JPS62176876A - Developer composition for pressure-sensitive copy paper - Google Patents
Developer composition for pressure-sensitive copy paperInfo
- Publication number
- JPS62176876A JPS62176876A JP61019228A JP1922886A JPS62176876A JP S62176876 A JPS62176876 A JP S62176876A JP 61019228 A JP61019228 A JP 61019228A JP 1922886 A JP1922886 A JP 1922886A JP S62176876 A JPS62176876 A JP S62176876A
- Authority
- JP
- Japan
- Prior art keywords
- latex
- polymer
- color
- paper
- leuco dye
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 14
- 239000004816 latex Substances 0.000 claims abstract description 34
- 229920000126 latex Polymers 0.000 claims abstract description 34
- 239000003094 microcapsule Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 230000008961 swelling Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 abstract description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 16
- 235000019198 oils Nutrition 0.000 description 16
- 239000000975 dye Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000011161 development Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 attapulgide Chemical compound 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- XQOPAAPKNCNLFX-UHFFFAOYSA-N 1-n,1-n-diethyl-3-n-fluoro-4-methylbenzene-1,3-diamine Chemical compound CCN(CC)C1=CC=C(C)C(NF)=C1 XQOPAAPKNCNLFX-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- UVRCNEIYXSRHNT-UHFFFAOYSA-N 3-ethylpent-2-enamide Chemical compound CCC(CC)=CC(N)=O UVRCNEIYXSRHNT-UHFFFAOYSA-N 0.000 description 1
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/132—Chemical colour-forming components; Additives or binders therefor
- B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は発色性及び印刷適性を改善した感圧複写紙用顕
色剤染料組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a developer dye composition for pressure-sensitive copying paper that has improved color development and printability.
（従来の技術）
感圧複写紙は通常電子供与性無色ロイコ染料と有機溶剤
を含有するマイクロカプセルを裏面に塗布した上用紙と
、無色ロイコ染料と反応し発色させる電子受容性の顕色
剤を表面に塗布した下用紙から成シ、各々の塗布面を対
向させ上用紙の上からゲール（ンやタイプライタ−など
で加圧印字することにより、マイクロカプセルが破壊さ
れ、マイクロカプセル中の無色ロイコ染料が有機溶剤と
共に下用紙へ移動し、顕色剤と反応して下用紙伶布面に
有色の記録像を得るものである。又、表面に顕色剤層、
裏面にマイクロカプセル層を設ケタ中用紙を上用紙と下
用紙の中間に挿入し、複数枚の複写も可能である。さら
に、別の形態として、シートの同一面に前記のマイクロ
カプセルと顕色剤の両者を塗布した単一記録シートある
いは単体発色紙と呼ばれるものがある。本発明にいう卯
色シートとは形態の如何を問わず、顕色剤を含むシート
状物を全て感圧複写紙用顕色シートとして包含するもの
である。(Prior art) Pressure-sensitive copying paper usually consists of an upper paper coated with microcapsules containing an electron-donating colorless leuco dye and an organic solvent on the back side, and an electron-accepting color developer that reacts with the colorless leuco dye to develop color. The microcapsules are destroyed and the colorless leuco in the microcapsules is destroyed by pressing the top paper with a gel or typewriter to print on the top paper with each coated surface facing each other. The dye moves to the lower paper together with the organic solvent and reacts with the color developer to obtain a colored recorded image on the surface of the lower paper.Also, there is a color developer layer on the surface,
With a microcapsule layer on the back side, it is possible to make multiple copies by inserting the middle paper between the upper and lower papers. Furthermore, as another form, there is a sheet called a single recording sheet or single coloring paper in which both the microcapsules and the color developer are coated on the same side of the sheet. The term "maroon color sheet" as used in the present invention includes all sheet-like materials containing a color developer, regardless of their form, as color developer sheets for pressure-sensitive copying paper.
感圧複写紙は近年、著しい需要の伸びを示しておシ、そ
の品質に対する要求も高度化してきている。特に発色面
となる顕色シートは鮮明な記録が得られることはもとよ
シ、高速印刷に耐えうる表面強度の改善が求められてい
る。Pressure-sensitive copying paper has shown remarkable growth in demand in recent years, and demands for its quality have also become more sophisticated. In particular, the color developing sheet, which serves as the coloring surface, is required not only to provide clear records but also to have improved surface strength that can withstand high-speed printing.
顕色シートに用いられるａ子受容性の顕色剤としては、
酸性白土、活性白土、焼成活性白土、焼成カオリン、ア
タパルガイド、ベントナイト、ゼオライト、シリケート
、タルクなどの無機顕色剤。As an a-child-receptive color developer used in a color developer sheet,
Inorganic color developers such as acid clay, activated clay, calcined activated clay, calcined kaolin, attapulgide, bentonite, zeolite, silicate, and talc.
フェノール化合物、フェノール樹脂、マレイン酸−ロジ
ン樹脂９部分的ないし全面的に加水分解されたスチレン
−無水マレイン酸共重合体、フェノール樹脂の多価金属
塩、芳香族カルゲン酸、芳香族カルゲン酸の多価金属塩
などの有機顕色剤が従来より知られている。Phenolic compounds, phenolic resins, maleic acid-rosin resins 9 Partially or fully hydrolyzed styrene-maleic anhydride copolymers, polyvalent metal salts of phenolic resins, aromatic cargenic acids, polyesters of aromatic cargenic acids, Organic color developers such as valent metal salts have been known for some time.
顕色シートは、上記の如き顕色剤を含有する塗液中に、
カオリン、炭酸カルシウム、タルクなどの無機顔料を加
え、さらにこれらの顕色剤および顔料を基体シートに接
着固定するためのバインダーとして澱粉、デキストリン
、カゼイン、アラビアデム、メチルセルローズ、エチル
セルローズ。The color developing sheet is a coating liquid containing a color developer as described above.
Inorganic pigments such as kaolin, calcium carbonate, and talc are added, and starch, dextrin, casein, arabic dem, methyl cellulose, and ethyl cellulose are used as binders to adhesively fix these color developers and pigments to the base sheet.
カルゲキシ・メチル・セルローズ、カル？キシ・エチル
セルローズ、ヒドロキシエチルセルローズ。Calgexi methyl cellulose, Cal? xyethylcellulose, hydroxyethylcellulose.
ポリビニルアルコール、ポリアクリルアマイドなどの水
溶性高分子、スチレンブタジェン共重合体。Water-soluble polymers such as polyvinyl alcohol and polyacrylamide, and styrene-butadiene copolymers.
メチルメタクリレートブタジェン共重合体、アクリロニ
トリルブタジェン共重合体、酢酸ビニル共重合体、アク
リル酸エステル共重合体、これら共重合体のカルはキシ
変性共重合体などの高分子ラテックス４どかあり、これ
らから選ばれたｉｆ！ｌ又は２種以上が添加され、更に
必要に応じて分数剤。Methyl methacrylate butadiene copolymer, acrylonitrile butadiene copolymer, vinyl acetate copolymer, acrylic acid ester copolymer, and polymer latexes such as xy-modified copolymers are available. If selected from! 1 or 2 or more are added, and if necessary, a fractional agent is added.
ｐ）ＩＮ整剤などを配合して、顕色剤塗料とし、この顕
色剤塗料を基体シートに塗布し、乾燥することによシ得
られる。p) It can be obtained by blending an IN preservative and the like to form a color developer paint, applying this color developer paint to a base sheet, and drying it.
特に、バインダーとして高分子ラテックス類を用いた場
合には他の水溶性高分子類のみをバインダーとして用い
た場合に比較して、高濃度且つ低粘度の顕色剤塗料が得
られるため、乾燥負荷の軽減が可能となると共に、エア
・ナイフ・コーター。In particular, when a polymer latex is used as a binder, a developer paint with a higher concentration and lower viscosity can be obtained compared to when only other water-soluble polymers are used as a binder, so the drying load is lower. Air knife coater.
ロール・コーター、及ヒブレード・コーターナトの多様
な塗工機に適用しうる利点がある。It has the advantage of being applicable to a variety of coating machines, including roll coaters and blade coaters.
顕色シートの発色性向上を目的として粒径の細かい顔料
を用いることも提案されているが、顔料が細かくなると
バインダー所要量が増大し、通常のバインダー使用値で
は相対的にバインダーが不足することにな９、顕色剤や
顔料を基体シートに接着することが困難になる。このた
め、印刷時に粉落ち現象を生じブランケットを汚したシ
版詰まりの原因となり、高速印刷などの実用に耐え得な
い。その対策として・々イングーの配合割合を高めると
表面強度は改善されるが、一方発色性の低下を招き、所
望の効果を得られない。It has been proposed to use pigments with fine particle diameters in order to improve the color development properties of color developing sheets, but as the pigments become finer, the amount of binder required increases, and the amount of binder used at normal binder usage levels is relatively insufficient. Also, it becomes difficult to adhere the color developer and pigment to the base sheet. For this reason, powder falls during printing, which causes plate jams that stain the blanket, making it unsuitable for practical applications such as high-speed printing. As a countermeasure to this problem, increasing the blending ratio of Ingu improves the surface strength, but on the other hand, this results in a decrease in color development, making it impossible to obtain the desired effect.
特公昭５８−１９４７５号公報及び特開昭５３−３１４
０５号公報には不飽和酸単量体含有量が数重量％でベン
ゼン不溶分（ｒル量）が９５〜１００１ｉ％の共重合体
ラテックスを顕色剤塗料用のバインダーとする感圧複写
紙用顕色紙が開示されている。Japanese Patent Publication No. 58-19475 and Japanese Patent Publication No. 53-314
Publication No. 05 discloses a pressure-sensitive copying paper using a copolymer latex with an unsaturated acid monomer content of several percent by weight and a benzene insoluble content (rul amount) of 95 to 1001i% as a binder for a color developer coating. A color developer paper is disclosed.
また、特開昭５７−１３３０９３号公報には平均粒径０
，０８μ以下のスチレン−ブタジェン共重合体ラテック
スを用いることが提案されている。さらに、特開昭６０
−２４９９２号公報には共重合体中のエチレン系不飽和
酸単量体を１０〜３０チすることが提案されている。In addition, Japanese Patent Application Laid-open No. 57-133093 describes that the average particle size is 0.
It has been proposed to use a styrene-butadiene copolymer latex having a particle diameter of .08μ or less. Furthermore, JP-A-60
JP-A-24992 proposes that the amount of ethylenically unsaturated acid monomer in the copolymer be 10 to 30.
さらには特公昭６０−３６９５３号公報にはマイクロカ
プセル中に包含されている油性芯物質に対する膨潤度が
６５％以下であるカルゲキシ変性重合体ラテックスを有
機呈色剤の接着剤として含有し九ことを特徴とする感圧
複写紙が開示されている。Furthermore, Japanese Patent Publication No. 60-36953 discloses that a calgexi-modified polymer latex having a swelling degree of 65% or less with respect to the oily core substance contained in the microcapsules is contained as an adhesive for an organic coloring agent. A pressure sensitive copying paper with features is disclosed.
しかしながら、これらの共重合体ラテックスをバインダ
ーとして用いても近年の呈色紙に対する発色性及び表面
強度への要求を溝たすには充分で危く改善が要望されて
いる。However, even the use of these copolymer latexes as binders is insufficient to meet the recent demands for color-forming properties and surface strength for color-forming papers, and improvements are desired.
（発明が解決しようとする間層点）
本発明者等はこの様な背景に鑑み、バインダー用重合体
ラテックスについて研究を重ねた結果、驚くべきことに
は無色ロイコ染料溶解油に対する膨潤度が１００係以上
の重合体ラテックスをバインダーとすることにより極め
て優れた発色性と表面強度を有する顕色紙が得られるこ
と、又ノ々インダーの使用量も少なくて済むことを見い
出し本発明を完成するに到った。(Interlayer point to be solved by the invention) In view of this background, the present inventors have conducted repeated research on polymer latex for binders, and have surprisingly found that the degree of swelling in colorless leuco dye-dissolved oil is 100. They discovered that by using the above polymer latex as a binder, a color developing paper with extremely excellent color development and surface strength could be obtained, and that the amount of the inder used could be reduced, and they were able to complete the present invention. It was.
（問題点を解決するための手段）
即ち１本発明はマイクロカプセル中に包含される油性芯
物質を構成する無色ロイコ染料溶解油に対する膨潤度が
１００％以上である重合体のラテックスをバインダーと
して含む感圧複写紙用顕色剤組成物を提供するものであ
る。(Means for Solving the Problems) Namely, 1. The present invention contains as a binder a latex of a polymer having a swelling degree of 100% or more with respect to colorless leuco dye-dissolved oil constituting the oily core substance contained in the microcapsules. A color developer composition for pressure-sensitive copying paper is provided.
（発明の効果）
本発明においてマイクロカプセル中に包含される油性芯
物質を構成する無色ａイコ染料溶解油とは、感圧記録紙
の上用紙及び中用紙の裏面に塗布されるマイクロカプセ
ル内に含有される、無色ロイコ染料を溶解している不揮
発性有機４剤をいう。(Effects of the Invention) In the present invention, the colorless a-ico-dye-dissolved oil constituting the oily core substance contained in the microcapsules is the colorless a-ico dye-dissolved oil that is contained in the microcapsules applied to the back surface of the upper and inner sheets of pressure-sensitive recording paper. It refers to the four nonvolatile organic agents contained in which the colorless leuco dye is dissolved.
該染料溶解油としては無色、無臭で無色ロイコ染料を溶
解でき、かつマイクロカプセル内で安定に存在し、かつ
無色ロイコ染料と顕色剤との発色反応を阻害しない様な
動物油、植物油、鉱物油、合成油が用いられる。例えば
、アルキルナフタレン。The dye-dissolving oil is an animal oil, vegetable oil, or mineral oil that is colorless, odorless, can dissolve the colorless leuco dye, exists stably within the microcapsules, and does not inhibit the coloring reaction between the colorless leuco dye and the color developer. , synthetic oil is used. For example, alkylnaphthalenes.
水素化ターフェニル、ジフェニルアルカン、トリアリー
ルジメタン、アルキルビフェニル、ケロシン、塩素化ノ
’Ｌ？ファイン、綿実油、アマニ油、大豆油、ナタネ油
危どが挙げられる。Hydrogenated terphenyl, diphenylalkane, triaryldimethane, alkyl biphenyl, kerosene, chlorinated no'L? Examples include fine oil, cottonseed oil, linseed oil, soybean oil, and rapeseed oil.
本発明において用いられる無色ロイコ染料は特に限定さ
れないが、具体例としては、クリスタルバイオレット２
クトンに代表されるトリフェニルメタン系化合物、ベン
ゾイルロイコメチレンプル−などのフェノチアジン系化
合物、３−ジエチルアミノ−６−メチル−７−フェニル
アミノフルオランなどのフルオラン系化合物などが挙げ
られる。The colorless leuco dye used in the present invention is not particularly limited, but specific examples include Crystal Violet 2
Examples include triphenylmethane compounds typified by Chthone, phenothiazine compounds such as benzoylleucomethylenepurine, and fluoran compounds such as 3-diethylamino-6-methyl-7-phenylaminofluorane.
本発明の顕色剤組成物はこれら公知の無色ロイコ染料類
に対して有効であるが、特にフルオラン系化合物を主体
とする発色剤に対して著効がある。The color developer composition of the present invention is effective against these known colorless leuco dyes, but is particularly effective against color formers mainly composed of fluoran compounds.
又、本発明においては公知の顕色剤を使用することがで
き、特に限定されない。Further, in the present invention, known color developers can be used and are not particularly limited.
本発明における重合体ラテックスは、マイクロカプセル
中に包含される油性芯物質を構成する無色ロイコ染料溶
解油に応じて選択されるが、該染料溶解油に対するラテ
ックスを構成する重合体の膨潤度が１００−以上である
ことが必須である◎１００チ未満では発色性と表面強度
が改善されない。好ましくは１５０ｅｓ以上である。The polymer latex in the present invention is selected depending on the colorless leuco dye-dissolving oil that constitutes the oily core substance contained in the microcapsules, and the degree of swelling of the polymer constituting the latex with respect to the dye-dissolving oil is 100. - It is essential that it is at least ◎ If it is less than 100 inches, the color development and surface strength will not be improved. Preferably it is 150es or more.
ラテックスを構成する重合体の該溶解油に対するｍａ度
を規制する要因としては単量体組成、分子量調整剤のｍ
類と更用歌、反応温度などがあるが、本発明においては
膨潤度を規制する方法は特に限定されない。Factors that regulate the ma degree of the polymer constituting the latex with respect to the dissolved oil are the monomer composition and the molar mass of the molecular weight regulator.
However, in the present invention, the method of controlling the degree of swelling is not particularly limited.
本発明で使用される重合体ラテックスとして、スチレン
−ブタジェン系共重合体ラテ、クス、メチルメタアクリ
レート−ブタノエン系共重合体ラテックス、アクリロニ
トリル−ブタジェン系共重合体ラテックス、アクリル酸
エステル系共重合体ラテックス及びこれらのカルゲキシ
ル化変性うテ、クス等が例示される。これらを詳しく述
べれば、単量体としては、ｌ、３−１タジエン、２−メ
チル−１，３−１タゾエン、２．３−ツメチル−１，３
−１タジエン、ハロゲン置換ブタジェンなどの脂肪族共
役ジオレフィン；スチレン、α−メチルスチレン、モノ
クロルスチレン、ビニルトルエンなどの芳香族ビニル化
合物；アクリル酸メチル、メタクリル酸メチル、アクリ
ル酸エチル、アクリル酸ブチルなどのアクリル酸および
メタクリル酸のアル中ルエステル類：アクリロニトリル
、メタクリロニトリルなどのエチレン系不飽和ニトリル
化合物。Examples of the polymer latex used in the present invention include styrene-butadiene copolymer latex, methyl methacrylate-butanoene copolymer latex, acrylonitrile-butadiene copolymer latex, and acrylic ester copolymer latex. Examples thereof include calgexylated modified caries, camphorax, and the like. To explain these in detail, the monomers include 1,3-1 tadiene, 2-methyl-1,3-1 tazoene, 2,3-tmethyl-1,3
Aliphatic conjugated diolefins such as -1-tadiene and halogen-substituted butadiene; aromatic vinyl compounds such as styrene, α-methylstyrene, monochlorostyrene, and vinyltoluene; methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, etc. alkyl esters of acrylic acid and methacrylic acid: ethylenically unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile.
などが挙げられる。さらには官能性共重合性単量体とし
てアクリル飲、メタアクリル岐、クロトン酸、ケイ皮酸
、イタコン酸、７マル酸、マレイン酸、ブテントリカル
？ン酸などの不飽和カルゲン酸；イタコン酸モノエチル
エステル、フマル酸モツプチルエステル、マレイン酸モ
ツプチルエステルなどの不飽和ジカルゲン酸のモノアル
牟ルエステル；アクリル酸スルフオニチルＮａ塩、メタ
クリル酸スルフォデロピルＮａ塩、アクリルアミドプロ
ノ母ンスルフォン酸などの不飽和スルフォン酸又はその
アルカリ塩などのエチレン系不砲和酸単世体を共重合す
ることが顕色剤塗料の配合安定性や表面強度の向上に有
効であり望ましい。Examples include. Furthermore, as functional copolymerizable monomers, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, hexamaric acid, maleic acid, butentrical? Unsaturated cargenic acids such as phosphoric acid; monoalcoholic esters of unsaturated dicargenic acids such as itaconic acid monoethyl ester, fumaric acid mottupyl ester, maleic acid mottupyl ester; sulfonityl acrylate Na salt, sulfoderopyl methacrylate Na salt, acrylamide Copolymerization of an unsaturated sulfonic acid such as pronosulfonic acid or an ethylenic unionized acid monomer such as an alkali salt thereof is effective and desirable for improving the formulation stability and surface strength of the color developer coating.
さらＫは、これらの単量体と共重合可能なアクリル酸−
β−ヒドロ牛クジエチルアクリルアマイド、メタクリル
アマイド、Ｎ−メチロールアクリルアマイド、ジアセト
ンアクリルアマイド、アクリル酸グリシジル、メタクリ
ル酸グリシジル、アクロレイン、アリルアルコール、ノ
ビニルベンゼン、ジアリルフタレート、ノアリルマレエ
ート。Furthermore, K is an acrylic acid copolymerizable with these monomers.
β-Hydrobovine diethyl acrylamide, methacrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, allyl alcohol, novinylbenzene, diallyl phthalate, noallyl maleate.
トリアリルシアヌレート、エチレングリコールノメタク
リレート、アリルアクリレート、Ｐ−インプロペニルス
テンなどのオレフィン系単量体を共重合することも可能
である。本発明における好ましい単量体組成を示せば、
脂肪族共役ジオレフィン系単叶体２０〜６０重ｈ１チ、
芳香族ビニル化合物２０〜７０重量％、不飽和カルゲン
酸０．５〜２０重ｔ＆％及びこれらと共重合可能な他の
オレフィン系単量体Ｏ〜５９．５重着チである。It is also possible to copolymerize olefinic monomers such as triallyl cyanurate, ethylene glycol methacrylate, allyl acrylate, and P-impropenylstene. The preferred monomer composition in the present invention is as follows:
Aliphatic conjugated diolefin monoleaf 20-60 h1chi,
20 to 70% by weight of an aromatic vinyl compound, 0.5 to 20% by weight of unsaturated cargenic acid, and 0 to 59.5% of other olefinic monomer copolymerizable with these.
本発明においては重合体ラテックスの製造方法自体は特
に制限されず例えば回分式乳化重合、連続式乳化重合な
どの公知の乳化重合方法が採用でき、またその際、公知
の各種乳化剤、重合開始剤、分子量調整剤、中レート剤
、電解質など、二股の乳化重合で用いられている各種の
添加剤を使用でき、また重合温度も高Ｗ、低温いずれで
も選ぶことができる。更に、重合終了后の共重合体ラテ
ックスに公知の一調整剤、分散剤、防腐剤などを添加す
ることもできる。In the present invention, the method for producing the polymer latex itself is not particularly limited, and for example, known emulsion polymerization methods such as batch emulsion polymerization and continuous emulsion polymerization can be employed. Various additives used in two-pronged emulsion polymerization, such as molecular weight regulators, intermediate rate agents, and electrolytes, can be used, and the polymerization temperature can be selected from either high W or low temperatures. Furthermore, known regulators, dispersants, preservatives, etc. may be added to the copolymer latex after the polymerization is completed.
感圧複写紙用顕色シートの製造工程は衆知であり、本発
明においても公知のｍ１色剤及びその基体シートへの加
工手段が適用できる。The manufacturing process of a color developing sheet for pressure-sensitive copying paper is well known, and the known m1 coloring agent and its processing means for the base sheet can be applied to the present invention.
本発明において顕色剤塗料を調整する際に前記共重合体
ラテックスを顕色剤の分散系中に混合きせるが、この分
散系中には従来感圧複写紙用顕色シート製造に用いられ
ている無機顔料、分散剤、消泡剤、界面活性剤、防腐剤
などを添加することができる。合成共重合体ラテックス
の添加ｔＶｉ顕色剤塗料１００ｉ１ｆｔ部（固形分）に
対して３〜３０重量部（固形分）含有させることが望ま
しい。さらに、従来から使用されている前記の如きバイ
ンダーの併用は本発明の効果を妨げない限り有効に行な
い得るものである。このようにして調整された顕色剤塗
料を基体シート上に固形分で通常３〜７ ｇｒ／ｍ２に
なるように塗布し、乾燥して得られた顕色シートに上用
紙を重ねてタイプ発色すると発色度の高い鮮明な記録が
得られた。また、顕色シートの顕色剤塗布面の表面強度
は強く優れた印刷適性を示した。In the present invention, when preparing a color developer coating, the copolymer latex is mixed into a color developer dispersion system. Inorganic pigments, dispersants, antifoaming agents, surfactants, preservatives, etc. can be added. Addition of synthetic copolymer latex tVi color developer It is desirable to contain 3 to 30 parts by weight (solid content) per 1 ft part (solid content) of the paint. Further, the use of conventionally used binders as described above can be effectively carried out as long as the effects of the present invention are not impaired. The color developer paint prepared in this way is applied onto the base sheet so that the solid content is usually 3 to 7 gr/m2, and then dried. As a result, clear records with high color development were obtained. In addition, the surface strength of the color developer-coated surface of the color developer sheet was strong and showed excellent printability.
尚、本発明における重合体の膨潤間は実施例記載の方法
によって求められる。Incidentally, the swelling period of the polymer in the present invention is determined by the method described in the Examples.
以下、本発明の実施例を示すが、勿論これらの実施例に
限定されるものではない。なお、以下の各実施例におい
て特に断わらない限９組成物の割合は重量部を示す。Examples of the present invention will be shown below, but it is of course not limited to these examples. In each of the following Examples, unless otherwise specified, the proportions of the 9 compositions are in parts by weight.
実施例
内容積約１１の耐圧ガラス＆）ルに水、乳化剤、無機塩
、キレート剤および重合開始剤と共に第１表に示す単量
体および分子量調整剤を仕込み、回転混合しながら７０
℃で１７時間反応を行なった。Example The monomers and molecular weight modifiers shown in Table 1 were charged into a pressure-resistant glass container having an internal volume of about 11 cm, along with water, emulsifiers, inorganic salts, chelating agents, and polymerization initiators, and mixed by rotation for 70 min.
The reaction was carried out at ℃ for 17 hours.
転化率はいずれも９９％以上に達した。得られた重合体
ラテックスを水冷し、未反応単量体を除去したのち、
ＮａＯＨでラテックスの−を７に調整した。The conversion rates reached 99% or higher in all cases. After cooling the obtained polymer latex with water and removing unreacted monomers,
The - of the latex was adjusted to 7 with NaOH.
これらのラテックスを構成する重合体のマイクロカプセ
ル中に包含される油性芯物質を構成する無色ロイコ染料
溶解油に対する膨潤度を第１表に付ｄ己し九。Table 1 shows the degree of swelling of the polymers constituting these latexes with respect to colorless leuco dye-dissolved oil constituting the oily core substance contained in the microcapsules.
重合体の膨潤度は次のようにし°Ｃ測定した。試料重合
体ラテックスを乾燥時の厚さが０．２１となるようにわ
く付きのガラス板上に流し、２０℃６５ ％ ＲＨの恒
温恒湿下に４８時間放置し、乾燥フィルムを調製する。The degree of swelling of the polymer was measured in °C as follows. A sample polymer latex is poured onto a glass plate with a frame so that the dry thickness is 0.21, and is left at constant temperature and humidity at 20° C. and 65% RH for 48 hours to prepare a dry film.
次いで、このフィルムを約１３角に切り、精秤し、マイ
クロカプセル中に包含される油性芯物質を構成する無色
ロイコ染料溶解油１００ｇｒに室温で２４時間浸漬する
。溶解油で膨潤したラテックス・フィルムを取シ出し、
表面に付着している余剰の溶解油をｐ紙等の紙でふき取
シ、精秤し念。次式によシ膨潤度（チ）を算出し念。Next, this film is cut into approximately 13 square pieces, accurately weighed, and immersed for 24 hours at room temperature in 100 gr of colorless leuco dye-dissolved oil constituting the oily core substance contained in the microcapsules. Take out the latex film swollen with dissolved oil,
Wipe off excess dissolved oil adhering to the surface with paper such as P paper, and weigh it carefully. Calculate the degree of swelling (chi) using the following formula.
第２表に示す該溶解油１００重歓部に無色ロイコ染料で
ある３−ジエチルアミノ−６−メチルーフーフエニルア
ミノフルオ２フ４重量部を溶解した。4 parts by weight of 3-diethylamino-6-methyl-phenylaminofluoride, which is a colorless leuco dye, was dissolved in 100 parts by weight of the dissolved oil shown in Table 2.
アクリル酸７０部、スチレンスルホン酸１５部メタクリ
ルヒドロキシルエチル１５部からなるアニオン性水溶性
共重合体１８部に脱イオン水６８部を加え、攪拌しなが
ら溶解した。更に尿素６部とレゾルシン０．８部を分散
溶解し、１０％苛性ソーダ水溶液を滴下し°ＣｐＨ３，
４とし念。この水溶性アニオン性共重合体等を含む水溶
液中に先に調製した無色ロイコ染料を溶解した溶解油を
混合した。68 parts of deionized water was added to 18 parts of an anionic water-soluble copolymer consisting of 70 parts of acrylic acid, 15 parts of styrene sulfonic acid, and 15 parts of methacrylic hydroxylethyl, and dissolved with stirring. Further, 6 parts of urea and 0.8 parts of resorcin were dispersed and dissolved, and a 10% aqueous solution of caustic soda was added dropwise to the solution at a pH of 3 °C.
4 thoughts. A dissolved oil in which the previously prepared colorless leuco dye was dissolved was mixed into the aqueous solution containing the water-soluble anionic copolymer and the like.
この混合物をホモミキサーで強攪拌し、乳化分散液を得
た。次いで３７％ホルムアルデヒド水溶液１５部を加え
、系の温度を５５℃に昇温し、２時間反応させた后、放
冷してマイクロカプセル分散液を得た。このマイクロカ
プセルの粒径は４．０μであった。This mixture was strongly stirred with a homomixer to obtain an emulsified dispersion. Next, 15 parts of a 37% formaldehyde aqueous solution was added, the temperature of the system was raised to 55° C., and after reacting for 2 hours, the mixture was allowed to cool to obtain a microcapsule dispersion. The particle size of this microcapsule was 4.0μ.
得られたマイクロカプセル分散液を第３表の配合により
マイクロカプセル塗布組成物とした。このマイクロカプ
セル塗布組成物を４０ ｇｒ／ｍ の原紙に固形分塗布
量５ ｇｒ／／ＰＩ となるように塗布、乾燥して、
マイクロカプセル塗布紙ヲ得た。The obtained microcapsule dispersion was made into a microcapsule coating composition according to the formulation shown in Table 3. This microcapsule coating composition was coated on a 40 gr/m2 base paper so that the solid content coating amount was 5 gr//PI, and dried.
I obtained microcapsule coated paper.
第２表
第３表
マイクロカプセル塗布組成物配合処方（固形分）マイク
ロカプセル １００部小麦デンプン（
平均粒径１７μ） ３８部Ｎ％ｐｏｌ Ｌｘ４
０７８ １２部（日本ゼオン（株
）製カル？キシ変性スチレンーブタジェン系共重合体う
テ、クス）
〔顔色シートの作成〕
第４表に示す配合処方にて、塗料固形分濃度が５５９６
となるように塗料を調製した。この塗料を使用し、４０
ｇｒ／ｍ２の原紙に塗布量が４〜５ｇｒ／Ｒ２となる
ように塗布し、乾燥して、顕色シートを得た。これらの
顕色シートの性能評ｌ１ＩＩｉは次のような方法で行な
った。Table 2 Table 3 Microcapsule coating composition formulation (solid content) Microcapsule 100 parts Wheat starch (
Average particle size 17μ) 38 parts N% pol Lx4
078 12 parts (Nippon Zeon Co., Ltd. Cal-Xy modified styrene-butadiene copolymer wax) [Preparation of complexion sheet] With the formulation shown in Table 4, the paint solids concentration is 5596
A paint was prepared so that Using this paint, 40
It was applied to a base paper of gr/m2 at a coating amount of 4 to 5 gr/R2 and dried to obtain a color developing sheet. Performance evaluation of these color developing sheets was carried out in the following manner.
第４表
沈降性炭酸カルシウム １００Ｐ−フェニ
ルフェノールレシン ２０酸化澱粉
１０
ラテックス ｌＯ■ 発色度
顕色シートに、無色ロイコ染料を含有するマイクロカプ
セルを塗布した市販上用紙を重ね、電動タイフライター
を使用して印字したものについて３０秒後の反射率を測
定し、次式により発色度（４）を求めた。Table 4 Precipitated calcium carbonate 100P-phenylphenol resin 20 oxidized starch
10 Latex lO■ Color Development A commercially available paper coated with microcapsules containing colorless leuco dye was layered on a color developer sheet, and the reflectance of the printed material was measured after 30 seconds using an electric tie-lighter. The degree of color development (4) was determined using the formula.
■ 表面強度
Ｒ１印刷適性試験機（明製作所）を使用して、り、クパ
リ、−１２のピッキング、テスト用インキを顕色シート
の塗工面に４回印刷し、粉落ち状態を官能的に評価した
。評価は下記の基準による５点法とした。■ Using a surface strength R1 printing suitability tester (Mei Seisakusho), pick and test inks of Ri, Kupari, and -12 were printed four times on the coated surface of the color developer sheet, and the state of powder fall was sensually evaluated. did. Evaluation was made on a 5-point scale based on the following criteria.
第５表に本発明例および比較例の顔色シートの評価結果
を示す。Table 5 shows the evaluation results of the complexion sheets of the invention examples and comparative examples.
第５表
第５表の結果から、本発明例では発色度と表面強度のい
ずれも優れているが、比較例では発色度あるいは表面強
度のいずれかあるいはいずれもが劣っていることが分る
。Table 5 From the results shown in Table 5, it can be seen that the examples of the present invention are excellent in both color development and surface strength, but the comparative examples are inferior in either or both of color development and surface strength.
Claims (1)
無色ロイコ染料溶解油に対する膨潤度が１００％以上で
ある重合体のラテックスをバインダーとして含むことを
特徴とする感圧複写紙用顕色剤組成物。A color developer composition for pressure-sensitive copying paper, comprising as a binder a latex of a polymer having a swelling degree of 100% or more with respect to colorless leuco dye-dissolved oil constituting the oily core substance contained in the microcapsules. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61019228A JPS62176876A (en) | 1986-01-31 | 1986-01-31 | Developer composition for pressure-sensitive copy paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61019228A JPS62176876A (en) | 1986-01-31 | 1986-01-31 | Developer composition for pressure-sensitive copy paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62176876A true JPS62176876A (en) | 1987-08-03 |
Family
ID=11993517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61019228A Pending JPS62176876A (en) | 1986-01-31 | 1986-01-31 | Developer composition for pressure-sensitive copy paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62176876A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6449678A (en) * | 1987-08-19 | 1989-02-27 | Mitsubishi Paper Mills Ltd | Non-carbon pressure-sensitive copying paper |
| JPH01234290A (en) * | 1988-03-15 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Coating composition for pressure-sensitive copying paper |
| JPH01234289A (en) * | 1988-03-15 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Coating composition for pressure-sensitive copying paper |
| JPH0327977A (en) * | 1989-06-26 | 1991-02-06 | Sumitomo Naugatuck Co Ltd | Paint composition for pressure-sensitive copy paper |
| JP2008143084A (en) * | 2006-12-12 | 2008-06-26 | Sato Corp | Sticker for application ticket, and method for attaching sticker for application ticket |
-
1986
- 1986-01-31 JP JP61019228A patent/JPS62176876A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6449678A (en) * | 1987-08-19 | 1989-02-27 | Mitsubishi Paper Mills Ltd | Non-carbon pressure-sensitive copying paper |
| JPH01234290A (en) * | 1988-03-15 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Coating composition for pressure-sensitive copying paper |
| JPH01234289A (en) * | 1988-03-15 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Coating composition for pressure-sensitive copying paper |
| JPH0327977A (en) * | 1989-06-26 | 1991-02-06 | Sumitomo Naugatuck Co Ltd | Paint composition for pressure-sensitive copy paper |
| JP2008143084A (en) * | 2006-12-12 | 2008-06-26 | Sato Corp | Sticker for application ticket, and method for attaching sticker for application ticket |
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