JPS6244257B2 - - Google Patents
Info
- Publication number
- JPS6244257B2 JPS6244257B2 JP15079478A JP15079478A JPS6244257B2 JP S6244257 B2 JPS6244257 B2 JP S6244257B2 JP 15079478 A JP15079478 A JP 15079478A JP 15079478 A JP15079478 A JP 15079478A JP S6244257 B2 JPS6244257 B2 JP S6244257B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- photosensitive
- compound
- photosensitive composition
- polyhydroxyphenyl
- 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
Links
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 17
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- 229940079877 pyrogallol Drugs 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- -1 quinone diazide compound Chemical class 0.000 description 35
- 239000010410 layer Substances 0.000 description 16
- 238000011282 treatment Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920001568 phenolic resin Polymers 0.000 description 6
- 229960001755 resorcinol Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 150000008049 diazo compounds Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000005660 hydrophilic surface Effects 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- KQSBZNJFKWOQQK-UHFFFAOYSA-N hystazarin Natural products O=C1C2=CC=CC=C2C(=O)C2=C1C=C(O)C(O)=C2 KQSBZNJFKWOQQK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- QFYYAIBEHOEZKC-UHFFFAOYSA-N 2-Methoxyresorcinol Chemical compound COC1=C(O)C=CC=C1O QFYYAIBEHOEZKC-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- 206010012442 Dermatitis contact Diseases 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JFTVVDRMEQULHW-UHFFFAOYSA-N 1,3-dihydroxy-5-methylanthracene-9,10-dione Chemical compound OC1=C2C(C=3C=CC=C(C3C(C2=CC(=C1)O)=O)C)=O JFTVVDRMEQULHW-UHFFFAOYSA-N 0.000 description 1
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- YJGHMLJGPSVSLF-UHFFFAOYSA-N 2-[2-(2-octanoyloxyethoxy)ethoxy]ethyl octanoate Chemical compound CCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCC YJGHMLJGPSVSLF-UHFFFAOYSA-N 0.000 description 1
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- GPJJASIJVRXZFI-UHFFFAOYSA-N 2-methoxyresorcinol Natural products COC1=CC=C(O)C=C1O GPJJASIJVRXZFI-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- YJERZJLSXBRUDQ-UHFFFAOYSA-N 2-o-(3,4-dihydroxybutyl) 1-o-methyl benzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OCCC(O)CO YJERZJLSXBRUDQ-UHFFFAOYSA-N 0.000 description 1
- BHWUCEATHBXPOV-UHFFFAOYSA-N 2-triethoxysilylethanamine Chemical compound CCO[Si](CCN)(OCC)OCC BHWUCEATHBXPOV-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- LZDOYVMSNJBLIM-UHFFFAOYSA-N 4-tert-butylphenol;formaldehyde Chemical compound O=C.CC(C)(C)C1=CC=C(O)C=C1 LZDOYVMSNJBLIM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NDKYEUQMPZIGFN-UHFFFAOYSA-N Butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC NDKYEUQMPZIGFN-UHFFFAOYSA-N 0.000 description 1
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- MPGOFFXRGUQRMW-UHFFFAOYSA-N [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC=CC1=O Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].O=C1C=CC=CC1=O MPGOFFXRGUQRMW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- HSUIVCLOAAJSRE-UHFFFAOYSA-N bis(2-methoxyethyl) benzene-1,2-dicarboxylate Chemical compound COCCOC(=O)C1=CC=CC=C1C(=O)OCCOC HSUIVCLOAAJSRE-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GMGLYSIINJPYLI-UHFFFAOYSA-N butan-2-one;propan-2-one Chemical compound CC(C)=O.CCC(C)=O GMGLYSIINJPYLI-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZLSPCFYPYRYKNF-UHFFFAOYSA-N formaldehyde;4-octylphenol Chemical compound O=C.CCCCCCCCC1=CC=C(O)C=C1 ZLSPCFYPYRYKNF-UHFFFAOYSA-N 0.000 description 1
- UMGLBLXWFVODRF-UHFFFAOYSA-N formaldehyde;4-phenylphenol Chemical compound O=C.C1=CC(O)=CC=C1C1=CC=CC=C1 UMGLBLXWFVODRF-UHFFFAOYSA-N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IWVKTOUOPHGZRX-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(=O)C(C)=C IWVKTOUOPHGZRX-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- PMDKYLLIOLFQPO-UHFFFAOYSA-N monocyclohexyl phthalate Chemical compound OC(=O)C1=CC=CC=C1C(=O)OC1CCCCC1 PMDKYLLIOLFQPO-UHFFFAOYSA-N 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003459 sulfonic acid esters Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Description
本発明はポジ型感光性組成物に関し、更に詳し
くはホジ型PS平板に好適に用いられる感光性ｏ
−キノンジアジド樹脂を含む感光性組成物に関す
るものである。
ｏ−キノンジアジド化合物に活性光線を照射す
ると分解して五員環のカルボン酸を生じ、アルカ
リ可溶性となり、この性質を利用して感光性ポジ
型平版印刷版がつくられる。
これらのジアゾ化合物は一般にハロゲノスルホ
ニル基を有するｏ−キノンジアジド化合物をモノ
またはポリヒドロキシフエニル化合物と縮合して
得られるスルホン酸エステルの形で平版印刷版に
適用される。
従来、ｏ−キノンジアジド化合物の縮合相手の
ヒドロキシフエニル化合物としては、２，2′−ジ
ヒドロキシ−ジフエニル、２，2′，４，４−テト
ラヒドロキシジフエニル、２，３−ジヒドロキシ
ナフタリン、２，７−ジヒドロキシナフタリン、
１，２−ジヒドロキシアントラキノン、２，３−
ジヒドロキシアントラキノン、５，７−ジヒドロ
キシ−１−メチルアントラキノン、クミルフエノ
ール等が知られている。
これらの縮合生成物を単独で感光性層に用いる
と結晶の析出が生じ、その結果画像の機戒的強度
が弱く、多数枚の印刷ができない。そこでフエノ
ールホルムアルデヒド樹脂、シエラツクまたはス
チレン−無水マレイン酸樹脂等のアルカリ可溶性
樹脂を結着剤として使用し、これらの結晶の析出
を防ぐと共に画像の機械的強度を補つている。し
かし、この種の感光性層は現像において露光部と
未露光部の間の溶解度の差が減少する欠陥があ
る。
このような欠点に対して、感光性化合物自体を
高分子化することにより結晶の析出を防止し、支
持体との接着性を改善して耐刷力を高める技術が
米国特許第3046120号明細書に開示されている。
また、アルミニウム板との接着に留意した感光性
物質として特公昭43−28403号公報にアセトンと
ピロガロールの縮重合により得られたポリヒドロ
キシフエニルのｏ−キノンジアジドスルホン酸エ
ステルが記載されている。さらに特公昭49−
24361号公報には、低級フエノールおよび２価の
高級フエノールとホルムアルデヒドとの共縮合物
とハロゲノスルホニル基を有するキノンジアジド
化合物とを縮合させて得た感光性樹脂を感光性成
分として含有する感光性組成物が開示されてい
る。しかし、これらは何れもアルカリ溶液に対す
る溶解性が過少で現像し難く、地汚れを生じ易い
か、またはアルカリ溶液に対する溶解度が過大で
感光性層が現像時に損傷し易く、アルカリ性を弱
めた現像液を用いると現像液の寿命が短くなる欠
点を有する。
本発明の目的は、アルカリ溶液に対する適度の
溶解性を有し、地汚れや現像時の画像の損傷を生
じ難い感光性組成物を堤供することである。
本発明のさらに他の目的は、アルカリ溶液に対
する可溶性を任意に調節可能な感光性組成物を提
供することにある。
前記の目的は、レゾルシノールおよびその誘導
体からなる群から選ばれた少なくとも１種および
ピロガロールとアセトンとを共縮重合して得られ
るポリヒドロキシフエニル化合物とハロゲノスル
ホニル基を有するｏ−キノンジアジド化合物とを
縮合させて得られる感光性樹脂を含む感光性組成
物により達成される。
本発明に用いられるレゾルシノール誘導体とし
ては、例えばクレゾルシン、オルシン、β−オル
シン、２−メチルレゾルシノール、２−メトキシ
レゾルシノール、２，６−ジオキシアセトフエノ
ン等が挙げられる。
レゾルシノールおよび／またはその誘導体なら
びにピロガロールとアセトンとを共縮重合させる
には公知の方法により酸性条件下において必要な
らば加熱して縮合させればよい。得られるポリヒ
ドロキシフエニル化合物は、平均分子量350〜
5000程度のものが好ましく、トルエン、キシレン
等の芳香族炭化水素類、アセトン、メチルエチル
ケトン、メチルイソブチルケトン、シクロヘキサ
ノン等のケトン類、エチレンジクロライド等の塩
素化炭化水素類、エチレングリコールモノメチル
エーテル、酢酸２−メトキシエチル、ジオキサン
等のグリコールエーテル類、酢酸エチル、酢酸ブ
チル等のエステル類などの溶剤に可溶なものが望
ましい。
本発明の感光性組成物のアルカリ溶液に対する
可溶性を調節するには、ボリヒドロキシフエニル
化合物の重合形態（例えば分子量、架橋等）およ
びフエノール性水酸基の数を調節すればよい。一
般的にはレゾルシノールおよび／またはその誘導
体１モルに対してピロガロールを２モル以上の比
率とし、平均分子量を1000〜3000程度にすること
が好ましい。
本発明におけるポリヒドロキシフエニル化合物
と縮合させるハロゲノスルホニル基を有するｏ−
キノンジアジド化合物としては、ｏ−ベンゾキノ
ンジアジド、１，２−ナフトキノン−１−ジアジ
ド、１，２−ナフトキノン−２−ジアジド、７−
メトキシ−１，２−ナフトキノン−２−ジアジ
ド、７−メトキシ−１，２−ナフトキノン−２−
ジアジド、６−クロロ−１，２−ナフトキノン−
２−ジアジド、７−クロロ−１，２−ナフトキノ
ン−２−ジアジド、６−ニトロ−１，２−ナフト
キノン−２−ジアジド、５−（カルボキシメチ
ル）−１，２−ナフトキノン−ジアジド、３，
3′，４，4′−ジフエニル−ビス−キノン−４，
4′−ジアジド、２，３−フエナントレン−α−ジ
アジド等が挙げられる。
ポリヒドロキシフエニル化合物とハロゲノスル
ホニル基を有するｏ−キノンジアジド化合物とを
縮合させるには、上記ポリヒドロキシフエニル化
合物と所望のエステル化度に見合つた量のハロゲ
ノスルホニルｏ−キノンジアジド化合物とをジオ
キサンに溶解し、40〜50℃に保ちながら混合溶液
が中性となるまで徐々に炭酸ナトリアム水溶液を
加え、ついで約２〜４時間撹拌しながら反応させ
れば良い。本発明の感光性樹脂において、上記の
ポリヒドロキシフエニル化合物のフエノール性水
酸基の全てが該ジアゾ化合物との縮合に供される
必要はなく、一部のフエノール性水酸基が該ジア
ゾ化合物と縮合しただけでも活性光線照射により
アルカリ性水溶液に可溶となるが、特にフエノー
ル性水酸基の５分の１以上が該ジアゾ化合物と縮
合していることが好ましい。
本発明のポリヒドロキシフエニル化合物とハロ
ゲノスルホニル基を有するｏ−キノンジアジド化
合物との縮合主成物である感光性樹脂はそれを単
独でアルミニウム板などの支持体上に感光層とし
て設け、画像露光後、アルカリ性水溶液で現像で
き感脂性に優れた平版印刷版を与えるが、好まし
くはアルカリ可溶性樹脂を結着剤として用いるこ
とにより、現像進行性の速い、しかも適正現像の
幅の広い、かつ感脂性に優れた感光性組成物が得
られる。さらに特公昭50−5083号、特開昭50−
36206号、特開昭50−125806号公報あるいは英国
特許第1329886号明細書等に開示されている親油
性のフエノール樹脂およびこれらの樹脂とｏ−キ
ノンジアジド化合物との縮合生成物を添加するこ
とにより感脂性をより向上できる。
本発明において用いられるアルカリ可溶性樹脂
としては、例えばフエノールホルムアルデヒド樹
脂、クレゾールホルムアルデヒド樹脂の如き水酸
基を有する樹脂、あるいはスチレン−無水マレイ
ン酸共重合体、メタクリル酸メチル−メタクリル
酸共重合体、ポリ（フタル酸モノビニルエステ
ル）などのようなカルボキシル基を有する樹脂な
どが挙げられる。
本発明に用いられる親油性のフエノール樹脂と
しては、ｐ−置換フエノールホルムアルデヒド樹
脂があり、該置換基として、ｔ−ブチル基、ｔ−
アミル基、オクチル基、ベンジル基、タミル基な
どの如き炭素原子数４〜10のアルキル基、フエニ
ル基、トリル基などのようなアリ−ル基がある。
かかるｐ−置換フエノールホルムアルデヒド樹脂
の具体例としてはｐ−ｔ−ブチルフエノールホル
ムアルデヒド樹脂、ｐ−ｔ−アミルフエノール−
ホルムアルデヒド樹脂、ｐ−オクチルフエノール
ホルムアルデヒド樹脂、ｐ−フエニルフエノール
−ホルムアルデヒド樹脂などがある。
本発明において用いられる親油性のフエノール
樹脂とｏ−キノンジアジド化合物との縮合生成物
としては、上記親油性のフエノール樹脂とハロゲ
ノスルホニル基を有するｏ−キノンジアジド化合
物とを縮合させたものを有効に用いることができ
る。
本発明において、本発明のポリヒドロキシフエ
ニル化合物をハロゲノスルホニル基を有するｏ−
キノンジアジド化合物とを縮合させて得られる感
光性樹脂（以下、本発明の感光性樹脂という）を
アルカリ可溶性樹脂と混合して使用する場合、ア
ルカリ可溶性樹脂の使用量は総重量に対し約10〜
90％含有させるのが適当であり、より好ましくは
50％〜80％である。また、親油性のフエノール樹
脂および／または親油性のフエノール樹脂とｏ−
キノンジアジド化合物との縮合生成物を併用する
場合には、感光性組成物の総重量に対して両者を
合計して20％程度までの量を加えるのが適当であ
る。これらの樹脂はアルカリ可溶性樹脂と併用す
ることが望ましい。このような感光性樹脂以外の
成分は90重量％以下とすることが適当である。
本発明の感光性組成物は、更に必要に応じて染
料、可塑剤、シランカツプリング剤、酸あるいは
酸無水物等の添加により性能の改良を図ることも
できる。
染料としては、例えば露光、あるいは現像によ
り可視像を与えるようにする為のアルコール可溶
性染料が挙げられる。好適な染料にはオイルレツ
ドRR、オイルスカーレツト＃308、オイルブル
ー、メチレンフルー、クリスタルバイオレツト、
ベイシツクブルーなどが包含される。かかる染料
は、本発明の感光性印刷版の露光および現像によ
り露光された支持体の親水性表面の色と、感光層
の残存する部分とが明確なコントラストを与える
に十分な量だけ添加すれば良く、一般的には感光
性組成物全量に対して約７重量％以下の範囲で含
有させるのが適当である。
また、エポキシ樹脂、塩化ビニルと酢酸ビニル
の共重合体、ポリ塩化ビニリデン、ポリ酢酸ビニ
ル、エチルセルロース、アセチルブチルセルロー
スなどの親油性高分子化合物を感光性組成物に含
有させることにより、耐摩耗性が若干改繕され
る。特にアセチルブチルセルロースを使用した場
合、その効果が大きいので好ましい。このような
親油性高分子化合物は感光性組成物全量に対して
約８重量％以下、好まくは５重量％以下の範囲で
含有させられる。
可塑剤は支持体に設けられた感光層が所望の可
撓性を有するようにするために有効であり、例え
ばジメチルフタレート、ジエチルフタレート、ジ
ブチルフタレート、ジイソブチルフタレート、ジ
オクチルフタレート、オクチルカプリールフタレ
ート、シシクロヘキシルフタレート、ジトリデシ
ルフタレート、ブチルベンジルフタレート、ジイ
ソデシルフタレート、シアリ−ルフタレートなど
のフタル酸エステル類、ジメチルグリコールフタ
レート、エチルフタリールエチルグリコレート、
メチルフタリールエチルクリコレート、ブチルフ
タリールブチルグリコレート、トリエチレングリ
コールジカプリル酸エステル等のグリコールエス
テル類、トリクレジールホスフエート、トリフエ
ニルホスフエートなどの燐酸エステル類、ジイソ
ブチルアジペート、ジオクチルアジペート、ジメ
チルセパケート、ジブチルセパケート、ジオクチ
ルアセレート、ジブチルマレエートなどの脂肪族
二塩基酸エステル類、ポリグリシジルメタクリレ
ート、クエン酸トリエチル、グリセリントリアセ
チルエステル、ラウリン酸ブチル等が有効であ
る。
可塑剤は、感光性組成物全量に対して約５重量
％以下含有させられる。
また、特開昭51−52002号公報等に記載される
シアンカツプリング剤（例えばアミノアルコキシ
シラン化合物）を感光層と支持体との接着を改良
する目的で添加することができる。適当なアミノ
アルコキシシラン化合物の例は次の化合物であ
る：
アミノメチルトリエトキシシラン
NH2−CH2−Si−（OC2H5）3
β−アミノエチルトリエトキシシラン
NH2−（CH2）2−Si−（OC2H5）3
γ−アミノフロヒルトリエトキシシラン
NH2−（CH2）3−Si−（OC2H5）3
γ−アミノプロピルトリメトキシシラン
NH2−（CH2）3−Si−（OCH3）3
Ｎ−（β−アミノエチル）−τ−アミノプロピルト
リメトキシシラン
NH2−CH2−CH2−NH−（CH2）3−Si−（OCH3）3
本発明に使用される支持体は、寸度的に安定な
板状物である。かかる寸度的に安定な板状物とし
ては、従来印刷版の支持体として使用されたもの
が含まれ、それらは本発明に好適に使用すること
ができる。かかる支持体としては、紙、プラスチ
ツクス（例えばポリエチレン、ポリプロピレン、
ポリスチレンなど）がラミネートされた紙、例え
ばアルミニウム（アルミニウム合金も含む。）亜
鉛、銅などのような金属の板、例えば二酢酸セル
ロース、三酢酸セルロース、プロピオン酸セルロ
ース、酪酸セルロース、酢酸酪酸セルロース、硝
酸セルロース、ポリエチレンテレフタレート、ポ
リエチレン、ポリスチレン、ポリプロピレン、ポ
リカーボネート、ポリビニルアセタールなどのよ
うなプラスチツクスのフイルム、上記の如き金属
がラミネートもしくは蒸着された紙もしくはプラ
スチツクスフイルムなどが含まれる。これらの支
持体のうち、アルミニウム板は寸度的に著しく安
定であり、しかも安価であるので特に好ましい。
更に、特公昭48−18327号公報に記されているよ
うなポリエチレンテレフタレートフイルム上にア
ルミニウムシートが結合された複合体シートも好
ましい。
PS平版に用いる支持体の表面は親水性でなけ
ればならない。本発明において、親水性表面とは
水との接触角が120以下のことを意味する。
かかる親水性表面を設けるには、種々の方法が
ある。
例えばプラスチツクスの表面を有する支持体の
場合には、化学的処理、放電処理、火焔処理、紫
外線処理、高周波処理、グロー放電処理、活性プ
ラズマ処理、レーザー処理などの所謂表面処理方
法（例えば米国特許第2764520号、3497407号、
3145242号、3376208号、3072483号、3475193号、
3360448号、英国特許第788365号明細書など）と
一旦これらの表面処理後、該プラスチツクスに下
塗層を塗布する方法とがある。
塗布方法としても色々工夫が行われており一層
としてプラスチツクスによく接着し、かつ溶解性
のよい疎水性の樹脂層を塗布し、二層として親水
性の樹脂層を塗布する重層法と同一重合体中に疎
水基と親水基を含有する樹脂層を塗布する単層法
とがある。
また、金属、特にアルミニウムの表面を有する
支持体の場合には、砂目立て処理、珪酸ソーダ、
弗化ジルコニウム酸カリウム、燐酸塩等の水溶液
への浸漬処理、あるいは陽極酸化処理などの表面
処理がなされていることが好ましい。また、米国
特許第2714066号明細書に記載されている如く、
砂目立てしたのちに珪酸ナトリウム水溶液に浸漬
処理されたアルミニウム板、特公昭47−5125号公
報に記載されているようにアルミニウム板を陽極
酸化処理したのちに、アルカリ金属珪酸塩の水溶
液に浸漬処理したものも好適に使用される。上記
陽極酸化処理は、例えば燐酸、クロム酸、硫酸、
硼酸等の無機酸、若しくは蓚酸、スルフアミン酸
等の有機酸またはこれらの塩の水溶液又は非水溶
液の単独又は二種以上を組み合わせた電極液中で
アルミニウム板を陽極として電流を流すことによ
り実施される。
また、米国特許3658662号明細書に記載されて
いるようなシリケート電著も有効である。
これらの親水化処理は、支持体の表面を親水性
とするために施こされる以外に、その上に設けら
れる感光性組成物との有害な反応を防ぐためや、
感光層との密着性の向上等の為に施されるもので
ある。とくに、アルミニウム支持体の場合、その
表面は、何ら親水化処理を施さなくても、充分な
親水性を示し（接触角約110）、従つて感光性組成
物との有害な反応および感光層と支持体表面との
密着性の向上を主目的とするものである。
上記の如き組成からなる感光性組成物は適当な
溶媒の溶液として親水性表面を有する支持体上に
塗布される。適当なる溶媒としてはエチレングリ
コールモノメチルエーテル、エチレングリコール
モノエチルエーテル、酢酸２−メトキシエチルな
どのグリコールエーテル類、アセトンメチルエチ
ルケトン、シクロヘキサノンなどのケトン類、エ
チレンジクロライド等の塩素化炭化水素類等に溶
解されて適当な支持体上に塗布される。
塗布方法は、従来公知の方法、例えばデイツプ
塗布、エアーナイフ塗布、ピード塗布、カーテン
塗布および米国特許第2681294号明細書に示され
ているようなホツパーを用いる押し出し塗布など
の種々の方法が可能である。
かかる支持体上に塗布される本発明の感光性組
成物の量は約0.5〜7.0ｇ／m2が適当であり1.5〜
3.0／m2がより好ましい。
本発明の感光性組成物を塗設した平版印刷版は
透明陽画フイルムを通してカーボンアーク灯、水
銀灯、キセノンランプ、タングステンランプなど
の活性光線の豊富な光線により露光されると、そ
の部分はアルカリ可溶性に変る。従つて珪酸ソー
ダ、燐酸ソーダのようなアルカリ水溶液又は更に
ベンジルアルコール、エチレングリコールモノブ
チルエーテルのような有機溶剤、又は界面活性剤
等を含有する溶液に浸漬すると溶解除去され、未
露光域のみが支持体表面に陽画像として残る。水
洗後印刷機に収付け常法に従つて印刷すると極め
てインキ着肉性に優れた損紙の少ない印刷版とし
て使用できる。
更に、本発明の感光性組成物はフオトレジスト
材料や、オーバーヘツドプロジエクター用画像の
作成にも使用することができる。更に、校正用に
使用されるカラープルーフの作成にも使用するこ
とができる。
以下、本発明を実施例に基いて、更に詳細に説
明する。なお％は重量％を示すものとする。
合成例 １
レゾルシン0.05モルとピロガロール0.15モルを
３モルのアセトンに溶解し、縮合触媒として、
0.016モルのオキシ塩化燐を加え、室温で１日放
置後多量の水の中へ撹拌しながら滴下し、フレー
ク状に沈澱した樹脂を得た。このフレーク状の樹
脂をさらに多量の水で水洗した後、乾燥して得た
樹脂の分子量分布をGPC（カラムとして昭和電
工(株)社製Shodex A802×A803×A804を使用し、
標品としてポリスチレンを用いて検量線を作製）
により求めると分子量分布の主たるピークは1850
であつた。
上記のポリヒドロキシフエニル30ｇをジオキサ
ン300mlに溶解し、68.4ｇの２−ジアゾ−１−ナ
フトール−５−スルホクロリドを加え、40〜45℃
に保ちながら溶液が完全に中和されるまで５％の
炭酸カリ溶液を撹拌しながら、ゆつくりと加え
た。添加終了後約１時間撹拌を続行した後、約４
の塩酸酸性水溶液中に滴下し析出する固形分を
濾集し、水洗して乾燥した。
合成例 ２
レゾルシンを２−メチルレゾルシンとした以外
は合成例１と同様にして得た樹脂の分子量分布を
前記GPCにより求めると、分子量分布の主たる
ピークは3000であつた。
この様にして得たポリヒドロキシフエニル8.3
ｇを100mlのジオキサンに溶解し、18.45ｇの２−
ジアゾ−１−ナフトール−５−スルホクロリドを
加えた以外は合成例１と同様にして黄褐色粉末状
の樹脂を得た。
実施例 １
合成例１，２にしたがい、レゾルシンあるいは
メチルレゾルシンとピロガロールの仕込みモル比
を変化させたポリヒドロキシフエニルを合成し、
電解研磨により砂目立てし、かつ陽極酸化処理お
よび熱水封孔処理したアルミニウム板上に下記組
成の感光液を乾燥重量が27mg／ｄm2になるように
ホアラーを用いて塗布した。
合成例１あるいは２で得られたポリヒドロキシ
フエニル １重量部
クレゾール−ホルムアルデヒド樹脂 3.25重量部
メチルセルソルブ 33重量部
80〜90℃で約２分間乾燥した後、50℃の乾燥器
中に１日放置したものを試料（75cm2）とし、メタ
ルハライドランプを光源として８×103μｗ／cm3
の光強度でステツプタブレツト（イーストマンコ
ダツク社製Photographic step tabletNo.２）を通
して70秒露光し、DP−１（富士写真フイルム(株)
社製：ケイ酸ナトリウム水溶液）の７倍希釈液
100c.c.で20℃で60秒間現像した。
この時、同一現像液で地汚れが生じない試料枚
数は表１に示す通りであつた。
また比較例１として特公昭43−28403号公報に
記載の方法により合成したピロガロールとアセト
ンからなるポリヒドロキシフエニルの２−ジアゾ
−１−ナフトール−５−スルホン酸エステルを用
いて同様に現像すると現像過多となり未露光部分
も溶解した。そこで、前記DP−１の15倍希釈液
（100c.c.）で20℃で60秒間現像したが、この場合は
現像液の疲労が速く、地汚れのない試料枚数は約
30枚であつた。
さらに、比較例２として特公昭49−24361号公
報に記載の低級フエノールと２価の高級フエノー
ルのホルムアルデヒドによる共縮合物の２−ジア
ゾ−１−ナフトール−５−スルホン酸エステルを
用いて実施例と同様に現像すると同一現像液で地
汚れが生じない試料枚数は約20枚であつた。
これらの結果から、本発明の感光性組成物は適
当なアルカリ溶解性を有し、地汚れや現像温度を
生じ難いことがわかる。
The present invention relates to a positive photosensitive composition, and more specifically to a photosensitive composition suitable for use in a positive type PS flat plate.
- It relates to a photosensitive composition containing a quinonediazide resin. When an o-quinonediazide compound is irradiated with actinic rays, it decomposes to produce a five-membered ring carboxylic acid, which becomes alkali-soluble, and this property is utilized to produce photosensitive positive-working lithographic printing plates. These diazo compounds are generally applied to lithographic printing plates in the form of sulfonic acid esters obtained by condensing an o-quinonediazide compound having a halogenosulfonyl group with a mono- or polyhydroxyphenyl compound. Conventionally, hydroxyphenyl compounds as condensation partners for o-quinonediazide compounds include 2,2'-dihydroxy-diphenyl, 2,2',4,4-tetrahydroxydiphenyl, 2,3-dihydroxynaphthalene, 2,7 -dihydroxynaphthalene,
1,2-dihydroxyanthraquinone, 2,3-
Dihydroxyanthraquinone, 5,7-dihydroxy-1-methylanthraquinone, cumylphenol, and the like are known. If these condensation products are used alone in the photosensitive layer, crystals will precipitate, and as a result, the mechanical strength of the image will be weak, making it impossible to print a large number of sheets. Therefore, an alkali-soluble resin such as a phenol formaldehyde resin, a Sierra resin, or a styrene-maleic anhydride resin is used as a binder to prevent the precipitation of these crystals and to supplement the mechanical strength of the image. However, this type of photosensitive layer has the drawback that the difference in solubility between exposed and unexposed areas decreases during development. To address these drawbacks, US Pat. No. 3,046,120 discloses a technology that prevents crystal precipitation by polymerizing the photosensitive compound itself, improves adhesion to the support, and increases printing durability. has been disclosed.
Further, as a photosensitive material with consideration given to adhesion to an aluminum plate, Japanese Patent Publication No. 43-28403 describes an o-quinonediazide sulfonic acid ester of polyhydroxyphenyl obtained by polycondensation of acetone and pyrogallol. In addition, the special public service in 1977-
Publication No. 24361 discloses a photosensitive composition containing as a photosensitive component a photosensitive resin obtained by condensing a cocondensate of a lower phenol and a divalent higher phenol with formaldehyde and a quinone diazide compound having a halogenosulfonyl group. is disclosed. However, all of these have low solubility in alkaline solutions and are difficult to develop, and tend to cause background smudges, or have excessive solubility in alkaline solutions and easily damage the photosensitive layer during development. If used, it has the disadvantage that the life of the developer will be shortened. An object of the present invention is to provide a photosensitive composition that has appropriate solubility in alkaline solutions and is less likely to cause scumming or damage to images during development. Still another object of the present invention is to provide a photosensitive composition whose solubility in an alkaline solution can be arbitrarily adjusted. The above object is to condense a polyhydroxyphenyl compound obtained by cocondensation polymerization of at least one member selected from the group consisting of resorcinol and its derivatives, pyrogallol, and acetone with an o-quinonediazide compound having a halogenosulfonyl group. This is achieved by a photosensitive composition containing a photosensitive resin obtained by Examples of the resorcinol derivatives used in the present invention include cresorcin, orcin, β-orcin, 2-methylresorcinol, 2-methoxyresorcinol, 2,6-dioxyacetophenone, and the like. Cocondensation polymerization of resorcinol and/or its derivatives, pyrogallol, and acetone may be carried out by a known method under acidic conditions, with heating if necessary. The obtained polyhydroxyphenyl compound has an average molecular weight of 350~
About 5000 is preferable, and aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, chlorinated hydrocarbons such as ethylene dichloride, ethylene glycol monomethyl ether, and acetic acid 2- Those soluble in solvents such as glycol ethers such as methoxyethyl and dioxane, and esters such as ethyl acetate and butyl acetate are desirable. In order to adjust the solubility of the photosensitive composition of the present invention in an alkaline solution, the polymerization form (eg, molecular weight, crosslinking, etc.) of the polyhydroxyphenyl compound and the number of phenolic hydroxyl groups may be adjusted. Generally, it is preferable that the ratio of pyrogallol to 1 mol of resorcinol and/or its derivative is 2 mol or more, and the average molecular weight is about 1000 to 3000. o- having a halogenosulfonyl group to be condensed with the polyhydroxyphenyl compound in the present invention
Examples of quinonediazide compounds include o-benzoquinonediazide, 1,2-naphthoquinone-1-diazide, 1,2-naphthoquinone-2-diazide, 7-
Methoxy-1,2-naphthoquinone-2-diazide, 7-methoxy-1,2-naphthoquinone-2-
Diazide, 6-chloro-1,2-naphthoquinone-
2-diazide, 7-chloro-1,2-naphthoquinone-2-diazide, 6-nitro-1,2-naphthoquinone-2-diazide, 5-(carboxymethyl)-1,2-naphthoquinone-diazide, 3,
3',4,4'-diphenyl-bis-quinone-4,
Examples include 4'-diazide and 2,3-phenanthrene-α-diazide. In order to condense a polyhydroxyphenyl compound and an o-quinonediazide compound having a halogenosulfonyl group, the polyhydroxyphenyl compound and an amount of the halogenosulfonyl o-quinonediazide compound corresponding to the desired degree of esterification are dissolved in dioxane. Then, while maintaining the temperature at 40 to 50°C, add an aqueous sodium carbonate solution gradually until the mixed solution becomes neutral, and then react while stirring for about 2 to 4 hours. In the photosensitive resin of the present invention, it is not necessary that all of the phenolic hydroxyl groups of the polyhydroxyphenyl compound described above be subjected to condensation with the diazo compound, but only some of the phenolic hydroxyl groups are condensed with the diazo compound. Although it becomes soluble in an alkaline aqueous solution by irradiation with actinic rays, it is particularly preferable that one-fifth or more of the phenolic hydroxyl groups are condensed with the diazo compound. The photosensitive resin which is the main condensation product of the polyhydroxyphenyl compound of the present invention and the o-quinonediazide compound having a halogenosulfonyl group is provided alone as a photosensitive layer on a support such as an aluminum plate, and after image exposure. provides a lithographic printing plate that can be developed with an alkaline aqueous solution and has excellent oil sensitivity. Preferably, by using an alkali-soluble resin as a binder, development progresses quickly, a range of appropriate development is wide, and oil sensitivity is achieved. An excellent photosensitive composition is obtained. In addition, JP-A No. 50-5083, JP-A No. 50-
36206, JP-A-50-125806, British Patent No. 1329886, etc., and the condensation products of these resins and o-quinonediazide compounds. Oiliness can be further improved. Examples of the alkali-soluble resin used in the present invention include resins having hydroxyl groups such as phenol formaldehyde resin and cresol formaldehyde resin, styrene-maleic anhydride copolymer, methyl methacrylate-methacrylic acid copolymer, and poly(phthalic acid) Examples include resins having a carboxyl group such as monovinyl ester). The lipophilic phenol resin used in the present invention includes p-substituted phenol formaldehyde resin, and the substituents include t-butyl group, t-
Examples include alkyl groups having 4 to 10 carbon atoms such as amyl, octyl, benzyl and tamyl groups, and aryl groups such as phenyl and tolyl groups.
Specific examples of such p-substituted phenol formaldehyde resins include p-t-butylphenol formaldehyde resin, p-t-amylphenol-
Examples include formaldehyde resin, p-octylphenol formaldehyde resin, and p-phenylphenol-formaldehyde resin. As the condensation product of a lipophilic phenol resin and an o-quinonediazide compound used in the present invention, a condensation product of the lipophilic phenol resin and an o-quinonediazide compound having a halogenosulfonyl group can be effectively used. Can be done. In the present invention, the polyhydroxyphenyl compound of the present invention is used as an o-
When using a photosensitive resin obtained by condensing a quinonediazide compound (hereinafter referred to as the photosensitive resin of the present invention) with an alkali-soluble resin, the amount of the alkali-soluble resin used is about 10 to 10% of the total weight.
It is appropriate to contain 90%, more preferably
It is between 50% and 80%. In addition, lipophilic phenolic resin and/or lipophilic phenolic resin and o-
When a condensation product with a quinonediazide compound is used in combination, it is appropriate to add the condensation product in an amount up to about 20% of the total weight of the photosensitive composition. It is desirable to use these resins together with an alkali-soluble resin. It is appropriate that the content of components other than the photosensitive resin be 90% by weight or less. The performance of the photosensitive composition of the present invention can be further improved by adding dyes, plasticizers, silane coupling agents, acids or acid anhydrides, etc., if necessary. Examples of the dye include alcohol-soluble dyes that provide a visible image upon exposure or development. Suitable dyes include Oil Red RR, Oil Scarlet #308, Oil Blue, Methylene Flu, Crystal Violet,
Includes basic blue, etc. Such a dye can be added in an amount sufficient to provide a clear contrast between the color of the hydrophilic surface of the support exposed by exposure and development of the photosensitive printing plate of the present invention and the remaining portion of the photosensitive layer. In general, it is appropriate that the content be within a range of about 7% by weight or less based on the total amount of the photosensitive composition. In addition, abrasion resistance can be improved by incorporating lipophilic polymer compounds such as epoxy resin, copolymer of vinyl chloride and vinyl acetate, polyvinylidene chloride, polyvinyl acetate, ethyl cellulose, and acetyl butyl cellulose into the photosensitive composition. It will be slightly renovated. Particularly, it is preferable to use acetyl butyl cellulose because its effect is large. Such a lipophilic polymer compound is contained in an amount of about 8% by weight or less, preferably 5% by weight or less, based on the total amount of the photosensitive composition. Plasticizers are effective for imparting desired flexibility to the photosensitive layer provided on the support, and include, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, and silicone. Phthalate esters such as cyclohexyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, sialyl phthalate, dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate,
Glycol esters such as methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate, phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, diisobutyl adipate, dioctyl adipate, dimethyl sepa Aliphatic dibasic acid esters such as cate, dibutyl sepacate, dioctyl acelate, and dibutyl maleate, polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, butyl laurate, and the like are effective. The plasticizer is contained in an amount of about 5% by weight or less based on the total amount of the photosensitive composition. Further, a cyan coupling agent (for example, an aminoalkoxysilane compound) described in JP-A-51-52002 and the like can be added for the purpose of improving the adhesion between the photosensitive layer and the support. Examples of suitable aminoalkoxysilane compounds are the following compounds: Aminomethyltriethoxysilane NH2 -CH2- Si-( OC2H5 ) 3 β-Aminoethyltriethoxysilane NH2- ( CH2 ) 2 -Si-(OC 2 H 5 ) 3 γ-Aminofurohyltriethoxysilane NH 2 -(CH 2 ) 3 -Si-(OC 2 H 5 ) 3 γ-Aminopropyltrimethoxysilane NH 2 -(CH 2 ) 3 -Si-( OCH3 ) 3N- (β-aminoethyl)-τ-aminopropyltrimethoxysilaneNH2-CH2 - CH2 - NH- ( CH2 ) 3- Si-( OCH3 ) 3 pieces The support used in the invention is a dimensionally stable plate. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and they can be suitably used in the present invention. Such supports include paper, plastics (e.g. polyethylene, polypropylene,
paper laminated with aluminum (including aluminum alloys); plates of metals such as zinc, copper, etc. (e.g. cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitric acid) Films of plastics such as cellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above are included. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive.
Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred. The surface of the support used in PS lithography must be hydrophilic. In the present invention, a hydrophilic surface means a surface having a contact angle with water of 120 or less. There are various ways to provide such a hydrophilic surface. For example, in the case of a support having a plastic surface, so-called surface treatment methods such as chemical treatment, electric discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, activated plasma treatment, laser treatment, etc. (for example, U.S. Pat. No. 2764520, No. 3497407,
No. 3145242, No. 3376208, No. 3072483, No. 3475193,
3360448, British Patent No. 788365, etc.) and a method in which a subbing layer is applied to the plastics after these surface treatments. A variety of coating methods have been devised, including a multi-layer method in which a hydrophobic resin layer that adheres well to plastics and has good solubility is applied as one layer, and a hydrophilic resin layer is applied as a second layer. There is a single layer method in which a resin layer containing hydrophobic groups and hydrophilic groups is applied during coalescence. In addition, in the case of a support having a surface of metal, especially aluminum, graining treatment, sodium silicate treatment,
It is preferable that the surface be subjected to a surface treatment such as immersion treatment in an aqueous solution of potassium fluorozirconate or phosphate, or anodization treatment. Also, as described in U.S. Patent No. 2,714,066,
Aluminum plate that was grained and then immersed in an aqueous solution of sodium silicate, an aluminum plate that was anodized and then immersed in an aqueous solution of an alkali metal silicate as described in Japanese Patent Publication No. 47-5125. Also preferably used. The above anodic oxidation treatment is performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing a current through an aluminum plate as an anode in an electrode solution consisting of an aqueous solution or a non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. . Furthermore, silicate crystals as described in US Pat. No. 3,658,662 are also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon,
This is applied to improve adhesion with the photosensitive layer. In particular, in the case of an aluminum support, its surface exhibits sufficient hydrophilicity (contact angle of about 110) without any hydrophilic treatment, thus preventing harmful reactions with the photosensitive composition and the photosensitive layer. The main purpose is to improve the adhesion to the surface of the support. The photosensitive composition having the above composition is applied as a solution in a suitable solvent onto a support having a hydrophilic surface. Suitable solvents include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 2-methoxyethyl acetate, ketones such as acetone methyl ethyl ketone and cyclohexanone, and chlorinated hydrocarbons such as ethylene dichloride. Coated onto a suitable support. Various methods can be used for the coating, such as dip coating, air knife coating, peel coating, curtain coating, and extrusion coating using a hopper as shown in US Pat. No. 2,681,294. be. The amount of the photosensitive composition of the present invention coated on such a support is suitably about 0.5 to 7.0 g/m2, and about 1.5 to 7.0 g/ m2 .
3.0/m 2 is more preferred. When a lithographic printing plate coated with the photosensitive composition of the present invention is exposed through a transparent positive film to a light beam rich in active light such as a carbon arc lamp, mercury lamp, xenon lamp, or tungsten lamp, the exposed portion becomes alkali-soluble. Change. Therefore, when immersed in an alkaline aqueous solution such as sodium silicate or sodium phosphate, or a solution containing an organic solvent such as benzyl alcohol or ethylene glycol monobutyl ether, or a surfactant, it is dissolved and removed, leaving only the unexposed area of the support. It remains as a positive image on the surface. After washing with water, the plate is placed in a printing machine and printed according to a conventional method, and can be used as a printing plate with extremely excellent ink receptivity and little paper loss. Furthermore, the photosensitive composition of the present invention can also be used as a photoresist material and in the production of images for overhead projectors. Additionally, it can be used to create color proofs used for proofing. Hereinafter, the present invention will be explained in more detail based on Examples. Note that % indicates weight %. Synthesis Example 1 0.05 mol of resorcinol and 0.15 mol of pyrogallol were dissolved in 3 mol of acetone, and as a condensation catalyst,
0.016 mol of phosphorus oxychloride was added, and after being left at room temperature for one day, it was dropped into a large amount of water with stirring to obtain a resin precipitated in the form of flakes. After washing this flaky resin with a large amount of water, the molecular weight distribution of the dried resin was measured using GPC (using Showa Denko Co., Ltd.'s Shodex A802×A803×A804 as a column).
Prepare a calibration curve using polystyrene as a standard)
The main peak of the molecular weight distribution is 1850
It was hot. Dissolve 30 g of the above polyhydroxyphenyl in 300 ml of dioxane, add 68.4 g of 2-diazo-1-naphthol-5-sulfochloride, and add at 40-45℃.
5% potassium carbonate solution was slowly added while stirring until the solution was completely neutralized. After continuing stirring for about 1 hour after the addition, about 4
was dropped into an acidic aqueous solution of hydrochloric acid, and the precipitated solid content was collected by filtration, washed with water, and dried. Synthesis Example 2 The molecular weight distribution of a resin obtained in the same manner as Synthesis Example 1 except that 2-methylresorcin was used instead of resorcin was determined by the above GPC, and the main peak of the molecular weight distribution was 3000. Polyhydroxyphenyl 8.3 obtained in this way
g in 100 ml of dioxane, 18.45 g of 2-
A yellowish brown powdery resin was obtained in the same manner as in Synthesis Example 1 except that diazo-1-naphthol-5-sulfochloride was added. Example 1 According to Synthesis Examples 1 and 2, polyhydroxyphenyl was synthesized by changing the charging molar ratio of resorcin or methylresorcin and pyrogallol,
A photosensitive solution having the following composition was coated using a hoarer to a dry weight of 27 mg/dm 2 on an aluminum plate that had been grained by electrolytic polishing, anodized, and sealed with hot water. Polyhydroxyphenyl obtained in Synthesis Example 1 or 2 1 part by weight Cresol-formaldehyde resin 3.25 parts by weight Methylcellosolve 33 parts by weight After drying at 80-90°C for about 2 minutes, it was placed in a dryer at 50°C for 1 day. The sample (75cm 2 ) left standing was used as a light source, and the light source was 8×10 3 μw/cm 3 .
It was exposed for 70 seconds through a step tablet (Photographic step tablet No. 2 manufactured by Eastman Kodak Co., Ltd.) at a light intensity of
Manufactured by: 7 times diluted solution of sodium silicate aqueous solution)
Developed at 100 c.c. for 60 seconds at 20°C. At this time, the number of samples without background smudge using the same developer was as shown in Table 1. In addition, as Comparative Example 1, 2-diazo-1-naphthol-5-sulfonic acid ester of polyhydroxyphenyl composed of pyrogallol and acetone synthesized by the method described in Japanese Patent Publication No. 43-28403 was used and developed in the same manner. It became too much and the unexposed areas were also dissolved. Therefore, development was performed at 20℃ for 60 seconds using a 15-fold diluted solution (100c.c.) of DP-1, but in this case, the developer fatigued quickly, and the number of samples without scumming was approximately
It was 30 pieces. Furthermore, as Comparative Example 2, 2-diazo-1-naphthol-5-sulfonic acid ester, which is a co-condensation product of lower phenol and divalent higher phenol with formaldehyde, described in Japanese Patent Publication No. 49-24361, was used. When developed in the same manner, the number of samples without background smudge using the same developer was about 20. These results show that the photosensitive composition of the present invention has appropriate alkali solubility and is unlikely to cause scumming or development temperature.
【表】
さらに本発明の感光性組成物を用いた印刷版は
皮膜強度が強く、インキ受容性に優れており、良
好な印刷物を得ることができる。[Table] Further, the printing plate using the photosensitive composition of the present invention has strong film strength and excellent ink receptivity, and can produce good printed matter.
Claims (1)
ら選はれた少なくとも１種およびピロガロールと
アセトンとの共縮合重合により得られるポリヒド
ロキシフエニル化合物とハロゲノスルホニル基を
有するｏ−キノンジアジド化合物とを縮合させて
得られる感光性樹脂を含む感光性組成物。 A photosensitive material obtained by condensing a polyhydroxyphenyl compound obtained by cocondensation polymerization of at least one member selected from the group consisting of resorcinol and its derivatives, pyrogallol, and acetone, and an o-quinonediazide compound having a halogenosulfonyl group. A photosensitive composition containing a photosensitive resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15079478A JPS5576346A (en) | 1978-12-05 | 1978-12-05 | Photosensitive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15079478A JPS5576346A (en) | 1978-12-05 | 1978-12-05 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5576346A JPS5576346A (en) | 1980-06-09 |
| JPS6244257B2 true JPS6244257B2 (en) | 1987-09-18 |
Family
ID=15504570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15079478A Granted JPS5576346A (en) | 1978-12-05 | 1978-12-05 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5576346A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314552A2 (en) | 1998-04-06 | 2003-05-28 | Fuji Photo Film Co., Ltd. | Photosensitive resin composition |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61107352A (en) * | 1984-10-31 | 1986-05-26 | Konishiroku Photo Ind Co Ltd | Positive plating material for lithographic printing |
| JPH0719050B2 (en) * | 1985-12-09 | 1995-03-06 | コニカ株式会社 | Photosensitive lithographic printing plate material |
| EP1884372B1 (en) | 2006-08-03 | 2009-10-21 | Agfa Graphics N.V. | A lithographic printing plate support |
| ES2344668T3 (en) | 2007-11-30 | 2010-09-02 | Agfa Graphics N.V. | METHOD TO TREAT A LITHOGRAPHIC PRINT IRON. |
| EP2098376B1 (en) | 2008-03-04 | 2013-09-18 | Agfa Graphics N.V. | A method for making a lithographic printing plate support |
| ES2365885T3 (en) | 2008-03-31 | 2011-10-13 | Agfa Graphics N.V. | A METHOD TO TREAT A LITHOGRAPHIC PRINT IRON. |
| EP3032334B1 (en) | 2014-12-08 | 2017-10-18 | Agfa Graphics Nv | A system for reducing ablation debris |
| CA3017777A1 (en) | 2016-03-16 | 2017-09-21 | Agfa Nv | Method for processing a lithographic printing plate |
| EP3637188A1 (en) | 2018-10-08 | 2020-04-15 | Agfa Nv | An effervescent developer precursor for processing a lithographic printing plate precursor |
-
1978
- 1978-12-05 JP JP15079478A patent/JPS5576346A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314552A2 (en) | 1998-04-06 | 2003-05-28 | Fuji Photo Film Co., Ltd. | Photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5576346A (en) | 1980-06-09 |
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