JPH0336215B2 - - Google Patents
Info
- Publication number
- JPH0336215B2 JPH0336215B2 JP57212233A JP21223382A JPH0336215B2 JP H0336215 B2 JPH0336215 B2 JP H0336215B2 JP 57212233 A JP57212233 A JP 57212233A JP 21223382 A JP21223382 A JP 21223382A JP H0336215 B2 JPH0336215 B2 JP H0336215B2
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl acetate
- photosensitive
- emulsion
- methyl
- seconds
- 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
- 239000011118 polyvinyl acetate Substances 0.000 claims description 61
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 60
- 239000000839 emulsion Substances 0.000 claims description 56
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 39
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 39
- -1 styryl compound Chemical class 0.000 claims description 25
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 238000004132 cross linking Methods 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 239000004744 fabric Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 26
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000003456 ion exchange resin Substances 0.000 description 24
- 229920003303 ion-exchange polymer Polymers 0.000 description 24
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000007127 saponification reaction Methods 0.000 description 11
- 230000035945 sensitivity Effects 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 229920001429 chelating resin Polymers 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- YVXDRFYHWWPSOA-BQYQJAHWSA-N 1-methyl-4-[(e)-2-phenylethenyl]pyridin-1-ium Chemical group C1=C[N+](C)=CC=C1\C=C\C1=CC=CC=C1 YVXDRFYHWWPSOA-BQYQJAHWSA-N 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- GJTITKGFCXYHQX-UHFFFAOYSA-N 4-(2,2-dimethoxyethoxy)benzaldehyde Chemical compound COC(OC)COC1=CC=C(C=O)C=C1 GJTITKGFCXYHQX-UHFFFAOYSA-N 0.000 description 3
- CJPBOQVYIQSEPF-UHFFFAOYSA-N 4-[2-(1-methylquinolin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound C1=CC2=CC=CC=C2[N+](C)=C1C=CC1=CC=C(C=O)C=C1 CJPBOQVYIQSEPF-UHFFFAOYSA-N 0.000 description 3
- QJNKRLXEVGOXGC-UHFFFAOYSA-N 4-[2-(1-methylquinolin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound C12=CC=CC=C2[N+](C)=CC=C1C=CC1=CC=C(C=O)C=C1 QJNKRLXEVGOXGC-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- IZPNVUYQWBZYEA-UHFFFAOYSA-N 1,4-dimethylpyridin-1-ium Chemical compound CC1=CC=[N+](C)C=C1 IZPNVUYQWBZYEA-UHFFFAOYSA-N 0.000 description 2
- OOEOEKXNRYUBJZ-UHFFFAOYSA-N 4-(2-pyridin-1-ium-1-ylethenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C=C[N+]1=CC=CC=C1 OOEOEKXNRYUBJZ-UHFFFAOYSA-N 0.000 description 2
- SPAGXWZCVRGWDO-UHFFFAOYSA-N 4-(2-quinolin-2-ylethenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C=CC1=CC=C(C=CC=C2)C2=N1 SPAGXWZCVRGWDO-UHFFFAOYSA-N 0.000 description 2
- QWWYFEXQBDOUPD-UHFFFAOYSA-M 4-[2-[4-(2,2-dimethoxybutoxy)phenyl]ethenyl]-1-methylpyridin-1-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(OCC(CC)(OC)OC)=CC=C1C=CC1=CC=[N+](C)C=C1 QWWYFEXQBDOUPD-UHFFFAOYSA-M 0.000 description 2
- SHVMDZXMMNNCCZ-UHFFFAOYSA-N 4-[2-[4-(2,2-dimethoxyethoxy)phenyl]ethenyl]-1-methylpyridin-1-ium Chemical compound C1=CC(OCC(OC)OC)=CC=C1C=CC1=CC=[N+](C)C=C1 SHVMDZXMMNNCCZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000036211 photosensitivity Effects 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- UCFSULAKAYDAAE-UHFFFAOYSA-N quinolin-1-ium;iodide Chemical compound I.N1=CC=CC2=CC=CC=C21 UCFSULAKAYDAAE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WUIJCMJIYQWIMF-UHFFFAOYSA-N 1,3-benzothiazole;hydroiodide Chemical compound [I-].C1=CC=C2SC=[NH+]C2=C1 WUIJCMJIYQWIMF-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical group C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKEMQXFWHOQUEA-UHFFFAOYSA-M 1,4-dimethylpyridin-1-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=[N+](C)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 DKEMQXFWHOQUEA-UHFFFAOYSA-M 0.000 description 1
- OHQGKTJQWANGLW-UHFFFAOYSA-N 1,4-dimethylquinolin-1-ium Chemical compound C1=CC=C2C(C)=CC=[N+](C)C2=C1 OHQGKTJQWANGLW-UHFFFAOYSA-N 0.000 description 1
- AVBSTNJSMHTZCU-UHFFFAOYSA-M 2-[2-[4-(2,2-dimethoxyethoxy)phenyl]ethenyl]-1-methylquinolin-1-ium;iodide Chemical compound [I-].C1=CC(OCC(OC)OC)=CC=C1C=CC1=CC=C(C=CC=C2)C2=[N+]1C AVBSTNJSMHTZCU-UHFFFAOYSA-M 0.000 description 1
- BQTGZDOWLHAXPI-UHFFFAOYSA-O 2-[4-[2-(4-formylphenyl)ethenyl]pyridin-1-ium-1-yl]acetamide Chemical compound C1=C[N+](CC(=O)N)=CC=C1C=CC1=CC=C(C=O)C=C1 BQTGZDOWLHAXPI-UHFFFAOYSA-O 0.000 description 1
- LILXDMFJXYAKMK-UHFFFAOYSA-N 2-bromo-1,1-diethoxyethane Chemical compound CCOC(CBr)OCC LILXDMFJXYAKMK-UHFFFAOYSA-N 0.000 description 1
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 description 1
- PCUPSMXBHNADJG-UHFFFAOYSA-N 3-[2-(1-methylpyridin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound C[N+]1=CC=CC=C1C=CC1=CC=CC(C=O)=C1 PCUPSMXBHNADJG-UHFFFAOYSA-N 0.000 description 1
- QMIQRMGOOAMDRB-UHFFFAOYSA-N 4-(2,2-diethoxyethoxy)-3-methoxybenzaldehyde Chemical compound CCOC(OCC)COC1=CC=C(C=O)C=C1OC QMIQRMGOOAMDRB-UHFFFAOYSA-N 0.000 description 1
- JLAKCHGEEBPDQI-UHFFFAOYSA-N 4-(4-fluorobenzyl)piperidine Chemical compound C1=CC(F)=CC=C1CC1CCNCC1 JLAKCHGEEBPDQI-UHFFFAOYSA-N 0.000 description 1
- HIZVNNYJSVZBEI-UHFFFAOYSA-N 4-[2-(1-benzylpyridin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C=CC1=CC=CC=[N+]1CC1=CC=CC=C1 HIZVNNYJSVZBEI-UHFFFAOYSA-N 0.000 description 1
- PIZINBUKAIYHQX-UHFFFAOYSA-N 4-[2-(1-benzylpyridin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C=CC(C=C1)=CC=[N+]1CC1=CC=CC=C1 PIZINBUKAIYHQX-UHFFFAOYSA-N 0.000 description 1
- CLPPEIXQNWNBBH-UHFFFAOYSA-N 4-[2-(1-ethylpyridin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound CC[N+]1=CC=CC=C1C=CC1=CC=C(C=O)C=C1 CLPPEIXQNWNBBH-UHFFFAOYSA-N 0.000 description 1
- OJAQJUMWXAAWFQ-UHFFFAOYSA-N 4-[2-(1-ethylpyridin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound C1=C[N+](CC)=CC=C1C=CC1=CC=C(C=O)C=C1 OJAQJUMWXAAWFQ-UHFFFAOYSA-N 0.000 description 1
- UYLFDGWVBBDGSS-UHFFFAOYSA-N 4-[2-(1-ethylquinolin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound C1=CC2=CC=CC=C2[N+](CC)=C1C=CC1=CC=C(C=O)C=C1 UYLFDGWVBBDGSS-UHFFFAOYSA-N 0.000 description 1
- KCWZBAGKKWMNAI-UHFFFAOYSA-N 4-[2-(1-ethylquinolin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound C12=CC=CC=C2[N+](CC)=CC=C1C=CC1=CC=C(C=O)C=C1 KCWZBAGKKWMNAI-UHFFFAOYSA-N 0.000 description 1
- MTOZJUDAPRQZML-UHFFFAOYSA-N 4-[2-(1-methylpyridin-1-ium-2-yl)ethenyl]benzaldehyde Chemical compound C[N+]1=CC=CC=C1C=CC1=CC=C(C=O)C=C1 MTOZJUDAPRQZML-UHFFFAOYSA-N 0.000 description 1
- RYLOLRAYISQACV-UHFFFAOYSA-N 4-[2-(1-methylpyridin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound C1=C[N+](C)=CC=C1C=CC1=CC=C(C=O)C=C1 RYLOLRAYISQACV-UHFFFAOYSA-N 0.000 description 1
- HRUNPGSMFWSHEJ-UHFFFAOYSA-N 4-[2-(3-ethyl-1-methylpyridin-1-ium-4-yl)ethenyl]benzaldehyde Chemical compound CCC1=C[N+](C)=CC=C1C=CC1=CC=C(C=O)C=C1 HRUNPGSMFWSHEJ-UHFFFAOYSA-N 0.000 description 1
- MPPXKIPCXOSEMW-UHFFFAOYSA-N 4-[2-[1-(2-hydroxyethyl)pyridin-1-ium-2-yl]ethenyl]benzaldehyde Chemical compound OCC[N+]1=CC=CC=C1C=CC1=CC=C(C=O)C=C1 MPPXKIPCXOSEMW-UHFFFAOYSA-N 0.000 description 1
- DWOIJHIIADRLSE-UHFFFAOYSA-N 4-[2-[1-(2-hydroxyethyl)pyridin-1-ium-4-yl]ethenyl]benzaldehyde Chemical compound C1=C[N+](CCO)=CC=C1C=CC1=CC=C(C=O)C=C1 DWOIJHIIADRLSE-UHFFFAOYSA-N 0.000 description 1
- LTLKJYMNUSSFAH-UHFFFAOYSA-N 4-chloro-1,1-dimethoxybutane Chemical compound COC(OC)CCCCl LTLKJYMNUSSFAH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- SGNAVSTUZPHFPI-UHFFFAOYSA-M [I-].C[S+]1C(=NC2=C1C=CC=C2)C Chemical compound [I-].C[S+]1C(=NC2=C1C=CC=C2)C SGNAVSTUZPHFPI-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical class [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical group C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005528 methosulfate group Chemical group 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】
本発明は、改良された性質をもつスクリーン印
刷版製造用感光性材料、特に感度、安定性に優
れ、しかも解像性及び耐久性の良好なスクリーン
印刷版製造用感光性材料に関するものである。ス
クリーン印刷は、アルミニウム枠又は木枠にスク
リーン（紗布）を張り、これに被膜を施し、この
被膜に文字、模様などの画像を形成させ、画線部
はインキを通し、被画線部はインキを通さないよ
うに目止めをした構造の版をつくり、これを用い
て画像を印刷する方法であるが、細かい線が刷れ
ること、印刷物に立体感が出ること、耐光性がよ
いこと、被印刷物の形状、素材にこだわらないこ
となど数多くの特徴をもつことから、スクリーン
なつ染旗やたれ幕、ポスター作成、プリント配線
盤の製造、陶磁器、プラスチツクス、ガラス、金
属などの成形品への模様付け等その利用範囲が著
しく拡大してきた。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photosensitive material for producing screen printing plates having improved properties, particularly a photosensitive material for producing screen printing plates having excellent sensitivity and stability, as well as good resolution and durability. It is related to sexual materials. In screen printing, a screen (gauze cloth) is stretched over an aluminum frame or a wooden frame, a film is applied to this, and images such as letters and patterns are formed on this film. This is a method of printing images by making a plate with a structure that is sealed so that it does not pass through, but it is possible to print fine lines, give the print a three-dimensional effect, have good light resistance, and the substrate Because it has many characteristics such as not being particular about the shape or material, it can be used for making screen dyed flags, hanging curtains, posters, printed wiring boards, and adding patterns to molded products such as ceramics, plastics, glass, and metal. The scope of its use has expanded significantly.
ところで、このスクリーン印刷に用いられる印
刷版は、通常、感光性樹脂をスクリーン（紗布）
上に塗布又は転写し、画像マスクを介して露光さ
せて露光部を不溶化又は可溶化させたのち、可溶
部分を溶解除去することによつて製造されてい
る。 By the way, the printing plate used for this screen printing usually uses a photosensitive resin on a screen (gauge cloth).
It is manufactured by coating or transferring onto the surface, exposing it to light through an image mask to insolubilize or solubilize the exposed area, and then dissolving and removing the soluble area.
この際に用いられる感光性樹脂としては、これ
まで重クロム酸アンモニウム塩−ポリビニルアル
コール系のものが最も広く用いられていたが、こ
れは塗布後の暗反応が速いため作業工程の制限を
受ける上に、六価クロム排出規制の問題もあつ
て、その使用は減少の傾向にある。これに代わる
べきものとして、ポリビニルアルコール−ジアゾ
系のもの、例えばｐ−ジアゾジフエニルアミンと
パラホルムアルデヒドとの縮重合物にポリビニル
アルコールを配合したものが提案されているが、
このものは重クロム酸アンモニウム−ポリビニル
アルコール系のものよりも感度が低いし、また暗
反応も徐々ではあるが進行するので適正な露光時
間の変化、現像作業性の低下などをもたらすとい
う欠点があり、必ずしも満足できるものとはいえ
ない。その後、少量の感光性基含量で極めて大き
い感光速度を有する感光性樹脂としてスチルバゾ
リウム基をもつポリビニルアルコール誘導体が開
始され（特開昭55−23163号公報）、これを感光性
成分とし、ポリ酢酸ビニルエマルジヨンをフイル
ム形成性成分として含有するスクリーン印刷版製
造用感光性材料が提案された（特開昭55−62446
号公報）。このものは環境汚染源となる金属を含
まず、ジアゾ樹脂−ポリビニルアルコール系のも
ののように暗反応を起こさないという長所を有す
るが、その反面解像力が低い上に、形成した膜が
水や有機溶剤などにより膨潤しやすく、機械的強
度が不足し、さらに多湿期に使用するとスクリー
ンから膜が剥離するという欠点がある。 Up until now, ammonium dichromate salt-polyvinyl alcohol-based photosensitive resins have been most widely used as the photosensitive resins used in this process, but this is subject to limitations in the work process due to its fast dark reaction after application. In addition, there are problems with hexavalent chromium emission regulations, and its use is on the decline. As an alternative to this, a polyvinyl alcohol-diazo type product, such as a polyvinyl alcohol blended with a condensation product of p-diazodiphenylamine and paraformaldehyde, has been proposed.
This has the disadvantage that it has lower sensitivity than ammonium dichromate-polyvinyl alcohol type, and the dark reaction progresses, albeit gradually, resulting in changes in the appropriate exposure time and a decrease in development workability. , cannot necessarily be said to be satisfactory. Subsequently, polyvinyl alcohol derivatives with stilbazolium groups were developed as photosensitive resins that have an extremely high photosensitive speed with a small content of photosensitive groups (Japanese Patent Application Laid-open No. 55-23163), and using this as a photosensitive component, polyvinyl acetate A photosensitive material for producing screen printing plates containing emulsion as a film-forming component was proposed (Japanese Patent Laid-Open No. 55-62446
Publication No.). This material does not contain metals that can be a source of environmental pollution, and has the advantage of not causing dark reactions like diazo resin-polyvinyl alcohol-based products. It has the disadvantage that it easily swells, lacks mechanical strength, and that the film peels off from the screen when used in humid periods.
これは、ポリ酢酸ビニルエマルジヨン中に存在
し、保護コロイドの役割を果たしているポリ酢酸
ビニルけん化物が、その原因になつている。すな
わち、ポリ酢酸ビニルエマルジヨン中では、酢酸
ビニル重合体分子に、共存するポリ酢酸ビニルけ
ん化物の一部がグラフト共重合し、かつその周囲
にさらに遊離状のポリ酢酸ビニルけん化物が吸着
して保護層を形成し、これによつてポリ酢酸ビニ
ルが安定な乳化分散状態を保つているが、これに
スチルバゾリウム基をもつポリビニルアルコール
誘導体を混合し、スクリーン上に塗布し、露光処
理した場合、酢酸ビニル重合体の粒子の周囲に形
成されている保護コロイド層と光照射により不溶
化された感光性樹脂との間は全く化学的な結合が
形成されることはないので、保護コロイド層は水
や有機溶剤との接触により膨潤したり流出する結
果、剥離や機械的強度の低下をもたらす。 This is caused by saponified polyvinyl acetate, which is present in the polyvinyl acetate emulsion and plays the role of a protective colloid. That is, in the polyvinyl acetate emulsion, a part of the coexisting saponified polyvinyl acetate is graft-copolymerized with the vinyl acetate polymer molecules, and free saponified polyvinyl acetate is further adsorbed around it. A protective layer is formed, which keeps polyvinyl acetate in a stable emulsified dispersion state. However, when a polyvinyl alcohol derivative having a stilbazolium group is mixed with this and applied on a screen and exposed to light, acetic acid Since no chemical bond is formed between the protective colloid layer formed around the vinyl polymer particles and the photosensitive resin insolubilized by light irradiation, the protective colloid layer is Swelling or flowing out due to contact with a solvent results in peeling and a decrease in mechanical strength.
本発明者らは、この点に着目し、種々研究を重
ねた結果、ポリ酢酸ビニルエマルジヨンに、あら
かじめの光架橋性基をもつ化合物を加えて反応さ
せ、その中に存在するポリ酢酸ビニルけん化物に
光架橋性を付与しておけば、前記の欠点を克服し
うることを見い出し、この知見に基づいて本発明
をなすに至つた。 The present inventors focused on this point, and as a result of various studies, the polyvinyl acetate emulsion was reacted with a compound having a photocrosslinkable group in advance. The inventors have discovered that the above-mentioned drawbacks can be overcome by imparting photo-crosslinking properties to the compound, and based on this finding, the present invention has been accomplished.
すなわち、本発明は、(A)保護コロイドとしてポ
リ酢酸ビニルけん化物を含むポリ酢酸ビニル水性
エルマジヨンに、一般式
又は
（式中のR1は四級化芳香族含窒素複素環残基、
R2は水素原子又は低級アルコキシ基、R3はそれ
ぞれ低級アルキル基であるか、あるいは２個の
R3で低級アルキレン基を形成するものであり、
ｎは１〜６の整数、ｍは０又は１である）
で表わされるスチリル化合物を加え、酸触媒の存
在下、反応させて得られる反応混合物から成る光
架橋性が付与されたフイルム形成性成分と、(B)前
記水性エマルジヨン中のポリ酢酸ビニル100重量
部当り５〜200重量部の光架橋性水溶性ポリビニ
ルアルコール誘導体から成る感光性成分とを含有
することを特徴とするスクリーン印刷版製造用感
光性材料を提供するものである。 That is, the present invention provides (A) polyvinyl acetate aqueous elmadion containing saponified polyvinyl acetate as a protective colloid, which has the general formula or (R 1 in the formula is a quaternized aromatic nitrogen-containing heterocyclic residue,
R 2 is a hydrogen atom or a lower alkoxy group, R 3 is each a lower alkyl group, or two
R 3 forms a lower alkylene group,
n is an integer of 1 to 6, m is 0 or 1) A film-forming component imparted with photo-crosslinking properties consisting of a reaction mixture obtained by adding a styryl compound represented by the following formula and reacting it in the presence of an acid catalyst. and (B) a photosensitive component consisting of a photocrosslinkable water-soluble polyvinyl alcohol derivative in an amount of 5 to 200 parts by weight per 100 parts by weight of polyvinyl acetate in the aqueous emulsion. The present invention provides a photosensitive material.
本発明において、(A)成分の調整に用いられるポ
リ酢酸ビニル水性エルマルジヨン中のポリ酢酸ビ
ニルの含有量は20〜60重量％の範囲が適当であ
る。またこの水性エマルジヨン中には、保護コロ
イドとしてポリ酢酸ビニルけん化物すなわちポリ
ビニルアルコールが含まれるが、これには重合度
が300〜3000の範囲で、けん化度75％以上の部分
けん化物又は完全けん化物を用いるのが好まし
く、その水性エマルジヨン中の含有量は、２〜10
重量％の範囲が適当である。 In the present invention, the content of polyvinyl acetate in the polyvinyl acetate aqueous emulsion used for preparing component (A) is suitably in the range of 20 to 60% by weight. In addition, this aqueous emulsion contains saponified polyvinyl acetate, that is, polyvinyl alcohol, as a protective colloid, which has a degree of polymerization in the range of 300 to 3000, and is partially saponified or completely saponified with a degree of saponification of 75% or more. is preferably used, and its content in the aqueous emulsion is from 2 to 10
A range of weight percent is suitable.
この保護コロイドとしてポリ酢酸ビニルけん化
物を含むポリ酢酸ビニル水性エマルジヨンは、市
販品をそのまま利用してもよいし、常法に従い、
ポリ酢酸ビニルけん化物、触媒、界面活性剤、そ
の他必要な成分を含む水性媒質中で、酢酸ビニル
を乳化重合させることにより調製したものを用い
てもよい。 The aqueous polyvinyl acetate emulsion containing saponified polyvinyl acetate as a protective colloid may be used as a commercially available product, or may be prepared using a conventional method.
One prepared by emulsion polymerization of vinyl acetate in an aqueous medium containing saponified polyvinyl acetate, a catalyst, a surfactant, and other necessary components may be used.
次に、本発明においては、この水性エマルジヨ
ンをフイルム形成性成分として用いるに先立つ
て、その中に保護コロイドとして存在している遊
離状又はグラフト化されたポリ酢酸ビニルけん化
物に光架橋性を付与する処理を施すことが必要で
あるが、これはポリ酢酸ビニル水性エマルジヨン
に、前記一般式（）又は（）で示されるスチ
リル化合物を加えて反応させ、ポリ酢酸ビニルけ
ん化物分子中に、一般式
（式中のR1、R2、ｎ、ｍは前記と同じ意味をも
つ）
で示される光架橋性基を導入させることによつて
行うことができる。この光架橋性基はポリ酢酸ビ
ニルけん化物のモノマー単位数に対し0.5〜10モ
ル％の範囲の割合で導入されれば十分であるが、
所望ならばポリ酢酸ビニルけん化物中の全てのア
ルコール基に導入することもできる。 Next, in the present invention, prior to using this aqueous emulsion as a film-forming component, photocrosslinking properties are imparted to the free or grafted saponified polyvinyl acetate present as a protective colloid therein. It is necessary to carry out a treatment in which a styryl compound represented by the above general formula () or () is added to a polyvinyl acetate aqueous emulsion and reacted, and the general formula (In the formula, R 1 , R 2 , n, and m have the same meanings as above.) This can be carried out by introducing a photocrosslinkable group represented by the following formula. It is sufficient that this photocrosslinkable group is introduced in a proportion ranging from 0.5 to 10 mol% based on the number of monomer units of the saponified polyvinyl acetate.
If desired, it can be introduced into all the alcohol groups in the saponified polyvinyl acetate.
この際に使用される前記一般式（）中のR1
は、環構成窒素原子の少なくとも１個が四級化さ
れた芳香族性含窒素環基であつて、このようなも
のとしては、例えばピリジニウム基、キノリニウ
ム基、イソキノリニウム基、ピリミジニウム基、
チアゾリウム基、ベンゾチアゾリウム基、ベンゾ
オキサゾリウム基などを挙げることができる。こ
れらの環には、さらにアルキル基、アルコキシル
基、アミノ基、カルバモイル基などの置換基が存
在してもよい。 R 1 in the general formula () used in this case
is an aromatic nitrogen-containing ring group in which at least one ring-constituting nitrogen atom is quaternized, such as a pyridinium group, a quinolinium group, an isoquinolinium group, a pyrimidinium group,
Examples include a thiazolium group, a benzothiazolium group, and a benzoxazolium group. These rings may further have substituents such as alkyl groups, alkoxyl groups, amino groups, and carbamoyl groups.
この一般式（）の化合物の例としては、１−
メチル−２−（ｐ−ホルミルスチリル）ピリジニ
ウム、１−メチル−４−（ｐ−ホルミルスチリル）
ピリジニウム、１−エチル−２−（ｐ−ホルミル
スチリル）ピリジニウム、１−エチル−４−（ｐ
−ホルミルスチリル）ピリジニウム、１−アリル
−４−（ｐ−ホルミルスチリル）ピリジニウム、
１−（２−ヒドロキシエチル）−２−（ｐ−ホルミ
ルスチリル）ピリジニウム、１−（２−ヒドロキ
シエチル）−４−（ｐ−ホルミルスチリル）ピリジ
ニウム、１−カルバモイルメチル−２−（ｐ−ホ
ルミルスチリル）ピリジニウム、１−カルバモイ
ルメチル−４−（ｐ−ホルミルスチリル）ピリジ
ニウム、１−メチル−２−（ｍ−ホルミルスチリ
ル）ピリジニウム、１−ベンジル−２−（ｐ−ホ
ルミルスチリル）ピリジニウム、１−ベンジル−
４−（ｐ−ホルミルスチリル）ピリジニウム、１
−メチル−４−（ｐ−ホルミルスチリル）−５−エ
チルピリジニウム、１−メチル−２−（ｐ−ホル
ミルスチリル）キノリニウム、１−エチル−２−
（ｐ−ホルミルスチリル）キノリニウム、１−エ
チル−４−（ｐ−ホルミルスチリル）キノリニウ
ム、１−メチル−２−（ｐ−ホルミルスチリル）
ベンゾチアゾリウム、１−エチル−２−（ｐ−ホ
ルミルスチリル）ベンゾチアゾリウム、１−メチ
ル−２−（ｐ−ホルミルスチリル）ベンゾオキサ
ゾリウムなどを挙げることができる。 Examples of compounds of this general formula () include 1-
Methyl-2-(p-formylstyryl)pyridinium, 1-methyl-4-(p-formylstyryl)
Pyridinium, 1-ethyl-2-(p-formylstyryl)pyridinium, 1-ethyl-4-(p
-formylstyryl)pyridinium, 1-allyl-4-(p-formylstyryl)pyridinium,
1-(2-hydroxyethyl)-2-(p-formylstyryl)pyridinium, 1-(2-hydroxyethyl)-4-(p-formylstyryl)pyridinium, 1-carbamoylmethyl-2-(p-formylstyryl) ) pyridinium, 1-carbamoylmethyl-4-(p-formylstyryl)pyridinium, 1-methyl-2-(m-formylstyryl)pyridinium, 1-benzyl-2-(p-formylstyryl)pyridinium, 1-benzyl-
4-(p-formylstyryl)pyridinium, 1
-Methyl-4-(p-formylstyryl)-5-ethylpyridinium, 1-methyl-2-(p-formylstyryl)quinolinium, 1-ethyl-2-
(p-formylstyryl)quinolinium, 1-ethyl-4-(p-formylstyryl)quinolinium, 1-methyl-2-(p-formylstyryl)
Examples include benzothiazolium, 1-ethyl-2-(p-formylstyryl)benzothiazolium, and 1-methyl-2-(p-formylstyryl)benzoxazolium.
また、一般式（）で示される化合物は、一般
式（）で示されるホルミル化合物のアセタール
であつて、このようなものとしては、例えば以下
の化学構造式をもつ化合物を挙げることができ
る。 Further, the compound represented by the general formula () is an acetal of the formyl compound represented by the general formula (), and examples of such compounds include compounds having the following chemical structural formula.
これらの一般式（）及び（）で示される化
合物は、ハロゲン化水素酸塩、ホスフエート、サ
ルフエート、メトサルフエート、エトサルフエー
ト、ｐ−トルエンスルホネート、過塩素酸塩、ホ
ウフツ化水素酸塩などの塩の形で使用される。 The compounds represented by these general formulas () and () can be used in the form of salts such as hydrohalides, phosphates, sulfates, methosulfates, ethosulfates, p-toluenesulfonates, perchlorates, and hydroborates. used.
水性エマルジヨン中のポリ酢酸ビニルけん化物
とこれらの化合物との反応は、酸触媒の存在下で
行われる。この酸触媒としては、塩酸、硫酸、リ
ン酸、過塩素酸、ホウフツ化水素酸のような無機
酸や、ベンゼンスルホン酸、ｐ−トルエンスルホ
ン酸のような有機酸が用いられる。この使用量は
多い程、短時間で反応が完了するが、通常は0.01
〜５規定度の濃度が選ばれる。反応温度としては
温室から100℃までの温度が選ばれ、反応は通常
１〜45時間程度で完了する。この酸触媒が水性エ
マルジヨン中に残存すると、エマルジヨンの分離
や得られた感光性樹脂組成物の感度の変動の原因
となるので、反応終了後例えば水酸化アルカリや
アンモニアなどにより、これを中和しておくのが
よい。特に好適なのは、塩基性イオン交換樹脂に
よる処理である。 The reaction of these compounds with saponified polyvinyl acetate in an aqueous emulsion is carried out in the presence of an acid catalyst. As this acid catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, and hydroborofluoric acid, and organic acids such as benzenesulfonic acid and p-toluenesulfonic acid are used. The larger the amount used, the faster the reaction will be completed, but usually 0.01
A concentration of ~5 normality is chosen. The reaction temperature is selected from a greenhouse to 100°C, and the reaction is usually completed in about 1 to 45 hours. If this acid catalyst remains in the aqueous emulsion, it will cause separation of the emulsion and fluctuations in the sensitivity of the resulting photosensitive resin composition. Therefore, after the reaction is complete, neutralize it with alkali hydroxide, ammonia, etc. It's good to keep it. Particularly suitable is treatment with a basic ion exchange resin.
このようにして得られたフイルム形成性成分
は、単独でも感光性を有するが、感度が低くスク
リーン印刷版製造用としては、不適当であるの
で、本発明においては、さらに所定の感光性成分
を配合することが必要である。 The film-forming component obtained in this way has photosensitivity even when used alone, but the sensitivity is low and it is unsuitable for producing screen printing plates. Therefore, in the present invention, a predetermined photosensitive component is further added to the film-forming component. It is necessary to mix them.
本発明において感光性成分として用いる光架橋
性水溶性ポリビニルアルコール誘導体は、ポリ酢
酸ビニルの完全けん化物又は部分けん化物に、光
架橋性基を導入することにより得られるものであ
るが、特に好適なのは、特開昭55−62446号公報
に記載されているスチルバゾリウム基をもつポリ
ビニルアルコール誘導体である。このようなポリ
ビニルアルコール誘導体は、例えば前記した保護
コロイドに光架橋性を付与させる方法と同じ方法
によつて製造することができる。すなわち、重合
度300〜3000の範囲のポリ酢酸ビニルをけん化し
て得られるけん化率75％以上の水溶性ポリビニル
アルコールに、前記一般式（）又は（）で示
されるホルミルスチリル化合物又はそのアセター
ルを、水性溶媒中酸触媒の存在下に反応させるこ
とにより製造することができる。この際の光架橋
性基の導入率はモノマー単位当り約0.5〜10モル
％程度が望ましく、これよりも低いと十分な光架
橋性が得られないし、これよりも高いと反応中に
ゲル化を生じる。また、触媒として用いた酸が反
応液中に残存すると貯蔵中に粘度が上昇したり、
(A)成分、すなわちフイルム形成性成分と混合した
場合、凝集を起こしたり、感光度が変動するなど
望ましくない結果をもたらすので、アルカリによ
る中和、陰イオン交換樹脂による処理などでこれ
を除去するか、あるいはアセトン、アルコール、
ジオキサンのような非溶剤を加え、感光性樹脂を
沈澱させ、単離したのち使用するのがよい。 The photocrosslinkable water-soluble polyvinyl alcohol derivative used as a photosensitive component in the present invention is obtained by introducing a photocrosslinkable group into a completely saponified or partially saponified polyvinyl acetate. , is a polyvinyl alcohol derivative having a stilbazolium group described in JP-A No. 55-62446. Such a polyvinyl alcohol derivative can be produced, for example, by the same method as that for imparting photocrosslinking properties to the protective colloid described above. That is, a formylstyryl compound represented by the general formula () or () or its acetal is added to water-soluble polyvinyl alcohol with a saponification rate of 75% or more obtained by saponifying polyvinyl acetate with a degree of polymerization in the range of 300 to 3000, It can be produced by reacting in an aqueous solvent in the presence of an acid catalyst. The introduction rate of the photocrosslinkable group at this time is preferably about 0.5 to 10 mol% per monomer unit; if it is lower than this, sufficient photocrosslinkability cannot be obtained, and if it is higher than this, gelation may occur during the reaction. arise. Additionally, if the acid used as a catalyst remains in the reaction solution, the viscosity may increase during storage.
If mixed with component (A), that is, a film-forming component, it will cause undesirable results such as aggregation and fluctuations in photosensitivity, so this should be removed by neutralization with an alkali, treatment with an anion exchange resin, etc. or acetone, alcohol,
It is preferable to add a non-solvent such as dioxane to precipitate and isolate the photosensitive resin before use.
本発明における(B)成分すなわち光架橋性水溶性
ポリビニルアルコール誘導体の配合量は、水性エ
マルジヨン中のポリ酢酸ビニル100重量部当り、
５〜200重量部の範囲内で選ばれる。この量が５
重量部末端では、耐溶剤性が悪く十分な強度をも
つたパターンを得ることができないし、またこの
量が200重量部よりも多くなると耐水性が悪くな
り、きれいな画像が得られず実用的でない。 The amount of component (B) in the present invention, that is, the photocrosslinkable water-soluble polyvinyl alcohol derivative, is based on 100 parts by weight of polyvinyl acetate in the aqueous emulsion.
It is selected within the range of 5 to 200 parts by weight. This amount is 5
At the end of the weight part, solvent resistance is poor and a pattern with sufficient strength cannot be obtained, and if this amount exceeds 200 parts by weight, water resistance becomes poor and a clear image cannot be obtained, making it impractical. .
本発明の感光性材料は、これを常法に従いスク
リーン（紗布）上に塗布し、乾燥したのち、ネガ
像を通して光を照射し、水その他の溶剤で洗い出
し現像することによりスクリーン印刷版を製造す
ることができる。このようにして形成された印刷
版は、画像が鮮明で印刷インキに対する耐性や機
械的強度が優れ、長期間にわたつて使用しても膨
潤や剥離などを生じることはない。 The photosensitive material of the present invention is applied onto a screen (gauze cloth) according to a conventional method, dried, and then irradiated with light through a negative image, washed out with water or other solvent, and developed to produce a screen printing plate. be able to. The printing plate thus formed has a clear image, excellent resistance to printing ink and mechanical strength, and does not swell or peel off even when used for a long period of time.
次に、参考例及び実施例により本発明をさらに
詳細に説明する。 Next, the present invention will be explained in more detail using reference examples and examples.
参考例 １
光架橋性基含有化合物の製造
(1) Ｎ−メチル−γ−（ｐ−ホルミルスチリル）
ピリジニウムメトサルフエート
Ｎ−メチル−γ−ピコリニウムメトサルフエ
ート10.96ｇとテレフタルアルデヒド20.12ｇを
メタノール40mlに熱時溶解して、ピペリジン
2.13ｇを加え４時間還流した。ジオレフイン型
化合物を熱時濾過除去後、酢酸エチル100mlを
加え一夜放置し、析出物を濾過回収してアセト
ンで十分に洗浄し真空乾燥した。収量12.1ｇで
Ｎ−メチル−γ−（ｐ−ホルミルスチリル）ピ
リジニウムメトサルフエートが得られた。この
ものの融点は210〜213℃であつた。Reference Example 1 Production of photocrosslinkable group-containing compound (1) N-methyl-γ-(p-formylstyryl)
Pyridinium methosulfate Dissolve 10.96 g of N-methyl-γ-picolinium methosulfate and 20.12 g of terephthalaldehyde in 40 ml of methanol under hot conditions,
2.13g was added and refluxed for 4 hours. After removing the diolefin type compound by filtration while hot, 100 ml of ethyl acetate was added and left overnight, and the precipitate was collected by filtration, thoroughly washed with acetone, and dried in vacuum. N-methyl-γ-(p-formylstyryl)pyridinium methosulfate was obtained in a yield of 12.1 g. The melting point of this product was 210-213°C.
(2) Ｎ−メチル−４−〔ｐ−（２、２−ジメトキシ
エトキシ）スチリル〕ピリジニウムメトサルフ
エート
ｐ−ヒドロキシベンズアルデヒド12.21ｇと
水酸化カリウム6.60ｇをジメチルスルホキシド
35mlに加熱溶解し、ベンゼンとの共沸蒸留によ
り脱水後クロルアセトアルデヒドジメチルアセ
タール12.88ｇを加え、かきまぜながら温度147
℃で20時間反応させた。反応液を冷却してから
トルエン100mlを加え、水、希アルカリ水溶液
及び水で順次洗浄した。このトルエン溶液を無
水硫酸ナトリウムで乾燥してから真空蒸留し、
圧力1Torrでの沸点が123℃のｐ−ホルミルフ
エノキシアセトアルデヒドジメチルアセタール
17.54ｇを得た。このようにして得られたｐ−
ホルミルフエノキシアセトアルデヒドジメチル
アセタール21.02ｇとＮ−メチル−γ−ピコリ
ニウムメトサルフエート21.93ｇをメタノール
90mlに溶解してからピペリジン4.26ｇを加え４
時間還流下に反応させた。この反応液に酢酸エ
チル200ml加え放冷し、析出物を濾過回収して
アセトンで十分に洗浄し真空乾燥した。このよ
うにして収量30.62ｇでＮ−メチル−４−〔ｐ−
（２、２−ジメトキシエトキシ）スチリル〕ピ
リジニウムメトサルフエートを得た。このもの
の融点は169〜170℃であつた。(2) N-Methyl-4-[p-(2,2-dimethoxyethoxy)styryl]pyridinium methosulfate 12.21 g of p-hydroxybenzaldehyde and 6.60 g of potassium hydroxide were dissolved in dimethyl sulfoxide.
Dissolve in 35ml by heating, dehydrate by azeotropic distillation with benzene, add 12.88g of chloroacetaldehyde dimethyl acetal, and bring to a temperature of 147ml while stirring.
The reaction was carried out at ℃ for 20 hours. After cooling the reaction solution, 100 ml of toluene was added, and the mixture was washed successively with water, a dilute aqueous alkali solution, and water. This toluene solution was dried with anhydrous sodium sulfate and then vacuum distilled.
p-formylphenoxyacetaldehyde dimethyl acetal with a boiling point of 123°C at a pressure of 1 Torr
17.54g was obtained. p− obtained in this way
21.02 g of formylphenoxyacetaldehyde dimethyl acetal and 21.93 g of N-methyl-γ-picolinium methosulfate were dissolved in methanol.
Dissolve in 90ml and add 4.26g of piperidine 4
The reaction was carried out under reflux for an hour. 200 ml of ethyl acetate was added to this reaction solution and allowed to cool, and the precipitate was collected by filtration, thoroughly washed with acetone, and dried in vacuum. In this way, the yield was 30.62 g, N-methyl-4-[p-
(2,2-dimethoxyethoxy)styryl]pyridinium methosulfate was obtained. The melting point of this product was 169-170°C.
(3) Ｎ−メチル−４−〔ｐ−（２、２−ジメトキシ
ブトキシ）スチリル〕ピリジニウムｐ−トルエ
ンスルホネート
ｐ−ヒドロキシベンズアルデヒド12.21ｇと
水酸化カリウム6.60ｇをジメチルスルホキシド
35mlに加熱溶解し、ベンゼンとの共沸蒸留によ
り脱水後、４−クロロブタナールジメチルアセ
タール15.26ｇを加え、かきまぜながら100℃の
温度で20時間反応させた。反応液を冷却してか
らトルエン100mlを加え水洗後、希アルカリ水
溶液で洗浄し、さらに水洗した。このトルエン
溶液を無水硫酸ナトリウムで乾燥してから真空
蒸留し、圧力1Torrでの沸点が140℃のｐ−ホ
ルミルフエノキシブチルアルデヒドジメチルア
セタール21.0ｇを得た。(3) N-Methyl-4-[p-(2,2-dimethoxybutoxy)styryl]pyridinium p-toluenesulfonate 12.21 g of p-hydroxybenzaldehyde and 6.60 g of potassium hydroxide were dissolved in dimethyl sulfoxide.
After heating and dissolving the mixture in 35 ml and dehydrating it by azeotropic distillation with benzene, 15.26 g of 4-chlorobutanal dimethyl acetal was added, and the mixture was reacted at 100° C. for 20 hours with stirring. After cooling the reaction solution, 100 ml of toluene was added and washed with water, followed by washing with a dilute aqueous alkaline solution, and further washing with water. This toluene solution was dried over anhydrous sodium sulfate and then vacuum distilled to obtain 21.0 g of p-formylphenoxybutyraldehyde dimethyl acetal having a boiling point of 140°C at a pressure of 1 Torr.
このようにして得られたｐ−ホルミルフエノ
キシブチルアルデヒドジメチルアセタール
23.83ｇとＮ−メチル−γ−ピコリニウムｐ−
トルエンスルホネート27.94ｇをメタノール90
mlに溶解してからピペリジン4.26ｇを加え、４
時間還流下に反応させた。この反応液に酢酸エ
チル200ml加え放冷した。析出物を濾過回収し
てアセトンで十分洗浄し真空乾燥した。このよ
うにして、融点169〜173℃のＮ−メチル−４−
〔ｐ−（２、２−ジメトキシブトキシ）スチリ
ル〕ピリジニウムｐ−トルエンスルホネート
32.79ｇが得られた。 p-formylphenoxybutyraldehyde dimethyl acetal thus obtained
23.83g and N-methyl-γ-picolinium p-
Toluene sulfonate 27.94g methanol 90g
ml, add 4.26 g of piperidine, and add 4.26 g of piperidine.
The reaction was carried out under reflux for an hour. 200 ml of ethyl acetate was added to this reaction solution and allowed to cool. The precipitate was collected by filtration, thoroughly washed with acetone, and dried under vacuum. In this way, N-methyl-4-
[p-(2,2-dimethoxybutoxy)styryl]pyridinium p-toluenesulfonate
32.79g was obtained.
(4) １−メチル−２−（ｐ−ホルミルスチリル）
キノリニウムメトサルフエート
２−メチルキノリン28.6ｇとテレフタルジア
ルデヒド67ｇを酢酸24ｇと無水酢酸45ｇと共に
８時間加熱還流した。冷却後、析出した結晶を
ジクロルメタンに溶かし、水洗し、次いで水酸
化ナトリウム溶液で洗つて酢酸を除去した。こ
のジクロメタン溶液に濃塩酸を加えると直ちに
かさ高い黄橙色の結晶が析出した。その結晶を
濾集し、水から再結晶したのち、約300mlのエ
タノール中に懸濁し、トリエチルアミンで中和
して加温することにより脱塩酸した。次いで不
溶のジオレフイン型化合物3.9ｇを濾別し、濾
液に水を加えて放置して２−（ｐ−ホルミルス
チリル）−キノリンの黄色結晶35ｇを得た。(4) 1-Methyl-2-(p-formylstyryl)
Quinolinium methosulfate 28.6 g of 2-methylquinoline and 67 g of terephthaldialdehyde were heated under reflux for 8 hours with 24 g of acetic acid and 45 g of acetic anhydride. After cooling, the precipitated crystals were dissolved in dichloromethane, washed with water, and then with sodium hydroxide solution to remove acetic acid. When concentrated hydrochloric acid was added to this dichloromethane solution, bulky yellow-orange crystals were immediately precipitated. The crystals were collected by filtration, recrystallized from water, suspended in about 300 ml of ethanol, neutralized with triethylamine, and heated to remove hydrochloric acid. Next, 3.9 g of the insoluble diolefin type compound was filtered off, water was added to the filtrate, and the mixture was allowed to stand to obtain 35 g of yellow crystals of 2-(p-formylstyryl)-quinoline.
m.p.112〜113℃λnax（クロロホルム）：297n
ｍ、360nｍ
このようにして得られた２−（ｐ−ホルミル
スチリル）−キノリン8.14ｇ酢酸エチル30mlに
溶解し、この溶液にジメチル硫酸9.0ｇを加え
て６時間加熱還流した。冷後、析出した結晶を
濾集し、水から再結晶して１−メチル−２−
（ｐ−ホルミルスチリル）キノリニウムメトサ
ルフエートの結晶11.8ｇを得た。 mp112~113℃λ nax (chloroform): 297n
m, 360 nm 8.14 g of the 2-(p-formylstyryl)-quinoline thus obtained was dissolved in 30 ml of ethyl acetate, 9.0 g of dimethyl sulfate was added to this solution, and the mixture was heated under reflux for 6 hours. After cooling, the precipitated crystals were collected by filtration and recrystallized from water to give 1-methyl-2-
11.8 g of crystals of (p-formylstyryl)quinolinium methosulfate were obtained.
m.p.204〜210℃λnax（水）：245nｍ、299nｍ、
366nｍ
(5) １−メチル−４−（ｐ−ホルミルスチリル）
キノリニウムメトサルフエート
１、４−ジメチルキノリニウムメトサルフエ
ート14.95ｇとテレフタルジアルデヒド22.35ｇ
をメタノール40ml中に熱時溶解してから、その
中にピペリジン0.5mlを加えて10時間加熱還流
した。冷後、約200mlのアセトンを加えると結
晶性の沈澱が析出した。 mp204~210℃λ nax (water): 245nm, 299nm,
366nm (5) 1-methyl-4-(p-formylstyryl)
Quinolinium methosulfate 1,4-dimethylquinolinium methosulfate 14.95g and terephthaldialdehyde 22.35g
was dissolved in 40 ml of methanol while hot, 0.5 ml of piperidine was added thereto, and the mixture was heated under reflux for 10 hours. After cooling, about 200 ml of acetone was added to form a crystalline precipitate.
これを濾集し、アセトンで洗つて１−メチル
−４−（ｐ−ホルミルスチリル）キノリニウム
メトサルフエートの粗製品15.73ｇを得た。
λnax（水）：245nｍ、332nｍ、376nｍ
この粗製品は、感光性樹脂の製造にそのまま
使用できる。 This was collected by filtration and washed with acetone to obtain 15.73 g of a crude product of 1-methyl-4-(p-formylstyryl)quinolinium methosulfate.
λ nax (water): 245 nm, 332 nm, 376 nm This crude product can be used as it is in the production of photosensitive resin.
(6) １−メチル−２−〔ｐ−（２、２−ジメトキシ
エトキシ）スチリル〕キノリニウムヨウ化物
１、２−ジメチルキノリニウムヨウ化物4.28
ｇとｐ−（２、２−ジメトキシエトキシ）−ベン
ズアルデヒド3.47ｇをメタノール20ml中に溶解
し、この溶液にピペリジン0.3mlを加えて７時
間加熱還流した。この反応後を冷却放置して析
出した結晶を濾集して、アセトンでよく洗つて
１−メチル−２−〔ｐ−（２、２−ジメトキシエ
トキシ）スチリル〕キノリニウムヨウ化物5.03
ｇを得た。(6) 1-Methyl-2-[p-(2,2-dimethoxyethoxy)styryl]quinolinium iodide 1,2-dimethylquinolinium iodide 4.28
3.47 g of p-(2,2-dimethoxyethoxy)-benzaldehyde were dissolved in 20 ml of methanol, 0.3 ml of piperidine was added to this solution, and the mixture was heated under reflux for 7 hours. After this reaction was left to cool, the precipitated crystals were collected by filtration and thoroughly washed with acetone to produce 1-methyl-2-[p-(2,2-dimethoxyethoxy)styryl]quinolinium iodide.
I got g.
m.p.209〜212℃λnax（水）：224nｍ、255nｍ、
399nｍ
(7) １−メチル−２−〔ｐ−（２、２−ジメトキシ
エトキシ）スチリル〕ベンゾチアゾリウムヨウ
化物
前記(2)で得られたｐ−ホルミルフエノキシア
セトアルデヒドジメチルアセタール2.42ｇと
１、２−ジメチルベンゾチアゾリウムヨウ化物
2.91ｇをメタノール10mlに溶解し、これにピペ
リジン４滴を添加して５時間半還流した。反応
後を冷却すると結晶が析出するからこれを濾過
して集め、冷メタノールで洗浄することにより
１−メチル−２−〔ｐ−（２、２−ジメトキシエ
トキシ）スチリル〕ベンゾチアゾリウムヨウ化
物2.16ｇを得た。 mp209~212℃λ nax (water): 224nm, 255nm,
399nm (7) 1-Methyl-2-[p-(2,2-dimethoxyethoxy)styryl]benzothiazolium iodide 2.42 g of p-formylphenoxyacetaldehyde dimethyl acetal obtained in (2) above and 1 , 2-dimethylbenzothiazolium iodide
2.91 g was dissolved in 10 ml of methanol, 4 drops of piperidine were added thereto, and the mixture was refluxed for 5 and a half hours. When the reaction is cooled, crystals will precipitate, so these are collected by filtration and washed with cold methanol to obtain 1-methyl-2-[p-(2,2-dimethoxyethoxy)styryl]benzothiazolium iodide2.16 I got g.
(8) １−メチル−４−〔3′−メトキシ−4′−（２、
２−ジエトキシエトキシ）スチリル〕キノリニ
ウムヨウ化物
バニリンのナトリウム塩10.00ｇとブロモア
セトアルデヒドジエチルアセタール13.6ｇをジ
メチルアセトアミド50mlに加えて200℃の温度
で３時間加熱反応させた。冷却後反応溶液にベ
ンゼン50mlを加え、水洗後希アルカリ水で洗浄
し、有機層を減圧蒸留することにより、沸点
166℃／１mmＨｇの３−メトキシ−４−（２、２
−ジエトキシエトキシ）ベンゾアルデヒド
10.78ｇを得た。このアルデヒド1.72ｇと１、
４−ジメチルキノリニウムヨウ化物1.65ｇをメ
タノール５mlに溶解し、これにピペリジン５滴
を添加して20時間還流した。これにアセトンと
酢酸エチルの混合溶媒を加え放置することによ
り、１−メチル−４−〔3′−メトキシ−4′（２、
２−ジエトキシエトキシ）スチリル〕キノリニ
ウムヨウ化物1.04ｇを得た。(8) 1-methyl-4-[3'-methoxy-4'-(2,
2-Diethoxyethoxy)styryl]quinolinium iodide 10.00 g of vanillin sodium salt and 13.6 g of bromoacetaldehyde diethyl acetal were added to 50 ml of dimethylacetamide and reacted by heating at 200° C. for 3 hours. After cooling, add 50 ml of benzene to the reaction solution, wash with water and dilute alkaline water, and distill the organic layer under reduced pressure to determine the boiling point.
3-methoxy-4-(2,2
-diethoxyethoxy)benzaldehyde
10.78g was obtained. 1.72g of this aldehyde and 1,
1.65 g of 4-dimethylquinolinium iodide was dissolved in 5 ml of methanol, 5 drops of piperidine were added thereto, and the mixture was refluxed for 20 hours. By adding a mixed solvent of acetone and ethyl acetate to this and leaving it to stand, 1-methyl-4-[3'-methoxy-4'(2,
1.04 g of 2-diethoxyethoxy)styryl]quinolinium iodide was obtained.
参考例 ２
光架橋性水溶性ポリビニルアルコール誘導体の
製造
(1) 感光性成分B1
参考例１の(1)で得られたＮ−メチル−γ−
（ｐ−ホルミルスチリル）ピリジニウムメトサ
ルフエート1.37ｇと重合度1700、けん化度88％
のポリ酢酸ビニルけん化物20ｇを蒸留水192ml
に溶解し、これに85％リン酸0.4ｇを加えた後、
45℃に加温し20時間かきまぜて反応させた。反
応液を弱塩基性イオン交換樹脂で中和して得ら
れたポリビニルアルコールは0.81モル％のスチ
ルバゾリウム基をもつことが紫外吸収スペクト
ルより認められた。Reference Example 2 Production of photocrosslinkable water-soluble polyvinyl alcohol derivative (1) Photosensitive component B 1 N-methyl-γ- obtained in Reference Example 1 (1)
(p-formylstyryl)pyridinium methosulfate 1.37g and degree of polymerization 1700, degree of saponification 88%
20g of saponified polyvinyl acetate and 192ml of distilled water
After adding 0.4 g of 85% phosphoric acid to this,
The mixture was heated to 45°C and stirred for 20 hours to react. The ultraviolet absorption spectrum showed that the polyvinyl alcohol obtained by neutralizing the reaction solution with a weakly basic ion exchange resin had 0.81 mol% of stilbazolium groups.
(2) 感光性成分B2
参考例１の(1)で得られたＮ−メチル−γ−
（ｐ−ホルミルスチリル）ピリジニウムメトサ
ルフエート3.28ｇと重合度500、けん化度88％
のポリ酢酸ビニルけん化物８ｇを蒸留水101ml
に溶解し、これに85％リン酸0.16ｇを加えた
後、かきまぜながら45℃の温度で20時間反応さ
せた。反応液を弱塩基性イオン交換樹脂で中和
して得られた樹脂は4.6モル％のスチルバゾリ
ウム基をもつことが紫外吸収スペクトルより確
認された。(2) Photosensitive component B 2 N-methyl-γ- obtained in (1) of Reference Example 1
(p-formylstyryl) pyridinium methosulfate 3.28g, polymerization degree 500, saponification degree 88%
8g of saponified polyvinyl acetate in 101ml of distilled water
After adding 0.16 g of 85% phosphoric acid thereto, the mixture was reacted at a temperature of 45° C. for 20 hours with stirring. It was confirmed by ultraviolet absorption spectrum that the resin obtained by neutralizing the reaction solution with a weakly basic ion exchange resin had 4.6 mol% of stilbazolium groups.
(3) 感光性成分B3
参考例１の(2)で得られたＮ−メチル−４−
〔ｐ−（２、２−ジメトキシエトキシ）スチリ
ル〕ピリジニウムメトサルフエート2.52ｇと重
合度1700、けん化率88％のポリ酢酸ビニルけん
化物20ｇを蒸留水192mlに溶解し、これにさら
に85％リン酸0.4ｇを加えた後、かきまぜなが
ら温度80℃で20時間反応させた。反応液を弱塩
基性イオン交換樹脂で中和したこの感光液中の
ポリビニルアルコールは1.46モル％のスチルバ
ゾリウム基が導入されていることが紫外吸収ス
ペクトルより確認された。(3) Photosensitive component B 3 N-methyl-4- obtained in (2) of Reference Example 1
2.52 g of [p-(2,2-dimethoxyethoxy)styryl]pyridinium methosulfate and 20 g of saponified polyvinyl acetate with a degree of polymerization of 1700 and a saponification rate of 88% are dissolved in 192 ml of distilled water, and to this is added 85% phosphoric acid. After adding 0.4 g, the mixture was reacted at a temperature of 80° C. for 20 hours while stirring. It was confirmed from the ultraviolet absorption spectrum that 1.46 mol% of stilbazolium groups were introduced into the polyvinyl alcohol in this photosensitive solution, which was obtained by neutralizing the reaction solution with a weakly basic ion exchange resin.
(4) 感光性成分B4
参考例１の(3)で得られたＮ−メチル−４−
〔ｐ−（２、２−ジメトキシブトキシ）スチリ
ル〕ピリジニウム・ｐ−トルエンスルホネート
3.05ｇと重合度1700、けん化度88％のポリ酢酸
ビニルけん化物20ｇを蒸留水192mlに溶解した。
これに85％リン酸0.4ｇを加えた後、かきまぜ
条件下に温度45℃で20時間反応させた。反応液
を弱塩基性イオン交換樹脂で中和した。この感
光液中のポリビニルアルコールには1.46モル％
のスチルバゾリウム基が導入されていることが
紫外吸収スペクトルより認められた。(4) Photosensitive component B 4 N-methyl-4- obtained in (3) of Reference Example 1
[p-(2,2-dimethoxybutoxy)styryl]pyridinium p-toluenesulfonate
3.05 g of saponified polyvinyl acetate with a degree of polymerization of 1700 and a degree of saponification of 88% were dissolved in 192 ml of distilled water.
After adding 0.4 g of 85% phosphoric acid to this, the mixture was reacted at a temperature of 45° C. for 20 hours under stirring conditions. The reaction solution was neutralized with a weakly basic ion exchange resin. Polyvinyl alcohol in this photosensitive solution contains 1.46 mol%
The introduction of stilbazolium groups was confirmed from the ultraviolet absorption spectrum.
(5) 感光性成分B5
参考例１の(4)で得られた１−メチル−２−
（ｐ−ホルミルスチリル）キノリニウムメトサ
ルフエート1.96ｇと重合度1700、けん化率88％
のポリ酢酸ビニルけん化物20ｇを蒸留水192ml
に溶解した。これにさらに85％リン酸0.4ｇを
加え、かきまぜながら温度45℃で20時間反応さ
せた。反応液を弱塩基性イオン交換樹脂で中和
したこの感光液中のポリビニルアルコールには
1.0モル％のスチリルキノリニウム基が導入さ
れていることが紫外吸収スペクトルより認めら
れた。(5) Photosensitive component B 5 1 -Methyl-2- obtained in (4) of Reference Example 1
(p-formylstyryl) quinolinium methosulfate 1.96g, polymerization degree 1700, saponification rate 88%
20g of saponified polyvinyl acetate and 192ml of distilled water
dissolved in. Further, 0.4 g of 85% phosphoric acid was added to this, and the mixture was allowed to react at a temperature of 45° C. for 20 hours while stirring. The polyvinyl alcohol in this photosensitive solution, in which the reaction solution is neutralized with a weakly basic ion exchange resin, contains
It was confirmed from the ultraviolet absorption spectrum that 1.0 mol% of styrylquinolinium groups were introduced.
(6) 感光性成分B6
参考例１の(5)で得られた１−メチル−４−
（ｐ−ホルミルスチリル）キノリニウムメトサ
ルフエート1.96ｇと重合度1700、けん化率88％
のポリ酢酸ビニルけん化物20ｇを蒸留水192ml
に溶解し、これにさらに85％リン酸0.4ｇを加
えた後、かきまぜながら温度45℃で20時間反応
させた。反応液を弱塩基性イオン交換樹脂で中
和した。感光液中のポリビニルアルコールは
1.0モル％のスチリルキノリニウム基が導入さ
れていることが紫外吸収スペクトルより確認さ
れた。(6) Photosensitive component B 6 1-Methyl-4- obtained in (5) of Reference Example 1
(p-formylstyryl) quinolinium methosulfate 1.96g, polymerization degree 1700, saponification rate 88%
20g of saponified polyvinyl acetate and 192ml of distilled water
After adding 0.4 g of 85% phosphoric acid thereto, the mixture was reacted at a temperature of 45° C. for 20 hours with stirring. The reaction solution was neutralized with a weakly basic ion exchange resin. Polyvinyl alcohol in the photosensitive solution
It was confirmed from the ultraviolet absorption spectrum that 1.0 mol% of styrylquinolinium groups were introduced.
(7) 感光性成分B7
参考例１の(6)で得られた１−メチル−２−
〔ｐ−（２、２−ジメトキシエトキシ）−スチリ
ル〕キノリニウムヨウ化物2.03ｇと重合度
1700、けん化率88％のポリ酢酸ビニルけん化物
20ｇを蒸留水192mlに溶解し、これにさらに85
％リン酸0.4ｇを加えた後、かきまぜながら温
度80℃で20時間反応させた。反応液を弱塩基性
イオン交換樹脂で中和した。この感光液中のポ
リビニルアルコールには1.0モル％のスチリル
キノリニウム基導入されていることが紫外吸収
スペクトルより認められた。(7) Photosensitive component B 7 1 -Methyl-2- obtained in (6) of Reference Example 1
[p-(2,2-dimethoxyethoxy)-styryl]quinolinium iodide 2.03g and degree of polymerization
1700, saponified polyvinyl acetate with a saponification rate of 88%
Dissolve 20g in 192ml of distilled water and add 85g to this.
After adding 0.4 g of % phosphoric acid, the mixture was reacted at a temperature of 80° C. for 20 hours while stirring. The reaction solution was neutralized with a weakly basic ion exchange resin. It was confirmed from the ultraviolet absorption spectrum that 1.0 mol % of styrylquinolinium groups were introduced into the polyvinyl alcohol in this photosensitive solution.
(8) 感光性成分B8
参考例１の(7)で得られた１−メチル−２−
〔ｐ−（２、２−ジメトキシエトキシ）スチリ
ル〕ベンゾチアゾリウムヨウ化物2.05ｇと重合
度1700、けん化率88％のポリ酢酸ビニルけん化
物20ｇを蒸留水192mlに溶解し、これにさらに
85％リン酸0.4ｇを加えた後、かきまぜながら
温度80℃で20時間反応させた。反応液を弱塩基
性イオン交換樹脂で中和して得られたこの感光
液中のポリビニルアルコールは1.0モル％のス
チリルベンゾチアゾリウム基をもつことが紫外
吸収スペクトルより認められた。(8) Photosensitive component B 8 1-Methyl-2- obtained in (7) of Reference Example 1
2.05 g of [p-(2,2-dimethoxyethoxy)styryl]benzothiazolium iodide and 20 g of saponified polyvinyl acetate with a degree of polymerization of 1700 and a saponification rate of 88% were dissolved in 192 ml of distilled water, and further
After adding 0.4 g of 85% phosphoric acid, the mixture was reacted at a temperature of 80° C. for 20 hours with stirring. The ultraviolet absorption spectrum showed that the polyvinyl alcohol in this photosensitive solution, which was obtained by neutralizing the reaction solution with a weakly basic ion exchange resin, had 1.0 mol% of styrylbenzothiazolium groups.
(9) 感光性成分B9
参考例１の(8)で得られた３−メトキシ−４−
〔ｐ−（２、２−ジメトキシエトキシ）スチリ
ル〕キノリニウムヨウ化物2.28ｇと重合度
1700、けん化率88％のポリ酢酸ビニルけん化物
20ｇを蒸留水192mlに溶解し、これにさらに85
％リン酸0.4ｇを加え、かきまぜながら温度80
℃で20時間反応させた。反応液を弱塩基性イオ
ン交換樹脂で中和した。得られた感光液中のポ
リビニルアルコールには1.0モル％のスチリル
キノリニウム基が導入されていることが紫外吸
収スペクトルより認められた。(9) Photosensitive component B 9 3-methoxy-4- obtained in (8) of Reference Example 1
[p-(2,2-dimethoxyethoxy)styryl]quinolinium iodide 2.28g and degree of polymerization
1700, saponified polyvinyl acetate with a saponification rate of 88%
Dissolve 20g in 192ml of distilled water and add 85g to this.
Add 0.4g of % phosphoric acid and bring to a temperature of 80% while stirring.
The reaction was carried out at ℃ for 20 hours. The reaction solution was neutralized with a weakly basic ion exchange resin. It was confirmed from the ultraviolet absorption spectrum that 1.0 mol % of styrylquinolinium groups were introduced into the polyvinyl alcohol in the obtained photosensitive liquid.
実施例 １
参考例１の(1)で得たＮ−メチル−γ−（ｐ−ホ
ルミルスチリル）ピリジニウムメトサルフエート
0.82ｇをポリ酢酸ビニルエマルジヨン（固形分50
％、PVA含有率４％）400ｇに加え、さらに85％
リン酸0.8ｇを加えた後45℃に加温して20時間か
きまぜ反応させた。続いて弱塩基性イオン交換樹
脂（アンバーライトIRA−45）6.0ｇを加えて静
かにかきまぜてリン酸を中和した後、400メツシ
ユテトロン製しや布でイオン交換樹脂を濾過除去
した。Example 1 N-methyl-γ-(p-formylstyryl)pyridinium methosulfate obtained in (1) of Reference Example 1
0.82g of polyvinyl acetate emulsion (solid content 50
%, PVA content 4%) 400g plus an additional 85%
After adding 0.8 g of phosphoric acid, the mixture was heated to 45°C and reacted with stirring for 20 hours. Subsequently, 6.0 g of a weakly basic ion exchange resin (Amberlite IRA-45) was added and stirred gently to neutralize the phosphoric acid, and then the ion exchange resin was filtered off using a 400 Metsu Tetron cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇに感光性成分B110ｇと感光性
成分B22.50ｇをよく混合した。この感光乳剤を
250メツシユテトロン製しや布に塗布し乾燥して
均一な膜を得た。この膜を４〓超高圧水銀灯で１
ｍの距離、レンジ４の条件で60秒照射し、硬化し
た膜を溶媒に24時間浸せきして膨潤率を測定し
た。この結果を、浸せき前の膜重量を100％とし
て以下に示す。 10 g of photosensitive component B 1 and 2.50 g of photosensitive component B 2 were thoroughly mixed with 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained. This light-sensitive emulsion
A uniform film was obtained by applying it to a cloth made of 250 mesh tetron and drying it. This film was coated with 4 〓 ultra-high pressure mercury lamp.
The cured film was irradiated for 60 seconds at a distance of m and in a microwave oven of 4, and the swelling ratio was measured by immersing the cured film in a solvent for 24 hours. The results are shown below, with the membrane weight before immersion being taken as 100%.
水140％、アセトン120％
また別に、この膜上にステツプ・タブレツトNo.
２（コダツク社製）を密着して置き、4kw超高圧
水銀灯で１ｍの距離、レンジ４の条件で照射し、
スプレーガンを用いて水現像したところ、30秒照
射でステツプ３段、60秒照射でステツプ５段が得
られた。さらに1.2ｍの距離、レンジ１の条件で
90秒照射によりステツプ３段、150秒照射でステ
ツプ５段が得られた。 140% water, 120% acetone Separately, Step Tablet No.
2 (manufactured by Kodatsu) and irradiated it with a 4kw ultra-high pressure mercury lamp at a distance of 1m under the condition of microwave oven 4.
When water development was performed using a spray gun, 3 steps were obtained after irradiation for 30 seconds, and 5 steps were obtained when irradiated for 60 seconds. Furthermore, at a distance of 1.2 m, under the condition of range 1
Three steps were obtained with irradiation for 90 seconds, and five steps were obtained with irradiation for 150 seconds.
比較例 １
感光性成分B110ｇと感光性成分B22.50ｇ混合
液にポリ酢酸ビニルエマルジヨン（固形分50％、
うちPVA含有率４％）3.75ｇをよく混合した。
この感光乳剤を250メツシユテトロン製しや布に
塗布し乾燥して均一な膜を得た。この膜を4kw超
高圧水銀灯で１ｍの距離、レンジ４の条件で60秒
照射し、硬化した膜を溶媒に24時間浸せきして膨
潤率を測定し、水175％、アセトン139％の結果が
得られた。Comparative Example 1 Polyvinyl acetate emulsion (solid content 50%,
Of this, 3.75 g (PVA content: 4%) were thoroughly mixed.
This light-sensitive emulsion was coated on a 250 mesh Tetron cloth and dried to obtain a uniform film. This film was irradiated with a 4kw ultra-high-pressure mercury lamp at a distance of 1 m for 60 seconds in microwave 4, and the cured film was immersed in a solvent for 24 hours to measure the swelling ratio, and the result was 175% water and 139% acetone. It was done.
また実施例１と同様の方法で硬化テストを行つ
たところ、30秒照射でステツプ１段、60秒照射で
ステツプ３段が得られた。同様に1.2ｍ、レンジ
１の条件で照射することにより、90秒でステツプ
１段、150秒でステツプ３段が得られた。 Further, when a curing test was conducted in the same manner as in Example 1, one step was obtained with irradiation for 30 seconds, and three steps were obtained with irradiation for 60 seconds. Similarly, by irradiating at 1.2 m and range 1, one step was obtained in 90 seconds and three steps were obtained in 150 seconds.
このように、フイルム形成性成分に光架橋性を
付与しないで用いた場合は、膨潤率が高く、感度
が低くなつている。 As described above, when the film-forming component is used without imparting photocrosslinkability, the swelling rate is high and the sensitivity is low.
実施例 ２
参考例１の(2)で得たＮ−メチル−４−〔ｐ−
（２、２−ジメトキシエトキシ）スチリル〕ピリ
ジニウムメトサルフエート1.0ｇをポリ酢酸ビニ
ルエマルジヨン（固形分50％、PVA含有率４％）
400ｇに加え、さらに85％リン酸0.8ｇを加えた
後、80℃の温度で20時間かきまぜ反応させた。続
いて弱塩基性イオン交換樹脂（アンバーライト
IRA−45）6.0ｇを加えて静かにかきまぜてリン
酸を中和した後、400メツシユテトロン製しや布
でイオン交換樹脂を濾過除去した。Example 2 N-methyl-4-[p-
(2,2-dimethoxyethoxy)styryl] 1.0 g of pyridinium methosulfate in polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
In addition to 400 g, 0.8 g of 85% phosphoric acid was added, and the mixture was stirred and reacted at a temperature of 80° C. for 20 hours. Next, weakly basic ion exchange resin (Amberlite)
After adding 6.0 g of IRA-45) and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 mesh tetron cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇに感光性成分B312.5ｇをよく
混合し、得られた感光乳剤を250メツシユテトロ
ン製しや布に塗布し乾燥して均一な膜を得た。 12.5 g of photosensitive component B 3 was thoroughly mixed with 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained, and the resulting photosensitive emulsion was applied to a 250-mesh Tetron cloth and dried to form an even layer. A film was obtained.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ２
段、60秒照射でステツプ４段が得られた。 In the same curing test as in Example 1, Step 2 was obtained by irradiating for 30 seconds at a distance of 1 m and under the condition of Range 4.
Four steps were obtained with irradiation for 60 seconds.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ２
感光性成分B312.50ｇとポリ酢酸ビニルエマル
ジヨン（固形分50％、PVA含有率４％）3.75ｇ
をよく混合し、調製された感光乳剤を250メツシ
ユテトロン製しや布に塗布し乾燥して均一な膜を
得た。Comparative Example 2 12.50 g of photosensitive component B 3 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
The prepared photosensitive emulsion was coated on a 250 mesh cloth and dried to obtain a uniform film.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ０
段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, Step 0 was achieved with irradiation for 30 seconds at a distance of 1 m and under the condition of range 4.
Two steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分に光架橋性を
付与しない場合は、感度が低い。 As described above, when the film-forming component is not imparted with photocrosslinking properties, the sensitivity is low.
実施例 ３
参考例１の(3)で得たＮ−メチル−４−〔ｐ−
（２、２−ジメトキシブトキシ）スチリル〕ピリ
ジニウムｐ−トルエンスルホネート1.22ｇをポリ
酢酸ビニルエマルジヨン（固形分50％、PVA含
有率４％）400ｇに加え、さらに85％リン酸0.8ｇ
を加えた後、温度45℃で20時間かきまぜながら反
応させた。続いて弱塩基性イオン交換樹脂（アン
バーライトIRA−45）6.0ｇを加えて静かにかき
まぜリン酸を中和した後、400メツシユテトロン
製しや布でイオン交換樹脂を濾過除去する。Example 3 N-methyl-4-[p-
Add 1.22 g of (2,2-dimethoxybutoxy)styrylpyridinium p-toluenesulfonate to 400 g of polyvinyl acetate emulsion (50% solids, 4% PVA content), and add 0.8 g of 85% phosphoric acid.
After adding, the mixture was reacted at a temperature of 45°C for 20 hours with stirring. Next, 6.0 g of a weakly basic ion exchange resin (Amberlite IRA-45) is added and stirred gently to neutralize the phosphoric acid, and then the ion exchange resin is filtered off using a 400 Metsu Tetron cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇと感光性成分B412.5ｇをよく
混合して調製した感光性樹脂組成物液を250メツ
シユテトロン製しや布に塗布し乾燥して均一な膜
が得られた。 A photosensitive resin composition liquid prepared by thoroughly mixing 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B 4 was applied to a 250-mesh Tetron cloth and dried. A uniform film was obtained.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ２
段、60秒照射でステツプ４段が得られた。 In the same curing test as in Example 1, Step 2 was obtained by irradiating for 30 seconds at a distance of 1 m and under the condition of Range 4.
Four steps were obtained with irradiation for 60 seconds.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ３
感光性成分B412.50ｇとポリ酢酸ビニルエマル
ジヨン（固形分50％、PVA含有率４％）3.75ｇ
をよく混合し、調製された感光乳剤を250メツシ
ユテトロン製しや布に塗布し乾燥して均一な膜を
形成させた。Comparative Example 3 12.50 g of photosensitive component B 4 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
The prepared photosensitive emulsion was coated on a 250 mesh cloth and dried to form a uniform film.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ０
段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, Step 0 was achieved with irradiation for 30 seconds at a distance of 1 m and under the condition of range 4.
Two steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分に光架橋性を
付与しないで用いた場合は、感度が低い。 As described above, when the film-forming component is used without imparting photocrosslinkability, the sensitivity is low.
実施例 ４
参考例１の(4)で得られた１−メチル−２−（ｐ
−ホルミルスチリル）−キノリニウムメトサルフ
エート0.94ｇをポリ酢酸ビニルエマルジヨン（固
形分50％、PVA含有率４％）400ｇに加え、さら
に85％リン酸0.8ｇを加えた後、かきまぜながら
温度45℃で20時間反応させた。続いて（アンバー
ライト（IRA−45）6.0ｇを加えて静かにかきま
ぜ、リン酸を中和した後400メツシユテトロン製
しや布でアンバーライトIRA−45を濾過除去し
た。Example 4 1-methyl-2-(p
-Formylstyryl)-quinolinium methosulfate (0.94g) was added to 400g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%), and after adding 0.8g of 85% phosphoric acid, the mixture was heated while stirring. The reaction was carried out at 45°C for 20 hours. Subsequently, 6.0 g of Amberlite (IRA-45) was added and stirred gently to neutralize the phosphoric acid, and then the Amberlite IRA-45 was filtered off using a 400 mesh cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇと感光性成分B512.5ｇをよく
混合する。この感光乳剤を250メツシユテトロン
製しや布に塗布し乾燥して均一な膜を得た。 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B 5 are thoroughly mixed. This light-sensitive emulsion was coated on a 250 mesh Tetron cloth and dried to obtain a uniform film.
実施例１と同様な硬化性テストにより、１ｍの
距離レンジ４の条件にて30秒照射でステツプ２
段、60秒照射でステツプ４段が得られた。 In the same curing test as in Example 1, Step 2 was obtained by irradiating for 30 seconds under the conditions of 1 m distance range 4.
Four steps were obtained with irradiation for 60 seconds.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ４
感光性成分B512.5ｇとポリ酢酸ビニルエマルジ
ヨン（固形分50％、PVA含有率４％）3.75ｇを
よく混合し、得られた感光乳剤を250メツシユテ
トロン製しや布に塗布し乾燥して均一な膜を得
た。Comparative Example 4 12.5 g of photosensitive component B 5 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) were thoroughly mixed, and the resulting photosensitive emulsion was coated on a 250 mesh tetron cloth. A uniform film was obtained by coating and drying.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ０
段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, Step 0 was achieved with irradiation for 30 seconds at a distance of 1 m and under the condition of range 4.
Two steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分に光架橋性を
付与しないで用いた場合は、感度が低い。 As described above, when the film-forming component is used without imparting photocrosslinkability, the sensitivity is low.
実施例 ５
参考例１の(5)で得られた１−メチル−４−（ｐ
−ホルミルスチリル）キノリニウムメトサルフエ
ート0.94ｇをポリ酢酸ビニルエマルジヨン（固形
分50％、PVA含有率４％）400ｇに加え、さらに
85％リン酸0.8ｇを加えた後、かきまぜながら温
度45℃で20時間反応させた。続いて塩基性イオン
交換樹脂（アンバーライトIRA−45）6.0ｇを加
えて静かにかきまぜリン酸を中和した後、400メ
ツシユテトロン製しや布でイオン交換樹脂を濾過
除去した。Example 5 1-methyl-4-(p
-Formylstyryl) quinolinium methosulfate (0.94 g) was added to 400 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%), and
After adding 0.8 g of 85% phosphoric acid, the mixture was reacted at 45° C. for 20 hours with stirring. Subsequently, 6.0 g of basic ion exchange resin (Amberlite IRA-45) was added and gently stirred to neutralize the phosphoric acid, and then the ion exchange resin was filtered off using a 400 Metsu Tetron cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇと感光性成分B612.5ｇをよく
混合して得られた感光性樹脂組成物乳剤を250メ
ツシユテトロン製しや布に塗布し乾燥して均一な
膜を得た。 A photosensitive resin composition emulsion obtained by thoroughly mixing 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B 6 was applied to a 250-mesh Tetron cloth. A uniform film was obtained after drying.
実施例１と同様な硬化性テストにより、１ｍの
距離レンジ４の条件にて30秒照射でステツプ３
段、60秒照射でステツプ５段が得られた。 In the same curing test as in Example 1, Step 3 was obtained by irradiating for 30 seconds under the conditions of 1 m distance range 4.
Five steps were obtained with irradiation for 60 seconds.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ５
感光性成分B612.5ｇとポリ酢酸ビニルエマルジ
ヨン3.75ｇ（固形分50％、PVA含有率４％）3.75
ｇを混合して得たた感光性組成物乳剤を250メツ
シユテトロン製しや布に塗布し乾燥して均一な膜
を得た。Comparative Example 5 12.5 g of photosensitive component B 6 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) 3.75
The photosensitive composition emulsion obtained by mixing g was coated on a 250 mesh tetron cloth and dried to obtain a uniform film.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ１
段、60秒照射でステツプ３段が得られた。 In the same curing test as in Example 1, Step 1 was obtained by irradiating for 30 seconds at a distance of 1 m and under the condition of Range 4.
Three steps were obtained with irradiation for 60 seconds.
実施例 ６
参考例１の(6)で得られた１−メチル−２−〔ｐ
−２，２−ジメトキシエトキシ）スチリル〕−キ
ノリニウムヨウ化物1.16ｇをポリ酢酸ビニルエマ
ルジヨン（固形分50％、PVA含有率４％）400ｇ
に加え、さらに85％リン酸0.8ｇを加えた後80℃
に加温して20時間反応させた。続いて塩基性イオ
ン交換樹脂（アンバーライトIRA−45）6.0ｇを
加えて静かにかきまぜリン酸を中和した後、400
メツシユテトロン製しや布でイオン交換樹脂を濾
過除去した。Example 6 1-methyl-2-[p obtained in (6) of Reference Example 1
-2,2-dimethoxyethoxy)styryl] - 1.16 g of quinolinium iodide to 400 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
80℃ after adding 0.8g of 85% phosphoric acid.
The mixture was heated to a temperature of 100 mL and allowed to react for 20 hours. Next, add 6.0 g of basic ion exchange resin (Amberlite IRA-45) and stir gently to neutralize the phosphoric acid.
The ion-exchange resin was removed by filtration using a cloth made by Metshu Tetron.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇと感光性成分B712.5ｇをよく
混合し、調製された感光乳剤を250メツシユテト
ロン製しや布に塗布し乾燥して均一な膜を得れ
た。 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B7 were thoroughly mixed, and the prepared photosensitive emulsion was applied to a 250-mesh Tetron cloth and dried to form a uniform layer. A good film was obtained.
実施例１と同様な硬化性テストにより１ｍの距
離、レンジ４の条件にて、30秒照射でステツプ２
段、60秒照射でステツプ４段が得られる。 The same hardening test as in Example 1 was carried out at a distance of 1 m, under the condition of range 4, and irradiation was performed for 30 seconds in step 2.
4 steps can be obtained with 60 seconds of irradiation.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ６
感光性成分B712.5ｇとポリ酢酸ビニルエマルジ
ヨン3.75ｇ（固形分50％、PVA含有率４％）を
よく混合し、得られた感光乳剤を250メツシユテ
トロン製しや布に塗布し乾燥して均一な膜を得
た。Comparative Example 6 12.5 g of photosensitive component B 7 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) were thoroughly mixed, and the resulting photosensitive emulsion was coated on a 250-mesh Tetron cloth. A uniform film was obtained by coating and drying.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ０
段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, Step 0 was achieved with irradiation for 30 seconds at a distance of 1 m and under the condition of range 4.
Two steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分に光架橋性を
付与しないで用いた場合は、感度が低い。 As described above, when the film-forming component is used without imparting photocrosslinkability, the sensitivity is low.
実施例 ７
参考例１の(7)で得られた１−メチル−２−〔ｐ
−（２、２ジメトキシエトキシ）スチリル〕ベン
ゾチアゾリウムヨウ化物1.17ｇをポリ酢酸ビニル
エマルジヨン（固形分50％、PVA含有率４％）
400ｇに加え、さらに85％リン酸0.8ｇを加えた
後、80℃かきまぜながら温度20時間反応させた。
続いて塩基性イオン交換樹脂（アンバーライト
IRA−45）6.0ｇを加えて静かにかきまぜ、リン
酸を中和した後、400メツシユテトロン製しや布
でイオン交換樹脂を濾過除去した。Example 7 1-methyl-2-[p obtained in (7) of Reference Example 1
-(2,2 dimethoxyethoxy)styryl] 1.17 g of benzothiazolium iodide in polyvinyl acetate emulsion (solid content 50%, PVA content 4%)
In addition to 400 g, 0.8 g of 85% phosphoric acid was added, and the mixture was reacted at 80° C. for 20 hours with stirring.
Next, basic ion exchange resin (Amberlite)
After adding 6.0 g of IRA-45) and stirring gently to neutralize the phosphoric acid, the ion exchange resin was removed by filtration using a 400 mesh tetron cloth.
このようにして得られた感光性ポリ酢酸ビニル
エマルジヨン3.75ｇと感光性成分B812.5ｇをよく
混合し、得られた感光性樹脂組成物乳剤を250メ
ツシユテトロン製しや布に塗布し乾燥して均一な
膜を得た。 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B8 were thoroughly mixed, and the resulting photosensitive resin composition emulsion was applied to a 250 mesh Tetron cloth. A uniform film was obtained after drying.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射にてステツプ
２段、60秒照射にてステツプ４段が得られた。 In the same curing test as in Example 1, two steps were obtained with irradiation for 30 seconds and four steps were obtained with irradiation for 60 seconds at a distance of 1 m under the condition of range 4.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ７
感光性成分B812.5ｇとポリ酢酸ビニルエマルジ
ヨン（固形分50％、PVA含有率４％）3.75ｇを
よく混合し、この感光乳剤を250メツシユテトロ
ン製しや布に塗布し乾燥して均一な膜を得た。Comparative Example 7 12.5 g of photosensitive component B 8 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) were mixed well, and this photosensitive emulsion was applied to a 250 mesh Utetron cloth. A uniform film was obtained after drying.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて、30秒照射でステツプ
０段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, at a distance of 1 m and under the condition of range 4, 0 steps were obtained with irradiation for 30 seconds, and 2 steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分を光架橋化処
理しないものは感度が低い。 As described above, those in which the film-forming component is not subjected to photo-crosslinking treatment have low sensitivity.
実施例 ８
参考例１の(7)で得られた１−メチル−４−
〔3′−メトキシ−4′−（２、２−ジエトキシエトキ
シ）スチリル〕キノリニウムヨウ化物1.30ｇをポ
リ酢酸ビニルエマルジヨン（固形分50％、PVA
含有率４％）400ｇに加え、さらに85％リン酸0.8
ｇを加えた後、かきまぜながら温度80℃に加温し
て20時間反応させた。続いて塩基性イオン交換樹
脂（アンバーライトIRA−45）6.0ｇを加えて静
かにかきまぜてリン酸を中和した後、400メツシ
ユテトロン製しや布でイオン交換樹脂を濾過除去
した。Example 8 1-Methyl-4- obtained in (7) of Reference Example 1
1.30 g of [3'-methoxy-4'-(2,2-diethoxyethoxy)styryl]quinolinium iodide was added to polyvinyl acetate emulsion (50% solids, PVA).
In addition to 400g (4% content), an additional 0.8% 85% phosphoric acid
After adding g, the mixture was heated to 80°C while stirring and allowed to react for 20 hours. Subsequently, 6.0 g of basic ion exchange resin (Amberlite IRA-45) was added and stirred gently to neutralize the phosphoric acid, and then the ion exchange resin was removed by filtration using a 400 Metsu Tetron cloth.
このようにして得た感光性ポリ酢酸ビニルエマ
ルジヨン3.75ｇと感光性成分B912.5ｇをよく混合
し、この感光乳剤を250メツシユテトロン製しや
布に塗布、乾燥して均一な膜を形成させた。 Thoroughly mix 3.75 g of the photosensitive polyvinyl acetate emulsion thus obtained and 12.5 g of photosensitive component B 9 , apply this photosensitive emulsion to a 250 mesh Utetron cloth, and dry to form a uniform film. formed.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて30秒照射でステツプ２
段、60秒照射でステツプ４段が得られた。 In the same curing test as in Example 1, Step 2 was obtained by irradiating for 30 seconds at a distance of 1 m and under the condition of Range 4.
Four steps were obtained with irradiation for 60 seconds.
また、このものは低い膨潤率を示した。 This product also showed a low swelling rate.
比較例 ８
感光性成分B912.5ｇとポリ酢酸ビニルエマルジ
ヨン（固形分50％、PVA含有率４％）3.75ｇを
よく混合した。この感光乳剤を250メツシユテト
ロン製しや布に塗布、乾燥して均一な膜を形成さ
せた。Comparative Example 8 12.5 g of photosensitive component B 9 and 3.75 g of polyvinyl acetate emulsion (solid content 50%, PVA content 4%) were thoroughly mixed. This photosensitive emulsion was applied to a 250 mesh Tetron cloth and dried to form a uniform film.
実施例１と同様な硬化性テストにより、１ｍの
距離、レンジ４の条件にて、30秒照射でステツプ
０段、60秒照射でステツプ２段が得られた。 In the same curing test as in Example 1, at a distance of 1 m and under the condition of range 4, 0 steps were obtained with irradiation for 30 seconds, and 2 steps were obtained with irradiation for 60 seconds.
このように、フイルム形成性成分に光架橋化処
理を施さない場合は感度が低い。 As described above, sensitivity is low when the film-forming component is not subjected to photo-crosslinking treatment.
Claims (1)
化物を含むポリ酢酸ビニル水性エマルジヨン
に、 一般式 又は （式中のR1は四級化芳香族含窒素複素関残基、
R2は水素原子又は低アルコキシ基、R3はそれ
ぞれ低級アルキル基であるか、あるいは２個の
R3で低級アルキレン基を形成するものであり、
ｎは１〜６の整数、ｍは０又は１である） で表わされるスチリル化合物を加え、酸触媒の
存在下、反応させて得られる反応混合物から成
る光架橋性が付与されたフイルム形成性成分
と、(B)前記水性エマルジヨン中のポリ酢酸ビニ
ル100重量部当り５〜200重量部の光架橋性水溶
性ポリビニルアルコール誘導体から成る感光性
成分とを含有することを特徴とするスクリーン
印刷版製造用感光性材料。[Scope of Claims] 1 (A) A polyvinyl acetate aqueous emulsion containing a saponified polyvinyl acetate as a protective colloid has the general formula or (R 1 in the formula is a quaternized aromatic nitrogen-containing heteroresidue,
R 2 is a hydrogen atom or a lower alkoxy group, R 3 is each a lower alkyl group, or two
R 3 forms a lower alkylene group,
n is an integer of 1 to 6, m is 0 or 1) A film-forming component imparted with photo-crosslinking properties consisting of a reaction mixture obtained by adding a styryl compound represented by the following formula and reacting it in the presence of an acid catalyst. and (B) a photosensitive component consisting of a photocrosslinkable water-soluble polyvinyl alcohol derivative in an amount of 5 to 200 parts by weight per 100 parts by weight of polyvinyl acetate in the aqueous emulsion. photosensitive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21223382A JPS59102232A (en) | 1982-12-03 | 1982-12-03 | Photosensitive resin composition for use in screen printing plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21223382A JPS59102232A (en) | 1982-12-03 | 1982-12-03 | Photosensitive resin composition for use in screen printing plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59102232A JPS59102232A (en) | 1984-06-13 |
| JPH0336215B2 true JPH0336215B2 (en) | 1991-05-30 |
Family
ID=16619160
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21223382A Granted JPS59102232A (en) | 1982-12-03 | 1982-12-03 | Photosensitive resin composition for use in screen printing plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59102232A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11214895B2 (en) | 2015-11-06 | 2022-01-04 | Inv Performance Materials, Llc | Low permeability and high strength fabric and methods of making the same |
| US11634841B2 (en) | 2017-05-02 | 2023-04-25 | Inv Performance Materials, Llc | Low permeability and high strength woven fabric and methods of making the same |
| US11708045B2 (en) | 2017-09-29 | 2023-07-25 | Inv Performance Materials, Llc | Airbags and methods for production of airbags |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0666030B2 (en) * | 1984-07-04 | 1994-08-24 | 工業技術院長 | Photosensitive resin composition for screen plate making |
| JPH0642077B2 (en) * | 1984-07-04 | 1994-06-01 | 工業技術院長 | Screen photosensitive material for plate making |
| US5246815A (en) * | 1984-07-04 | 1993-09-21 | Gen. Director Of The Agency Of Industrial Science & Technology | Photosensitive material for screen processing |
| JPH0640220B2 (en) * | 1984-07-04 | 1994-05-25 | 工業技術院長 | Manufacturing method of photosensitive material |
| JPS6187150A (en) * | 1984-09-11 | 1986-05-02 | Agency Of Ind Science & Technol | Photosensitive resin composition |
| JPS61184534A (en) * | 1985-02-13 | 1986-08-18 | Agency Of Ind Science & Technol | Production of aqueous solution of photosensitive resin |
| JP2587458Y2 (en) * | 1990-07-21 | 1998-12-16 | 貞義 坂井 | Scaffolding fittings |
| JP4890541B2 (en) | 2006-05-17 | 2012-03-07 | 株式会社ムラカミ | Photosensitive resin composition, photosensitive film using the same, and stencil for screen printing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523163A (en) * | 1978-08-09 | 1980-02-19 | Agency Of Ind Science & Technol | Polyvinyl alcohol type photosensitive resin and its preparation |
| JPS5562446A (en) * | 1978-11-06 | 1980-05-10 | Agency Of Ind Science & Technol | Photosensitive resin composition for screen printing plate |
-
1982
- 1982-12-03 JP JP21223382A patent/JPS59102232A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523163A (en) * | 1978-08-09 | 1980-02-19 | Agency Of Ind Science & Technol | Polyvinyl alcohol type photosensitive resin and its preparation |
| JPS5562446A (en) * | 1978-11-06 | 1980-05-10 | Agency Of Ind Science & Technol | Photosensitive resin composition for screen printing plate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11214895B2 (en) | 2015-11-06 | 2022-01-04 | Inv Performance Materials, Llc | Low permeability and high strength fabric and methods of making the same |
| US11634841B2 (en) | 2017-05-02 | 2023-04-25 | Inv Performance Materials, Llc | Low permeability and high strength woven fabric and methods of making the same |
| US11708045B2 (en) | 2017-09-29 | 2023-07-25 | Inv Performance Materials, Llc | Airbags and methods for production of airbags |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59102232A (en) | 1984-06-13 |
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