JP6045022B2 - Label adhesive and adhesive tape - Google Patents
Label adhesive and adhesive tape Download PDFInfo
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- JP6045022B2 JP6045022B2 JP2012216390A JP2012216390A JP6045022B2 JP 6045022 B2 JP6045022 B2 JP 6045022B2 JP 2012216390 A JP2012216390 A JP 2012216390A JP 2012216390 A JP2012216390 A JP 2012216390A JP 6045022 B2 JP6045022 B2 JP 6045022B2
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- 239000000853 adhesive Substances 0.000 title claims description 72
- 230000001070 adhesive effect Effects 0.000 title claims description 72
- 239000002390 adhesive tape Substances 0.000 title claims description 4
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 53
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 50
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 claims description 46
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 42
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 25
- 230000009477 glass transition Effects 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 claims description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 79
- 239000000839 emulsion Substances 0.000 description 75
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000012153 distilled water Substances 0.000 description 38
- LWNSNYBMYBWJDN-UHFFFAOYSA-N octyl 3-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCS LWNSNYBMYBWJDN-UHFFFAOYSA-N 0.000 description 37
- 239000000523 sample Substances 0.000 description 26
- 239000012986 chain transfer agent Substances 0.000 description 24
- 239000004094 surface-active agent Substances 0.000 description 24
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 22
- 239000003999 initiator Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 19
- 230000032683 aging Effects 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 229920006267 polyester film Polymers 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 230000002265 prevention Effects 0.000 description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 150000001717 carbocyclic compounds Chemical class 0.000 description 7
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 7
- 229920001519 homopolymer Polymers 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 1
- XFZOHDFQOOTHRH-UHFFFAOYSA-N 7-methyloctyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C(C)=C XFZOHDFQOOTHRH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229910001065 Chromium-vanadium steel Inorganic materials 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 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
- 239000010410 layer Substances 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Description
本発明は強い粘着力と良好な端末剥がれ防止性を両立したエマルジョン型粘着剤及びそれを用いた粘着テープ、粘着シート等に関する。 The present invention relates to an emulsion-type pressure-sensitive adhesive that has both strong adhesive strength and good terminal peeling prevention properties, and a pressure-sensitive adhesive tape, pressure-sensitive adhesive sheet and the like using the same.
従来より、径の小さなケーブルや電線などに巻きつけて、結束や表示に用いる粘着テープ等に有用である、高い粘着力と端末剥がれ防止性の両立をはかった有機溶剤型粘着剤が提案されている。例えば特許文献１には、細線に巻きつけたときの端末剥がれや、金属板との成形品との曲面接着部に適用したときの金属板の弾性戻りなどによる接着不良を改善すべく、初期接着力と耐残留応力性並びに高度の耐久性を図った、（メタ）アクリル酸アルキルエステルを主成分とするモノマーから形成されるアクリル系ポリマー及び有機溶媒とを含む、有機溶剤型粘着剤の一種である感圧性接着剤が提案されている。 Conventionally, organic solvent-type adhesives that have both high adhesive strength and prevention of terminal peeling have been proposed, which are useful for adhesive tapes used for bundling and display by wrapping around small diameter cables and electric wires. Yes. For example, Patent Document 1 discloses an initial adhesion in order to improve adhesion failure due to peeling of a terminal when wound around a thin wire or elastic return of a metal plate when applied to a curved adhesion portion with a molded product with the metal plate. A type of organic solvent-type pressure-sensitive adhesive containing an acrylic polymer and an organic solvent formed from a monomer based on (meth) acrylic acid alkyl ester, which has high strength, residual stress resistance and high durability. Certain pressure sensitive adhesives have been proposed.
近年、安全と環境の両方への配慮から、粘着テープ等に使用される粘着剤は、有機溶剤型粘着剤から無溶剤系であるエマルジョン型粘着剤へと徐々に切り替えられつつある。しかしながら、今に至るまで、エマルジョン型粘着剤において、強い粘着力と強タックを備え、且つ、良好な端末剥がれ防止性も十分に満足できる粘着剤は提案されていない。 In recent years, pressure sensitive adhesives used for pressure sensitive adhesive tapes and the like have been gradually switched from organic solvent type pressure sensitive adhesives to solventless emulsion type pressure sensitive adhesives in consideration of both safety and the environment. However, until now, no adhesive has been proposed as an emulsion-type pressure-sensitive adhesive that has a strong adhesive force and a strong tack, and that also has satisfactory satisfactory terminal peeling prevention properties.
本発明は、上記課題を解決するものであり、すなわち、強粘着力、強タックと良好な端末剥がれ防止性を十分に両立させたエマルジョン型粘着剤を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems, that is, to provide an emulsion-type pressure-sensitive adhesive that sufficiently achieves both strong adhesive strength, strong tack and good terminal peeling prevention properties.
本発明者らは、前記課題を解決するために鋭意研究を行った結果、強い粘着力と強いタック、及び端末剥がれ防止性の向上を図るため、エマルジョン系の粘着剤組成物に含まれる共重合体のモノマー組成や分子量、また該共重合体のガラス転移温度等を種々検討したところ、主モノマーとして、特定のアルキル鎖長のアルキル（メタ）アクリレートであり、且つ、該モノマーをポリマーとした時のガラス転移温度が−４０℃以下となるモノマーを選択し、副モノマーとしてラジカル重合性二重結合含有炭素環式化合物を選択し、さらにラジカル重合性カルボキシル基含有モノマーを用い、これら３種のモノマーを乳化重合して得られる共重合体において、ガラス転移温度が−５５〜−３０℃の温度範囲にある共重合体を粘着剤組成物として用いることにより、上記課題を解決できることを見出した。さらに本発明者らは、上記乳化重合時に連鎖移動剤を用いて分子量を調整することにより、より強い粘着力とと強タックが得られることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that the co-polymer contained in the emulsion-based pressure-sensitive adhesive composition has a strong adhesive strength, a strong tack, and an improvement in terminal peeling prevention. As a result of various studies on the monomer composition and molecular weight of the coalescence and the glass transition temperature of the copolymer, the main monomer is an alkyl (meth) acrylate having a specific alkyl chain length, and the monomer is a polymer. A monomer having a glass transition temperature of −40 ° C. or lower is selected, a radical polymerizable double bond-containing carbocyclic compound is selected as a submonomer, and a radical polymerizable carboxyl group-containing monomer is used, and these three monomers are used. In the copolymer obtained by emulsion polymerization, a copolymer having a glass transition temperature in the temperature range of −55 to −30 ° C. is used as an adhesive composition. The Rukoto have found the above problems can be solved. Furthermore, the present inventors have found that stronger adhesive force and stronger tack can be obtained by adjusting the molecular weight using a chain transfer agent during the emulsion polymerization, thus completing the present invention.
すなわち本発明は、下記成分（ａ）、（ｂ）及び（ｃ）：
（ａ）少なくとも１種の、アルキル基の炭素原子数が１乃至１８のアルキル（メタ）アクリレートモノマーであって、該モノマーを（共）重合して得られるポリマーのガラス転移温度が−４０℃以下である、モノマー
（ｂ）ラジカル重合性二重結合含有炭素環式化合物
（ｃ）ラジカル重合性カルボキシル基含有モノマー
を乳化重合して得られる共重合体を含み、該共重合体は−５５〜−３０℃のガラス転移温
度を有する、粘着剤組成物に関する。
That is, the present invention includes the following components (a), (b) and (c):
(A) at least one alkyl (meth) acrylate monomer having 1 to 18 carbon atoms in the alkyl group, the polymer obtained by (co) polymerizing the monomer having a glass transition temperature of −40 ° C. or lower A copolymer obtained by emulsion polymerization of a monomer (b) a radical polymerizable double bond-containing carbocyclic compound (c) a radical polymerizable carboxyl group-containing monomer, the copolymer being -55 to- The present invention relates to a pressure-sensitive adhesive composition having a glass transition temperature of 30 ° C.
本発明によれば、さらに以下の実施態様が提供される。
１．前記成分（ａ）が、ｎ−ブチルアクリレート、２−エチルヘキシルアクリレート、ｎ−オクチルアクリレート、イソオクチルアクリレート、ｎ−ノニルアクリレート及びイソノニルアクリレートからなる群から選択される少なくとも１種のモノマーである、前記粘着剤組成物。
２．前記成分（ｂ）が、成分（ａ）乃至成分（ｃ）の総質量に基いて３．０質量％以上含まれる、前記粘着剤組成物
３．前記成分（ｂ）が、脂環構造を有する（メタ）アクリレートである、前記粘着剤組成物
４．前記成分（ｂ）が、イソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート（ＣＨ（Ｍ）Ａ）、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート及びジシクロペンタニル（メタ）アクリレートからなる群から選択される少なくとも１種の脂環構造を有する（メタ）アクリレートである、前記粘着剤組成物。
５．前記成分（ｃ）が、アクリル酸、メタクリル酸、イタコン酸及びカルボキシエチルアクリレートからなる群から選択されるラジカル重合性カルボキシル基含有モノマーである、前記粘着剤組成物。
６．前記共重合体が、成分（ａ）乃至成分（ｃ）の総量１００質量部に対して、０．１２５質量部以下の連鎖移動剤の存在下で乳化重合を行い得られたものである、前記粘着剤組成物。
７．前記粘着剤組成物を基材に塗布してなる粘着テープ又は粘着シート。
According to the present invention, the following embodiments are further provided.
1. The component (a) is at least one monomer selected from the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, n-nonyl acrylate and isononyl acrylate, Adhesive composition.
2. 2. The pressure-sensitive adhesive composition, wherein the component (b) is contained in an amount of 3.0% by mass or more based on the total mass of the components (a) to (c). 3. The pressure-sensitive adhesive composition, wherein the component (b) is a (meth) acrylate having an alicyclic structure. The component (b) is isobornyl (meth) acrylate, cyclohexyl (meth) acrylate (CH (M) A), dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meth) ) The pressure-sensitive adhesive composition, which is a (meth) acrylate having at least one alicyclic structure selected from the group consisting of acrylates.
5. The pressure-sensitive adhesive composition, wherein the component (c) is a radical polymerizable carboxyl group-containing monomer selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and carboxyethyl acrylate.
6). The copolymer is obtained by emulsion polymerization in the presence of a chain transfer agent of 0.125 parts by mass or less with respect to 100 parts by mass of the total amount of components (a) to (c), Adhesive composition.
7). The adhesive tape or adhesive sheet formed by apply | coating the said adhesive composition to a base material.
本発明によれば、強い粘着力と強いタック、及び端末剥がれ防止性が両立したエマルジョン型の粘着剤組成物を得られる。
そして本発明は、上記粘着剤組成物を塗布して粘着テープ又は粘着シートとすることにより、強い粘着力と強タックを有し、細線等に巻きつけたときの端末剥がれが起こりにくいテープ及びシートを提供できる。
According to the present invention, an emulsion-type pressure-sensitive adhesive composition having both strong adhesive strength, strong tack, and terminal peeling prevention properties can be obtained.
And this invention is tape and sheet which have strong adhesive force and strong tack by applying the above-mentioned adhesive composition, and are not easily peeled off when wound around a thin wire or the like. Can provide.
上述したように、粘着テープ等に使用される粘着剤が有機溶剤型粘着剤から無溶剤型粘着剤へ切り替えられつつある中、出願人はエマルジョン型粘着剤において粘着力及びタック（粘着性）並びに端末剥がれ防止性を全て満足できる粘着剤の構成を種々検討した。
従来より、粘着力、タック及び端末剥がれ防止性といった性能に影響を及ぼす要素の一つとして粘着剤の弾性率が考慮されている。例えば粘着剤が硬いと、端末剥がれ防止性は比較的良好であるが低タックとなり、粘着剤が柔らかいと、高タックではあるが端末剥がれ防止性が不足することが考えられる。
さて、有機溶剤型粘着剤の製造において適用される溶液重合法で製造した重合体と比較して、エマルジョン型粘着剤の製造において適用される乳化重合法で製造した重合体は、より高分子量の重合体となることが知られている。このため、乳化重合法で製造した粘着剤は溶液重合法で製造した粘着剤と比べて強タックになりづらいと考えられる。
そのため、乳化重合時、強タック化を狙い、得られる重合体を低分子量化させる目的で連鎖移動剤を添加すると、今度は低分子量体が多くなりすぎ、凝集力が低下し端末剥がれ防止性が低下する虞がある。また、強タックにするため、ガラス転移温度（Ｔｇ）を下げ
るべく重合体の設計を図った場合には、今度は凝集力不足により端末剥がれ防止性が悪くなることが考えられる。
このように、乳化重合法により製造されるエマルジョン型粘着剤は、単に分子量の操作やガラス転移温度の設定といった事項だけでは、強粘着力・強タック・良好な端末剥がれ防止性の全てを同時に実現することは難しく、有機溶剤型粘着剤における知見をそのまま適用するだけでは、上述の課題を解決できる粘着剤を構成することは困難であった。
As described above, while the pressure-sensitive adhesive used for the pressure-sensitive adhesive tape is being switched from the organic solvent-type pressure-sensitive adhesive to the solventless-type pressure-sensitive adhesive, the applicant applies the adhesive force and tack (adhesiveness) in the emulsion-type pressure-sensitive adhesive and Various configurations of pressure-sensitive adhesives that can satisfy all terminal peeling prevention properties were studied.
Conventionally, the elastic modulus of an adhesive has been considered as one of the factors affecting performance such as adhesive strength, tack, and terminal peeling prevention. For example, if the pressure-sensitive adhesive is hard, the terminal peeling prevention property is relatively good but has a low tack, and if the pressure-sensitive adhesive is soft, the terminal peeling prevention property may be insufficient although the tack is high.
Now, compared with the polymer produced by the solution polymerization method applied in the production of the organic solvent-type pressure-sensitive adhesive, the polymer produced by the emulsion polymerization method applied in the production of the emulsion-type pressure-sensitive adhesive has a higher molecular weight. It is known to be a polymer. For this reason, it is considered that the pressure-sensitive adhesive produced by the emulsion polymerization method is less likely to have a strong tack than the pressure-sensitive adhesive produced by the solution polymerization method.
Therefore, at the time of emulsion polymerization, if a chain transfer agent is added for the purpose of reducing the molecular weight of the resulting polymer with the aim of strengthening the tackiness, the amount of low molecular weight will increase too much, and the cohesive force will be reduced and terminal peeling will be prevented. May decrease. Further, when the polymer is designed to lower the glass transition temperature (Tg) in order to make it strong tack, it is considered that the terminal peeling prevention property is deteriorated due to insufficient cohesive force.
In this way, the emulsion-type pressure-sensitive adhesive produced by the emulsion polymerization method achieves all of strong adhesive strength, strong tack, and good terminal peeling prevention at the same time by simply adjusting the molecular weight and setting the glass transition temperature. However, it is difficult to construct a pressure-sensitive adhesive that can solve the above-described problems by simply applying the knowledge of the organic solvent-type pressure-sensitive adhesive as it is.
ここで本発明者らは、まず共重合体のガラス転移温度を特定の数値範囲とすべく共重合体組成を検討し、さらに、副モノマーとしてラジカル重合性二重結合含有炭素環式化合物を添加することにより、凝集力不足を解消するだけでなく、端末剥がれ防止性の向上にも寄与することを見出し、本発明の完成に至った。
そして本発明者らは、下記に詳述する成分（ａ）アルキル（メタ）アクリレートモノマー、成分（ｂ）ラジカル重合性二重結合含有炭素環式化合物及び（ｃ）ラジカル重合性カルボキシル基含有モノマーを乳化重合して得られる共重合体であって、−５５〜−３０℃のガラス転移温度を有する共重合体を含む粘着剤組成物という構成を見出した。
以下、本発明に用いる各成分、原料について以下詳細に述べる。
Here, the inventors first studied the copolymer composition so that the glass transition temperature of the copolymer was in a specific numerical range, and further added a radical polymerizable double bond-containing carbocyclic compound as a secondary monomer. As a result, it was found that not only the lack of cohesive force was resolved, but also the improvement of the terminal peeling prevention property, and the present invention was completed.
Then, the present inventors include component (a) alkyl (meth) acrylate monomer, component (b) radical polymerizable double bond-containing carbocyclic compound and (c) radical polymerizable carboxyl group-containing monomer described in detail below. The present inventors have found a constitution of a pressure-sensitive adhesive composition containing a copolymer obtained by emulsion polymerization and having a glass transition temperature of −55 to −30 ° C.
Hereafter, each component and raw material used for this invention are described in detail below.
なお本発明において、ガラス転移温度（Ｔｇ）は、その目安の温度を、以下の計算式より使用するモノマーのホモポリマーとしたときのガラス転移温度より算出することができる。
１００/Ｔｇ＝Ｗ１/Ｔｇ１ ＋ Ｗ２/Ｔｇ２ ＋ Ｗ３/Ｔｇ３＋・・・＋Ｗｎ/Ｔｇｎ
・Ｗ１、Ｗ２、Ｗ３・・・Ｗｎ：各モノマーの質量％（総量：１００％）
・Ｔｇ１、Ｔｇ２、Ｔｇ３、・・・Ｔｇｎ：各モノマーをホモポリマーとしたときの理論Ｔｇ（単位 Ｋ：ケルビン）
In the present invention, the glass transition temperature (Tg) can be calculated from the glass transition temperature when the reference temperature is a homopolymer of a monomer to be used from the following formula.
100 / Tg = W 1 / Tg 1 + W 2 / Tg 2 + W 3 / Tg 3 + ··· + W n / Tg n
W 1 , W 2 , W 3 ... W n : mass% of each monomer (total amount: 100%)
Tg 1 , Tg 2 , Tg 3 ,... Tg n : Theoretical Tg when each monomer is a homopolymer (unit K: Kelvin)
＜（ａ）アルキル（メタ）アクリレートモノマー＞
本発明で使用する成分（ａ）は、アルキル基の炭素原子数が１乃至１８のアルキル（メタ）アクリレートモノマーであり、且つ、該モノマーを（共）重合して得られるポリマーのガラス転移温度が−４０℃以下である、モノマーである。
<(A) Alkyl (meth) acrylate monomer>
Component (a) used in the present invention is an alkyl (meth) acrylate monomer having 1 to 18 carbon atoms in the alkyl group, and the glass transition temperature of the polymer obtained by (co) polymerizing the monomer is It is a monomer that is −40 ° C. or lower.
ここで、アルキル（メタ）アクリレートモノマーにおけるアルキル基の炭素原子数とは、（メタ）アクリル酸のエステル結合部分に結合するアルキル基の炭素原子数を表す。
上記アルキル基の炭素原子数が１乃至１８のアルキル（メタ）アクリレートとしては、例えば、アクリル酸メチル、メタクリル酸メチル（アルキル基の炭素原子数が１）、アクリル酸エチル、メタクリル酸エチル（アルキル基の炭素原子数が２）、ｎ−ブチルアクリレート、ｎ−ブチルメタクリレート（アルキル基の炭素原子数が４）、２−エチルヘキシルアクリレート、２−エチルへキシルメタクリレート、ｎ−オクチルアクリレート、ｎ−オクチルメタクリレート、イソオクチルアクリレート、イソオクチルメタクリレート（アルキル基の炭素原子数が８）、ｎ−ノニルアクリレート、ｎ−ノニルメタクリレート、イソノニルアクリレート、イソノニルメタクリレート（アルキル基の炭素原子数が９）、ステアリルアクリレート、ステアリルメタクリレート（アルキル基の炭素原子数が１８）などが挙げられるが、これらに限定されない。
中でも、アルキル基の炭素原子数が３乃至１０のアルキルアクリレートモノマーがより好ましく、炭素原子数が４乃至９のアルキルアクリレートモノマーがさらにより好ましい。特に好ましいモノマーは、ｎ−ブチルアクリレートとイソノニルアクリレートである。
これらモノマーは、一種を単独で、或いは二種以上を併用して用いることができる。
Here, the carbon atom number of the alkyl group in the alkyl (meth) acrylate monomer represents the carbon atom number of the alkyl group bonded to the ester bond portion of (meth) acrylic acid.
Examples of the alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group include, for example, methyl acrylate, methyl methacrylate (the alkyl group has 1 carbon atom), ethyl acrylate, and ethyl methacrylate (alkyl group). Has 2 carbon atoms, n-butyl acrylate, n-butyl methacrylate (alkyl group has 4 carbon atoms), 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, Isooctyl acrylate, isooctyl methacrylate (alkyl group has 8 carbon atoms), n-nonyl acrylate, n-nonyl methacrylate, isononyl acrylate, isononyl methacrylate (alkyl group has 9 carbon atoms), stearyl acrylate, stear Although methacrylate (number of carbon atoms in the alkyl group 18), and the like, but not limited to.
Of these, alkyl acrylate monomers having 3 to 10 carbon atoms in the alkyl group are more preferable, and alkyl acrylate monomers having 4 to 9 carbon atoms are even more preferable. Particularly preferred monomers are n-butyl acrylate and isononyl acrylate.
These monomers can be used alone or in combination of two or more.
本発明において、成分（ａ）モノマーとしては、上述のモノマーを単独重合又は共重合させて得られるホモポリマー又はコポリマーのガラス転移温度が−４０℃以下となるもの、好ましくは−８５℃〜−５５℃となるものを選択する。
ホモポリマー／コポリマーのガラス転移温度が−４０℃以下である上記モノマーの組み合わせとしては、例えば、ｎ−ブチルアクリレート（ｎＢａ）０．５３質量部とイソノニルアクリレート（ＩＮＡ）０．４７質量部との組み合わせ（ガラス転移温度：ｎＢＡホモポリマーＴｇ＝−５５℃（２１８Ｋ）、ＩＮＡホモポリマーＴｇ＝−８５℃（１８８Ｋ）として、前述の式より算出した計算値：−７０．２℃）、また、ｎ−ブチルアクリレート０．６７質量部とイソノニルアクリレート０．３３質量部との組み合わせ（ガラス転移温度 前述の式より算出した計算値：−６５．９℃）などが考えられるが、無論これらに限定されない。
また、主モノマーである成分（ａ）モノマーのホモポリマー／コポリマーのガラス転移温度を適宜調整し選択することにより、成分（ｂ）及び（ｃ）成分と共に共重合体を為した際の該共重合体のガラス転移温度範囲を好適な範囲（−５５〜−３０℃）に調整することができる。
In the present invention, as the component (a) monomer, a homopolymer or copolymer obtained by homopolymerization or copolymerization of the above-mentioned monomers has a glass transition temperature of −40 ° C. or lower, preferably −85 ° C. to −55. Select the one that will be at ℃.
As a combination of the above monomers whose homopolymer / copolymer has a glass transition temperature of −40 ° C. or less, for example, 0.53 parts by mass of n-butyl acrylate (nBa) and 0.47 parts by mass of isononyl acrylate (INA) Combination (glass transition temperature: nBA homopolymer Tg = −55 ° C. (218 K), INA homopolymer Tg = −85 ° C. (188 K), calculated from the above formula: −70.2 ° C.), n -A combination of 0.67 parts by mass of butyl acrylate and 0.33 parts by mass of isononyl acrylate (glass transition temperature: calculated from the above formula: -65.9 ° C) is conceivable, but of course not limited thereto. .
In addition, by adjusting and selecting the glass transition temperature of the homopolymer / copolymer of the component (a) monomer as the main monomer as appropriate, the copolymer weight when the copolymer is formed together with the components (b) and (c) The glass transition temperature range of the coalescence can be adjusted to a suitable range (−55 to −30 ° C.).
＜（ｂ）ラジカル重合性二重結合含有炭素環式化合物＞
本発明で使用するラジカル重合性二重結合含有炭素環式化合物は特に限定されないが、好ましくは脂環構造を有する（メタ）アクリレートが好ましい。
脂環構造を有する（メタ）アクリレートとしては、例えばイソボルニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等を好ましいものとして挙げることができ、特に好ましいのはイソボルニルアクリレートである。
<(B) Radical polymerizable double bond-containing carbocyclic compound>
Although the radically polymerizable double bond containing carbocyclic compound used by this invention is not specifically limited, Preferably the (meth) acrylate which has an alicyclic structure is preferable.
Examples of the (meth) acrylate having an alicyclic structure include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth). Acrylates and the like can be mentioned as preferred, and isobornyl acrylate is particularly preferred.
＜（ｃ）ラジカル重合性カルボキシル基含有モノマー＞
本発明で使用するラジカル重合カルボキシル基含有モノマーとしては特に限定されないが、例えばアクリル酸、メタクリル酸、イタコン酸、カルボキシエチルアクリレートなどを挙げることができ、特にアクリル酸を好ましいものとして挙げることができる。
<(C) Radical polymerizable carboxyl group-containing monomer>
Although it does not specifically limit as a radical polymerization carboxyl group containing monomer used by this invention, For example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate etc. can be mentioned, Especially acrylic acid can be mentioned as a preferable thing.
〔共重合体〕
本発明の粘着剤組成物に含まれる共重合体は、前記成分（ａ）乃至成分（ｃ）を乳化重合して得られる。
このとき、成分（ａ）乃至成分（ｃ）の各成分の配合割合は以下のとおりであることが好ましい。
・成分（ａ）アルキル（メタ）アクリレートモノマー：
成分（ａ）乃至成分（ｃ）の総質量に基いて、４０質量％以上９６．５質量％以下の割合で含まれていることが好ましく、より好ましくは５０質量％乃至９０質量％、特に好ましくは６０質量％乃至９０質量％。
・成分（ｂ）ラジカル重合性二重結合含有炭素環式化合物：
成分（ａ）乃至成分（ｃ）の総質量に基いて、３．０質量％以上含まれていることが好ましく、より好ましくは５質量％乃至４０質量％、特に好ましくは５質量％乃至２５質量％。
・成分（ｃ）ラジカル重合性カルボキシル基含有モノマー：
成分（ａ）乃至成分（ｃ）の総質量に基いて、０．５質量％乃至１０質量％、より好ましくは１質量％乃至８質量％、さらに好ましくは２質量％乃至７．５質量％。
[Copolymer]
The copolymer contained in the pressure-sensitive adhesive composition of the present invention is obtained by emulsion polymerization of the components (a) to (c).
At this time, it is preferable that the mixture ratio of each component of a component (a) thru | or a component (c) is as follows.
Component (a) Alkyl (meth) acrylate monomer:
Based on the total mass of component (a) to component (c), it is preferably contained in a proportion of 40% by mass or more and 96.5% by mass or less, more preferably 50% by mass to 90% by mass, particularly preferably. Is 60 mass% to 90 mass%.
Component (b) radical polymerizable double bond-containing carbocyclic compound:
The content is preferably 3.0% by mass or more, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 25% by mass based on the total mass of the components (a) to (c). %.
Component (c) radical polymerizable carboxyl group-containing monomer:
Based on the total mass of component (a) to component (c), 0.5 mass% to 10 mass%, more preferably 1 mass% to 8 mass%, still more preferably 2 mass% to 7.5 mass%.
また乳化重合の際に、本発明の効果に悪影響を与えない程度まで連鎖移動剤を添加して重合を行なってもよい。
連鎖移動剤は前記成分（ａ）乃至成分（ｃ）の総量 １００質量部に対して、０．１２５質量部以下の添加量であることが好ましく、より好ましくは０質量部〜０．０７５質量部、特に好ましくは０質量部〜０．０６０質量部である。連鎖移動剤を０．１２５質量部を超えて添加すると端末剥がれ防止性に悪影響を与える虞がある。
連鎖移動剤は特に限定されないが、チオール系（メルカプト系）が好ましい。特にｎ−オクチル−３−メルカプトプロピオネート（ＮＯＭＰ）が好ましい。
Further, at the time of emulsion polymerization, polymerization may be carried out by adding a chain transfer agent to such an extent that the effect of the present invention is not adversely affected.
The chain transfer agent is preferably added in an amount of 0.125 parts by mass or less, more preferably 0 parts by mass to 0.075 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (c). Particularly preferred is 0 to 0.060 parts by mass. When a chain transfer agent is added exceeding 0.125 mass part, there exists a possibility of having a bad influence on terminal peeling prevention property.
The chain transfer agent is not particularly limited, but thiol (mercapto) is preferable. In particular, n-octyl-3-mercaptopropionate (NOMP) is preferable.
乳化重合の手順は、具体的な配合量を示して一例を挙げると、モノマー総量１００質量部に対して、連鎖移動剤を０〜０．０７５質量部、乳化させるための界面活性剤１．５〜３．０質量部、水５０質量部を撹拌混合し、乳化液を得る。反応釜に、この乳化液５〜３０質量部、界面活性剤０〜０．２質量部、水５０質量部を投入し、６０℃〜７０℃程度に昇温させる。ここに開始剤（過硫酸アンモニウム等）０．３質量部を添加し、初期反応を１０分間させた後、残りの乳化液を２．５時間かけ反応釜に滴下添加し、その後さらに３時間熟成反応させる。こうしてエマルジョン型粘着剤を得ることができる。
なお乳化重合時に使用する界面活性剤としては、好ましくはアニオン性界面活性剤、さらに好ましくは反応性界面活性剤であり、特に好ましくはアニオン性反応性界面活性剤である。
The procedure of emulsion polymerization shows a specific blending amount and, for example, a surfactant 1.5 for emulsifying 0 to 0.075 parts by mass of a chain transfer agent with respect to 100 parts by mass of the total amount of monomers. ˜3.0 parts by mass and 50 parts by mass of water are stirred and mixed to obtain an emulsion. 5-30 parts by mass of this emulsion, 0-0.2 parts by mass of surfactant, and 50 parts by mass of water are charged into a reaction kettle, and the temperature is raised to about 60 ° C to 70 ° C. To this, 0.3 parts by weight of an initiator (ammonium persulfate, etc.) was added, and the initial reaction was allowed to proceed for 10 minutes. Then, the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours, and then aged for 3 hours. Let Thus, an emulsion-type pressure-sensitive adhesive can be obtained.
The surfactant used during emulsion polymerization is preferably an anionic surfactant, more preferably a reactive surfactant, and particularly preferably an anionic reactive surfactant.
得られたエマルジョン型粘着剤において、成分（ａ）乃至成分（ｃ）から構成される共重合体は、ガラス転移温度が−５５〜−３０℃であり、好ましくは−５０℃〜−４０℃であることが望ましい。 In the obtained emulsion-type pressure-sensitive adhesive, the copolymer composed of the components (a) to (c) has a glass transition temperature of −55 to −30 ° C., preferably −50 ° C. to −40 ° C. It is desirable to be.
こうして調製した本発明の粘着剤組成物は、基材に適量塗布し乾燥させることで、本発明の粘着テープ又はシートを得ることができる。粘着剤層の厚さは用途に応じて適宜選択され得、通常、乾燥後の厚さが５μｍ乃至１０００μｍより選択されることが好ましい。
基材は、特に限定されないが、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル系樹脂、塩化ビニル系樹脂、アクリル系樹脂、ポリスチレン等の芳香族ビニル系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリカーボネート系樹脂、セルローストリアセテート等の合成樹脂からなるフィルム、紙、布、等が挙げられる。これらの中でも、ポリプロピレン、硬質塩化ビニル、ポリエステル系樹脂等のフィルムが好ましい。基材の厚みは、使用目的に応じて適宜定めることができるが、約２０〜６０μｍの範囲内であることが好ましい。
The pressure-sensitive adhesive composition of the present invention thus prepared can be applied to a substrate and dried to obtain the pressure-sensitive adhesive tape or sheet of the present invention. The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application, and it is usually preferable that the thickness after drying is selected from 5 μm to 1000 μm.
The substrate is not particularly limited. For example, polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, vinyl chloride resins, acrylic resins, aromatic vinyl resins such as polystyrene, polyamide resins, Examples include films made of synthetic resins such as polyimide resins, polycarbonate resins, and cellulose triacetate, paper, and cloth. Among these, films such as polypropylene, hard vinyl chloride, and polyester resins are preferable. The thickness of the substrate can be appropriately determined according to the purpose of use, but is preferably in the range of about 20 to 60 μm.
以下に実施例を挙げて、本発明をさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。
なお本実施例及び比較例で使用した化合物等は以下のとおりである。
・ｎ−ブチルアクリレート（ｎＢＡ） （株）日本触媒製
・イソノニルアクリレート（ＩＮＡ） （株）日本触媒製
・イソボルニルアクリレート（ＩＢＸＡ） 共栄社化学（株）製
・アクリル酸（ＡＡ） （株）日本触媒製
・ジシクロペンタニルアクリレート 日立化成工業（株）製 ＦＡ５１３ＡＳ
・シクロヘキシルアクリレート（ＣＨＡ） 共栄社化学（株）製
・メチルメタクリレート（ＭＭＡ） 共栄社化学（株）製
・開始剤 過硫酸アンモニウム（ＡＰＳ） （株）ＡＤＥＫＡ製
・界面活性剤 ＰＤ−１０５、花王（株）製
・連鎖移動剤 ｎ−オクチル−３−メルカプトプロピオネート（ＮＯＭＰ） 日油（株）製
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
The compounds used in the examples and comparative examples are as follows.
-N-butyl acrylate (nBA) made by Nippon Shokubai Co., Ltd.-isononyl acrylate (INA) made by Nippon Shokubai Co., Ltd.-isobornyl acrylate (IBXA) made by Kyoeisha Chemical Co., Ltd.-acrylic acid (AA) Made by Nippon Shokubai, dicyclopentanyl acrylate Hitachi Chemical Co., Ltd. FA513AS
・ Cyclohexyl acrylate (CHA) manufactured by Kyoeisha Chemical Co., Ltd. ・ Methyl methacrylate (MMA) manufactured by Kyoeisha Chemical Co., Ltd. ・ Initiator ammonium persulfate (APS) manufactured by ADEKA Co., Ltd. ・ surfactant PD-105, manufactured by Kao Corporation Chain transfer agent n-octyl-3-mercaptopropionate (NOMP) NOF Corporation
［実施例１］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して界面活性剤（ＰＤ−１０５）１．５質量部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
[Example 1]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass Surfactant (PD-105) 1.5 parts by mass and distilled water 50 parts by mass were mixed and stirred to obtain an emulsion 151.5 parts by mass. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then 136.5 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
［実施例２］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例１の構成に、さらにモノマー１００質量部に対しＮＯＭＰを０．０５０質量部添加した例である。
[Example 2]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.050 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water was mixed and stirred. 55 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This example is an example in which 0.050 parts by mass of NOMP is further added to the configuration of Example 1 with respect to 100 parts by mass of the monomer.
［実施例３］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．１００質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．６質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．６質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例１の構成に、さらにモノマー１００質量部に対しＮＯＭＰを０．１００質量部添加した例である。
[Example 3]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.100 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water was mixed and stirred. 6 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was performed for 10 minutes, and then 136.6 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
In this example, 0.100 parts by mass of NOMP was further added to the structure of Example 1 with respect to 100 parts by mass of the monomer.
［比較例１］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．１５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸
留水５０質量部を混合撹拌し、乳化液１５１．６５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．６５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本比較例は、実施例１の構成に、さらにモノマー１００質量部に対しＮＯＭＰを０．１５０質量部添加した例である。
[Comparative Example 1]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.150 parts by weight of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by weight of distilled water was mixed and stirred. 65 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then 136.65 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This comparative example is an example in which 0.150 parts by mass of NOMP is further added to the configuration of Example 1 with respect to 100 parts by mass of the monomer.
［実施例４］
・ｎ−ブチルアクリレート（ｎＢＡ） ６０質量部
・イソノニルアクリレート（ＩＮＡ） １５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例２の構成において、ｎＢＡ／ＩＮＡ比（質量比）を４０／３５から６０／１５に変更した例である。
[Example 4]
· N-butyl acrylate (nBA) 60 parts by mass · isononyl acrylate (INA) 15 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.050 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water was mixed and stirred. 55 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
The present example is an example in which the nBA / INA ratio (mass ratio) is changed from 40/35 to 60/15 in the configuration of the second example.
［実施例５］
・ｎ−ブチルアクリレート（ｎＢＡ） ２５質量部
・イソノニルアクリレート（ＩＮＡ） ５０質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例２の構成において、ｎＢＡ／ＩＮＡ比（質量比）を４０／３５から２５／５０に変更した例である。
[Example 5]
· N-butyl acrylate (nBA) 25 parts by mass · isononyl acrylate (INA) 50 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.050 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water was mixed and stirred. 55 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
The present example is an example in which the nBA / INA ratio (mass ratio) is changed from 40/35 to 25/50 in the configuration of the second example.
［参考例６］
・ｎ−ブチルアクリレート（ｎＢＡ） ３５質量部
・イソノニルアクリレート（ＩＮＡ） ４０質量部
・ジシクロペンタニルアクリレート（ＦＡ５１３ＡＳ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本参考例は、実施例２の構成において、（ｂ）成分のイソボルニルアクリレートをジシクロペンタニルアクリレートに置き換えた例である。
[ Reference Example 6]
· N-butyl acrylate (nBA) 35 parts by mass · isononyl acrylate (INA) 40 parts by mass · dicyclopentanyl acrylate (FA513AS) 20 parts by mass · acrylic acid (AA) 5 parts by mass Then, 0.050 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water are mixed and stirred, and an emulsion 151 Obtained .55 parts by weight. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This reference example is an example in which the isobornyl acrylate of the component (b) is replaced with dicyclopentanyl acrylate in the configuration of Example 2.
［参考例７］
・ｎ−ブチルアクリレート（ｎＢＡ） ６０質量部
・イソノニルアクリレート（ＩＮＡ） １５質量部・シクロヘキシルアクリレート（ＣＨＡ） ２０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、のポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本参考例は、実施例４の構成において、（ｂ）成分のイソボルニルアクリレートをシクロヘキシルアクリレートに置き換えた例である。
[ Reference Example 7]
・ 60 parts by mass of n-butyl acrylate (nBA) 15 parts by mass of isononyl acrylate (INA) 20 parts by mass of cyclohexyl acrylate (CHA) 5 parts by mass of acrylic acid (AA) Chain transfer with respect to 100 parts by mass of the above monomers in total 0.050 parts by mass of an agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water are mixed and stirred, and 151.55 masses of an emulsion. Got a part. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. A sample was prepared by applying this emulsion type adhesive to a polyester film (thickness: 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm.
This reference example is an example in which the isobornyl acrylate of the component (b) is replaced with cyclohexyl acrylate in the configuration of Example 4.
［実施例８］
・ｎ−ブチルアクリレート（ｎＢＡ） ６０質量部
・イソノニルアクリレート（ＩＮＡ） ２５質量部
・イソボルニルアクリレート（ＩＢＸＡ） １０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例４の構成において、イソボルニルアクリレートの配合量を２０質量部から１０質量部に減らし、イソノニルアクリレートの配合量を１５質量部から２５質量部に増やした例である。
[Example 8]
· N-butyl acrylate (nBA) 60 parts by mass · isononyl acrylate (INA) 25 parts by mass · isobornyl acrylate (IBXA) 10 parts by mass · acrylic acid (AA) 5 parts by mass A mixture of 0.050 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water was mixed and stirred. 55 parts by mass were obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This example is an example in which the blending amount of isobornyl acrylate is reduced from 20 parts by weight to 10 parts by weight and the blending amount of isononyl acrylate is increased from 15 parts by weight to 25 parts by weight in the configuration of Example 4. .
［実施例９］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・メチルメタクリレート（ＭＭＡ） ５質量部
・イソボルニルアクリレート（ＩＢＸＡ） １５質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例４の構成において、（ａ）成分にＴｇの高いメチルメタクリレートを５質量部添加し、その分イソボルニルアクリレートの配合量を２０質量部から１５質量部に減らした例である。
[Example 9]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · methyl methacrylate (MMA) 5 parts by mass · isobornyl acrylate (IBXA) 15 parts by mass · acrylic acid (AA) 5 parts by mass 0.050 parts by mass of chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of surfactant (PD-105) and 50 parts by mass of distilled water with respect to 100 parts by mass of the above monomers. Were mixed and stirred to obtain 151.55 parts by mass of an emulsion. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
In this example, in the configuration of Example 4, 5 parts by mass of methyl methacrylate having a high Tg was added to the component (a), and the amount of isobornyl acrylate was reduced from 20 parts by mass to 15 parts by mass. It is.
［実施例１０］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・メチルメタクリレート（ＭＭＡ） １０質量部
・イソボルニルアクリレート（ＩＢＸＡ） １０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例８の構成において、（ａ）成分にＴｇの高いメチルメタクリレートを１０質量部添加し、（ａ）成分のｎ−ブチルアクリレートと（ｂ）成分のイソボルニルアクリレートの配合量をそれぞれ５質量部ずつ減らした例である。
[Example 10]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · methyl methacrylate (MMA) 10 parts by mass · isobornyl acrylate (IBXA) 10 parts by mass · acrylic acid (AA) 5 parts by mass 0.050 parts by mass of chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of surfactant (PD-105) and 50 parts by mass of distilled water with respect to 100 parts by mass of the above monomers. Were mixed and stirred to obtain 151.55 parts by mass of an emulsion. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
In this example, in the configuration of Example 8, 10 parts by mass of methyl methacrylate having a high Tg was added to (a) component, and (b) component n-butyl acrylate and (b) component isobornyl acrylate were blended. This is an example in which the amount is reduced by 5 parts by mass.
［実施例１１］
・ｎ−ブチルアクリレート（ｎＢＡ） ４２．５質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ２．５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例２の構成において、アクリル酸の配合量を半量（２．５質量部）とし、その分ｎ−ブチルアクリレートの配合量をわずかに増やした（４２．５質量部）例で
ある。
[Example 11]
· N-butyl acrylate (nBA) 42.5 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 2.5 parts by mass The above monomers total 100 parts by mass A mixture of 0.50 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water with respect to parts, 151.55 parts by mass of an emulsion was obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
In this example, in the configuration of Example 2, the blending amount of acrylic acid was half (2.5 parts by mass), and the blending amount of n-butyl acrylate was slightly increased by that amount (42.5 parts by mass). It is.
［実施例１２］
・ｎ−ブチルアクリレート（ｎＢＡ） ３７．５質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ２０質量部
・アクリル酸（ＡＡ） ７．５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本実施例は、実施例２の構成において、アクリル酸の配合量を７．５質量部とし、その分ｎ−ブチルアクリレートの配合量を３７．５質量部に減らした例である。
[Example 12]
· N-butyl acrylate (nBA) 37.5 parts by mass · isononyl acrylate (INA) 35 parts by mass · isobornyl acrylate (IBXA) 20 parts by mass · acrylic acid (AA) 7.5 parts by mass The above monomers total 100 parts by mass A mixture of 0.50 parts by mass of a chain transfer agent (n-octyl-3-mercaptopropionate: NOMP), 1.5 parts of a surfactant (PD-105) and 50 parts by mass of distilled water with respect to parts, 151.55 parts by mass of an emulsion was obtained. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This example is an example in which the blending amount of acrylic acid is 7.5 parts by mass, and the blending amount of n-butyl acrylate is reduced to 37.5 parts by mass.
［比較例２］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ３５質量部
・メチルメタクリレート（ＭＭＡ） ２０質量部
・アクリル酸５ 質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本比較例は、実施例２の構成において、本発明において必須とされている（ｂ）成分を配合せず、代わりに（ａ）成分にメチルメタクリレートを２０質量部追加した例である。
[Comparative Example 2]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 35 parts by mass · methyl methacrylate (MMA) 20 parts by mass · acrylic acid 5 parts by mass Chain transfer agent (n -Octyl-3-mercaptopropionate: NOMP) 0.050 part by mass, surfactant (PD-105) 1.5 part and 50 parts by mass of distilled water are mixed and stirred to obtain 151.55 parts by mass of an emulsion. It was. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
This comparative example is an example in which 20 parts by mass of methyl methacrylate is added to the component (a) instead of blending the component (b) essential in the present invention in the configuration of Example 2.
［比較例３］
・ｎ−ブチルアクリレート（ｎＢＡ） ９５質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
本比較例は、本発明において必須とされている（ｂ）成分を配合せず、（ａ）成分はｎ−ブチルアクリレート１種のみとした例である。
[Comparative Example 3]
-N-butyl acrylate (nBA) 95 parts by mass-Acrylic acid (AA) 5 parts by mass The chain transfer agent (n-octyl-3-mercaptopropionate: NOMP) 0.050 mass with respect to 100 parts by mass of the above monomers. Parts, surfactant (PD-105) 1.5 parts and distilled water 50 parts by mass were mixed and stirred to obtain 151.55 parts by mass of emulsion. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
In this comparative example, the component (b), which is essential in the present invention, is not blended, and the component (a) is only one type of n-butyl acrylate.
［比較例４］
・ｎ−ブチルアクリレート（ｎＢＡ） ２０質量部
・イソノニルアクリレート（ＩＮＡ） ７０質量部
・イソボルニルアクリレート（ＩＢＸＡ） ５質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
[Comparative Example 4]
· N-butyl acrylate (nBA) 20 parts by mass · isononyl acrylate (INA) 70 parts by mass · isobornyl acrylate (IBXA) 5 parts by mass · acrylic acid (AA) 5 parts by mass Surfactant (PD-105) 1.5 parts and distilled water 50 parts by mass were mixed and stirred to obtain an emulsion 151.5 parts by mass. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then 136.5 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
［比較例５］
・ｎ−ブチルアクリレート（ｎＢＡ） ４０質量部
・イソノニルアクリレート（ＩＮＡ） ５０質量部
・シクロヘキシルアクリレート（ＣＨＡ） ５質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
[Comparative Example 5]
· N-butyl acrylate (nBA) 40 parts by mass · isononyl acrylate (INA) 50 parts by mass · cyclohexyl acrylate (CHA) 5 parts by mass · acrylic acid (AA) 5 parts by mass 1.5 parts of the agent (PD-105) and 50 parts by mass of distilled water were mixed and stirred to obtain 151.5 parts by mass of an emulsion. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then 136.5 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
［比較例６］
・ｎ−ブチルアクリレート（ｎＢＡ） １５質量部
・イソノニルアクリレート（ＩＮＡ） ６５質量部
・イソボルニルアクリレート（ＩＢＸＡ） １５質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５質量部を得た。窒素導入管を備えた反応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
[Comparative Example 6]
· N-butyl acrylate (nBA) 15 parts by mass · isononyl acrylate (INA) 65 parts by mass · isobornyl acrylate (IBXA) 15 parts by mass · acrylic acid (AA) 5 parts by mass Surfactant (PD-105) 1.5 parts and distilled water 50 parts by mass were mixed and stirred to obtain an emulsion 151.5 parts by mass. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then 136.5 parts by mass of the remaining emulsion was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
［比較例７］
・ｎ−ブチルアクリレート（ｎＢＡ） ６５質量部
・イソボルニルアクリレート（ＩＢＸＡ） ３０質量部
・アクリル酸（ＡＡ） ５質量部
上記モノマー合計１００質量部に対して連鎖移動剤（ｎ−オクチル−３−メルカプトプロピオネート：ＮＯＭＰ）０．０５０質量部と界面活性剤（ＰＤ−１０５）１．５部と蒸留水５０質量部を混合撹拌し、乳化液１５１．５５質量部を得た。窒素導入管を備えた反
応釜に、この乳化液のうち１５質量部と、蒸留水５０質量部を投入し、６６℃まで昇温した。さらに開始剤（過硫酸アンモニウム）０．３質量部を添加し、初期反応を１０分間行った後、残りの乳化液１３６．５５質量部を２．５時間かけて反応釜に滴下添加して重合を行い、滴下完了後、さらに３時間熟成反応を行い、エマルジョン型粘着剤を得た。このエマルジョン型粘着剤を、ポリエステルフィルム（厚さ３８μｍ）に乾燥後の粘着剤厚が１８μｍとなるようアプリケーターで塗布して試料を作成した。
[Comparative Example 7]
-N-butyl acrylate (nBA) 65 parts by mass-Isobornyl acrylate (IBXA) 30 parts by mass-Acrylic acid (AA) 5 parts by mass Chain transfer agent (n-octyl-3- Mercaptopropionate (NOMP) 0.050 part by mass, surfactant (PD-105) 1.5 part and distilled water 50 part by mass were mixed and stirred to obtain 151.55 part by mass of an emulsion. In a reaction kettle equipped with a nitrogen introduction tube, 15 parts by mass of this emulsion and 50 parts by mass of distilled water were added, and the temperature was raised to 66 ° C. Further, 0.3 parts by mass of an initiator (ammonium persulfate) was added and the initial reaction was carried out for 10 minutes, and then the remaining emulsion (136.55 parts by mass) was added dropwise to the reaction kettle over 2.5 hours for polymerization. Then, after completion of the dropwise addition, an aging reaction was further performed for 3 hours to obtain an emulsion-type pressure-sensitive adhesive. This emulsion type adhesive was applied to a polyester film (thickness 38 μm) with an applicator so that the thickness of the adhesive after drying was 18 μm to prepare a sample.
得られた実施例１乃至実施例５、参考例６及び参考例７、実施例８乃至実施例１２及び比較例１乃至比較例７の各試料について、それぞれ（１）対粘着力、（２）ボールタック、（３）プローブタック、（４）端末剥がれを下記の方法に従って測定した、得られた結
果を表１乃至表３に示す。
About each sample of obtained Example 1 thru | or Example 5, Reference Example 6 and Reference Example 7, Example 8 thru | or Example 12, and Comparative Example 1 thru | or Comparative Example 7, (1) adhesive force, (2) Tables 1 to 3 show the results obtained by measuring ball tack, (3) probe tack, and (4) terminal peeling according to the following method.
（１）対粘着力：
粘着力はＪＩＳ Ｚ０２３７に基づき、ＳＵＳ３０４鋼鈑に対する１８０°引きはがし粘着力を測定した。４．０Ｎ／１２ｍｍ以上であれば強い粘着力を有していると評価できる。
（２）ボールタック：
ボールタックはＪＩＳ Ｚ０２３７のタック試験法（転球法）に基づいて測定した。
（３）プローブタック：
プローブタックはＡＳＴＭ Ｄ２９７９に基づいて測定した。
（４）端末剥がれ：
端末剥がれは、図１に示すように六角レンチ（クロムバナジウム鋼製、ＰＢスイスツールズ製、サイズ：８ｍｍ）に試料を巻きつけるように貼付し（図中、太線部分が試料である）、４０℃７２時間静置した。その後、貼付したｎ個のサンプルのうち剥がれが発生した個数ｘを測定し、剥がれの発生する割合［（ｘ／ｎ）×１００（％）］で評価した。なお六角レンチは、３年程度の間、通常使用したもの（六角旧）と、購入したばかりの新しいもの（六角新）とを使用した。
数値が大きいほど端末剥がれが起こり易いことを示し、２５％以下であると端末剥がれ防止性が良いと評価できる。
(1) Adhesive strength:
The adhesive strength was measured based on JIS Z0237, and the adhesive strength was measured by peeling 180 ° against a SUS304 steel plate. If it is 4.0 N / 12mm or more, it can be evaluated that it has strong adhesive force.
(2) Ball tack:
Ball tack was measured based on the tack test method (rolling ball method) of JIS Z0237.
(3) Probe tack:
The probe tack was measured based on ASTM D2979.
(4) Device peeling:
As shown in FIG. 1, the terminal peeling is pasted so as to wrap the sample around a hexagon wrench (made of chrome vanadium steel, PB Swiss tools, size: 8 mm) (the bold line portion is the sample in the figure), and 40 ° C. It was left for 72 hours. Then, the number x where peeling occurred among the n samples attached was measured and evaluated by the rate [(x / n) × 100 (%)] where peeling occurred. The hexagonal wrench used was the one that was normally used for about 3 years (the old hexagonal) and the new one just purchased (the new hexagonal).
A larger value indicates that terminal peeling is more likely to occur. If the value is 25% or less, it can be evaluated that the terminal peeling prevention property is good.
上記表１乃至表３に示すように、実施例１乃至実施例５、実施例８乃至実施例１２はいずれも高い粘着力、ボールタック及びプローブタックを示し、すなわち強い粘着力と強タックを示すとともに、端末剥がれ発生率が低く、端末剥がれ防止性も良好であった。
一方、比較例１は連鎖移動剤を本発明で定める数値範囲より過剰量添加したため、粘着剤が柔らかくなりすぎたことにより、１００％の確率で端末剥がれを発生した。比較例２及び比較例３は本発明で必須としている（ｂ）成分を欠き、粘着力が弱いのみならず端末剥がれ防止性も不良であった。比較例４〜比較例６は成分（ａ）乃至成分（ｃ）を乳化重合して得られる共重合体のガラス転移温度が−５５〜−３０℃の温度範囲からはずれ、ガラス転移温度が下限値を下回っており、粘着力が弱いのみならず端末剥がれ発生率が非常に高いとする結果となった。また上記ガラス転移温度が、上記温度範囲の上限値を上回った比較例７は、タックが不足とする結果となった。
As shown in Table 1 to Table 3, Examples 1 to 5 and Examples 8 to 12 all show high adhesive strength, ball tack and probe tack, that is, strong adhesive strength and strong tack. In addition, the terminal peeling rate was low, and the terminal peeling prevention property was also good.
On the other hand, in Comparative Example 1, since the chain transfer agent was added in an excessive amount from the numerical range defined in the present invention, the adhesive was too soft, and terminal peeling occurred with a probability of 100%. Comparative Example 2 and Comparative Example 3 lacked component (b), which is essential in the present invention, and had not only weak adhesive strength but also poor terminal peeling prevention properties. In Comparative Examples 4 to 6, the glass transition temperature of the copolymer obtained by emulsion polymerization of the components (a) to (c) is out of the temperature range of −55 to −30 ° C., and the glass transition temperature is the lower limit. As a result, not only the adhesive strength was weak but also the terminal peeling occurrence rate was very high. Moreover, the comparative example 7 in which the said glass transition temperature exceeded the upper limit of the said temperature range resulted in the tack becoming insufficient.
Claims (5)
該方法は、下記成分（ａ）、（ｂ）及び（ｃ）を、成分（ａ）乃至成分（ｃ）の総量１００質量部に対して、０質量部〜０．１２５質量部の連鎖移動剤の存在下で乳化重合を行い共重合体を得る工程を含み、
該共重合体は−５５〜−３０℃のガラス転移温度を有する、方法。
（ａ）少なくとも１種の、アルキル基の炭素原子数が１乃至１８のアルキル（メタ）アクリレートモノマーであって、該モノマーを（共）重合して得られるポリマーのガラス転移温度が−４０℃以下である、モノマー
（ｂ）イソボルニル（メタ）アクリレート
（ｃ）ラジカル重合性カルボキシル基含有モノマー A method for producing a pressure-sensitive adhesive composition containing a copolymer,
In this method, the following components (a), (b) and (c) are added in an amount of 0 to 0.125 parts by mass with respect to 100 parts by mass of the total amount of components (a) to (c). Including a step of obtaining a copolymer by emulsion polymerization in the presence of
The copolymer has a glass transition temperature of -55 to-30 ° C., method.
(A) at least one alkyl (meth) acrylate monomer having 1 to 18 carbon atoms in the alkyl group, the polymer obtained by (co) polymerizing the monomer having a glass transition temperature of −40 ° C. or lower A monomer (b) isobornyl (meth) acrylate (c) a radical polymerizable carboxyl group-containing monomer
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