JPH0136512B2 - - Google Patents
Info
- Publication number
- JPH0136512B2 JPH0136512B2 JP3543782A JP3543782A JPH0136512B2 JP H0136512 B2 JPH0136512 B2 JP H0136512B2 JP 3543782 A JP3543782 A JP 3543782A JP 3543782 A JP3543782 A JP 3543782A JP H0136512 B2 JPH0136512 B2 JP H0136512B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- parts
- emulsion
- sensitive adhesive
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000839 emulsion Substances 0.000 claims description 72
- 239000000178 monomer Substances 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 64
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000010419 fine particle Substances 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000003995 emulsifying agent Substances 0.000 claims description 15
- 239000003505 polymerization initiator Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 125000005907 alkyl ester group Chemical group 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000002245 particle Substances 0.000 description 18
- 230000001070 adhesive effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- -1 fatty acid salts Chemical class 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 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 description 2
- 239000004908 Emulsion polymer Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental 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
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 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
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明はエマルジヨン系感圧性接着剤に係り、
更に詳しくは、エマルジヨン粒子核となる特定範
囲の微細な粒径を有し、かつ架橋された重合体エ
マルジヨン中の微粒子存在下にて、感圧性接着剤
を生成する単量体混合物をラジカル重合して得ら
れる新規なエマルジヨン系感圧性接着剤およびそ
の製法に関するものである。
近年アクリル系感圧性接着剤は、その優れた接
着特性と耐久性の長所の故に、従来の天然ゴム
系、合成ゴム系の感圧性接着剤に代わつて広く普
及してきている。
また、この種の感圧性接着剤のなかでも、有機
溶剤を使用しないエマルジヨン系感圧性接着剤は
省資源、無公害、環境衛生などの観点から最近特
に重要視されてきている。従来知られているアク
リル系のエマルジヨン系感圧性接着剤は、一般に
アクリル酸エステル、メタクリル酸エステルなど
のアクリル系単量体をベースとして、必要に応じ
てアクリル酸、スチレン、アクリロニトリルなど
の改質用単量体を添加して水媒体中で乳化重合さ
せることにより得ているのであるが、感圧性接着
テープに適用した場合、製造直後の乾燥状態と経
日等による吸水状態とでは接着特性が大幅に変化
する欠点が見られる。
この理由は、乳化重合時に使用されるアニオン
系界面活然剤、非イオン系界面活性剤などの乳化
剤が剤化重合操作の面よりもむしろ、生成したエ
マルジヨン系の安定を保持する必要性の観点から
多量に使用されているからである。そのため、上
記の重合体エマルジヨンから加熱乾燥して得られ
る感圧性接着剤皮膜は、吸水率が高く接着特性の
耐水性に乏しく、また水に浸漬した場合には24時
間以内に白化して殆んど機能を失つてしまう。
また、これらのアクリル系のエマルジヨン系感
圧性接着剤は、一般に重合後架橋剤として種々の
ものが添加されて使用に供されている。この際エ
マルジヨン系重合体に架橋剤を加えた時にエマル
ジヨンの安定性が悪くなる、また架橋剤の均一混
合が困難である、混合工程が必要などの問題点が
挙げられる。
本発明者達は、エマルジヨン系感圧性接着剤に
おけるエマルジヨン自体の安定性及び最終皮膜形
態とての感圧性接着剤層の感圧接着剤特性および
その耐水性向上について鋭意研究の結果、反応条
件を制御することによつて得られる特定範囲の微
細な粒径を有しかつ架橋された重合体エマルジヨ
ン中の微粒子存在下にて、感圧性接着剤を生成す
る単量体混合物をラジカル重合させる事により高
接着力・高凝集力を保持する優れた感圧性接着剤
特性を確保し、かつエマルジヨン自体の安定性及
び耐水性向上を同時に確保しうることを見い出し
本発明に至つたものである。
すなわち本発明は、エチレン性二重結合１個を
有する単量体と共重合性多官能単量体との混合物
を比較的多量の乳化剤および重合開始剤を含む水
媒体中で乳化重合して得られる架橋された平均粒
径250〜850Åの微粒子からなる重合体エマルジヨ
ンの存在下で、アクリル酸又はメタクリル酸のア
ルキルエステル単量体（アルキル基の炭素数１〜
10個）およびこれらと共重合可能なビニル系単量
体を主体とする重合により感圧性接着剤を生成す
る単量体混合物をラジカル重合させて得られる重
合体エマルジヨン組成物からなる新規なエマルジ
ヨン系感圧性接着剤を提供するものである。
本発明において、母体となる架橋された微粒子
からなる重合体エマルジヨンは、平均粒径250〜
850Åの範囲であることが必要である。平均粒径
が850Å以上になると、次の段階で感圧性接着剤
を生成する単量体混合物を粒子存在下でラジカル
重合させた重合体エマルジヨン組成物の機械的、
化学的な安定性が損われ、感圧性接着剤としての
各種特性が低下する傾向が現われる。
一方、平均粒径250Å以下にすると、微粒子エ
マルジヨン重合体を得る反応操作で水媒体中に極
めて多量の乳化剤を添加する必要が生じ、次の段
階で得られる重合体エマルジヨン組成物は本発明
の目的とする、耐水性向上の効果が期待できなく
なる。
本発明において上記微粒子を構成する化合物と
しては、エチレン性二重結合を１個有する単量体
と架橋を具備させるための共重合性多官能単量体
との混合物が用いられる。
エチレン性二重結合を１個有する単量体として
は、アクリル酸又はメタクリル酸のアルキルエス
テル（アルキル基の炭素数１〜10個）もしくは上
記アルキルエステルと共重合可能な他のビニル系
単量体が好適に用いられ、アクリル酸又はメタク
リル酸のアルキルエステルとしては、アクリル酸
エチル、アククリル酸プロピル、アクリル酸ブチ
ル、アクリル酸２エチルヘキシル、メタクリル酸
メチル、メタクリル酸エチル、メタクリル酸プロ
ピル、メタクリル酸ブチルなどが挙げられ１種も
しくは２種以上を併用してもよい。また、これら
のアルキルエステルと共重合可能な他のビニル系
単量体としては、アクリル酸、メタクリル酸、フ
マール酸、イタコン酸、マレイン酸、アクリロニ
トリル、酢酸ビニル、メタクリロニトリル、スチ
レンなどが挙げられ、上記アルキルエステル単量
体の50重量％以下の範囲で混合される。
一方、共重合性多官能単量体としては、多価ア
ルコールのポリアクリル酸（又はメタクリル酸）
エステル単量体およびジビニルベンゼンが好適に
用いられ、上記エステル単量体としてはエチレン
グリコールジメタクリレート（又はアクリレー
ト）、ジエチレングリコールジメタクリレート
（又はアクリレート）、トリエチレングリコールジ
メタクリレート（又はアクリレート）、ポリエチ
レングリコールジメタクリレート（又はアクリレ
ート）、ポリプロピレングリコールジメタクリレ
ート（又はアクリレート）、トリメチロールプロ
パントリメタクリレート（又はアクリレート）、
テトラメチロールメタンテトラメタクリレート
（又はアクリレート）などが挙げられる。
これらの共重合性多官能単量体は、重合体エマ
ルジヨンの微粒子を架橋せしめる成分であり、前
記エチレン性二重結合を１個有する単量体100重
量部に対して５〜40重量部の範囲で使用するのが
好ましい。これにより、乳化重合による重合体エ
マルジヨンの微粒子生成時に架橋構造が与えられ
るため、この重合体エマルジヨンの存在下にて感
圧性接着剤を生成する単量体混合物をラジカル重
合させて得られるエマルジヨン系感圧性接着剤
は、優れた凝集力および接着力を発揮する特徴が
現われる。また、新たに架橋剤を添加する必要が
ないことは、エマルジヨンの安定性向上にも寄与
する。エマルジヨン微粒子の架橋度合いは、アセ
トン抽出（24時間）にてそのゲル分率が約50〜95
％が適当であり、ゲル分率が比較的高い方が好ま
しい。
而して、重合体エマルジヨンを生成するエチレ
ン性二重結合を１個有する単量体と共重合性多官
能単量体との混合物を乳化重合して、平均粒径
250〜850Åの架橋された微粒子を生成するに際し
ては、比較的多量の乳化剤および重合開始剤を用
いるが、微粒子生成後次の段階で感圧性接着剤成
分である単量体混合物をラジカル重合させる時
に、新たな粒子が形成されない範囲で過剰になら
ないように乳化剤および重合開始剤の使用量を決
定すべきである。
かかる理由から、乳化剤は前記重合体エマルジ
ヨンを生成する単量体混合物100重量部に対して
２〜20重量部、好ましくは４〜18重量部の範囲で
使用され、重合開始剤は該単量体混合物100重量
部に対して0.5〜５重量部、好ましくは１〜３重
量部の範囲で使用される。このように通常の乳化
重合に比べて比較的多量の乳化剤および重合開始
剤を用いることにより、乳化剤にて形成される水
媒体中でのミセル数が増大され且つ発生するラジ
カル数が多いものとなり、その結果生成される重
合体エマルジヨンの粒子数が多くなり所定の粒径
を有する微粒子を得ることができるのである。し
かし、乳化剤の使用量は後述のように最終的に得
られる重合体エマルジヨン組成物のポリマー成分
中には少量しか含まれず、約0.04〜３重量％、実
用的には約0.1〜１重量％の範囲とされるのであ
る。
本発明に使用される乳化剤としては、脂肪酸
塩、高級アルコール硫酸エステル塩、アルキルベ
ンゼンスルホン酸塩、アルキルナフタレンスルホ
ン酸塩、ジアルキルスルコハク酸塩、アルキルフ
オスフエート塩、ポリオキシエチレンサルフエー
ト塩などの陰イオン性界面活性剤が利用でき、ま
た通常の乳化重合に使用される非イオン界面活性
剤との併用も可能である。また、重合開始剤とし
ては過硫酸アンモニウム、過硫酸カリウムの如き
過硫酸塩、過酸化水素、過酸化ベンゾイルの如き
過酸化物あるいは、過硫酸塩とアルカリ金属の亜
硫酸塩、重亜硫酸塩などのような還元剤を組み合
わせたレドツクス系などが挙げられる。
本発明に係るエマルジヨン系感圧性接着剤の好
ましい製造法を示すと、先ず特定粒径の微粒子を
含む重合体エマルジヨンを製造するには、前記単
量体混合物をその乳化剤の種類および使用量を調
整して水媒体中に均一に分散混合させた後、所定
の重合開始剤を加えて60〜80℃の加熱下に１〜３
時間乳化重合を行なう。次いで、微粒子を含む重
合体エマルジヨンが生成した後、追加の重合開始
剤を添加し（乳化剤は追加せず）感圧性接着剤成
分となる単量体混合物を滴下しながら、60〜80℃
の加熱下に１〜４時間かけて第１段階の反応で得
られた重合体エマルジヨンの架橋された微粒子存
在下でラジカル重合させて重合体エマルジヨン組
成物を得る。このラジカル重合によつて、エマル
ジヨン中の上記微粒子表面には感圧性接着剤の厚
層状の壁が生成すると推測される。
ここで使用されるラジカル重合によつて感圧性
接着剤を生成する単量体混合物は、アクリル酸又
はメタクリル酸のアルキルエステル単量体（アル
キル基の炭素数１〜10個）および官能基を有する
ビニル系単量体を主体とする単量体混合物が用い
られ、その使用量は多く設定され架橋された微粒
子を構成する前記単量体混合物１重量部に対して
５〜50重量部の範囲で使用される。また、追加の
重合開始剤としては、第１段階の反応に用いたも
のと同様の開始剤が用いられ、その使用量は感圧
性接着剤を生成する単量体混合物100重量部に対
して0.05〜0.5重量部が適当である。
上記の感圧性接着剤を生成する単量体混合物と
しては、具体的にはアクリル酸２エチルヘキシ
ル、アクリル酸ブチル、アクリル酸イソオクチ
ル、メタクリル酸ブチル、メタクリル酸プロピル
などのアクリル酸又はメタクリル酸のアルキルエ
ステル単量体100重量部に対して、アクリル酸、
イタコン酸、マレイン酸、フマール酸、メタクリ
ル酸、アクリル酸ヒドロキシエチル、メタクリル
酸ヒドロキシエチルなどの官能基を有するビニル
系単量体１〜10重量部からなる混合物が使用され
るが、場合によりスチレン、アクリロニトリル、
酢酸ビニル、メタクリロニトリル等の共重合可能
な単量体を併用することができる。ここでアクリ
ル酸又はメタクリル酸のアルキルエステル単量体
は、感圧性接着剤特性を付与する主たる成分であ
り、官能基を有するビニル系単量体は被着体への
接着性向上または改質用に使用されるものであ
る。
このようにして調整された重合体エマルジヨン
組成物は、機械的、化学的に安定なエマルジヨン
形態を提供し、乾燥後の皮膜は良好な接着力と凝
集力を有し、かつ耐水性が良好であり比較的高湿
下でも凝集力の低下が殆んど見られない優れた感
圧性接着剤特性を示す。
かかる好結果を示す理由については明確ではな
いが、重合体エマルジヨンの微粒子が架橋構造を
有するため、感圧性接着剤成分となる単量体混合
物を重合したあとの重合体エマルジヨン組成物か
ら得られる皮膜は、高凝集力を保持し、かつ高接
着力を有するものと考えられる。また、重合体エ
マルジヨンの架橋された微粒子を生成する単量体
混合物１重量部に対して、感圧性接着剤を生成す
る単量体混合物を５〜50重量部の範囲で使用する
事により、微粒子を生成する単量体混合物量に比
べて感圧性接着剤を生成する単量体混合物量が多
いため、最終的に得られる重合体エマルジヨン組
成物に占める乳化剤量はポリマー成分に対して約
0.04〜３重量％、実用的には約0.1〜１重量％と
少なくなり、従つて乾燥後の接着剤皮膜は耐水性
が大幅に向上するものと推察される。
本発明のエマルジヨン系感圧性接着剤は、さら
に必要に応じて着色剤、充填剤、老化防止剤など
の配合剤を添加することができる。
このようにして得られた感圧性接着剤は、エマ
ルジヨン自体機械的、化学的に安定であり、乾燥
後の接着剤皮膜は良好な接着力と凝集力を有し、
かつ耐水性が優れているため、感圧性接着テー
プ、シート類、ラベル等の各種用途に有用であ
る。
以下、本発明を実施例により具体的に説明する
が、これらの実施例に限定されるものではない。
なお、以下において部とあるのは重量部を意味
し、また接着力、凝集力および吸水率の試験は下
記の方法で測定したものである。
〔接着力〕
25μmのポリエステルフイルムの両面にエマル
ジヨン系感圧性接着剤を乾燥後の厚さが各々
50μmとなるように塗布し、100℃で３分間乾燥し
て両面接着テープを作製し、JISZ―1528に準じ
て180度引剥し接着力（ｇ／20mm）を測定した。
〔凝集力〕
接着力試験に用いたものと同様の両面接着テー
プの25cm×25cm角片を、２枚のアルミニウム板
（１mm厚）の間に貼り合わせ、せん断接着力
（Kg／cm2）を測定した。
〔吸水率〕
25μmのポリエステルフイルムの片面にエマル
ジヨン系感圧性接着剤を乾燥後の厚さが50μmと
なるように塗布し、100℃で３分間乾燥した後、
水中に浸漬し所定時間後に引上げ、表面の水滴を
除去してその重量を測定し吸水率（％）を求め
た。
実施例 １
温度計、撹拌器、窒素導入管および還流冷却管
を備えた500ml反応容器内に、アクリル酸エチル
２部、アクリル酸ブチル2.25部、エチレングリコ
ールジメタクリレート（新中村化学工業社製NK
エステルIG）0.75部、ラウリル硫酸ソーダ0.75部
およびイオン交換水160部からなる混合物を加え、
窒素気流下にて撹拌しながら加熱し、反応系が約
65℃に達した時点で重合開始剤として過硫酸アン
モニウム0.1部を加えて重合を開始させ、約１時
間重合反応を行ない平均粒径470Å、重合率約100
％の重合体エマルジヨンを得た。この微粒子エマ
ルジヨンのアセトン抽出（24時間）でのゲル分率
は85％であつた。
次いで、重合開始剤として0.2部の過硫酸アン
モニウムを上記重合体エマルジヨン中に添加し、
アクリル酸ブチル92.5部、アクリル酸2.5部から
なる単量体混合物を約２時間かけて滴下しながら
65℃にて反応させた。重合終了後、約75℃まで反
応系を昇温させ、約１時間熟成させて重合体エマ
ルジヨン組成物を得た。このエマルジヨン組成物
の平均粒径は1480Å、PH約３、粘度約0.2ポイズ
であつた。
上記重合体エマルジヨン組成物を撹拌しなが
ら、約25％アンモニア水溶液を滴下して約50ポイ
ズの粘度に増粘した後、25μmのポリエステルフ
イルムの片面もしくは両面に乾燥後の厚さ50μm
になるように塗布乾燥して、感圧性接着テープ試
料を作成した。
比較例 １
アクリル酸エチル２部、アクリル酸ブチル３
部、ラウリル硫酸ソーダ0.75部およびイオン交換
水160部からなる混合物を実施例１と同様の反応
容答器内に仕込み、重合開始剤として過硫酸アン
モニウム0.1部を加えて65℃の加熱下で１時間重
合反応を行ない、平均粒径450Åの重合体エマル
ジヨンを得た。
次いで、過硫酸アンモニウム0.2部を上記重合
体エマルジヨン中に添加し、アクリル酸ブチル
92.5部およびアクリル酸2.5部の混合物を約２時
間かけて滴下しながら65℃にて反応させた。さら
に熟成を行なつて平均粒径1400Åの重合体エマル
ジヨン組成物を得た。
次に、上記組成物を用いて実施例１と同様にし
て感圧性接着テープ試料を作成した。
比較例 ２
アクリル酸ブチル94.75部、アクリル酸エチル
２部、アクリル酸2.5部、エチレングリコールジ
メタクリレート（新中村化学工業社製商品名NK
エステルIG）0.75部、ラウリル硫酸ソーダ0.75部
およびイオン交換水160部からなる混合物を実施
例１と同様の反応容器内に仕込み、重合開始剤と
して過硫酸アンモニウム0.2部を添加し65℃の加
熱下にて約２時間乳化重合させ、次いで約75℃で
１時間熟成して平均粒径2300Åの重合体エマルジ
ヨン組成物を得た。この組成物は、実施例１に使
用した単量体のすべてを同時に乳化重合させたも
のである。
次に、上記組成物を用いて実施例１と同様にし
て感圧性接着テープ試料を作成した。
比較例 ３
アクリル酸２エチルヘキシル15部、アクリル酸
５部、ジエチレングリコールジメタクリレート
（新中村化学工業社製商品名NKエステル2G）0.5
部、ラウリル硫酸ソーダ0.075部およびイオン交
換水160部からなる混合物を実施例１と同様の反
応容器内に仕込み、過硫酸アンモニウム0.1部を
加えて65℃の加熱下で１時間重合反応を行ない、
平均粒径1050Åの重合体エマルジヨンを得た。
次いで、過硫酸アンモニウム0.2部を上記エマ
ルジヨン中に添加し、アクリル酸ブチル75部およ
びメタアクリル酸4.5部の混合物を約２時間かけ
て滴下しながら65℃で反応させた。さらに熱成を
行なつて平均粒径3200Åの重合体エマルジヨン組
成物を得た。この組成物を用いて実施例１と同様
にして、感圧性接着テープ試料を作成した。
上記実施例１および比較例１〜３の各感圧性接
着テープ試料の接着力、吸水率、凝集力および白
化の度合について試験した結果は、第１表の通り
であつた。
The present invention relates to an emulsion-based pressure-sensitive adhesive,
More specifically, a monomer mixture that produces a pressure-sensitive adhesive is radically polymerized in the presence of fine particles in a crosslinked polymer emulsion that have a fine particle size within a specific range and serve as emulsion particle cores. The present invention relates to a new emulsion-based pressure-sensitive adhesive obtained by the method and a method for producing the same. In recent years, acrylic pressure-sensitive adhesives have become widely used in place of conventional natural rubber-based and synthetic rubber-based pressure-sensitive adhesives because of their excellent adhesive properties and durability. Furthermore, among this type of pressure-sensitive adhesives, emulsion-based pressure-sensitive adhesives that do not use organic solvents have recently become particularly important from the viewpoints of resource saving, non-pollution, and environmental hygiene. Conventionally known acrylic emulsion pressure-sensitive adhesives are generally based on acrylic monomers such as acrylic esters and methacrylic esters, and optionally contain modified acrylic acid, styrene, acrylonitrile, etc. It is obtained by adding monomers and emulsion polymerizing in an aqueous medium, but when applied to pressure-sensitive adhesive tapes, the adhesive properties are significantly different between the dry state immediately after production and the water absorption state over time. You can see the shortcomings that change. The reason for this is that the emulsifiers used during emulsion polymerization, such as anionic surfactants and nonionic surfactants, are required to maintain the stability of the produced emulsion system, rather than from the viewpoint of the agent polymerization operation. This is because it is used in large quantities. Therefore, the pressure-sensitive adhesive film obtained by heating and drying the above polymer emulsion has a high water absorption rate and poor water resistance in terms of adhesive properties, and when immersed in water, it turns white within 24 hours and almost disappears. Some functions will be lost. Furthermore, these acrylic emulsion pressure-sensitive adhesives are generally used with various crosslinking agents added after polymerization. In this case, there are problems such as the stability of the emulsion deteriorates when a crosslinking agent is added to the emulsion polymer, it is difficult to mix the crosslinking agent uniformly, and a mixing step is required. The present inventors have conducted intensive research on the stability of the emulsion itself in emulsion-based pressure-sensitive adhesives, the pressure-sensitive adhesive properties of the pressure-sensitive adhesive layer as a final film form, and the improvement of its water resistance. By radically polymerizing a monomer mixture to form a pressure-sensitive adhesive in the presence of fine particles in a crosslinked polymer emulsion with a fine particle size in a specific range obtained by controlling The present invention was developed based on the discovery that it is possible to secure excellent pressure-sensitive adhesive properties that maintain high adhesive strength and high cohesive strength, and to simultaneously secure improvements in the stability and water resistance of the emulsion itself. That is, the present invention provides a mixture of a monomer having one ethylenic double bond and a copolymerizable polyfunctional monomer obtained by emulsion polymerization in an aqueous medium containing a relatively large amount of an emulsifier and a polymerization initiator. In the presence of a polymer emulsion consisting of crosslinked fine particles with an average particle diameter of 250 to 850 Å, an alkyl ester monomer of acrylic acid or methacrylic acid (alkyl group having 1 to
A new emulsion system consisting of a polymer emulsion composition obtained by radical polymerization of a monomer mixture that produces a pressure-sensitive adhesive by polymerization mainly consisting of 10 pieces) and vinyl monomers copolymerizable with these monomers. A pressure sensitive adhesive is provided. In the present invention, the polymer emulsion consisting of crosslinked fine particles serving as a matrix has an average particle size of 250 to 250.
It needs to be in the range of 850 Å. When the average particle size is 850 Å or more, the next step is to mechanically polymerize the polymer emulsion composition by radically polymerizing the monomer mixture in the presence of the particles to form the pressure-sensitive adhesive.
There is a tendency for chemical stability to be impaired and various properties as a pressure-sensitive adhesive to deteriorate. On the other hand, if the average particle size is 250 Å or less, it becomes necessary to add an extremely large amount of emulsifier to the aqueous medium in the reaction operation to obtain the fine-particle emulsion polymer, and the polymer emulsion composition obtained in the next step is not suitable for the purpose of the present invention. Therefore, the effect of improving water resistance cannot be expected. In the present invention, the compound constituting the fine particles used is a mixture of a monomer having one ethylenic double bond and a copolymerizable polyfunctional monomer for providing crosslinking. As a monomer having one ethylenic double bond, an alkyl ester of acrylic acid or methacrylic acid (alkyl group having 1 to 10 carbon atoms) or other vinyl monomer copolymerizable with the above alkyl ester are preferably used, and examples of alkyl esters of acrylic acid or methacrylic acid include ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. These may be used alone or in combination of two or more. Other vinyl monomers that can be copolymerized with these alkyl esters include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, acrylonitrile, vinyl acetate, methacrylonitrile, and styrene. , is mixed in an amount of 50% by weight or less of the above alkyl ester monomer. On the other hand, as a copolymerizable polyfunctional monomer, polyacrylic acid (or methacrylic acid), which is a polyhydric alcohol, is used.
Ester monomers and divinylbenzene are preferably used, and examples of the ester monomers include ethylene glycol dimethacrylate (or acrylate), diethylene glycol dimethacrylate (or acrylate), triethylene glycol dimethacrylate (or acrylate), and polyethylene glycol dimethacrylate (or acrylate). methacrylate (or acrylate), polypropylene glycol dimethacrylate (or acrylate), trimethylolpropane trimethacrylate (or acrylate),
Examples include tetramethylolmethanetetramethacrylate (or acrylate). These copolymerizable polyfunctional monomers are components that crosslink the fine particles of the polymer emulsion, and are in the range of 5 to 40 parts by weight per 100 parts by weight of the monomer having one ethylenic double bond. It is preferable to use it in As a result, a crosslinked structure is imparted to the polymer emulsion during the generation of fine particles through emulsion polymerization, so that the emulsion-like structure obtained by radical polymerization of the monomer mixture that forms the pressure-sensitive adhesive in the presence of this polymer emulsion Pressure adhesives exhibit excellent cohesive and adhesive strength. Moreover, the fact that there is no need to newly add a crosslinking agent also contributes to improving the stability of the emulsion. The degree of crosslinking of emulsion fine particles is determined by the gel fraction of approximately 50 to 95 in acetone extraction (24 hours).
% is appropriate, and it is preferable that the gel fraction is relatively high. A mixture of a monomer having one ethylenic double bond and a copolymerizable polyfunctional monomer to form a polymer emulsion is emulsion polymerized to obtain an average particle size.
When producing crosslinked fine particles of 250 to 850 Å, relatively large amounts of emulsifier and polymerization initiator are used. The amounts of the emulsifier and polymerization initiator to be used should be determined so that new particles are not formed and are not excessive. For this reason, the emulsifier is used in an amount of 2 to 20 parts by weight, preferably 4 to 18 parts by weight, based on 100 parts by weight of the monomer mixture forming the polymer emulsion, and the polymerization initiator is used in an amount of 4 to 18 parts by weight based on 100 parts by weight of the monomer mixture forming the polymer emulsion. It is used in an amount of 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the mixture. In this way, by using a relatively large amount of emulsifier and polymerization initiator compared to normal emulsion polymerization, the number of micelles formed by the emulsifier in the aqueous medium is increased, and the number of generated radicals is increased. As a result, the number of particles of the polymer emulsion produced increases, and fine particles having a predetermined particle size can be obtained. However, as described below, the amount of emulsifier used is only a small amount in the polymer component of the final polymer emulsion composition, about 0.04 to 3% by weight, and practically about 0.1 to 1% by weight. It is considered a range. Examples of emulsifiers used in the present invention include fatty acid salts, higher alcohol sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfuccinates, alkyl phosphate salts, and polyoxyethylene sulfate salts. Anionic surfactants can be used, and they can also be used in combination with nonionic surfactants commonly used in emulsion polymerization. In addition, as a polymerization initiator, persulfates such as ammonium persulfate and potassium persulfate, peroxides such as hydrogen peroxide and benzoyl peroxide, or sulfites and bisulfites of persulfates and alkali metals are used. Examples include redox systems that combine reducing agents. A preferred method for producing the emulsion-based pressure-sensitive adhesive according to the present invention is as follows: First, in order to produce a polymer emulsion containing fine particles of a specific particle size, the monomer mixture is mixed with the monomer mixture and the type and amount of emulsifier used are adjusted. After uniformly dispersing and mixing in an aqueous medium, a specified polymerization initiator is added and heated at 60 to 80°C for 1 to 3 hours.
Carry out time emulsion polymerization. Then, after a polymer emulsion containing fine particles is formed, an additional polymerization initiator is added (no emulsifier is added) and the monomer mixture that will become the pressure-sensitive adhesive component is added dropwise at 60-80°C.
A polymer emulsion composition is obtained by radical polymerization in the presence of crosslinked fine particles of the polymer emulsion obtained in the first stage reaction over a period of 1 to 4 hours under heating. It is presumed that this radical polymerization produces a thick wall of pressure-sensitive adhesive on the surface of the fine particles in the emulsion. The monomer mixture used here to produce the pressure-sensitive adhesive by radical polymerization is an alkyl ester monomer of acrylic acid or methacrylic acid (alkyl group having 1 to 10 carbon atoms) and a functional group. A monomer mixture mainly composed of vinyl monomers is used, and the amount used is set in a large amount, ranging from 5 to 50 parts by weight per 1 part by weight of the monomer mixture constituting the crosslinked fine particles. used. Further, as an additional polymerization initiator, the same initiator as that used in the first stage reaction is used, and the amount used is 0.05 parts by weight per 100 parts by weight of the monomer mixture forming the pressure-sensitive adhesive. ~0.5 part by weight is suitable. The monomer mixture forming the pressure-sensitive adhesive mentioned above specifically includes alkyl esters of acrylic acid or methacrylic acid such as 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate, butyl methacrylate, propyl methacrylate, etc. For 100 parts by weight of monomer, acrylic acid,
A mixture consisting of 1 to 10 parts by weight of a vinyl monomer having a functional group such as itaconic acid, maleic acid, fumaric acid, methacrylic acid, hydroxyethyl acrylate, or hydroxyethyl methacrylate is used, but in some cases styrene, acrylonitrile,
Copolymerizable monomers such as vinyl acetate and methacrylonitrile can be used in combination. Here, the alkyl ester monomer of acrylic acid or methacrylic acid is the main component that imparts pressure-sensitive adhesive properties, and the vinyl monomer with a functional group is used to improve or modify the adhesion to the adherend. It is used for. The polymer emulsion composition prepared in this way provides a mechanically and chemically stable emulsion form, and the film after drying has good adhesion and cohesion, and good water resistance. It exhibits excellent pressure-sensitive adhesive properties with almost no decrease in cohesive strength even under relatively high humidity conditions. The reason for such good results is not clear, but because the fine particles of the polymer emulsion have a crosslinked structure, the film obtained from the polymer emulsion composition after polymerizing the monomer mixture that becomes the pressure-sensitive adhesive component is not clear. is considered to have high cohesive strength and high adhesive strength. In addition, by using 5 to 50 parts by weight of the monomer mixture that forms the pressure-sensitive adhesive for 1 part by weight of the monomer mixture that forms the crosslinked fine particles of the polymer emulsion, the fine particles Since the amount of the monomer mixture that forms the pressure-sensitive adhesive is larger than the amount of the monomer mixture that forms the pressure-sensitive adhesive, the amount of emulsifier in the final polymer emulsion composition is approximately
The amount is as low as 0.04 to 3% by weight, practically about 0.1 to 1% by weight, and it is therefore presumed that the water resistance of the adhesive film after drying is greatly improved. The emulsion-based pressure-sensitive adhesive of the present invention may further contain additives such as colorants, fillers, and anti-aging agents, if necessary. The pressure-sensitive adhesive thus obtained is mechanically and chemically stable as an emulsion itself, and the adhesive film after drying has good adhesive strength and cohesive strength.
Since it also has excellent water resistance, it is useful for various applications such as pressure-sensitive adhesive tapes, sheets, and labels. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to these examples.
In addition, in the following, parts mean parts by weight, and tests for adhesive strength, cohesive strength, and water absorption were measured by the following methods. [Adhesive strength] Emulsion-based pressure-sensitive adhesive is applied to both sides of a 25μm polyester film to a different thickness after drying.
It was applied to a thickness of 50 μm and dried at 100° C. for 3 minutes to produce a double-sided adhesive tape, and the adhesive strength (g/20 mm) was measured at 180 degrees according to JISZ-1528. [Cohesive strength] A 25 cm x 25 cm square piece of double-sided adhesive tape similar to that used in the adhesive strength test was pasted between two aluminum plates (1 mm thick), and the shear adhesive strength (Kg/cm 2 ) was measured. It was measured. [Water absorption rate] Emulsion-based pressure-sensitive adhesive was applied to one side of a 25μm polyester film to a dry thickness of 50μm, and after drying at 100℃ for 3 minutes,
It was immersed in water and pulled out after a predetermined period of time, water droplets on the surface were removed, and its weight was measured to determine the water absorption rate (%). Example 1 In a 500 ml reaction vessel equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 2 parts of ethyl acrylate, 2.25 parts of butyl acrylate, and ethylene glycol dimethacrylate (NK manufactured by Shin Nakamura Chemical Co., Ltd.) were added.
Add a mixture consisting of 0.75 parts of ester IG), 0.75 parts of sodium lauryl sulfate, and 160 parts of ion-exchanged water,
Heat while stirring under a nitrogen stream until the reaction system reaches approx.
When the temperature reached 65°C, 0.1 part of ammonium persulfate was added as a polymerization initiator to initiate polymerization, and the polymerization reaction was carried out for about 1 hour, resulting in an average particle size of 470 Å and a polymerization rate of about 100.
% polymer emulsion was obtained. The gel fraction of this fine particle emulsion after acetone extraction (24 hours) was 85%. Then, 0.2 parts of ammonium persulfate was added as a polymerization initiator into the polymer emulsion,
A monomer mixture consisting of 92.5 parts of butyl acrylate and 2.5 parts of acrylic acid was added dropwise over about 2 hours.
The reaction was carried out at 65°C. After the polymerization was completed, the reaction system was heated to about 75°C and aged for about 1 hour to obtain a polymer emulsion composition. This emulsion composition had an average particle size of 1480 Å, a pH of about 3, and a viscosity of about 0.2 poise. While stirring the above polymer emulsion composition, about 25% ammonia aqueous solution was added dropwise to increase the viscosity to about 50 poise, and then it was coated on one or both sides of a 25 μm polyester film to a thickness of 50 μm after drying.
A pressure-sensitive adhesive tape sample was prepared by applying and drying the adhesive tape so as to give a pressure-sensitive adhesive tape sample. Comparative example 1 2 parts of ethyl acrylate, 3 parts of butyl acrylate
A mixture of 0.75 parts of sodium lauryl sulfate and 160 parts of ion-exchanged water was placed in the same reaction vessel as in Example 1, 0.1 part of ammonium persulfate was added as a polymerization initiator, and the mixture was heated at 65°C for 1 hour. A polymerization reaction was carried out to obtain a polymer emulsion with an average particle size of 450 Å. Next, 0.2 parts of ammonium persulfate was added to the above polymer emulsion, and butyl acrylate was added.
A mixture of 92.5 parts of acrylic acid and 2.5 parts of acrylic acid was added dropwise over about 2 hours to react at 65°C. Further aging was performed to obtain a polymer emulsion composition with an average particle size of 1400 Å. Next, a pressure sensitive adhesive tape sample was prepared in the same manner as in Example 1 using the above composition. Comparative Example 2 94.75 parts of butyl acrylate, 2 parts of ethyl acrylate, 2.5 parts of acrylic acid, ethylene glycol dimethacrylate (trade name: NK, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
A mixture consisting of 0.75 parts of ester IG), 0.75 parts of sodium lauryl sulfate, and 160 parts of ion-exchanged water was placed in the same reaction vessel as in Example 1, 0.2 parts of ammonium persulfate was added as a polymerization initiator, and the mixture was heated at 65°C. The mixture was subjected to emulsion polymerization for about 2 hours, and then aged at about 75° C. for 1 hour to obtain a polymer emulsion composition with an average particle size of 2300 Å. In this composition, all of the monomers used in Example 1 were simultaneously emulsion polymerized. Next, a pressure sensitive adhesive tape sample was prepared in the same manner as in Example 1 using the above composition. Comparative Example 3 15 parts of 2-ethylhexyl acrylate, 5 parts of acrylic acid, 0.5 parts of diethylene glycol dimethacrylate (trade name: NK Ester 2G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A mixture consisting of 0.075 parts of sodium lauryl sulfate and 160 parts of ion-exchanged water was placed in the same reaction vessel as in Example 1, 0.1 part of ammonium persulfate was added, and a polymerization reaction was carried out under heating at 65°C for 1 hour.
A polymer emulsion with an average particle size of 1050 Å was obtained. Next, 0.2 parts of ammonium persulfate was added to the above emulsion, and a mixture of 75 parts of butyl acrylate and 4.5 parts of methacrylic acid was added dropwise over about 2 hours to react at 65°C. Further thermal formation was performed to obtain a polymer emulsion composition with an average particle size of 3200 Å. A pressure-sensitive adhesive tape sample was prepared using this composition in the same manner as in Example 1. The pressure-sensitive adhesive tape samples of Example 1 and Comparative Examples 1 to 3 were tested for adhesive strength, water absorption, cohesive force, and degree of whitening, and the results are shown in Table 1.
【表】
(注) ○：ほとんど白化が認められない
△：少々の白化が認められる。
×：白化の度合いが激しい。
実施例 ２〜５
実施例１の単量体配合に代えて第２表に示す単
量体群を用い、他は実施例１と同様の反応条件で
重合体エマルジヨンおよび重合体エマルジヨン組
成物からなる感圧性接着剤を製造した。
なお、第２表においては、、微粒子を生成する
ための単量体群を「単量体混合物Ａ」とし、感圧
性接着剤成分となる単量体群を「単量体混合物
Ｂ」として示した。
また、第３表は実施例２〜５のエマルジヨン系
感圧性接着剤を用いて、実施例１と同様にして作
成した感圧性接着テープ試料の試験結果を示して
いる。[Table] (Note) ○: Almost no whitening observed
Δ: Slight whitening is observed.
×: Severe degree of whitening.
Examples 2 to 5 Polymer emulsions and polymer emulsion compositions were prepared using the monomer groups shown in Table 2 in place of the monomer blend in Example 1, and using the same reaction conditions as in Example 1 except for the monomer groups shown in Table 2. A pressure sensitive adhesive was produced. In addition, in Table 2, the monomer group for producing fine particles is shown as "monomer mixture A," and the monomer group that becomes the pressure-sensitive adhesive component is shown as "monomer mixture B." Ta. Further, Table 3 shows the test results of pressure sensitive adhesive tape samples prepared in the same manner as in Example 1 using the emulsion type pressure sensitive adhesives of Examples 2 to 5.
【表】【table】
【表】【table】
【表】
(注) 両面テープの白化の度合の項の記号は第１表
と同じ
[Table] (Note) The symbols for the degree of whitening of double-sided tape are the same as in Table 1.
Claims (1)
重合性多官能単量体との混合物を比較的多量の乳
化剤および重合開始剤（該混合物100重量部に対
して乳化剤２〜20重量部および重合開始剤0.5〜
５重量部）を含む水媒体中で乳化重合して得られ
る架橋された平均粒径250〜850Åの微粒子からな
る重合体エマルジヨンの存在下で、アクリル酸又
はメタクリル酸のアルキルエステル単量体（アル
キル基の炭素数１〜10個）およびこれらと共重合
可能なビニル系単量体を主体とする重合により感
圧性接着剤を生成する単量体混合物をラジカル重
合させて得られる重合体エマルジヨン組成物から
なる新規なエマルジヨン系感圧性接着剤。 ２ エチレン性二重結合を１個有する単量体が、
アクリル酸又はメタクリル酸のアルキルエステル
単量体（アルキル基の炭素数１〜10個）もしく
は、上記アルキルエステル単量体と共重合可能な
他のビニル系単量体であり、共重合性多官能単量
体が多価アルコールのポリアクリル酸（又はメタ
クリル酸）エステル単量体およびジビニルベンゼ
ンから選ばれたものである特許請求の範囲第１項
記載のエマルジヨン系感圧性接着剤。 ３ 微粒子からなる重合体エマルジヨンを生成す
る単量体混合物はエチレン性二重結合を１個有す
る単量体100重量部に対して、共重合性多官能単
量体が５〜40重量部配合されている特許請求の範
囲第１項ないし第２項記載のエマルジヨン系感圧
性接着剤。 ４ 微粒子からなる重合体エマルジヨンを生成す
る単量体混合物１重量部に対して、感圧性接着剤
を生成する単量体混合物５〜50重量部の割合で使
用する特許請求の範囲第１項ないし第３項記載の
エマルジヨン系感圧性接着剤。[Claims] 1. A mixture of a monomer having one ethylenic double bond and a copolymerizable polyfunctional monomer is mixed with a relatively large amount of an emulsifier and a polymerization initiator (per 100 parts by weight of the mixture). 2-20 parts by weight of emulsifier and 0.5-20 parts by weight of polymerization initiator
An alkyl ester monomer of acrylic acid or methacrylic acid (alkyl A polymer emulsion composition obtained by radical polymerization of a monomer mixture that produces a pressure-sensitive adhesive by polymerization, mainly consisting of a group having 1 to 10 carbon atoms) and a vinyl monomer copolymerizable with these. A new emulsion-based pressure-sensitive adhesive consisting of: 2 A monomer having one ethylenic double bond is
It is an alkyl ester monomer of acrylic acid or methacrylic acid (alkyl group has 1 to 10 carbon atoms) or other vinyl monomer that can be copolymerized with the above alkyl ester monomer, and is a copolymerizable polyfunctional The emulsion-based pressure-sensitive adhesive according to claim 1, wherein the monomer is selected from polyacrylic acid (or methacrylic acid) ester monomers of polyhydric alcohols and divinylbenzene. 3. The monomer mixture for producing a polymer emulsion consisting of fine particles contains 5 to 40 parts by weight of a copolymerizable polyfunctional monomer to 100 parts by weight of a monomer having one ethylenic double bond. An emulsion-based pressure-sensitive adhesive according to claims 1 and 2. 4. Claims 1 to 4 in which the monomer mixture forming the pressure-sensitive adhesive is used in a ratio of 5 to 50 parts by weight per 1 part by weight of the monomer mixture forming the polymer emulsion consisting of fine particles. The emulsion-based pressure-sensitive adhesive according to item 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3543782A JPS58152078A (en) | 1982-03-05 | 1982-03-05 | Novel emulsion-type pressure-sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3543782A JPS58152078A (en) | 1982-03-05 | 1982-03-05 | Novel emulsion-type pressure-sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58152078A JPS58152078A (en) | 1983-09-09 |
| JPH0136512B2 true JPH0136512B2 (en) | 1989-08-01 |
Family
ID=12441822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3543782A Granted JPS58152078A (en) | 1982-03-05 | 1982-03-05 | Novel emulsion-type pressure-sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58152078A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63270780A (en) * | 1986-12-06 | 1988-11-08 | Lion Corp | Adhesive composition |
| AT394779B (en) * | 1988-12-20 | 1992-06-25 | Universale Grundbau | INCLINATION MEASURING SYSTEM FOR SLOT WALLS |
| US7531595B2 (en) * | 2006-03-08 | 2009-05-12 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing silica nanoparticles |
| US7645827B2 (en) * | 2006-03-08 | 2010-01-12 | 3M Innovative Properties Company | High shear pressure-sensitive adhesive |
| JP6561476B2 (en) * | 2015-01-21 | 2019-08-21 | 日本ゼオン株式会社 | Acrylic rubber, acrylic rubber composition and extruded product |
-
1982
- 1982-03-05 JP JP3543782A patent/JPS58152078A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58152078A (en) | 1983-09-09 |
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