源強度計は
前述の測定器を使用した。)硬度計はショアーAタイプ
を使用した。反発弾性測定は、金属定盤の上に試料を浮
かないように置き、試料より30cmの高さから直径10.5mm
の鋼球を自然落下させ跳ね返った高さを測定し戻り率を
もって反発弾性とした。Hardness, hard ball drop type rebound resilience measurement: A solid plate with a thickness of 6 mm was prepared by irradiating ultraviolet rays from both sides (irradiation:
1400 mJ / cm 2 was applied from both sides. The light source intensity meter used the measuring device described above. ) A Shore A type hardness meter was used. For rebound resilience measurement, place the sample on a metal surface plate so that it does not float, and measure the height from 30 cm above the sample to 10.5 mm in diameter.
The steel ball was dropped naturally and the height at which it rebounded was measured.
引張物性:JIS K6301に準拠した。試料調製は次のよ
うにして行なった。1mm厚のスペーサーを用い、片面か
ら1400mJ/cm2の光量(光源はケミカルランプ)を順次其
々の面から照射し厚さ約1mmの硬化試料を作成した。Tensile properties: Based on JIS K6301. The sample was prepared as follows. Using a 1 mm thick spacer, a light amount of 1400 mJ / cm 2 (light source was a chemical lamp) was sequentially irradiated from each side from one side to prepare a cured sample having a thickness of about 1 mm.
耐ノッチ亀裂性:前述の寸法で実施 以上の方法で測定した結果を表−2にまとめた。 Notch crack resistance: Implemented with the dimensions described above The results measured by the above method are summarized in Table-2.
応 用 例 実施例、比較例で得られた感光性樹脂組成物を用い、
旭化成工業株式会社製APR製版装置「AJF」型を使用し、
全厚約7mm、バック析出厚み(支持体込み)約1mm、マス
ク厚み(支持体込み)約4.5mmの印刷版を製版した。こ
れらの版をキャリアーシートを介して段ボール印刷機に
装着し段ボール印刷を行なった。その結果を表−3に示
した。表−3に示されている通り、従来の耐ノッチ亀裂
性の劣る版は引張物性が同じ程度でも耐刷性や象限操作
時の傷の走りの点でおとり、本発明の版はこれらの点で
優れていることが明らかである。 Application Examples Using the photosensitive resin compositions obtained in Examples and Comparative Examples,
Using Asahi Kasei Kogyo's APR plate making machine `` AJF '' type,
A printing plate having a total thickness of about 7 mm, a back deposition thickness (including the support) of about 1 mm, and a mask thickness (including the support) of about 4.5 mm was prepared. These plates were mounted on a cardboard printing machine via a carrier sheet, and cardboard printing was performed. The results are shown in Table-3. As shown in Table 3, the conventional plate having poor notch cracking resistance is detracted in terms of printing durability and scratch running during operation of a quadrant even if the tensile properties are the same, and the plate of the present invention has these points. It is clear that it is excellent.
〔発明の効果〕 以上の説明で明らかなように、段ボール印刷用版等の
フレキソ印刷版の耐刷版や版操作時の耐久性が、従来技
術に比べ、本発明では大幅に改良された。その結果、版
としての寿命が長くなり、印刷作業性及び版取り扱い性
が改善されるという効果が得られた。 [Effects of the Invention] As is clear from the above description, the present invention has greatly improved the printing plate durability and durability during plate operation of a flexographic printing plate such as a cardboard printing plate as compared with the prior art. As a result, the effect that the life as a plate was prolonged and the printing workability and the plate handling property were improved was obtained.
第1図は耐ノッチ亀裂性の測定に用いる試料の調製を示
す概略の断面図であり、第2図は測定用試料片の斜視図
であり、第3図は該試料片の測定時の状況を示す該酪側
面図である。FIG. 1 is a schematic sectional view showing the preparation of a sample used for measuring notch crack resistance, FIG. 2 is a perspective view of a sample for measurement, and FIG. FIG.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭49−133104(JP,A) 特開 昭49−109105(JP,A) 特開 昭50−19504(JP,A) 特開 昭50−108388(JP,A) 特開 平1−100535(JP,A) (58)調査した分野(Int.Cl.6,DB名) G03F 7/027 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-133104 (JP, A) JP-A-49-109105 (JP, A) JP-A-50-19504 (JP, A) JP-A 50-108 108388 (JP, A) JP-A-1-100535 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) G03F 7/027
Claims (1)
以上のポリエーテルジオールとポリエステルジオールを
セグメントとし、該両ジオールのモル比が1/2〜2/1の範
囲にあり、且つその両末端が(メタ)アクリル化されて
いて、重量平均分子量が2.3×104〜5.0×104であるプレ
ポリマー100重量部と、 下記一般式Iで示される単官能モノマー45〜95重量
%と一般式IIで示される多官能モノマー5〜15重量%を
含有するエチレン付加重合性モノマー20〜60重量部と、 一般式I… H2C=C(R1)−COO−R2 一般式II… (H2C=C(R1)−COOnx 〔両式中のR1はH又はCH3、R2は分子量2.0×102〜1.0×
103のアルコール残基、Xは分子量60〜5.0×102のポリ
オール残基を表わす。n=2〜6である。但し、上記分
子量は分子量分布を有さない化合物の場合は分子量を、
又分子量分布を有する化合物の場合は数平均分子量を意
味する。〕 光重合開始剤を上記+の全量に対し0.1〜5.0重
量%と、 熱重合禁止剤を上記+の全量に対し0.01〜1.0
重量%とを必須成分とする感光性樹脂組成物であって、 該組成物の硬化物の耐ノッチ亀裂性が20秒以上であ
ることを特徴とするフレキソ印刷版用液状感光性樹脂組
成物。The weight average molecular weight is 1.0 × 10 3 each.
The above polyether diol and polyester diol are used as segments, the molar ratio of both diols is in the range of 1/2 to 2/1, and both ends are (meth) acrylated, and the weight average molecular weight is 2.3 It contains 100 parts by weight of a prepolymer of × 10 4 to 5.0 × 10 4 , 45 to 95% by weight of a monofunctional monomer represented by the following general formula I, and 5 to 15% by weight of a polyfunctional monomer represented by a general formula II. ethylene addition polymerizable monomer 20 to 60 parts by weight, the general formula I ... H 2 C = C ( R 1) -COO-R 2 formula II ... (H 2 C = C (R 1) -COO n x [both In the formula, R 1 is H or CH 3 , and R 2 has a molecular weight of 2.0 × 10 2 to 1.0 ×
Alcohol residue of 10 3, X represents a polyol residue having a molecular weight 60 to 5.0 × 10 2. n = 2-6. However, the molecular weight is the molecular weight in the case of a compound having no molecular weight distribution,
In the case of a compound having a molecular weight distribution, it means a number average molecular weight. 0.1 to 5.0% by weight of the photopolymerization initiator with respect to the total amount of +, and 0.01 to 1.0% by weight of the thermal polymerization inhibitor with respect to the total amount of +.
% By weight of a photosensitive resin composition for a flexographic printing plate, wherein a cured product of the composition has notch crack resistance of 20 seconds or more.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2207975A JP2944164B2 (en) | 1990-08-08 | 1990-08-08 | Liquid photosensitive resin composition for flexographic printing plates |
FR9110041A FR2665774A1 (en) | 1990-08-08 | 1991-08-07 | Liquid composition based on a photosetting resin for the production of a flexographic printing plate |
ES09101857A ES2034890B1 (en) | 1990-08-08 | 1991-08-08 | "LIQUID COMPOSITE OF PHOTOCURABLE RESIN FOR THE MANUFACTURE OF PLATES FOR FLEXOGRAPHIC PRINTING AND ITS MANUFACTURING PROCEDURE". |
BE9100731A BE1004496A5 (en) | 1990-08-08 | 1991-08-08 | Liquid composition containing an photocurable resin for producing printing plate flexographic. |
ITMI912228A IT1251162B (en) | 1990-08-08 | 1991-08-08 | PHOTO-HARDENABLE RESIN LIQUID COMPOSITION TO PRODUCE A PLATE FOR FLEXOGRAPHIC PRINTING |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2207975A JP2944164B2 (en) | 1990-08-08 | 1990-08-08 | Liquid photosensitive resin composition for flexographic printing plates |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0495959A JPH0495959A (en) | 1992-03-27 |
JP2944164B2 true JP2944164B2 (en) | 1999-08-30 |
Family
ID=16548607
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2207975A Expired - Lifetime JP2944164B2 (en) | 1990-08-08 | 1990-08-08 | Liquid photosensitive resin composition for flexographic printing plates |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP2944164B2 (en) |
BE (1) | BE1004496A5 (en) |
ES (1) | ES2034890B1 (en) |
FR (1) | FR2665774A1 (en) |
IT (1) | IT1251162B (en) |
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GB2283244B (en) * | 1993-06-18 | 1997-08-13 | Asahi Chemical Ind | A photosensitive resin composition used for a corrugated board printing plate |
AU684151B2 (en) * | 1994-03-04 | 1997-12-04 | Asahi Kasei Kogyo Kabushiki Kaisha | Liquid photosensitive resin composition for forming relief structures |
JP5164982B2 (en) | 2007-06-18 | 2013-03-21 | 旭化成イーマテリアルズ株式会社 | Photosensitive resin composition, flexographic printing plate, and method for producing flexographic printing plate |
JP5466689B2 (en) * | 2011-11-30 | 2014-04-09 | 富士フイルム株式会社 | Resin composition for flexographic printing plate, flexographic printing plate precursor and production method thereof, and flexographic printing plate and production method thereof |
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NL129237C (en) * | 1965-03-11 | |||
JPS53143669A (en) * | 1977-05-23 | 1978-12-14 | Asahi Chem Ind Co Ltd | Elimination of surface tuckiness of radically-polymerizable resin cured product |
ZA851456B (en) * | 1984-03-06 | 1985-10-30 | Uniroyal Inc | Tapered di-block copolymer photopolymerizable composition |
GB2179360B (en) * | 1985-08-12 | 1989-08-02 | Uniroyal Plastics | Aqueous developable photopolymeric compositions containing chlorosulfonated polyethylene |
JPH07113767B2 (en) * | 1986-10-02 | 1995-12-06 | 旭化成工業株式会社 | Photosensitive resin printing plate for step ball printing |
JP2653458B2 (en) * | 1988-03-26 | 1997-09-17 | 旭化成工業株式会社 | Photosensitive resin composition for letterpress printing plates |
EP0348063B1 (en) * | 1988-06-10 | 1993-05-26 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic elastomer and photosensitive resin composition based thereon, and printing plate precursor comprising the composition |
EP0356954A3 (en) * | 1988-08-30 | 1991-05-08 | E.I. Du Pont De Nemours And Company | A plasticized polyvinyl alcohol release layer for a flexographic printing plate |
CA2045292A1 (en) * | 1990-07-26 | 1992-01-27 | John A. Martens | Flexographic printing plate compositions |
-
1990
- 1990-08-08 JP JP2207975A patent/JP2944164B2/en not_active Expired - Lifetime
-
1991
- 1991-08-07 FR FR9110041A patent/FR2665774A1/en active Granted
- 1991-08-08 ES ES09101857A patent/ES2034890B1/en not_active Expired - Fee Related
- 1991-08-08 BE BE9100731A patent/BE1004496A5/en not_active IP Right Cessation
- 1991-08-08 IT ITMI912228A patent/IT1251162B/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
FR2665774A1 (en) | 1992-02-14 |
ES2034890B1 (en) | 1995-11-01 |
ITMI912228A1 (en) | 1992-02-09 |
BE1004496A5 (en) | 1992-12-01 |
FR2665774B1 (en) | 1997-02-14 |
ES2034890A1 (en) | 1993-04-01 |
JPH0495959A (en) | 1992-03-27 |
IT1251162B (en) | 1995-05-04 |
ITMI912228A0 (en) | 1991-08-08 |
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