JP2006249632A - Repeelable pressure-bonded recording paper - Google Patents
Repeelable pressure-bonded recording paper Download PDFInfo
- Publication number
- JP2006249632A JP2006249632A JP2005071503A JP2005071503A JP2006249632A JP 2006249632 A JP2006249632 A JP 2006249632A JP 2005071503 A JP2005071503 A JP 2005071503A JP 2005071503 A JP2005071503 A JP 2005071503A JP 2006249632 A JP2006249632 A JP 2006249632A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- ethylenically unsaturated
- unsaturated monomer
- parts
- ethylene
- 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
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- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material 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
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 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
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001869 inorganic persulfate Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 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 1
- QANMHLXAZMSUEX-UHFFFAOYSA-N kinetin Chemical compound N=1C=NC=2N=CNC=2C=1NCC1=CC=CO1 QANMHLXAZMSUEX-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940094506 lauryl betaine Drugs 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-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
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 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
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-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
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 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
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- NEUOBESLMIKJSB-UHFFFAOYSA-J tetrasodium;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O NEUOBESLMIKJSB-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KGDQKMRJLRNYEX-UHFFFAOYSA-N tridecyl 2-sulfanylpropanoate Chemical class SC(C(=O)OCCCCCCCCCCCCC)C KGDQKMRJLRNYEX-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Credit Cards Or The Like (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Paper (AREA)
Abstract
Description
本発明は、耐酸化劣化性能、耐熱性能、耐ＵＶ性能、耐ブロッキング性能、印刷性能、印字性能及び圧着性能に優れ、空気中に放置されたり、加熱されたり、紫外線（ＵＶ）を照射されたりしても接着力が低下しにくい再剥離性圧着記録用紙の提供である。 The present invention is excellent in oxidation resistance degradation performance, heat resistance performance, UV resistance performance, blocking resistance performance, printing performance, printing performance and pressure bonding performance, and is left in the air, heated, or irradiated with ultraviolet rays (UV). Even so, the present invention provides a releasable pressure-sensitive recording paper that does not easily lower the adhesive force.
近年、銀行、クレジット会社、保険会社、官庁等から各個人宛に貯金、残金状況等個人情報を通知する手段として、親展はがきが普及している。親展はがきは基材に感圧接着剤を塗布した後、共通情報はオフセット印刷、グラビア印刷等で行い（酸化重合インキタイプ、ＵＶ硬化型インキタイプ）、個人情報はレーザービーム方式、インクジェット（ＩＪ）方式等で印刷した後、印刷面同士を適度の圧力を加えることで接着させ、各個人に郵送された後、再剥離することで情報を得ることができる。 In recent years, private postcards have been widely used as means for notifying personal information such as savings, balances, etc. to individual individuals from banks, credit companies, insurance companies, government agencies, and the like. After applying a pressure sensitive adhesive on the base material for confidential postcards, common information is offset printing, gravure printing, etc. (oxidation polymerization ink type, UV curable ink type), personal information is laser beam method, inkjet (IJ) After printing by a method or the like, it is possible to obtain information by adhering the printed surfaces to each other by applying an appropriate pressure, mailing to each individual, and then re-peeling.
従来、感圧接着剤には、主にメタクリル酸メチルグラフト共重合天然ゴム系接着剤が主に使用されてきたが、耐紫外線（ＵＶ）性能、耐湿性能、耐熱性能に劣る為、オフセット印刷時のＵＶ照射により接着力が低下し、また黄変化、接着力の低下、硬化に代表されるように経時的に劣化する（以下老化現象という）ものであり、その性能変化は著しい。そのため郵送中等に自然に剥離し第３者の目に情報がふれ、親展はがきとしての本来の機能を果たさなくなる問題があった。そこで接着性能を改善するため、天然ゴム系接着剤の代替として安定性が高いスチレン−ブタジエンゴム（ＳＢＲ）系樹脂やエチレン−酢酸ビニル系樹脂を接着剤として用いることが提案されている。（特許文献１〜３参照）
しかしＳＢＲ系接着剤は、天然ゴム系接着剤よりも安定性は高いが、欠点として、オフセット印刷時のＵＶ照射をする際に分子中の不飽和結合が壊される為に分子構造が変化し接着性能等が低下する等の問題がある。またＳＢＲ系接着剤は親水性が低い為に、配合量が増加するとＩＪ適性が低下する問題もある。
Conventionally, methyl methacrylate graft copolymer natural rubber adhesives have been mainly used for pressure sensitive adhesives, but they are inferior in ultraviolet resistance (UV) performance, moisture resistance performance, and heat resistance performance. UV irradiation reduces the adhesive strength, and deteriorates with time as represented by yellowing, adhesive strength reduction, and curing (hereinafter referred to as aging phenomenon), and the performance change is remarkable. For this reason, there has been a problem that it peels off naturally during mailing, etc., and the information of the third party is touched and the original function as a confidential postcard cannot be performed. In order to improve the adhesive performance, it has been proposed to use a highly stable styrene-butadiene rubber (SBR) resin or ethylene-vinyl acetate resin as an adhesive instead of a natural rubber adhesive. (See Patent Documents 1 to 3)
However, SBR adhesives are more stable than natural rubber adhesives. However, the disadvantage is that the unsaturated bonds in the molecules are broken when UV irradiation is performed during offset printing, and the molecular structure changes, resulting in adhesion. There is a problem such as a decrease in performance. In addition, since the SBR adhesive has low hydrophilicity, there is a problem that IJ suitability decreases when the blending amount increases.
エチレン−酢酸ビニル系接着剤は、耐ＵＶ性能やＩＪ適性には優れているが、欠点として、工程上の加熱により接着性能が低下したり、オフセット印刷工程において使用されるインキの成分が、樹脂中の未反応アクリルモノマーと反応しやすいため、圧着を行った際に印刷された部分のインキが反対面の塗工層と反応して転写を生じてしまう為に、内容が読みにくくなったりする等の問題がある。さらにエチレン−酢酸ビニル接着剤は耐水性が劣るという問題がある為、湿度による水分によって経時で剥離強度が低下する等の問題がある。 Ethylene-vinyl acetate adhesive is excellent in UV resistance and IJ suitability, but as a disadvantage, the adhesive performance is lowered by heating in the process, or the ink component used in the offset printing process is resin It is easy to react with the unreacted acrylic monomer in the inside, so the printed part of the ink reacts with the coating layer on the opposite side when it is crimped, resulting in transfer, making the content difficult to read There are problems such as. Further, since the ethylene-vinyl acetate adhesive has a problem that the water resistance is inferior, there is a problem that the peel strength decreases with time due to moisture due to humidity.
本発明者は、特願２００４−３０６７２１号において、−５０℃〜０℃のガラス転移温度（Ｔｇ）のスチレン−ブタジエン共重合体エマルジョン（ＳＢＲラテックス）と、下記一般式で表されるアルカン酸ビニル及びエチレンの共重合体エマルジョンの存在下で、エチレン性不飽和単量体のシード重合によって得られるエマルジョンとを固形分重量比０．５：９．５〜７：３で混合した接着剤基材と、微粒子充填剤を含有することを特徴とする再剥離性圧着記録用紙を提案している：
Ｒ１Ｏ
｜ ‖
Ｒ２−Ｃ−Ｃ−Ｏ−ＣＨ＝ＣＨ２
｜
Ｒ３
（式中、Ｒ１、Ｒ２及びＲ３は、それらの合計の炭素数が６以上の直鎖のアルキル基であって少なくとも１つはメチル基を表す。）
この再剥離性圧着記録用紙は、耐ＵＶ性能に加えて印刷・印字性能も優れており、１４０℃で３０分の熱負荷に耐える程度の耐熱性能を有している。しかし、最近、１８０℃で３０分の熱負荷に耐える再剥離性圧着記録用紙が要求されてきている。
R 1 O
｜ ‖
R 2 —C—C—O—CH═CH 2
｜
R 3
(In the formula, R 1 , R 2 and R 3 are linear alkyl groups having 6 or more carbon atoms in total, and at least one of them represents a methyl group.)
This releasable pressure-sensitive recording paper has excellent printing and printing performance in addition to UV resistance, and has heat resistance enough to withstand a heat load of 30 minutes at 140 ° C. Recently, however, a releasable pressure-sensitive recording sheet that can withstand a heat load of 30 minutes at 180 ° C. has been demanded.
従って、本発明の目的は、従来の問題を解決し、耐ＵＶ性能および印刷・印字性能に加えて、１８０℃で３０分の熱負荷に耐える耐熱性能を有する再剥離性圧着記録用紙を提供することである。 Accordingly, an object of the present invention is to solve the conventional problems and provide a releasable pressure-sensitive recording sheet having heat resistance capable of withstanding a heat load of 30 minutes at 180 ° C. in addition to UV resistance and printing / printing performance. That is.
本発明者は、上記の課題を解決する為に鋭意研究を行った結果、常温、常圧では粘着性、接着性を示さず、加圧時に接着性を示し、圧着後に剥離可能である感圧接着剤層を少なくとも片面に有する再剥離性圧着記録用紙において、前記感圧接着剤組成物が、共役ジエン系単量体とエチレン系不飽和単量体を乳化重合させて得られたものであり、そのトルエン不溶分（以下、「ゲル分」という。）が５０％以下で、かつそのガラス転移温度（Tg）が−５０未満〜−８０℃である共重合体ラテックスと、下記一般式で表されるアルカン酸ビニルとエチレンとのアルカン酸ビニル・エチレン共重合体水性エマルジョンの存在下でエチレン性不飽和単量体のシード重合によって得られるエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンを、固形分重量比１：９〜９：１で混合した感圧接着剤組成物１００重量部（固形分）と、微粒子充填剤３０〜２００重量部（固形分）を含有することを特徴とする再剥離性圧着記録用紙によって解決されることを見出した。 As a result of earnest research to solve the above-mentioned problems, the present inventor does not exhibit tackiness and adhesiveness at normal temperature and normal pressure, exhibits adhesiveness when pressed, and can be peeled off after pressure bonding. In a releasable pressure-sensitive recording paper having an adhesive layer on at least one side, the pressure-sensitive adhesive composition is obtained by emulsion polymerization of a conjugated diene monomer and an ethylenically unsaturated monomer. A copolymer latex having a toluene insoluble content (hereinafter referred to as “gel content”) of 50% or less and a glass transition temperature (Tg) of less than −50 to −80 ° C., and represented by the following general formula: Ethylenically unsaturated monomer-vinyl alkanoate-ethylene copolymer obtained by seed polymerization of ethylenically unsaturated monomer in the presence of an aqueous emulsion of vinyl alkanoate-ethylene copolymer of vinyl alkanoate and ethylene Polymer 100 parts by weight (solid content) of a pressure-sensitive adhesive composition obtained by mixing a water-soluble emulsion in a solid content weight ratio of 1: 9 to 9: 1 and 30 to 200 parts by weight (solid content) of a fine particle filler. It has been found that the problem is solved by the releasable pressure-sensitive recording paper.
Ｒ１Ｏ
｜ ‖
Ｒ２−Ｃ―Ｃ−Ｏ−ＣＨ＝ＣＨ２
｜
Ｒ３
（式中、Ｒ１、Ｒ２及びＲ３は、それらの合計の炭素数が６以上の直鎖のアルキル基であって少なくとも１つはメチル基を表す）
R 1 O
｜ ‖
R 2 —C—C—O—CH═CH 2
｜
R 3
(In the formula, R 1 , R 2 and R 3 are linear alkyl groups having a total carbon number of 6 or more, and at least one represents a methyl group)
この様な構成を有する感圧接着剤組成物は剥離強度、ブロッキング性、印刷適性、印字適性などに優れた効果を奏しそして１８０℃で３０分の熱負荷に耐える。 The pressure-sensitive adhesive composition having such a configuration exhibits excellent effects such as peel strength, blocking property, printability, printability, and the like and withstands a heat load of 30 minutes at 180 ° C.
以下、本発明について更に詳しく説明する。即ち本発明の再剥離性圧着記録用紙は、感圧接着剤組成物について、共役ジエン系単量体とエチレン系不飽和単量体を乳化重合させて得られたものであり、そのゲル分が５０％以下で、かつそのガラス転移温度（Tg）が−５０未満〜−８０℃であることを特徴とする共重合体ラテックスと、アルカン酸ビニル及びエチレンのアルカン酸ビニル・エチレン共重合体水性エマルジョンの存在下でエチレン性不飽和単量体のシード重合によって得られるエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンを、固形分重量比１：９〜９：１で混合した感圧接着剤組成物１００重量部（固形分）と、微粒子充填剤３０〜２００重量部（固形分）を含有することで優れた再剥離性圧着記録用紙を得ることが可能になった。 Hereinafter, the present invention will be described in more detail. That is, the releasable pressure-sensitive adhesive recording paper of the present invention is obtained by emulsion polymerization of a conjugated diene monomer and an ethylenically unsaturated monomer with respect to the pressure-sensitive adhesive composition, and the gel content thereof is Copolymer latex having a glass transition temperature (Tg) of less than −50 to −80 ° C. and a vinyl alkanoate / ethylene copolymer alkanoate / ethylene copolymer aqueous emulsion having a glass transition temperature (Tg) of less than −50 to −80 ° C. An ethylenically unsaturated monomer-vinyl alkanoic acid-ethylene copolymer aqueous emulsion obtained by seed polymerization of an ethylenically unsaturated monomer in the presence of water is mixed in a solid content weight ratio of 1: 9 to 9: 1. By including 100 parts by weight (solid content) of the pressure-sensitive adhesive composition and 30 to 200 parts by weight (solid content) of the fine particle filler, an excellent releasable pressure-sensitive recording sheet can be obtained.
また、該感圧接着剤組成物中の共重合体ラテックス：エチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンの比率が固形分重量比１：９〜９：１、好ましくは２：８〜８：２であることで、上記諸特性の改良効果をより確実にすることができる。 Further, the ratio of copolymer latex: ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion in the pressure-sensitive adhesive composition is preferably a solid content weight ratio of 1: 9 to 9: 1. Is from 2: 8 to 8: 2, the effect of improving the above characteristics can be further ensured.
本発明の感圧接着剤組成物の共重合体ラテックスに用いられる共役ジエン系単量体としては、例えば１，３−ブタジエン、イソプレン、２−クロロ−１，３−ブタジエン、２−メチル−１，３−ブタジエン等を挙げることができる。これらの共役ジエン系単量体は、単独で、又は２種以上を組み合わせて用いられる。本発明においては、特に、１，３−ブタジエンが好ましく用いられる。本発明において用いるエチレン系不飽和単量体としては、スチレン，α−メチルスチレン，ビニルトルエン，ｐ−メチルスチレン等の芳香族ビニル化合物；アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸エチル、メタクリル酸メチル等のエチレン系不飽和カルボン酸アルキルエステル；アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物；アクリル酸、メタクリル酸、クロトン酸等のモノカルボン酸；マレイン酸、フマル酸、イタコン酸等のジカルボン酸や、それらの無水物；マレイン酸メチル、イタコン酸メチル等のジカルボン酸のモノエステル、即ち、エチレン系不飽和カルボン酸の半エステル；アクリルアミド、メタクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド等のエチレン系不飽和カルボン酸アミド化合物；アクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシンアルキル等の不飽和カルボン酸ヒドロキシアルキルエステル化合物；メチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジブチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、２―ビニルピリジン等のエチレン系不飽和アミン；酢酸ビニル等のカルボン酸ビニルエステル類等を挙げることができる。エチレン系不飽和単量体は、単独で、または２種以上を組み合わせて用いられる。 Examples of the conjugated diene monomer used in the copolymer latex of the pressure-sensitive adhesive composition of the present invention include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and 2-methyl-1. , 3-butadiene and the like. These conjugated diene monomers are used alone or in combination of two or more. In the present invention, 1,3-butadiene is particularly preferably used. Examples of the ethylenically unsaturated monomer used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, and ethyl methacrylate. , Ethyl unsaturated carboxylic acid alkyl esters such as methyl methacrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; maleic acid, fumaric acid and itaconic acid Dicarboxylic acids and anhydrides thereof; monoesters of dicarboxylic acids such as methyl maleate and methyl itaconate, ie, half esters of ethylenically unsaturated carboxylic acids; acrylamide, methacrylamide, N, N-dimethylacrylamide, N -Methylol acrylic Ethylenically unsaturated carboxylic acid amide compounds such as amides; unsaturated carboxylic acid hydroxyalkyl ester compounds such as 2-hydroxyethyl acrylate and 2-hydroxyn alkyl methacrylate; methylaminoethyl (meth) acrylate, dimethylaminoethyl (meta ) Acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, 2-vinylpyridine and other ethylenically unsaturated amines; vinyl acetate, etc. And carboxylic acid vinyl esters. The ethylenically unsaturated monomers are used alone or in combination of two or more.
本発明の感圧接着剤組成物において用いられる共重合体ラテックスの共重合体のＴｇは−５０未満〜−８０℃が好ましい。Ｔｇが−５０℃以上だと剥離強度が減少する為、共重合体ラテックスがむしろ接着力を阻害する方に作用する。接着力が阻害された場合、接着性能を発現する為に圧着時に大きな圧力を必要とするが、これにより印刷部分のインキが対向面の塗工層に取られる原因となり、その結果対向面へのインキ転写が生じてしまう恐れがあり好ましくない。またＴｇが−８０℃より低いとオフセット印刷において塗工層が脱落しやすくなるだけでなく耐熱性の悪化やブロッキングの原因にもなる。 The Tg of the copolymer latex copolymer used in the pressure-sensitive adhesive composition of the present invention is preferably less than −50 to −80 ° C. When Tg is −50 ° C. or higher, the peel strength decreases, so that the copolymer latex rather acts on the way of inhibiting the adhesive force. If the adhesive force is hindered, a large pressure is required at the time of pressure bonding in order to develop the adhesive performance, but this causes the ink of the printed part to be taken by the coating layer on the opposite surface, and as a result Ink transfer may occur, which is not preferable. On the other hand, if Tg is lower than −80 ° C., not only the coating layer is easily removed in offset printing, but also heat resistance is deteriorated and blocking is caused.
本発明の共重合体ラテックスは乳化重合で得られる。本発明の共重合体ラテックスの製造方法においては、従来より知られている乳化重合の方法、すなわち、例えば、水のような水性媒体中に単量体混合物、重合開始剤、界面活性剤および重合連鎖移動剤等を適宜加えて乳化重合が行われる。 The copolymer latex of the present invention is obtained by emulsion polymerization. In the method for producing the copolymer latex of the present invention, a conventionally known emulsion polymerization method, that is, a monomer mixture, a polymerization initiator, a surfactant and a polymerization in an aqueous medium such as water, for example. Emulsion polymerization is performed by appropriately adding a chain transfer agent or the like.
ここに、重合開始剤は、特に制限されるものではなく、過硫酸カリウム，過硫酸ナトリウム，過硫酸アンモニウム等の無機系過硫酸塩；クメンハイドロパーオキサイド，ベンゾイルパーオキサイド，イソプロピルベンゼンヒドロパーオキサイド、ｔ−ブチルヒドロパーオキサイド、ｐ−メンタンヒドロパーオキサイド、ジ−ｔ−ブチルパーオキサイド等の有機系過酸化物；アゾイソブチロニトリル等のアゾ系の開始剤等を用いることができる。これらは、単独でまたは２種以上を組み合わせて使用することができる。特に、本発明において、上記した重合開始剤は、重亜硫酸ナトリウム，硫酸第１鉄、アスコルビン酸、ナトリウムホルムアルデヒドスルホキシレート等の還元剤と組み合わせてなるいわゆるレドックス系重合開始剤として使用することが好ましい。さらに、重合開始剤として有機系過酸化物と還元剤を組み合わせたレドックス系重合開始剤が好ましい。 Here, the polymerization initiator is not particularly limited, and inorganic persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, isopropylbenzene hydroperoxide, t Organic peroxides such as -butyl hydroperoxide, p-menthane hydroperoxide, and di-t-butyl peroxide; azo initiators such as azoisobutyronitrile can be used. These can be used alone or in combination of two or more. In particular, in the present invention, the polymerization initiator described above is preferably used as a so-called redox polymerization initiator that is combined with a reducing agent such as sodium bisulfite, ferrous sulfate, ascorbic acid, sodium formaldehyde sulfoxylate, and the like. . Furthermore, a redox polymerization initiator in which an organic peroxide and a reducing agent are combined is preferable as the polymerization initiator.
本発明の共重合体ラテックスの製造方法において、重合開始剤の使用量は、全単量体１００重量部当たりに、通常、０．０１〜５重量部程度であり、好ましくは、０．０３〜３重量部程度である。還元剤を使用する場合は、還元剤の使用量が重合開始剤の使用量に対して０．１〜３倍の範囲、好ましくは０．２〜２倍の範囲になる様にする。本発明に用いられる界面活性剤としては、例えば、オレイン酸塩、ステアリン酸塩、ロジン酸塩等のカルボン酸塩を有する界面活性剤；アルキルりん酸エステル塩、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、ドデシルジフェニルエーテルジスルホン酸ナトリウム、コハク酸ジアルキルエステルスルホン酸ナトリウム等のアニオン系界面活性剤；ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルアミン、ポリオキシエチレンアルキルエステル等のノニオン系界面活性剤；ラウリルベタイン、ステアリルベタインの塩等のアルキルベタイン型の塩；ラウリル−β−アラニン、ラウリルジ（アミノエチル）グリシン、オクチルジ（アミノエチル）グリジンの塩等のアミノ酸型などの両性界面活性剤を挙げることができる。これらは単独で、または２種以上を組み合わせて用いることができる。 In the method for producing a copolymer latex of the present invention, the amount of the polymerization initiator used is usually about 0.01 to 5 parts by weight, preferably 0.03 to 100 parts by weight of all monomers. About 3 parts by weight. When the reducing agent is used, the amount of the reducing agent used is in the range of 0.1 to 3 times, preferably 0.2 to 2 times the amount of the polymerization initiator used. Examples of the surfactant used in the present invention include surfactants having carboxylates such as oleate, stearate, and rosinate; alkyl phosphate ester salts, sodium dodecylbenzenesulfonate, sodium lauryl sulfate Anionic surfactants such as sodium dodecyl diphenyl ether disulfonate and sodium dialkyl ester succinate; nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine and polyoxyethylene alkyl ester; lauryl betaine , Alkylbetaine type salts such as stearyl betaine salts; amphoteric surface actives such as lauryl-β-alanine, lauryl di (aminoethyl) glycine, octyldi (aminoethyl) glycine salts, etc. Agent can be mentioned. These can be used alone or in combination of two or more.
本発明に用いられる重合連鎖移動剤も、特に制限されるものではなく、例えば、ヘキシルメルカプタン、オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ヘキサデシルメルカプタン、ｎ−テトラデシルメルカプタン等のアルキルメルカプタン類；四塩化炭素、四臭化炭素、臭化エチレン等のハロゲン化炭化水素；メルカプト酢酸２−エチルヘキシルエステル、メルカプトプロピオン酸２−エチルヘキシルエステル、メルカプトプロピオン酸トリデシルエステル等のメルカプトカルボン酸アルキルエステル；メルカプト酢酸メトキシブチルエステル、メルカプトプロピオン酸メトキシブチルエステル等のメルカプトカルボン酸アルコキシアルキルエステル；オクタン酸２−メルカプトエチルエステル等のカルボン酸メルカプトアルキルエステル；及びα−メチルスチレンダイマー、ターピノーレン、α−テルピネン、γ−テルピネン、ジペンテン、アニソール、アリルアルコール等を挙げることができる。 The polymerization chain transfer agent used in the present invention is not particularly limited, and examples thereof include hexyl mercaptan, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, and n-tetradecyl mercaptan. Alkyl mercaptans; halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide and ethylene bromide; alkyl mercaptocarboxylates such as mercaptoacetic acid 2-ethylhexyl ester, mercaptopropionic acid 2-ethylhexyl ester, mercaptopropionic acid tridecyl ester Esters; mercaptocarboxylic acid alkoxyalkyl esters such as mercaptoacetic acid methoxybutyl ester and mercaptopropionic acid methoxybutyl ester; octanoic acid 2-mercaptoethyl ester Bon acid mercaptoalkyl esters; and alpha-methylstyrene dimer, terpinolene, alpha-terpinene, .gamma.-terpinene, mention may be made of dipentene, anisole, and allyl alcohol.
これらの重合連鎖移動剤は、単独で、または２種以上を組み合わせて用いられる。本発明においては、アルキルメルカプタン類、四塩化炭素、オクタン酸２−メルカプトエチルエステル、α−メチルスチレンダイマー、ターピノーレン等が好ましく用いられる。本発明において、これら重合連鎖移動剤の使用量は、全単量体１００重量部に対して、通常、０〜５重量部、好ましくは、０〜３重量部である。本発明における単量体混合物、重合開始剤、界面活性剤や重合連鎖移動剤の添加方法は、一括添加方式、分割添加方式、連続添加方式あるいはこれらの組み合わせのいずれでもよい。また分割添加方式の場合、単量体混合物、重合開始剤、界面活性剤や重合連鎖移動剤の組成と使用量を各段階で変化させてもよい。連続添加方式の場合も、単量体混合物、重合開始剤、界面活性剤や重合連鎖移動剤の組成と使用量を添加時間とともに連続的に、または断続的に変化させてもよい。また、本発明の方法においては、必要に応じて、乳化重合をエチレンジアミン四酢酸ナトリウム等のキレート剤、ポリアクリル酸ナトリウム、ナフタレン−ホルマリン縮合物のスルホン酸塩等の分散剤やピロりん酸カリウム、ピロりん酸ナトリウム、りん酸三ナトリウム、りん酸水素二ナトリウム、トリポリりん酸ナトリウム等の無機塩等の存在下に行ってもよい。 These polymerization chain transfer agents are used alone or in combination of two or more. In the present invention, alkyl mercaptans, carbon tetrachloride, octanoic acid 2-mercaptoethyl ester, α-methylstyrene dimer, terpinolene and the like are preferably used. In this invention, the usage-amount of these polymerization chain transfer agents is 0-5 weight part normally with respect to 100 weight part of all monomers, Preferably, it is 0-3 weight part. In the present invention, the monomer mixture, polymerization initiator, surfactant or polymerization chain transfer agent may be added by any of a batch addition method, a divided addition method, a continuous addition method, or a combination thereof. In the case of the divided addition method, the composition and amount of the monomer mixture, polymerization initiator, surfactant or polymerization chain transfer agent may be changed at each stage. Also in the case of the continuous addition method, the composition and amount of the monomer mixture, polymerization initiator, surfactant or polymerization chain transfer agent may be changed continuously or intermittently with the addition time. In the method of the present invention, if necessary, emulsion polymerization may be carried out by using a chelating agent such as sodium ethylenediaminetetraacetate, a dispersant such as sodium acrylate, sulfonate of naphthalene-formalin condensate, potassium pyrophosphate, The reaction may be carried out in the presence of an inorganic salt such as sodium pyrophosphate, trisodium phosphate, disodium hydrogen phosphate, or sodium tripolyphosphate.
また、共重合体ラテックスのゲル分(トルエン不溶分)は、水濡れ後の接着強度、接着性、耐熱性、耐候性、保存安定性、耐ブロッキング性等を損なわない範囲であればよく、例えば、５０重量％以下、好ましくは４０重量％以下、さらに好ましくは３０重量％以下である。このようにして、本発明によって得られる共重合体ラテックスは、感圧接着剤基材として好適に用いることができる。 Further, the gel content (toluene insoluble content) of the copolymer latex may be in a range that does not impair the adhesive strength after water wetting, adhesiveness, heat resistance, weather resistance, storage stability, blocking resistance, etc. , 50% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less. Thus, the copolymer latex obtained by the present invention can be suitably used as a pressure-sensitive adhesive substrate.
本発明の感圧接着剤組成物において用いられる、化１で示されるアルカン酸ビニルとエチレンを共重合したアルカン酸ビニル・エチレン共重合体水性エマルジョンの存在下でエチレン性不飽和単量体をシード重合して得た水性エマルジョン（エチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョン）は、化１で示すような直鎖のアルキル基を有することで、耐水性、接着性に優れる。そのため接着剤として使用した場合、湿度に対する劣化が少なく、低温時の剥離力に優れる。 The ethylenically unsaturated monomer is seeded in the presence of an aqueous emulsion of vinyl alkanoate / ethylene copolymer obtained by copolymerizing vinyl alkanoate and ethylene represented by Chemical Formula 1, which is used in the pressure-sensitive adhesive composition of the present invention. An aqueous emulsion (ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion) obtained by polymerization has a linear alkyl group as shown in Chemical Formula 1 to provide water resistance and adhesion. Excellent. Therefore, when used as an adhesive, there is little deterioration with respect to humidity, and excellent peel strength at low temperatures.
アルカン酸ビニルとエチレンとのアルカン酸ビニル・エチレン共重合体水性エマルジョンは、通常の乳化重合によって得られる。安定化剤は特に限定されないが水溶性高分子を用いることが好ましい。ノニオン性乳化剤等は湿度によって経時で剥離強度が低下するため好ましくない。水溶性高分子としては、ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ポリビニルピロリドン等が挙げられる。これらは、単独使用でも相互の併用でも構わない。 An aqueous emulsion of vinyl alkanoate / ethylene copolymer of vinyl alkanoate and ethylene can be obtained by ordinary emulsion polymerization. The stabilizer is not particularly limited, but a water-soluble polymer is preferably used. Nonionic emulsifiers and the like are not preferred because the peel strength decreases with time due to humidity. Examples of the water-soluble polymer include polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone and the like. These may be used alone or in combination.
アルカン酸ビニル・エチレン共重合体水性エマルジョンの製造ではアルカン酸ビニルおよびエチレンの他に、共重合可能なエチレン性不飽和単量体を併用できる。この場合に使用できるエチレン性不飽和単量体には例えば、プロピオン酸ビニル、（メタ）アクリル酸エステル類等が挙げられる。さらには、必要に応じて架橋性単量体を使用することもできる。例えば、Ｎ−メチロール（メタ）アクリルアミドに代表されるメチロール基含有（メタ）アクリルアミド類やアリル（メタ）アクリレート、ジアリルフタレート等の多官能ビニル化合物が挙げられる。アルカン酸ビニル・エチレン共重合体水性エマルジョンをシードとして、エチレン性不飽和単量体をシード重合することで、更に接着力を向上させることができる。 In the production of a vinyl alkanoate / ethylene copolymer aqueous emulsion, a copolymerizable ethylenically unsaturated monomer can be used in addition to vinyl alkanoate and ethylene. Examples of the ethylenically unsaturated monomer that can be used in this case include vinyl propionate and (meth) acrylic acid esters. Furthermore, a crosslinkable monomer can also be used as needed. Examples thereof include polyfunctional vinyl compounds such as methylol group-containing (meth) acrylamides represented by N-methylol (meth) acrylamide, allyl (meth) acrylate, and diallyl phthalate. Adhesive strength can be further improved by seed polymerization of ethylenically unsaturated monomer using vinyl alkanoate / ethylene copolymer aqueous emulsion as a seed.
シード重合に使用できるエチレン性不飽和単量体としては、例えば、メチル（メタ）アクリレート、アクリロニトリル、ブチル（メタ）アクリレート、エチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、酢酸ビニル、（メタ）アクリル酸等が挙げられ、これら単量体は単独または２種以上共重合しても良い。 Examples of the ethylenically unsaturated monomer that can be used for seed polymerization include methyl (meth) acrylate, acrylonitrile, butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, vinyl acetate, (meth ) Acrylic acid and the like, and these monomers may be used alone or in combination of two or more.
本発明で使用されるエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンは、アルカン酸ビニル・エチレン共重合体水性エマルジョンの共重合体にエチレン性不飽和単量体を膨潤含有させた後、シード重合法によりラジカル重合を行うことによって得られる。アルカン酸ビニル・エチレン共重合体水性エマルジョンの共重合体にエチレン性不飽和単量体を膨潤含有させた後、ラジカル重合を行う際に使用される重合開始剤は、特に限定されないが、膨潤含有させるエチレン性不飽和単量体に溶解させて使用する場合は、油溶性重合開始剤が好ましい。具体的には、２，２´−アゾビスイソブチロニトリル、ベンゾイルペルオキシド、クメンヒドロペルオキシド等が挙げられる。水溶性が高い重合開始剤である過硫酸塩類や水溶性アゾ系開始剤を用いた場合、被膨潤粒子内部に開始剤ラジカルやオリゴマーラジカルが存在もしくは進入しにくく、円滑な重合を行うことが困難である。 The ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion used in the present invention swells the ethylenically unsaturated monomer into the copolymer of vinyl alkanoate / ethylene copolymer aqueous emulsion. After containing, it is obtained by performing radical polymerization by a seed polymerization method. The polymerization initiator used when radical polymerization is carried out after the ethylenically unsaturated monomer is swollen and contained in the copolymer of the vinyl alkanoate / ethylene copolymer aqueous emulsion is not particularly limited. When it is used by dissolving in the ethylenically unsaturated monomer to be used, an oil-soluble polymerization initiator is preferred. Specific examples include 2,2'-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and the like. When persulfates or water-soluble azo initiators, which are highly water-soluble polymerization initiators, are used, it is difficult for initiator radicals and oligomer radicals to exist or enter the swollen particles, making smooth polymerization difficult. It is.
場合に応じて重合開始剤とともに還元剤を使用できる。還元剤としては、アスコルビン酸、酒石酸、クエン酸、ブドウ糖、ホルムアルデヒドスルホキシラート金属塩等の還元性有機化合物やチオ硫酸ナトリウム、亜硫酸ナトリウム、重亜硫酸ナトリウム等の還元性無機化合物が挙げられる。 Depending on the case, a reducing agent can be used together with a polymerization initiator. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salts, and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, and sodium bisulfite.
アルカン酸ビニル・エチレン共重合体水性エマルジョンの共重合体のＴｇは、−２０〜２０℃が好ましい。２０℃より高いと十分な剥離力が得られず、−２０℃未満では耐ブロッキング性能が劣り好ましくない。このアルカン酸ビニル・エチレン共重合体エマジョンの存在下にシード重合によりエチレン性不飽和単量体を重合してエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体を得る。エチレン性不飽和単量体の重合体のＴｇは、−５０〜２０℃で好ましくは−３０〜０℃である。Ｔｇが−５０℃より低いと耐ブロッキング性が低下し、２０℃より高いと接着力が低下するため好ましくない。 The Tg of the copolymer of the vinyl alkanoate / ethylene copolymer aqueous emulsion is preferably -20 to 20 ° C. If it is higher than 20 ° C, sufficient peeling force cannot be obtained, and if it is lower than -20 ° C, the anti-blocking performance is inferior. An ethylenically unsaturated monomer is polymerized by seed polymerization in the presence of this vinyl alkanoate / ethylene copolymer emulsion to obtain an ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer. The Tg of the ethylenically unsaturated monomer polymer is -50 to 20 ° C, preferably -30 to 0 ° C. When Tg is lower than −50 ° C., the blocking resistance is lowered, and when Tg is higher than 20 ° C., the adhesive force is lowered, which is not preferable.
アルカン酸ビニル・エチレン共重合体水性エマルジョンの存在下でエチレン性不飽和単量体を共重合することで、耐熱性が飛躍的に向上することを見出した。エチレン性不飽和単量体として酢酸ビニルを使用すると、エチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体の耐熱性が優れているため、アルカン酸ビニル・エチレン水性エマルジョン存在下で酢酸ビニルを重合することで耐熱性が特に向上できる。しかし酢酸ビニルのポリマーはＴｇが３０℃と高く接着力が低下するため、更に酢酸ビニル以外のエチレン性不飽和単量体も共重合させることで、耐湿性、耐熱性、接着性を飛躍的に向上できることを見出した。従ってエチレン性不飽和単量体として酢酸ビニルを使用する場合には、他のエチレン性不飽和単量体も使用するのが好ましい。 It has been found that heat resistance is dramatically improved by copolymerizing an ethylenically unsaturated monomer in the presence of an aqueous emulsion of vinyl alkanoate / ethylene copolymer. When vinyl acetate is used as the ethylenically unsaturated monomer, the heat resistance of the ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer is excellent. The heat resistance can be particularly improved by polymerizing vinyl. However, the polymer of vinyl acetate has a high Tg of 30 ° C. and its adhesive strength is reduced. By further copolymerizing ethylenically unsaturated monomers other than vinyl acetate, the moisture resistance, heat resistance, and adhesion are dramatically improved. I found that it can be improved. Therefore, when vinyl acetate is used as the ethylenically unsaturated monomer, it is preferable to use other ethylenically unsaturated monomers.
アルカン酸ビニル・エチレン共重合体水性エマルジョンの共重合体粒子に膨潤含有させる酢酸ビニルは、アルカン酸ビニル・エチレン共重合体水性エマルジョンの固形分１００重量部に対して５〜５０重量部であり、好ましくは、１０〜３０重量部である。５重量部未満の場合、耐熱性向上の効果が少なく、５０重量部を超えると、剥離力が低下し好ましくない。 The vinyl acetate to be swelled and contained in the copolymer particles of the vinyl alkanoate / ethylene copolymer aqueous emulsion is 5 to 50 parts by weight based on 100 parts by weight of the solid content of the vinyl alkanoate / ethylene copolymer aqueous emulsion, Preferably, it is 10-30 weight part. When the amount is less than 5 parts by weight, the effect of improving the heat resistance is small, and when it exceeds 50 parts by weight, the peeling force is undesirably lowered.
更にエチレン性不飽和単量体は、アルカン酸ビニル・エチレン共重合体水性エマルジョンの固形分１００重量部に対し１０〜５０重量部であり、好ましくは１０〜３０重量部である。５重量部未満の場合は、接着力の向上が認められず、５０重量部を超えると、耐ブロッキング性が低下し好ましくない。エチレン性不飽和単量体の重合体のＴｇは、−５０〜２０℃で好ましくは−３０〜０℃である。 Further, the ethylenically unsaturated monomer is 10 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the solid content of the vinyl alkanoate / ethylene copolymer aqueous emulsion. When the amount is less than 5 parts by weight, no improvement in the adhesive strength is observed, and when it exceeds 50 parts by weight, the blocking resistance is undesirably lowered. The Tg of the ethylenically unsaturated monomer polymer is -50 to 20 ° C, preferably -30 to 0 ° C.
アルカン酸ビニル・エチレン共重合体水性エマルジョンにアクリルアミドを共重合することで、エマルジョンの安定性が向上するため、安定化剤として使用している水溶性高分子等の使用量を減らすことができる。安定化剤に使用する水溶性高分子等は耐湿性を低下させるため、使用量は極力少ない方が好ましい。安定化剤として水溶性高分子等がアルカン酸ビニル・エチレン共重合樹脂１００重量部に対し１０重量部以上は必要で、それ以下では重合時の安定性、保存安定性等が悪く好ましくない。アクリルアミドを共重合することで、安定性が飛躍的に向上し、安定化剤の使用量をアルカン酸ビニル・エチレン共重合樹脂１００重量部に対し２重量部まで減量しても、重合安定性、保存安定性を向上でき、そのことにより耐湿性が更に向上することを見出した。アクリルアミドの使用量は、アルカン酸ビニル・エチレン共重合樹脂に対し１〜５重量部で１重量部未満では効果がなく、５重量部を超えると重合が困難であるため好ましくない。 By copolymerizing acrylamide with a vinyl alkanoate / ethylene copolymer aqueous emulsion, the stability of the emulsion is improved, so that the amount of water-soluble polymer used as a stabilizer can be reduced. The amount of water-soluble polymer used for the stabilizer is preferably as small as possible because it reduces the moisture resistance. As a stabilizer, 10 parts by weight or more of a water-soluble polymer or the like is necessary with respect to 100 parts by weight of vinyl alkanoate / ethylene copolymer resin, and if it is less than that, it is not preferable because stability during polymerization and storage stability are poor. By copolymerizing acrylamide, the stability is dramatically improved. Even if the amount of stabilizer used is reduced to 2 parts by weight with respect to 100 parts by weight of vinyl alkanoate / ethylene copolymer resin, It has been found that the storage stability can be improved, thereby further improving the moisture resistance. The amount of acrylamide used is 1 to 5 parts by weight with respect to the vinyl alkanoate / ethylene copolymer resin, and if it is less than 1 part by weight, no effect is obtained.
これらの接着剤基材には、必要に応じて粘着付与剤（テルペンフェノール樹脂、ポリブテン樹脂、ロジンエステル樹脂、石油樹脂）の公知のものの中から一種または二種以上を使用することができる。 As these adhesive base materials, one or more of known tackifiers (terpene phenol resin, polybutene resin, rosin ester resin, petroleum resin) can be used as necessary.
共重合体ラテックスとエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンとの配合割合は、固形分重量比で１：９〜９：１が望ましい。この混合比の範囲を外れると、それぞれの特徴が感圧接着剤層に大きく影響を与えることになる。すなわちエチレン性不飽和単量体−アルカン酸ビニル・エチレン水性エマルジョンのようなアクリル系共重合体を含有する接着剤が過多の場合には、この種の接着剤の欠点で熱による接着力の劣化や、圧着物を剥がす際の対向面へのインキ転写が生じやすくなる。逆に共重合体ラテックスが過多である場合には、この種の接着剤の欠点であるＵＶ照射による接着力の劣化や、フェザリング等のＩＪ適性の悪化が顕著に現れるため、これら該接着剤の混合比の調節が重要である。 The blending ratio of the copolymer latex and the ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion is desirably 1: 9 to 9: 1 in terms of a solid content weight ratio. If the mixing ratio is out of the range, each characteristic greatly affects the pressure-sensitive adhesive layer. That is, when there are too many adhesives containing an acrylic copolymer such as an ethylenically unsaturated monomer-vinyl alkanoate / ethylene aqueous emulsion, the adhesive strength deteriorates due to heat due to the disadvantages of this type of adhesive. In addition, ink transfer to the facing surface when the pressure-bonded material is peeled off easily occurs. On the other hand, when the copolymer latex is excessive, deterioration of adhesive strength due to UV irradiation and deterioration of IJ suitability such as feathering, which are disadvantages of this type of adhesive, appear remarkably. It is important to adjust the mixing ratio.
本発明における微粒子充填剤としては、シリカ、炭酸カルシウム、カオリン、合成ゼオライト、水酸化アルミニウム、クレー、酸化マグネシウム、水酸化マグネシウム、タルク、クレー、酸化チタン、酸化亜鉛、硫酸カルシウム、硫酸バリウム、澱粉粒子、球状アクリル樹脂、球状メタクリル樹脂、球状ポリエチレン、尿素ホルマリン樹脂等の公知のものの中から一種または二種以上を使用することができる。 As the fine particle filler in the present invention, silica, calcium carbonate, kaolin, synthetic zeolite, aluminum hydroxide, clay, magnesium oxide, magnesium hydroxide, talc, clay, titanium oxide, zinc oxide, calcium sulfate, barium sulfate, starch particles In addition, one or two or more of known materials such as spherical acrylic resin, spherical methacrylic resin, spherical polyethylene, and urea formalin resin can be used.
本発明において感圧接着剤組成物１００重量部に対して微粒子充填剤を３０〜２００重量部使用する。微粒子充填剤の使用量が感圧接着剤組成物１００重量部に対して３０重量部より少ないと耐ブロッキング性が悪く好ましくない。また２００重量部より多いと剥離強度が低下し好ましくない。 In the present invention, 30 to 200 parts by weight of the fine particle filler is used with respect to 100 parts by weight of the pressure-sensitive adhesive composition. When the amount of the fine particle filler used is less than 30 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive composition, the blocking resistance is not preferable. Moreover, when it exceeds 200 weight part, peeling strength will fall and it is unpreferable.
本発明に使用される再剥離性圧着記録用紙の基材シートは、紙、布、不織布、紙の上に樹脂フィルムをラミネートしたシート、フィルムシート等の公知のものの中から適宜選択して使用することができる。 The substrate sheet of the releasable pressure-sensitive recording paper used in the present invention is appropriately selected from known materials such as paper, cloth, nonwoven fabric, a sheet obtained by laminating a resin film on paper, and a film sheet. be able to.
また、感圧接着剤組成物中には、必要に応じて、分散剤、消泡剤、界面活性剤、老化防止剤、紫外線吸収剤、酸化防止剤、防黴剤、消臭剤、耐水化剤、蛍光増白剤等の添加剤を添加することができる。 In addition, in the pressure-sensitive adhesive composition, if necessary, a dispersant, an antifoaming agent, a surfactant, an anti-aging agent, an ultraviolet absorber, an antioxidant, an antifungal agent, a deodorant, water resistance Additives such as an agent and a fluorescent brightening agent can be added.
上記感圧接着剤組成物は、エアーナイフコーター、ロールコーター、ブレードコーター、ロッドブレードコーター、バーコーター、ダイコーター等の一般的なコーターによって塗工されるが、塗工量は乾燥重量で３〜１５ｇ／ｍ２の範囲で調整されるのが望ましい。塗工量を上記範囲に限定した理由は、３ｇ／ｍ２未満では印字品位や印刷上がりなどの視感的な面で劣り、更に剥離強度が低下し、好ましくないためである。また、塗工量が１５ｇ／ｍ２を越えると、印字品位や印刷上がりなどの視感的な見栄えは向上するが、経済的な面から実用性が劣り、筆記性が乏しく、紙粉が発生しやすく、好ましくない。 The pressure-sensitive adhesive composition is applied by a general coater such as an air knife coater, roll coater, blade coater, rod blade coater, bar coater, die coater, etc., but the coating amount is 3 to 3 by dry weight. It is desirable to adjust in the range of 15 g / m 2 . The reason why the coating amount is limited to the above range is that if it is less than 3 g / m 2, it is not preferable because it is inferior in terms of visual quality such as print quality and printing finish, and further the peel strength is lowered. On the other hand, when the coating amount exceeds 15 g / m 2 , the visual appearance such as the print quality and the printed finish is improved, but the practicality is inferior from the economical viewpoint, the writing property is poor, and paper dust is generated. It is easy to do and is not preferable.
本発明を以下の実施例、比較例により説明するが、本発明はこれらの例に限定されるものではない。なお、実施例、比較例の重量部数（部）は、全て固形分換算での数値で示すものとする。
「共重合体ラテックスの製造方法」
（製造例１）
窒素で内部を置換した５Ｌ反応釜に、ブタジエン７５部，スチレン２５部，クメンヒドロペルオキシド１部，イオン交換水３００部，りん酸三ナトリウム塩０．５部、四酢酸ナトリウム０.２部を仕込み、撹拌しながら、２０℃にて反応した。重合転化率が６５％に達した時点で重合停止剤を添加して反応を止めた。水酸化カリウムを用いて、ｐＨ１０に調整した。次いで、反応混合物に水蒸気を吹き込み、未反応単量体を除去した後、ポリオキシエチレンアルキルフェニルエーテル１０部を添加し、目的とする共重合体ラテックスを得た。この共重合体ラテックスのゲル分は１０％であり、共重合体のガラス転移温度（Ｔｇ）は−５７℃である。
「エチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合水性エマルジョンの製造方法」
（製造例２）
イオン交換水２００部に部分ケン化ポリビニルアルコール（ケン化度８８、重合度５００）１０部を分散させて加熱溶解し、１Ｌの高圧反応釜に仕込んだ。エチレンで釜内の空気を置換した後、エチレン圧を３．９ＭＰａに調整し、攪拌しながら６５℃に昇温した。ＶＶ−９（アルカン酸ビニルモノマー、シェル社製、炭素数９）４０７部を２０％部分ケン化ポリビニルアルコール（ケン化度８８、重合度５００）溶液２５０部で乳化し、２％の過硫酸アンモニウム水溶液４０部及び２％の重亜硫酸ナトリウム２０部を釜内に５時間で滴下し反応を行った。その後２時間６５℃に保った後、イオン交換水１２０部を反応釜にフィードした後、ブチルアクリレート５０部、５％ｔ−ブチルペルオキシド水溶液１０部、３％重亜硫酸ナトリウム１０部を１時間で滴下し、１時間６５℃に保った後、冷却し反応を終了した。得られたエマルジョンの不揮発分は５０．５％であった。エマルジョン状態の得られたコア−シェル型共重合体のコア部（アルカン酸ビニル・エチレン共重合体）のＴｇは−２２℃でありそしてシェル部（ブチルアクリレート重合体）のＴｇは−９℃である。
The present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples. In addition, all the weight parts (part) of an Example and a comparative example shall show with the numerical value in conversion of solid content.
"Method for producing copolymer latex"
(Production Example 1)
A 5L reaction kettle whose interior is replaced with nitrogen is charged with 75 parts of butadiene, 25 parts of styrene, 1 part of cumene hydroperoxide, 300 parts of ion-exchanged water, 0.5 part of trisodium phosphate, and 0.2 part of sodium tetraacetate. The reaction was carried out at 20 ° C. with stirring. When the polymerization conversion rate reached 65%, a polymerization terminator was added to stop the reaction. The pH was adjusted to 10 using potassium hydroxide. Next, water vapor was blown into the reaction mixture to remove unreacted monomers, and then 10 parts of polyoxyethylene alkylphenyl ether was added to obtain a target copolymer latex. This copolymer latex has a gel content of 10%, and the glass transition temperature (Tg) of the copolymer is -57 ° C.
"Method for producing ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion"
(Production Example 2)
10 parts of partially saponified polyvinyl alcohol (saponification degree 88, polymerization degree 500) was dispersed in 200 parts of ion-exchanged water, dissolved by heating, and charged into a 1 L high-pressure reaction kettle. After replacing the air in the kettle with ethylene, the ethylene pressure was adjusted to 3.9 MPa, and the temperature was raised to 65 ° C. while stirring. 407 parts of VV-9 (vinyl alkanoate monomer, manufactured by Shell, carbon number 9) were emulsified with 250 parts of a 20% partially saponified polyvinyl alcohol (saponification degree 88, polymerization degree 500) solution, and a 2% ammonium persulfate aqueous solution. 40 parts and 20 parts of 2% sodium bisulfite were dropped into the kettle over 5 hours to carry out the reaction. After maintaining at 65 ° C. for 2 hours, 120 parts of ion exchange water was fed to the reaction kettle, and then 50 parts of butyl acrylate, 10 parts of 5% t-butyl peroxide aqueous solution and 10 parts of 3% sodium bisulfite were added dropwise over 1 hour. Then, after maintaining at 65 ° C. for 1 hour, the reaction was terminated by cooling. The non-volatile content of the obtained emulsion was 50.5%. The core part (vinyl alkanoate / ethylene copolymer) of the obtained core-shell type copolymer in the emulsion state has a Tg of -22 ° C and the Tg of the shell part (butyl acrylate polymer) has a -9 ° C. is there.
製造例１で得られた共重合体ラテックス５０部、製造例２で得られたアルカン酸ビニル・エチレン水性エマルジョン５０部を接着剤基材とし、微粒子充填剤として非晶質シリカ（水澤化学工業社製、ミズカシルＰ−７８Ａ）１２０部を配合して本発明の目的とする感圧接着剤組成物を得た。次にこの感圧接着剤組成物を１２７．９ｇ／ｍ２の上質紙に塗工量が７ｇ／ｍ２（乾燥重量）になるように塗工して再剥離性圧着記録用紙を得た。これを実施例１とした。 50 parts of the copolymer latex obtained in Production Example 1 and 50 parts of the vinyl alkanoate / ethylene aqueous emulsion obtained in Production Example 2 were used as an adhesive base material, and amorphous silica (Mizusawa Chemical Co., Ltd.) was used as the fine particle filler. Manufactured by Mizukasil P-78A) to obtain a pressure-sensitive adhesive composition of the present invention. Next, this pressure-sensitive adhesive composition was coated on 127.9 g / m 2 high-quality paper so that the coating amount was 7 g / m 2 (dry weight) to obtain a releasable pressure-sensitive recording sheet. This was designated Example 1.
得られた再剥離性圧着記録用紙について剥離強度試験、印刷適性試験、ノンインパクトプリンティング（ＮＩＰ）適性試験、ＩＪ適性試験、ブロッキング性試験、インキ転写性試験、耐ＵＶ試験、耐熱試験で評価した。 The obtained releasable pressure-sensitive recording paper was evaluated by a peel strength test, a printability test, a non-impact printing (NIP) suitability test, an IJ suitability test, a blocking property test, an ink transfer property test, a UV resistance test, and a heat resistance test.
実施例１の感圧接着剤組成物で共重合体ラテックスの配合部数を２０部、エチレン性不飽和単量体−アルカン酸ビニル・エチレン水性エマルジョンを８０部、非晶質シリカの配合部数を２００部に変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを実施例２とした。 In the pressure-sensitive adhesive composition of Example 1, 20 parts of the copolymer latex was blended, 80 parts of the ethylenically unsaturated monomer-vinyl alkanoate / ethylene aqueous emulsion was blended, and 200 parts of the amorphous silica was blended. A removable pressure-sensitive recording sheet was prepared in the same manner as in Example 1 except that the part was changed to that of Example 1.
実施例２の感圧接着剤組成物で非晶質シリカの配合部数を３０部に変更した以外は、実施例２と同様にして再剥離性圧着記録用紙を作成し、これを実施例３とした。 A releasable pressure-sensitive recording sheet was prepared in the same manner as in Example 2 except that the number of blended parts of amorphous silica in the pressure-sensitive adhesive composition of Example 2 was changed to 30 parts. did.
実施例２の感圧接着剤組成物で共重合体ラテックスの配合部数を８０部、エチレン性不飽和単量体−アルカン酸ビニル・エチレン水性エマルジョンを２０部に変更した以外は、実施例２と同様にして再剥離性圧着記録用紙を作成し、これを実施例４とした。 Example 2 with the exception that the pressure-sensitive adhesive composition of Example 2 was changed to 80 parts of the copolymer latex and 20 parts of the ethylenically unsaturated monomer-vinyl alkanoate / ethylene aqueous emulsion. Similarly, a releasable pressure-sensitive recording paper was prepared, and this was designated as Example 4.
実施例４の感圧接着剤組成物で非晶質シリカの配合部数を３０部に変更した以外は、実施例４と同様にして再剥離性圧着記録用紙を作成し、これを実施例５とした。 A releasable pressure-sensitive recording sheet was prepared in the same manner as in Example 4 except that the number of blended parts of amorphous silica was changed to 30 parts in the pressure-sensitive adhesive composition of Example 4. did.
実施例１の感圧接着剤組成物で接着剤基材をメタクリル酸メチルグラフト共重合天然ゴムラテックスに変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを比較例１とした。 A releasable pressure-sensitive recording sheet was prepared in the same manner as in Example 1 except that the adhesive base material was changed to methyl methacrylate graft copolymer natural rubber latex in the pressure-sensitive adhesive composition of Example 1, and this was prepared. It was set as Comparative Example 1.
実施例１の感圧接着剤組成物で非晶質シリカの配合部数を２５０部に変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを比較例２とした。 A releasable pressure-sensitive adhesive recording sheet was prepared in the same manner as in Example 1 except that the amorphous silica was changed to 250 parts in the pressure-sensitive adhesive composition of Example 1, and this was compared with Comparative Example 2. did.
実施例１の感圧接着剤組成物で非晶質シリカの配合部数を２０部に変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを比較例３とした。 A releasable pressure-sensitive recording sheet was prepared in the same manner as in Example 1 except that the number of blended parts of amorphous silica in the pressure-sensitive adhesive composition of Example 1 was changed to 20 parts. did.
実施例１の感圧接着剤組成物で共重合体ラテックスの配合部数を１００部、エチレン性不飽和単量体−アルカン酸ビニル・エチレン水性エマルジョンを０部に変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを比較例４とした。 Example 1 with the exception that the pressure-sensitive adhesive composition of Example 1 was changed to 100 parts of the copolymer latex and 0 parts of the ethylenically unsaturated monomer-vinyl alkanoate / ethylene aqueous emulsion. Similarly, a releasable pressure-sensitive recording sheet was prepared, and this was designated as Comparative Example 4.
実施例１の感圧接着剤組成物で共重合体ラテックスの配合部数を０部、エチレン性不飽和単量体−アルカン酸ビニル・エチレン水性エマルジョンを１００部に変更した以外は、実施例１と同様にして再剥離性圧着記録用紙を作成し、これを比較例５とした。 Example 1 with the exception that the pressure-sensitive adhesive composition of Example 1 was changed to 0 part by weight of the copolymer latex and 100 parts of the ethylenically unsaturated monomer-vinyl alkanoate / ethylene aqueous emulsion. In the same manner, a releasable pressure-sensitive recording sheet was prepared, and this was designated as Comparative Example 5.
以上の実施例、比較例で得られた再剥離性圧着記録用紙を下記試験方法に従って諸特性の評価を行なった。 Various characteristics of the releasable pressure-sensitive recording paper obtained in the above Examples and Comparative Examples were evaluated according to the following test methods.
剥離強度試験：幅１００ｍｍ、長さ１００ｍｍに裁断し、塗工面同士を重ね合わせてドライシーラー（プレッスルエコノ：トッパン・フォームズ株式会社製）を用いて加圧接着した。次にこの試料の幅方向中央部を２５ｍｍ幅に断裁して、２３℃、５０％Ｒ．Ｈ環境下でストログラフＭ−１型（東洋精機製作所製）で速度３００ｍ／分、剥離（Ｔ型剥離）強度で剥離してその抵抗値を平均化して剥離強度ｇｆ／２５ｍｍを求める。◎：１００〜１５０ｇｆ／２５ｍｍ、○：５０〜１００ｇｆ／２５ｍｍ未満、△：２０〜５０ ｇｆ／２５ｍｍ未満、×：０〜２０ ｇｆ／２５ｍｍ未満、◎と○は実用レベルの剥離強度を示し、△と×は実用に耐えないレベルを示す。以下いずれも、◎は特に優れた性能を、○は実用レベルの性能を、△は実用に不足する性能をそして×は実用に耐えない低レベルの性能を示す。 Peel strength test: Cut into a width of 100 mm and a length of 100 mm, and the coated surfaces were overlapped and pressure-bonded using a dry sealer (Pressle Econo: manufactured by Toppan Foams Co., Ltd.). Next, the width direction center part of this sample was cut | judged to 25 mm width, and 23 degreeC and 50% R. Under a H environment, the film is peeled at a speed of 300 m / min and peel (T-type peel) strength with a strograph M-1 type (manufactured by Toyo Seiki Seisakusho), and the resistance value is averaged to obtain a peel strength gf / 25 mm. A: 100 to 150 gf / 25 mm, O: 50 to less than 100 gf / 25 mm, Δ: 20 to less than 50 gf / 25 mm, X: 0 to less than 20 gf / 25 mm, A and O indicate a practical level of peel strength, Δ And x indicate levels that cannot be practically used. In the following, ◎ indicates particularly excellent performance, ○ indicates performance at practical level, Δ indicates performance that is insufficient for practical use, and × indicates low level performance that cannot withstand practical use.
印刷適性試験：ＲＩ−３型印刷適性試験機（明製作所製）を使用してインキ濃度、耐刷力等を目視により観察し評価を行った。インキによる塗工層剥け、紙剥けなどが全くないものから◎、○、△、×とした。 Printing suitability test: An RI-3 type printing suitability tester (manufactured by Meisei Seisakusho) was used to visually observe and evaluate ink density, printing durability, and the like. The case where there was no peeling of the coating layer with ink or paper was marked as ◎, ○, Δ, ×.
ノンインパクトプリンティング（ＮＩＰ）印字適性試験：レーザービームプリンター（Ｃａｎｏｎ社製、ＬＡＳＥＲ ＳＨＯＴ ＬＢＰ−９５０）を用いてテスト印字パターン（文字、線、ベタ）を印字し、視感で評価した。鮮明な画像、印字が得られたものから◎、○、△、×とした。 Non-impact printing (NIP) printability test: A test print pattern (characters, lines, solid) was printed using a laser beam printer (Canon, LASER SHOT LBP-950) and evaluated by visual sensation. The clear images and prints obtained were marked with ◎, ○, Δ, and ×.
インクジェット（ＩＪ）印字適性試験：インクジェットプリンター（ヒューレットパッカード社製 ＨＰ ＤｅｓｋＪｅｔ５６０Ｊ）のインクカートリッジにサイテックス１０３６黒インクを注入し、テスト印字パターン（文字、線、ベタ）を印字し、視感で評価した。鮮明な画像、印字が得られたものから◎、○、△、×とした。 Inkjet (IJ) printability test: Cytex 1036 black ink was injected into an ink cartridge of an inkjet printer (HP DeskJet 560J, manufactured by Hewlett Packard), and a test print pattern (characters, lines, solid) was printed and evaluated by visual feeling. . The clear images and prints obtained were marked with ◎, ○, Δ, and ×.
ブロッキング適性試験：両面塗工した試料を重ね合わせ、５００ｇ／ｃｍ２の圧力を加えつつ、２３℃、５０％ＲＨ環境下で所定荷重をかけて放置し、２４時間後に手で剥がし、評価した。◎：ブロッキングが全く発生していない、○：ブロッキングがほとんど発生していない、△：少しブロッキングが発生している、×：完全にブロッキングしている。 Blocking aptitude test: The samples coated on both sides were superposed, left under a predetermined load in a 23 ° C., 50% RH environment while applying a pressure of 500 g / cm 2 , and peeled off by hand after 24 hours for evaluation. (Double-circle): Blocking has not generate | occur | produced at all, (circle): Blocking has hardly generate | occur | produced, (triangle | delta): Blocking has generate | occur | produced a little, X: It has blocked completely.
インキ転写性試験：ＲＩ−３型印刷適性試験機（明製作所製）を使用して印刷し、乾燥させたものを、前記剥離強度試験に準じて、剥離（Ｔ型剥離）強度が４０ｇｆ／２５ｍｍになるように圧着。その後剥がしたものについて、インキの転写の程度を視感で評価した。転写のないものから◎、○、△、×とした。 Ink transfer property test: A peeled (T-type peel) strength is 40 gf / 25 mm according to the peel strength test, after printing and drying using a RI-3 type printability tester (manufactured by Meisei Seisakusho). Crimp to be. Thereafter, the degree of ink transfer was evaluated visually for those peeled off. Those with no transfer were marked with ◎, ○, Δ, and ×.
耐ＵＶ適性試験：試料を、アイグラフィック製メタルハライドランプを使用して、５７ｍＪ／ｃｍ2 の紫外線（ＵＶ）を照射した後に上記のようにして剥離（Ｔ型剥離）強度を測定する。◎：剥離強度が８５〜１００％保持、○：剥離強度が６０〜８５％未満保持、△：剥離強度が４５〜６０％未満保持、×：剥離強度が４５％未満。 UV resistance test: A sample is irradiated with 57 mJ / cm 2 of ultraviolet (UV) using an eye graphic metal halide lamp, and the peel (T-type peel) strength is measured as described above. A: Peel strength is 85 to 100%, O: Peel strength is kept less than 60 to 85%, A: Peel strength is kept less than 45 to 60%, X: Peel strength is less than 45%.
耐熱適性試験：試料を、１８０℃に予熱したステンレス板に挟み、３０分放置した後に上記のようにして剥離（Ｔ型剥離）強度を測定する。◎：剥離強度が８５〜１００％保持、○：剥離強度が６０〜８５％未満保持、△：剥離強度が４５〜６０％未満保持、×：剥離強度が４５％未満。 Heat aptitude test: A sample is sandwiched between stainless steel plates preheated to 180 ° C. and left for 30 minutes, and then the peel strength (T-type peel strength) is measured as described above. A: Peel strength is 85 to 100%, O: Peel strength is kept less than 60 to 85%, A: Peel strength is kept less than 45 to 60%, X: Peel strength is less than 45%.
実施例１〜５及び比較例１〜５で作成した再剥離性圧着記録用紙の、各試験結果を下記表１に示す。 The test results of the releasable pressure-sensitive recording paper prepared in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1 below.
表１からもわかる通り、実施例１〜５の本発明の再剥離性圧着記録用紙は、剥離強度、ブロッキング性、印刷適性、印字適性に加えて紫外線照射及び１８０℃で３０分の熱負荷に耐え熱による剥離強度劣化が小さいなど優れた効果を奏する。 As can be seen from Table 1, the releasable pressure-sensitive recording sheets of Examples 1 to 5 were subjected to ultraviolet irradiation and a heat load of 30 minutes at 180 ° C. in addition to peel strength, blocking property, printability and printability. Excellent effects such as small deterioration of peel strength due to heat resistance.
これに対して、接着剤が従来技術のメタクリル酸メチルグラフト共重合体天然ゴムラテックスである比較例１の場合には、再剥離性圧着記録用紙の耐ＵＶ適性、耐熱適性がない。接着剤組成物の接着剤が共重合体ラテックスだけである比較例４の場合には、ＮＩＰ適性、ブロッキング適性、耐ＵＶ適性が不足しており、実用に耐えない。また接着剤組成物の接着剤がエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンだけである比較例５の場合には、対向面にインキ転写の発生や耐熱適性が無い為、実用に耐えない。 On the other hand, in the case of Comparative Example 1 where the adhesive is a conventional methyl methacrylate graft copolymer natural rubber latex, the releasable pressure-sensitive recording paper does not have UV resistance and heat resistance. In the case of Comparative Example 4 in which the adhesive of the adhesive composition is only a copolymer latex, NIP suitability, blocking suitability, and UV suitability are insufficient and cannot be put into practical use. In the case of Comparative Example 5 in which the adhesive of the adhesive composition is only an ethylenically unsaturated monomer-vinyl alkanoate / ethylene copolymer aqueous emulsion, there is no occurrence of ink transfer or heat resistance on the opposite surface. Therefore, it cannot stand practical use.
本発明に係わる再剥離性圧着記録用紙は感圧接着剤組成物が、共役ジエン系単量体とエチレン系不飽和単量体を乳化重合させて得られたものであり、そのゲル分が５０％以下で、かつそのガラス転移温度（Tg）が−５０未満〜−８０℃である共重合体のラテックスと、下記一般式で表されるアルカン酸ビニルとエチレンとのアルカン酸ビニル・エチレン共重合体水性エマルジョンの存在下でエチレン性不飽和単量体のシード重合によって得られるエチレン性不飽和単量体−アルカン酸ビニル・エチレン共重合体水性エマルジョンを、固形分重量比１：９〜９：１で混合した感圧接着剤組成物１００重量部（固形分）と、微粒子充填剤３０〜２００重量部（固形分）を含有することにより、紫外線照射及び１８０℃で３０分の熱負荷に耐え熱による剥離強度劣化が無い再剥離性圧着記録用紙を提供することができる。 The releasable pressure-sensitive recording sheet according to the present invention is obtained by emulsion-polymerizing a conjugated diene monomer and an ethylenically unsaturated monomer, and having a gel content of 50. % Of the copolymer latex having a glass transition temperature (Tg) of less than −50 to −80 ° C. and a vinyl alkanoate / ethylene copolymer of vinyl alkanoate and ethylene represented by the following general formula: An ethylenically unsaturated monomer-vinyl alkanoic acid-ethylene copolymer aqueous emulsion obtained by seed polymerization of an ethylenically unsaturated monomer in the presence of a combined aqueous emulsion is a solid content weight ratio of 1: 9 to 9: By containing 100 parts by weight (solid content) of the pressure-sensitive adhesive composition mixed in 1 and 30 to 200 parts by weight (solid content) of the fine particle filler, it can withstand ultraviolet irradiation and a heat load of 30 minutes at 180 ° C. To heat Can provide removability crimping recording paper is not peel strength degradation that.
Claims (1)
Ｒ１Ｏ
｜ ‖
Ｒ２−Ｃ―Ｃ−Ｏ−ＣＨ＝ＣＨ２
｜
Ｒ３
（式中、Ｒ１、Ｒ２及びＲ３は、それらの合計の炭素数が６以上の直鎖のアルキル基であって少なくとも１つはメチル基を表す） In pressure-sensitive adhesive recording paper having a pressure-sensitive adhesive layer on at least one side that does not exhibit tackiness and adhesiveness at normal temperature and normal pressure, but exhibits adhesiveness when pressed and can be peeled after pressure bonding. The agent composition is obtained by emulsion polymerization of a conjugated diene monomer and an ethylenically unsaturated monomer, the gel content is 50% or less, and the glass transition temperature (Tg) is − An ethylenically unsaturated monomer in the presence of a latex of a copolymer having a temperature of less than 50 to −80 ° C. and an aqueous emulsion of vinyl alkanoate / ethylene copolymer of vinyl alkanoate and ethylene represented by the following general formula: 100 parts by weight of a pressure-sensitive adhesive composition obtained by mixing an ethylenically unsaturated monomer-vinyl alkanoic acid / ethylene copolymer aqueous emulsion obtained by seed polymerization in a solid content weight ratio of 1: 9 to 9: 1 ( Solid content If, removability crimping recording sheet characterized by containing particulate filler 30 to 200 parts by weight (solids).
R 1 O
｜ ‖
R 2 —C—C—O—CH═CH 2
｜
R 3
(In the formula, R 1 , R 2 and R 3 are linear alkyl groups having a total carbon number of 6 or more, and at least one represents a methyl group)
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| JP4738850B2 JP4738850B2 (en) | 2011-08-03 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8702893B2 (en) | 2006-10-13 | 2014-04-22 | Datacard Corporation | In-line gift card personalization and packaging process |
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| JPH0757864B2 (en) * | 1988-09-14 | 1995-06-21 | カネボウ・エヌエスシー株式会社 | Method for producing emulsion-type pressure-sensitive adhesive in which tackifier resin coexists in polymer particles |
| JPH11269447A (en) * | 1998-03-19 | 1999-10-05 | Chuo Rika Kogyo Corp | Vinyl acetate resin emulsion adhesive composition |
| JP2001277415A (en) * | 2000-03-29 | 2001-10-09 | Mitsubishi Paper Mills Ltd | Press bonding recording paper |
| JP2003160764A (en) * | 2001-11-26 | 2003-06-06 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
| JP2003231874A (en) * | 2002-02-08 | 2003-08-19 | Chuo Rika Kogyo Corp | Pressure sensitive adhesive resin composition and pressure sensitive adhesive sheet using the same |
| JP2003327930A (en) * | 2002-05-14 | 2003-11-19 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
| JP2005162923A (en) * | 2003-12-04 | 2005-06-23 | Hokuetsu Paper Mills Ltd | Pressure-sensitive adhesive composition and removable pressure-sensitive recording paper using the same |
| JP2006117783A (en) * | 2004-10-21 | 2006-05-11 | Hokuetsu Paper Mills Ltd | Removable pressure-sensitive recording paper sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0757864B2 (en) * | 1988-09-14 | 1995-06-21 | カネボウ・エヌエスシー株式会社 | Method for producing emulsion-type pressure-sensitive adhesive in which tackifier resin coexists in polymer particles |
| JPH11269447A (en) * | 1998-03-19 | 1999-10-05 | Chuo Rika Kogyo Corp | Vinyl acetate resin emulsion adhesive composition |
| JP2001277415A (en) * | 2000-03-29 | 2001-10-09 | Mitsubishi Paper Mills Ltd | Press bonding recording paper |
| JP2003160764A (en) * | 2001-11-26 | 2003-06-06 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
| JP2003231874A (en) * | 2002-02-08 | 2003-08-19 | Chuo Rika Kogyo Corp | Pressure sensitive adhesive resin composition and pressure sensitive adhesive sheet using the same |
| JP2003327930A (en) * | 2002-05-14 | 2003-11-19 | Oji Paper Co Ltd | Pressure-sensitive adhesive sheet |
| JP2005162923A (en) * | 2003-12-04 | 2005-06-23 | Hokuetsu Paper Mills Ltd | Pressure-sensitive adhesive composition and removable pressure-sensitive recording paper using the same |
| JP2006117783A (en) * | 2004-10-21 | 2006-05-11 | Hokuetsu Paper Mills Ltd | Removable pressure-sensitive recording paper sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8702893B2 (en) | 2006-10-13 | 2014-04-22 | Datacard Corporation | In-line gift card personalization and packaging process |
| US9378449B2 (en) | 2006-10-13 | 2016-06-28 | Entrust Datacard Corporation | In-line gift card personalization and packaging process |
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| JP4738850B2 (en) | 2011-08-03 |
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