JPS61268481A - Latex for pressure-sensitive manifold paper - Google Patents
Latex for pressure-sensitive manifold paperInfo
- Publication number
- JPS61268481A JPS61268481A JP60109387A JP10938785A JPS61268481A JP S61268481 A JPS61268481 A JP S61268481A JP 60109387 A JP60109387 A JP 60109387A JP 10938785 A JP10938785 A JP 10938785A JP S61268481 A JPS61268481 A JP S61268481A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer latex
- latex
- paper
- color development
- synthetic copolymer
- 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.)
- Granted
Links
- 239000004816 latex Substances 0.000 title claims abstract description 40
- 229920000126 latex Polymers 0.000 title claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 150000001993 dienes Chemical class 0.000 claims abstract description 5
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011161 development Methods 0.000 abstract description 24
- 239000000853 adhesive Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 14
- 238000006116 polymerization reaction Methods 0.000 abstract description 8
- 239000004927 clay Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000005011 phenolic resin Substances 0.000 abstract description 3
- 229920001568 phenolic resin Polymers 0.000 abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic diolefin Chemical class 0.000 description 5
- 238000004040 coloring Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000012546 transfer Methods 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
- 150000007513 acids Chemical class 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
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000499 gel 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
- 150000002825 nitriles Chemical class 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
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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
- 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-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
- 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
- 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
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 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
- 239000003086 colorant Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 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
- 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
- 239000000463 material 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
- 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
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
- Color Printing (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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性及び黒発色
性を付与させる合成共重合体ラテックスに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a synthetic copolymer latex that provides excellent blue and black coloring properties as a pressure-sensitive copying paper.
〔従来の技術）
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。[Prior Art] In recent years, pressure-sensitive copying paper has shown a remarkable growth in demand with the rationalization of office work, the development of the information industry, and the spread of computers, and its uses have also been diversifying.
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 of pressure-sensitive copying paper is color development, which is the essence 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
子供与性の無色又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。Color-forming refers to paper coated with fine capsules containing an electron-donating colorless or light-colored leuco dye dissolved in an organic solvent (capsule oil), an electron-accepting color developer, and an adhesive. The two coated surfaces, each consisting of a bottom paper with a color developing layer on the surface containing leuco dye, are placed facing each other, and printing pressure is applied to destroy the capsule, and the capsule oil containing the leuco dye is transferred to the color developing layer. 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。Currently, the most popular colors in the market are blue and black.
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−
５１１９号公報等に記載されている。Synthetic copolymer latexes conventionally used as compositions for pressure-sensitive copying paper are disclosed in, for example, Japanese Patent Publication No. 19475/1983, Japanese Patent Application Laid-open No. 31405/1983, and Japanese Patent Application Laid-open No. 51-1989.
It is described in Publication No. 5119 and the like.
特公昭５Ｂ−１９４７５号公報及び特開昭５３−３１４
０５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
和ニトリル系単重体を使用することによシ、発色性を向
上させるという内容である。Japanese Patent Publication No. 5B-19475 and Japanese Patent Application Publication No. 53-314
What is stated in Publication No. 05 is that color development is significantly improved in the high gel content region, and JP-A No. 51-5119 discloses that unsaturated nitrile monomers are used. By doing so, the color development is improved.
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＼、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
ととが判明した。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＼、青発色を低下させることが判明
した。As a result of examining the relationship between synthetic copolymer latex and color development, the present inventors found that synthetic copolymer latex with a high gel content significantly improves blue color development, while conversely, black color development significantly improves. It was found that the surface adhesion strength also decreased. It has also been found that unsaturated nitrile monomers improve black color development and reduce 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 has been found that when a conventional synthetic copolymer latex is used as an adhesive for a lower sheet for pressure-sensitive copying paper, blue color development and black color development are 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、一方を立てれば、
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 mentioned above, when conventional synthetic copolymer latex is used as an adhesive for lower paper for pressure-sensitive copying paper, blue coloration and black coloration exhibit contradictory phenomena.
It will be understood that it is extremely difficult to improve both properties without the benefit of one in the case of conventional synthetic copolymer latexes.
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 that can be used as a pressure-sensitive copying paper and simultaneously imparts excellent blue color development and black color development.
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ぽ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云う技術課
題が一挙に解決することを見い出した。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云う意外な事実を見い出し
、本発明を完成するに至った。The inventors of the present invention have conducted intensive research to simultaneously improve blue color development and black color development of pressure-sensitive copying paper. As a result, by specifying the amount of ethylenically unsaturated carboxylic acid in the synthetic copolymer latex and the swell index of the latex film, the technical problem of simultaneously improving blue and black color development, which had been considered difficult in the past, was solved at once. I found something to do. Furthermore, the present inventors surprisingly discovered that when the amount of unsaturated carboxylic acid in the synthetic copolymer latex and the swell index of the latex film are defined, adhesive strength is also exhibited, leading to the completion of the present invention.
〔問題点を解決するだめの手段と作用〕本発明は、脂肪
族ジオレフィン３５〜６０重量％、エチレン系不飽和カ
ルジン酸６〜１９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２１〜５９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５〜３０
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。[Means and effects for solving the problems] The present invention comprises 35 to 60% by weight of aliphatic diolefin, 6 to 19% by weight of ethylenically unsaturated caldicic acid, and other monoolefin monomers copolymerizable with these. consisting of 21 to 59% by weight,
Swell index of latex film is 5-30
This invention relates to a synthetic copolymer latex for pressure-sensitive copying paper.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用される脂肪族共役ジオレフィンとしては、
ブタジェンやイソプレン等がある。通常これらの単量体
は、合成共重合体は適度女弾性を与える。The aliphatic conjugated diolefin used in the present invention includes:
Examples include butadiene and isoprene. Usually, these monomers provide a synthetic copolymer with moderate elasticity.
３５重量％未満では充分な弾性が得られず接着強度があ
る。また６０重量％をこえると青発色が著しく減少する
。If it is less than 35% by weight, sufficient elasticity will not be obtained and adhesive strength will be insufficient. Moreover, if it exceeds 60% by weight, the blue coloring will be significantly reduced.
エチレン系不飽和カルジン酸としては、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
びジカル昶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ジン酸は
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。Examples of ethylenically unsaturated caldicic acids include anhydrides or monoalkyl esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and dicarboxylic acid. These ethylenically unsaturated caldic acids improve adhesiveness and also improve blue color development and black color development.
６重量％未満では、これらの物性の向上が認められたい
。１９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製した后の残
渣量が急激に増加する。When the amount is less than 6% by weight, improvements in these physical properties are observed. When the amount exceeds 19% by weight, the improvement in these physical properties becomes saturated and the amount of residue after producing the synthetic copolymer latex rapidly increases.
これらと共重合し得るモノオレフィン系単量体トシては
、スチレン、α−メチルスチレン、♂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
へキシルアクリレート、２−ヒｒロキシエチルアクリレ
ート、２−ヒｒロキシプロビルアクリレート、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Ｐロキシエチルメタクリレート、２−ヒｒロキシゾロ
ビルメタクリレート、ク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ｒ１
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。Monoolefin monomers that can be copolymerized with these include aromatic vinyl monomers such as styrene, α-methylstyrene, male nyltoluene, methyl acrylate,
Acrylate monomers exemplified by ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hyroxyethyl acrylate, 2-hyroxyprobyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, 2-
Methacrylate monomers exemplified by hyPoxyethyl methacrylate, 2-hyroxyzolobyl methacrylate, chrycidyl methacrylate, acrylamide r1
Examples include N-methylol acrylamide and acrylonitrile.
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３４〜４６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 an amount of 34 to 46 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５〜３０の範囲である。スウェルインデッ
クスが５未満では、接着強度が低下するばかシか黒発色
が著しく減少する。一方３０をこえると青発色が著しく
減少する。The swell index of the synthetic copolymer latex film of the present invention ranges from 5 to 30. When the swell index is less than 5, adhesive strength decreases and black coloring is significantly reduced. On the other hand, when it exceeds 30, the blue coloring decreases significantly.
址だ合成共重合体ラテックスフィルムのスウェルインデ
ックスの調整に重要な薬品として連鎖移動剤がある。Chain transfer agents are important chemicals for adjusting the swell index of synthetic copolymer latex films.
一般に使用されている連鎖移動剤は、例えばｔ−ｒ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。Commonly used chain transfer agents include, for example, tr-decyl 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
加法のいずれでも差支えない。Further, these chain transfer agents may be used alone or in combination of two or more. Furthermore, the addition method may be either 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７＋？キシル変性スチレン−ブタジェン
系共重合体ラテックスを製造するのに用いられるもので
良く、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, as an emulsifier,
Anionic ones are best. Anionic surfactant is normal Cal7+? Any material used for producing the xyl-modified styrene-butadiene copolymer latex may be used, such as higher alcohol sulfuric esters, alkylbenzene sulfonates, aliphatic sulfonates, and the like.
本発明の合成共重合体を得るために、重合開始剤として
は過流酸ナトリウム、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、あるいはしＰツ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、無機塩等も乳化
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, the polymerization initiator is a water-soluble initiator such as sodium persulfate, potassium persulfate, or ammonium persulfate, an oil-soluble initiator such as benzoyl peroxide, or Any initiator can be used. Further, if necessary, chelating agents, inorganic salts, etc. known for 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１．６ツチ
重合方式及び連続重合方式いずれでもよい。The polymerization method of the synthetic copolymer latex of the present invention may be either a 1.6-inch polymerization method or a continuous polymerization method.
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た下葉紙を形成
させる。The synthetic copolymer latex thus obtained is applied as an adhesive along with a color developer to one side of a substrate to form a base 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ｒ
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。Color developers include inorganic color developers such as acid clay, activated clay, calcined activated clay, etc., phenolic compounds, phenolic resins, maleic acid-rosin resins, partially or fully hydrolyzed styrene-maleic anhydride. Copolymer, polyvalent metal salt of phenolic resin, aromatic carboxylic acid-aldehyde
Organic color developers such as polymeric polyvalent metal salts and the like can be used.
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、ホリヒニルア
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。In addition to the synthetic copolymer latex, in order to sufficiently retain pigments and various additives other than the color developer, starches, casein, gelatin, gum arabic, hollyhinyl alcohol, methyl cellulose, ethyl cellulose, etc. are usually used. Adhesives are 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, 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 include antifoaming agents, waterproofing agents, lubricants, dispersants, etc., 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１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、青発色及び黒発色共大巾に減少する。When the synthetic copolymer latex of the present invention is used as an adhesive for lower paper for pressure-sensitive copying paper, it is preferably used in an amount of 5 to 25 parts by weight per 100 parts by weight of pigment and color developer. If the amount of synthetic copolymer latex used is less than 5 parts by weight, the surface adhesive strength of the bottom paper for pressure-sensitive copying paper will be significantly inferior. On the other hand, if the amount exceeds 25 parts by weight, both blue color development and black color development are significantly reduced.
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、きわめて優れだ
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 was used as an adhesive for lower paper for pressure-sensitive copying paper, it imparted extremely excellent blue and black coloring and exhibited excellent adhesive strength. Copy paper can be provided.
次に実施例及び比較例を示す。以下の２及び部は、特に
断シのない限り重量表示である。Next, examples and comparative examples will be shown. The numbers 2 and parts below 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、
次に示すとおシである。The method for measuring each physical property in Examples and Comparative Examples is as follows:
The following is an example.
（１）塗工紙の接着強度：明製作所社製ＲＩ印刷試験機
を使用し、タック１０のインキで数回重ね刷シを行い、
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 Mei Seisakusho Co., Ltd., overprinting was performed several times with ink of tack 10.
Visually judge the picking state of the printed surface. 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、■ＧＴ試験機によ
シ印圧をかける。（印圧：３５却、スプリングＭ）発色
層３０秒たった后の発色濃度をハンタ一式白色度計にて
測定する。数字小の方が良好である。(2) Color development of coated paper: Layer a lower paper containing each synthetic copolymer latex and a commercially available upper paper, and apply printing pressure using a GT tester. (Printing pressure: 35 mm, spring M) After 30 seconds of color development, the color density was measured using a Hunter whiteness meter. Lower numbers are better.
（３） ラテックスフィルムのスウェルインデックス
＝２３℃×６５％ＲＨの雰囲気中で２４時間常温成膜さ
せる。このものを約０．５２とＪＪ３０ｚ）ルエン溶液
に浸漬し、振とう器で約４時間攪拌溶解し、２００メツ
シユの金網で濾過する。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后の残留物重量との割
合で示す。(3) Latex film is formed at room temperature for 24 hours in an atmosphere with a swell index of 23° C. and 65% RH. This product is immersed in a luene solution of about 0.52 and JJ30z), stirred and dissolved in a shaker for about 4 hours, and filtered through a 200-mesh wire mesh. It is expressed as a ratio between the weight of the toluene-containing residue filtered on a wire mesh and the weight of the residue after drying.
実施例１〜６、比較例１〜６
１）合成共重合体ラテックス
実施例１では、ブタジェン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リツトル、オートクレーブ中に仕込み、窒
素雰囲気中で攪拌しながら、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 6, Comparative Examples 1 to 6 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, and sodium hydrogen carbonate. 0.9 parts of potassium persulfate, 0.5 parts of sodium alkylbenzenesulfonate, and 150 parts of polymerized water were placed in an autoclave and reacted for 9 hours at 80°C while stirring in a nitrogen atmosphere. Ta. The polymerization conversion rate of monomers 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ない、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１６００Ｘ一様ｒ売。In Comparative Example 1, 9 parts of carbon tetrachloride was used under the above conditions to obtain a synthetic copolymer latex. The polymerization conversion rate of monomers was 99.6%. The monomer compositions of other examples and comparative examples of the synthetic copolymer latex are as shown in Table 1, and the listed parts were polymerized under the same polymerization conditions as above,
Each synthetic copolymer latex was obtained. The pH of the synthetic copolymer latex was adjusted to 8 with sodium hydroxide, and water vapor and nitrogen blowing were performed to remove residual monomers to obtain a desired synthetic copolymer latex. The average particle size of this copolymer is approximately 1600X uniform.
２）感圧複写紙用下葉紙としての評価
下記の塗工液を作製し、この塗工液を５ｏｙ７ｍ２の成
紙の片面に乾燥重量で５１７ｍ２になるように塗布し、
乾燥し、下葉紙を得た。2) Evaluation as a bottom sheet for pressure-sensitive copying paper The following coating solution was prepared, and this coating solution was applied to one side of a 5oy7m2 sheet of paper to a dry weight of 517m2.
It was dried to obtain a paper sheet.
クレー ８０ 部
ポリアクリル酸ソーダ ０．５ＮａＯＨ０，５
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１〜６及び比較例１〜６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。さらに下葉紙その
も′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 Sodium polyacrylate 0.5 NaOH 0.5 Oxidized starch 6 Synthetic copolymer latex 12 Solid content (wt%) 30 Coated surface of lower paper obtained in Examples 1 to 6 and Comparative Examples 1 to 6 A color development test was conducted by stacking commercially available paper sheets so that the coated sides were facing each other. Furthermore, the adhesion strength of the coated surface of the bottom paper itself was evaluated using an RI printing machine. The results are shown in Table 2.
以下余白 第 １ 表 第 ２ 表Below margin Table 1 Table 2
Claims (2)
レン系不飽和カルボン酸６〜１９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２１〜５９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５〜３０である感圧複写紙用合成共重合体ラテッ
クス(1) A latex film consisting of 35 to 60% by weight of aliphatic conjugated diolefin, 6 to 19% by weight of ethylenically unsaturated carboxylic acid, and 21 to 59% by weight of other monoolefin monomers copolymerizable with these. A synthetic copolymer latex for pressure-sensitive copying paper having a swell index of 5 to 30.
範囲第１項記載の合成共重合体ラテックスを５〜２５重
量部含有することを特徴とする感圧複写紙用組成物(2) A composition for pressure-sensitive copying paper, characterized in that it contains 5 to 25 parts by weight of the synthetic copolymer latex described in claim 1 per 100 parts by weight of the pigment and color developer.
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 true JPS61268481A (en) | 1986-11-27 |
| JPH0822610B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3828084A1 (en) * | 1987-08-19 | 1989-03-02 | Mitsubishi Paper Mills Ltd | CARBON-FREE, PRESSURE-SENSITIVE RECORDING PAPER |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5266009A (en) * | 1975-11-28 | 1977-06-01 | Sumitomo Naugatuck | Color papers for presure sensitized copy |
| 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
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5266009A (en) * | 1975-11-28 | 1977-06-01 | Sumitomo Naugatuck | Color papers for presure sensitized copy |
| JPS6024992A (en) * | 1983-07-21 | 1985-02-07 | Nippon Zeon Co Ltd | Color developer coating composition for pressure- sensitive copying paper |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3828084A1 (en) * | 1987-08-19 | 1989-03-02 | Mitsubishi Paper Mills Ltd | CARBON-FREE, PRESSURE-SENSITIVE RECORDING PAPER |
| US4931422A (en) * | 1987-08-19 | 1990-06-05 | Mitsubishi Paper Mills Limited | No-carbon pressure-sensitive copying paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0822610B2 (en) | 1996-03-06 |
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