JPH0822610B2 - Latex for pressure-sensitive copying paper - Google Patents
Latex for pressure-sensitive copying paperInfo
- Publication number
- JPH0822610B2 JPH0822610B2 JP60109387A JP10938785A JPH0822610B2 JP H0822610 B2 JPH0822610 B2 JP H0822610B2 JP 60109387 A JP60109387 A JP 60109387A JP 10938785 A JP10938785 A JP 10938785A JP H0822610 B2 JPH0822610 B2 JP H0822610B2
- Authority
- JP
- Japan
- Prior art keywords
- synthetic copolymer
- pressure
- copolymer latex
- paper
- sensitive copying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000126 latex Polymers 0.000 title claims description 36
- 239000004816 latex Substances 0.000 title claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 3
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 238000011161 development Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- -1 aliphatic diolefin Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229950005228 bromoform Drugs 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
- 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
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 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
- 239000002245 particle Substances 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
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Color Printing (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、感圧複写紙として優れた青発色及び黒発色
性に加え、優れた接着強度を有する合成共重合体ラテッ
クスに関する。Description: TECHNICAL FIELD The present invention relates to a synthetic copolymer latex having excellent blue and black color development as a pressure-sensitive copying paper and excellent adhesive strength.
感圧複写紙は、近年、事務の合理化、情報産業の発展
及びコンピューターの普及に伴って著しい需要の伸びを
示すと共に、その用途も多様化してきている。In recent years, pressure-sensitive copying paper has shown remarkable growth in demand due to the rationalization of office work, the development of the information industry, and the spread of computers, and its uses have been diversified.
感圧複写紙に要求される最も重要な物性は、感圧複写
紙の本命である発色性である。The most important physical property required for pressure-sensitive copying paper is color development, which is the favorite of pressure-sensitive copying paper.
発色性とは、有機溶剤（カプセルオイル）に溶解した
電子供与性の無色または淡色のロイコ染料を含有する微
細なカプセルを裏面に塗布した上葉紙と、電子受容性の
顕色剤及び接着剤等を含む顕色層を表面に設けた下葉紙
とからなる２種類の塗布面を向かい合わせ、印圧を加
え、カプセルが破壊され、ロイコ染料を含むカプセルオ
イルが顕色層に転移し、ロイコ染料と顕色剤が発色反応
を示すことである。Chromogenicity refers to top paper coated with fine capsules containing an electron-donating colorless or pale-colored leuco dye dissolved in an organic solvent (capsule oil) on the back surface, and an electron-accepting color developer and adhesive. Two kinds of coated surfaces consisting of a lower leaf paper having a color developing layer containing, etc. on the surface are opposed to each other, a printing pressure is applied, the capsule is broken, and the capsule oil containing the leuco dye is transferred to the color developing layer, That is, the leuco dye and the color developer exhibit a color-forming reaction.
現在、市場で主流をしめている発色の色は、青発色と
黒発色である。従来、感圧複写紙用組成物として使用さ
れている合成共重合体ラテックスは、例えば特公昭58−
19475号公報、特開昭53−31405号公報及び特開昭51−51
19号公報などに記載されている。Currently, the most popular colors in the market are blue and black. Synthetic copolymer latex conventionally used as a composition for pressure-sensitive copying paper is disclosed in, for example, JP-B-58-
19475, JP-A-53-31405 and JP-A-51-51
It is described in Japanese Patent Publication No. 19 and the like.
特公昭58−19475号公報及び特開昭53−31405号公報に
記載されている内容は、要するに高ゲル含有量領域にお
いて発色性が著しく改善されているということであり、
また特開昭51−5119号公報は、不飽和ニトリル系単量体
を使用することにより、発色性を向上させるという内容
である。The contents described in JP-B-58-19475 and JP-A-53-31405 are, in short, that the color developability is remarkably improved in the high gel content region.
Further, JP-A No. 51-5119 discloses that the coloring property is improved by using an unsaturated nitrile monomer.
本発明者らは、合成共重合体ラテックスと発色の色と
の関係について検討した結果、高ゲル含有量の合成共重
合体ラテックスは、青発色を著しく向上させるものの、
逆に黒発色が著しく低下し、かつ表面接着強度も低下す
ることが判明した。また不飽和ニトリル系単量体は、黒
発色を向上させるものの、青発色を低下させることが判
明した。The present inventors have studied the relationship between the color of the synthetic copolymer latex and the color developed, the high gel content of the synthetic copolymer latex significantly improves the blue color development,
On the contrary, it was found that the black coloration was remarkably lowered and the surface adhesive strength was also lowered. It was also found that the unsaturated nitrile-based monomer improves black color development but reduces blue color development.
すなわち、従来の合成共重合体ラテックスを感圧複写
紙用下葉紙の接着剤として使用した場合、青発色と黒発
色は、まったく逆相関になることがわかった。That is, it was found that when the conventional synthetic copolymer latex was used as an adhesive for pressure-sensitive copying paper, the blue color development and the black color development were completely inversely correlated.
上述のとおり、従来の合成共重合体ラテックスを感圧
複写紙用下葉紙の接着剤として使用した場合、青発色と
黒発色は、互いに相反する現象を示し、一方の立てれ
ば、一方が立たず、両方の性質を共に向上することは、
従来の合成共重合体ラテックスでは極めて困難なことが
理解されよう。As described above, when a conventional synthetic copolymer latex is used as an adhesive for pressure-sensitive copying paper bottom paper, blue color development and black color development show mutually opposite phenomena. First, improving both properties together
It will be appreciated that conventional synthetic copolymer latices are extremely difficult.
本発明の目的は、感圧複写紙として優れた青発色及び
黒発色を同時に付与させる合成共重合体ラテックスを提
供することである。An object of the present invention is to provide a synthetic copolymer latex capable of simultaneously imparting excellent blue color development and black color development as a pressure-sensitive copying paper.
本発明者らは、感圧複写紙の青発色と黒発色の同時向
上のために鋭意研究を行った。その結果、合成共重合体
ラテックスのエチレン系不飽和カルボン酸量とラテック
スフィルムのスウェルインデックスを規定すると、従来
困難とされていた青発色と黒発色の同時向上という技術
課題が一挙に解決することを見いだした。さらに驚くべ
きことに該合成共重合体ラテックスの不飽和カルボン酸
量とラテックスフィルムのスウェルインデックスを規定
すると、接着強度も発揮するという意外な事実を見出
し、本発明を完成するに至った。The inventors of the present invention have conducted intensive studies for simultaneously improving blue color development and black color development of pressure-sensitive copying paper. As a result, by defining the amount of ethylenically unsaturated carboxylic acid of the synthetic copolymer latex and the swell index of the latex film, the technical problem of simultaneous improvement of blue color development and black color development, which was conventionally difficult, was solved at once. I found it. Surprisingly, the inventors have found that, when the unsaturated carboxylic acid content of the synthetic copolymer latex and the swell index of the latex film are specified, the adhesive strength is also exhibited, and the present invention has been completed.
本発明は、脂肪族ジオレフィン40〜55重量％、エチレ
ン系不飽和カルボン酸６〜17重量％およびこれらと共重
合可能な他のモノオレフィン系単量体34〜49重量％から
成り、ラテックスフィルムのスウェルインデックスが10
〜18である感圧複写紙用合成共重合体ラテックスに関す
るものである。The present invention comprises 40 to 55% by weight of an aliphatic diolefin, 6 to 17% by weight of an ethylenically unsaturated carboxylic acid, and 34 to 49% by weight of another monoolefinic monomer copolymerizable therewith, and a latex film. Has a swell index of 10
The present invention relates to a synthetic copolymer latex for pressure-sensitive copying paper, wherein
以下に本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明で使用される脂肪族共役ジオレフィンとして
は、ブタジエンやイソプレン等がある。通常これらの単
量体は、合成共重合体に適度な弾性を与える。Examples of the aliphatic conjugated diolefin used in the present invention include butadiene and isoprene. Usually, these monomers give the synthetic copolymer appropriate elasticity.
40重量％未満では充分な弾性が得られず接着強度が低
下する。また55重量％をこえると青発色が不十分とな
る。If it is less than 40% by weight, sufficient elasticity cannot be obtained and the adhesive strength is lowered. Further, if it exceeds 55% by weight, blue coloration becomes insufficient.
エチレン系不飽和カルボン酸としては、アクリル酸、
メタクリル酸、マレイン酸、フマール酸、イタコン酸お
よびジカルボン酸の無水物またはモノアルキルエステル
等があげられる。これらのエチレン系不飽和カルボン酸
は接着性を向上させるとともに青発色及び黒発色を向上
させる。As ethylenically unsaturated carboxylic acids, acrylic acid,
Examples thereof include anhydrides or monoalkyl esters of methacrylic acid, maleic acid, fumaric acid, itaconic acid and dicarboxylic acid. These ethylenically unsaturated carboxylic acids improve the adhesiveness and the blue and black colors.
６重量％未満では、これらの物性の向上が認められな
い。17重量％をこえると、これらの物性の向上が飽和す
るとともに、合成共重合体ラテックスを作成したあとの
残渣量が急激に増加する。If it is less than 6% by weight, no improvement in these physical properties is observed. When it exceeds 17% by weight, the improvement in these physical properties is saturated and the amount of residue after the synthetic copolymer latex is rapidly increased.
これらと共重合し得るモノオレフィン系単量体として
は、スチレン、α−メチルスチレン、ビニルトルエン等
で例示される芳香族ビニル単量体、メチルアクリレー
ト、エチルアクリレート、ブチルアクリレート、２−エ
チルヘキシルアクリレート、２−ヒドロキシエチルアク
リレート、２−ヒドロキシプロピルアクリレート、グリ
シジルアクリレート等で例示されるアクリレート系単量
体類、メチルメタクリレート、エチルメタクリレート、
２−ヒドロキシエチルメタクリレート、２−ヒドロキシ
プロピルメタクリレート、グリシジルメタクリレート等
で例示されるメタクリレート系単量体類、アクリルアミ
ド、Ｎ−メチロールアクリルアミド、アクリロニトリル
等があげられる。Examples of the monoolefin-based monomer that can be copolymerized with these include aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Acrylate-based monomers exemplified by 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate,
Examples thereof include methacrylate-based monomers exemplified by 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, acrylamide, N-methylol acrylamide, acrylonitrile and the like.
これらは上記脂肪族共役ジオレフィンおよびエチレン
系不飽和カルボン酸単量体と容易に共重合し、通常これ
らの単量体は34〜49重量部の範囲で使用される。These are easily copolymerized with the aliphatic conjugated diolefin and the ethylenically unsaturated carboxylic acid monomer, and these monomers are usually used in the range of 34 to 49 parts by weight.
本発明の合成共重合体ラテックスフィルムのスウェル
インデックスは10〜18の範囲である。スウェルインデッ
クスが10未満では、接着強度が低下するばかりか黒発色
が再現しにくくなる。一方18をこえると青発色が発現し
にくくなる。The swell index of the synthetic copolymer latex film of the present invention is in the range of 10-18. When the swell index is less than 10, not only the adhesive strength is lowered, but also it is difficult to reproduce black color. On the other hand, when it exceeds 18, blue color is hardly developed.
また合成共重合体ラテックスフイルムのスウェルイン
デックスの調整に重要な薬品として連鎖移動剤がある。A chain transfer agent is an important chemical for adjusting the swell index of the synthetic copolymer latex film.
一般に使用されている連鎖移動剤は、例えばｔ−ドデ
シルメルカプタン、四塩化炭素、ブロモホルム、チオグ
リコール酸を用いることができる。Examples of commonly used chain transfer agents include t-dodecyl mercaptan, carbon tetrachloride, bromoform and thioglycolic acid.
またこれらの連鎖移動剤は一種または二種以上で使用
される。さらに添加方法については一括添加法或は連続
添加法のいずれかでも差し支えない。Further, these chain transfer agents are used alone or in combination of two or more. Further, the addition method may be a batch addition method or a continuous addition method.
本発明の合成共重合体を得るために、乳化剤として
は、アニオン性のものが最適である。アニオン性界面活
性剤は、通常のカルボキシル変性スチレン−ブタジエン
系共重合体ラテックスを製造するのに用いられるのでよ
く、例えば高級アルコールの硫酸エステル、アルキルベ
ンゼンスルフォン酸塩、脂肪族スルフォン酸塩などが挙
げられる。In order to obtain the synthetic copolymer of the present invention, an anionic emulsifier is most suitable. The anionic surfactant may be used for producing an ordinary carboxyl-modified styrene-butadiene copolymer latex, and examples thereof include sulfuric acid ester of higher alcohol, alkylbenzene sulfonate, and aliphatic sulfonate. .
本発明の合成共重合体を得るために、重合開始剤とし
ては過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモ
ニウム等の水溶性開始剤、過酸化ベンゾイル等の油溶性
開始剤、あるいはレドックス系開始剤のいずれでも使用
できる。さらに必要に応じてキレート剤、無機塩なども
乳化重合として公知のものが用いられる。In order to obtain the synthetic copolymer of the present invention, as the polymerization initiator, a water-soluble initiator such as sodium persulfate, potassium persulfate, or ammonium persulfate, an oil-soluble initiator such as benzoyl peroxide, or a redox initiator is used. Either can be used. Further, if necessary, a chelating agent, an inorganic salt and the like known in the emulsion polymerization may be used.
本発明の合成共重合ラテックスの重合方式は、バッチ
重合方式及び連続重合方式いずれでもよい。このように
して得られた合成共重合体ラテックスを接着剤として、
顕色剤と共に基体片面に塗布し、下葉紙を形成させる。The polymerization method of the synthetic copolymer latex of the present invention may be either a batch polymerization method or a continuous polymerization method. The synthetic copolymer latex thus obtained as an adhesive,
A developer is applied to one side of the substrate to form a lower leaf paper.
顕色剤としては、酸性白土、活性白土、焼成活性白土
等の如き無機顕色剤、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、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、芳香族カルボン酸−アルデヒ
ド重合体の多価金属塩等の如き有機顕色剤が、使用可能
である。また顕色剤以外の顔料及び各種添加剤を十分に
保持せしめるため、通常、合成共重合体ラテックス以外
に、澱粉類、カゼイン、ゼラチン、アラビアゴム、ポリ
ビニルアルコール、メチルセルローズ及びエチルセルロ
ーズ等の接着剤も共用される。Examples of the color developer include inorganic color developers such as acid clay, activated clay, and calcined activated clay, phenol compounds, phenol resins, maleic acid-rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride. Organic developers such as copolymers, polyvalent metal salts of phenolic resins, polyvalent metal salts of aromatic carboxylic acid-aldehyde polymers can be used. In addition to the synthetic copolymer latex, adhesives such as starches, casein, gelatin, gum arabic, polyvinyl alcohol, methyl cellulose and ethyl cellulose are usually used in order to sufficiently hold pigments and various additives other than the color developer. Is also shared.
本発明に共用可能な顔料は、クレー、二酸化チタン、
サチン白、炭酸カルシウム及び水酸化マグネシウム等で
ある。Pigments that can be used in the present invention include clay, titanium dioxide,
Examples include satin white, calcium carbonate and magnesium hydroxide.
本発明に共用可能な各種添加剤は通常の紙塗工分野で
使用されている消泡剤、耐水化剤、滑剤及び分散剤等で
ある。Various additives that can be used in the present invention are antifoaming agents, water resistance agents, lubricants, dispersants and the like which are commonly used in the field of paper coating.
本発明の合成共重合体ラテックスを感圧複写紙用下葉
紙の接着剤として使用した場合、顔料及び顕色剤100重
量部に対して５〜25重量部が望ましい。合成共重合体ラ
テックスの使用量が５重量部未満では、感圧複写紙用下
葉紙の表面接着強度が著しく劣る。一方25重量部をこえ
ると、青発色及び黒発色とも不十分で発色不良となる。When the synthetic copolymer latex of the present invention is used as an adhesive for pressure-sensitive copying paper bottom paper, it is preferably 5 to 25 parts by weight per 100 parts by weight of the pigment and the color developer. When the amount of the synthetic copolymer latex used is less than 5 parts by weight, the surface adhesive strength of the lower paper for pressure-sensitive copying paper is significantly deteriorated. On the other hand, if the amount exceeds 25 parts by weight, the blue and black colorings are insufficient and the coloring is poor.
本発明の特異な合成共重合体ラテックスを、感圧複写
紙用下葉紙の接着剤として使用した場合、きわめて優れ
た青発色及び黒発色を付与し、かつ優れた接着強度を発
揮した感圧複写紙を提供することが出来る。When the unique synthetic copolymer latex of the present invention is used as an adhesive for a pressure-sensitive copying paper underleaf paper, it gives a very excellent blue and black color development and exerts excellent adhesive strength. Copy paper can be provided.
次に実施例及び比較例を示す。以下の％及び部は、特
に断りのない限り重量表示である。Next, examples and comparative examples will be shown. The following percentages and parts are by weight unless otherwise specified.
なお、実施例及び比較例における各物性の測定方法
は、次に示すとおりである。In addition, the measuring method of each physical property in an Example and a comparative example is as showing below.
（１） 塗工紙の接着強度：明製作所製RI印刷試験機を
使用し、タック10のインキで数回重ね刷りを行い、印刷
面のピッキング状態を肉眼判定する。数字大の方が良好
である。(1) Adhesive strength of coated paper: Using an RI printing tester manufactured by Meisho Co., Ltd., multiple overprints were performed with the ink of Tack 10 several times, and the picking state of the printed surface was visually judged. Larger numbers are better.
（２） 塗工紙の発色性：各合成共重合体ラテックスを
含有した下葉紙と市販の上葉紙を重ね、IGT試験機によ
り印圧をかける。（印圧:35kg、スプリングＭ）発色後3
0秒たった後の発色濃度をハンター式白色度計にて測定
する。数字小の方が良好である。(2) Color development of coated paper: Lower paper containing each synthetic copolymer latex and commercially available upper paper are overlaid, and printing pressure is applied by an IGT tester. (Printing pressure: 35 kg, spring M) 3 after coloring
The color density after 0 seconds is measured with a Hunter whiteness meter. Smaller numbers are better.
（３） ラテックスフィルムのスウェルインデックス:2
3℃×65％RHの雰囲気中で24時間常温成膜させる。この
ものを約0.5gとり、30ccトルエン溶液に浸漬し、振とう
器で約４時間撹拌溶解し、200メッシュの金網で濾過す
る。金網上に濾別されたトルエン含有の残留物重量とそ
れを乾燥した後の残留物重量との割合で示す。(3) Swell index of latex film: 2
Deposition at room temperature for 24 hours in an atmosphere of 3 ° C x 65% RH. About 0.5 g of this product was taken, immersed in a 30 cc toluene solution, dissolved by stirring for about 4 hours on a shaker, and filtered through a 200-mesh wire net. The weight of the toluene-containing residue filtered off on the wire mesh and the weight of the residue after drying it are shown as a ratio.
＜実施例１〜４、比較例１〜12＞ （１） 合成共重合体ラテックス 実施例１では、ブタジエン40部、アクリル酸８部、イ
タコン酸３部、スチレン49部、四塩化炭素４部、炭酸水
素ナトリウム0.9部、過硫酸カリウム0.9部、アルキルベ
ンゼンスルホン酸ナトリウム0.5部、重合水150部を５リ
ットル、オートクレーブ中に仕込み、窒素雰囲気中で撹
拌しながら、80℃で９時間反応させた。単量体の重合転
化率は、99.5％であった。 <Examples 1 to 4, Comparative Examples 1 to 12> (1) Synthetic Copolymer Latex In Example 1, 40 parts of butadiene, 8 parts of acrylic acid, 3 parts of itaconic acid, 49 parts of styrene, 4 parts of carbon tetrachloride, 5 parts of 0.9 parts of sodium hydrogencarbonate, 0.9 parts of potassium persulfate, 0.5 parts of sodium alkylbenzenesulfonate and 150 parts of polymerization water were charged into an autoclave and reacted at 80 ° C. for 9 hours while stirring in a nitrogen atmosphere. The polymerization conversion rate of the monomer was 99.5%.
比較例１では、上記条件で四塩化炭素を９部使用し、
合成共重合体ラテックスを得た。なお単量体の重合転化
率は99.6％であった。合成共重合体ラテックスのその他
の実施例及び比較例の単量体組成は、第１表に示すとお
りで、記載の部数を上記と同様の重合条件で重合し、各
合成共重合体ラテックスを得た。水酸化ナトリウム水溶
液で合成共重合体ラテックスのpHを８に調整し、残留モ
ノマー除去のため、水蒸気及び窒素ブローを行い、望ま
しい合成共重合体ラテックスを得た。この共重合体の平
均粒子径は約1600Åであった。In Comparative Example 1, 9 parts of carbon tetrachloride was used under the above conditions,
A synthetic copolymer latex was obtained. The polymerization conversion rate of the monomer was 99.6%. The monomer compositions of the other examples and comparative examples of the synthetic copolymer latex are as shown in Table 1, and the number of parts described is polymerized under the same polymerization conditions as above to obtain each synthetic copolymer latex. It was The pH of the synthetic copolymer latex was adjusted to 8 with an aqueous sodium hydroxide solution, and steam and nitrogen were blown to remove residual monomers to obtain a desired synthetic copolymer latex. The average particle size of this copolymer was about 1600Å.
（２） 感圧複写紙用下葉紙としての評価 下記の塗工液を作成し、この塗工液を50g/m2の原紙の
片面に乾燥重量で5g/m2になるように塗布し、乾燥し、
下葉紙を得た。(2) Evaluation as bottom paper for pressure-sensitive copying paper The following coating solution was prepared and applied to one side of 50 g / m 2 base paper so that the dry weight was 5 g / m 2. Dried,
I got a bottom paper.
クレー 80部 フェノール樹脂（ｐ−フェニールフェノールアルデヒド
重縮合体） 20 ポリアクリル酸ソーダ 0.5 NaOH 0.5 酸化澱粉 ６ 合成共重合体ラテックス 12 固形分（wt％） 30 実施例１〜４及び比較例１〜７で得られた下葉紙の塗
布面と市販されている上葉紙の塗布面を対向するように
重ね合わせ、発色性の試験を実施した。さらに上葉紙そ
のものの塗布面接着強度をRI印刷機にて評価した。その
結果を第２表に示す。Clay 80 parts Phenolic resin (p-phenylphenolaldehyde polycondensate) 20 Sodium polyacrylate 0.5 NaOH 0.5 Oxidized starch 6 Synthetic copolymer latex 12 Solid content (wt%) 30 Examples 1 to 4 and Comparative Examples 1 to 7 The coated surface of the lower leaf paper obtained in 1. and the coated surface of the commercially available upper leaf paper were superposed so as to face each other, and a test for color development was conducted. Furthermore, the adhesive strength of the coated surface of the top paper itself was evaluated with an RI printer. Table 2 shows the results.
また、比較例８〜12は、連鎖移動剤量とスウェルイン
デックスとの関係を示すものであり、その結果を表２に
示す。Comparative Examples 8 to 12 show the relationship between the amount of chain transfer agent and the swell index, and the results are shown in Table 2.
Claims (1)
チレン系不飽和カルボン酸６〜17重量％およびこれらと
共重合可能な他のモノオレフィン系単量体34〜49重量％
から成り、ラテックスフィルムのスウェルインデックス
が10〜18である感圧複写紙用合成共重合体ラテックス。1. An aliphatic conjugated diolefin 40 to 55% by weight, an ethylenically unsaturated carboxylic acid 6 to 17% by weight, and another monoolefin monomer 34 to 49% by weight copolymerizable therewith.
A synthetic copolymer latex for pressure-sensitive copying paper, which comprises a latex film having a swell index of 10 to 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60109387A JPH0822610B2 (en) | 1985-05-23 | 1985-05-23 | Latex for pressure-sensitive copying paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60109387A JPH0822610B2 (en) | 1985-05-23 | 1985-05-23 | Latex for pressure-sensitive copying paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61268481A JPS61268481A (en) | 1986-11-27 |
| JPH0822610B2 true JPH0822610B2 (en) | 1996-03-06 |
Family
ID=14508941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60109387A Expired - Lifetime JPH0822610B2 (en) | 1985-05-23 | 1985-05-23 | Latex for pressure-sensitive copying paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0822610B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4931422A (en) * | 1987-08-19 | 1990-06-05 | Mitsubishi Paper Mills Limited | No-carbon pressure-sensitive copying paper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5819475B2 (en) * | 1975-11-28 | 1983-04-18 | 住友ノ−ガタック株式会社 | Colored paper for pressure-sensitive copying paper |
| JPS6024992A (en) * | 1983-07-21 | 1985-02-07 | Nippon Zeon Co Ltd | Color developer coating composition for pressure- sensitive copying paper |
-
1985
- 1985-05-23 JP JP60109387A patent/JPH0822610B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61268481A (en) | 1986-11-27 |
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