JPH0527669B2 - - Google Patents
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- Publication number
- JPH0527669B2 JPH0527669B2 JP59273857A JP27385784A JPH0527669B2 JP H0527669 B2 JPH0527669 B2 JP H0527669B2 JP 59273857 A JP59273857 A JP 59273857A JP 27385784 A JP27385784 A JP 27385784A JP H0527669 B2 JPH0527669 B2 JP H0527669B2
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- JP
- Japan
- Prior art keywords
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- weight
- polymer
- monomer
- spheres
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000000178 monomer Substances 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 239000007900 aqueous suspension Substances 0.000 claims description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 9
- 239000002998 adhesive polymer Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000005907 alkyl ester group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 description 21
- 230000001070 adhesive effect Effects 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 239000000123 paper Substances 0.000 description 7
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 229940048053 acrylate Drugs 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 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 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- XTSFUENKKGFYNX-UHFFFAOYSA-N bis(aziridin-1-yl)methanone Chemical compound C1CN1C(=O)N1CC1 XTSFUENKKGFYNX-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 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
- 239000000463 material Substances 0.000 description 2
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-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
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxypropyl Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-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
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
〔発明の目的〕
（産業上の利用分野）
本発明は各種被着体に対し被着体を汚さず、貼
付−剥離を繰り返し行うことのできる再剥離型粘
着剤組成物に関するものである。
粘着剤は簡便に接着できる特徴を有し、その作
業性、作業環境上の利点から多種多様の用途に使
用されており、各々の用途、耐性に応じた粘着剤
の設計が要望されている。その中で再剥離性を有
する粘着剤に対する開発への要望も強くなつてい
る。
従来の粘着剤を用いたシートやテープなどは
紙、プラスチツク、金属、ガラスなどの被着体に
貼付した後、これを剥離する際、粘着剤が残つて
被着体を汚したり、紙などの被着体が破断あるい
は紙などの基材が破断することが多く発生する。
また、貼付−剥離を繰り返し使用できない欠点も
有していた。
これら従来の粘着剤と異なり、再剥離型粘着剤
はシートやテープ等に利用する事により繰り返し
て貼つたり、剥離したりする事が可能になり、糊
移行もなく被着体を汚すこともなくなる。
（従来の技術）
再剥離型粘着シートは特開昭50−2736号公報に
示されている。この技術はアクリル酸アルキルエ
ステルとイオン性モノマーからなるモノマーを水
性懸濁重合することにより得られる重合球体と、
それを固着させ、接着剤表面から球体がはがれる
のを防止するため使用される結合剤からなつてい
る。結合剤は重合球体に化学的に作用してはなら
ない、換言すれば、固着作用をする結合剤は重合
球体に対し不活性であるべきであるとされてお
り、このようにして得られた粘着剤を用いること
により、貼付−剥離を繰り返し行うことができる
とされている。また、結合剤が重合球体に不活性
であるため結合剤と重合球体の密着性に欠け、貼
付−剥離の繰り返し使用時重合球体が被着体など
へ転移し、被着体やテープの背面を汚してしまう
ことが多い。
（発明が解決しようとする問題点）
本発明者らは上記の如き欠陥を除くために研究
した結果、極めて工業的に製造し易く、貯蔵安定
性、結合剤と重合球体の密着性、基材への密着
性、塗工性等に優れ、被着体やテープ背面を汚す
ことのない水性懸濁重合から得られる粘着性重合
球体を水性懸濁液のまま安定、均一に結合剤系に
分散する再剥離型粘着剤を得ることを見出し本発
明に至つたものである。
〔発明の構成〕
（問題点を解決するための手段）
即ち、本発明は、(a)炭素数４〜12のアルキル基
を有する（メタ）アクリル酸のアルキルエステル
80〜99.9重量％、(b) α−モノオレフインカルボ
ン酸もしくはそのアンモニウム塩0.1〜10重量％、
および(c)上記(a)、(b)両成分以外の共重合可能な単
量体０〜19.9重量％とからなる単量体成分を水性
懸濁重合することにより得られる平均粒子径が６
〜120μの粘着性重合球体(A)100重量部と、（メタ）
アクリル酸アルキルエステル系単量体を主成分と
し、共重合可能で反応性基を有する単量体を0.1
〜15重量％含有するビニル系単量体混合物を水性
媒体中で重合することにより得られる重合体(B)20
〜150重量部と、重合球体(A)中に含まれるカルボ
キシル基および重合体(B)中に含まれる反応性基と
反応する基を一分子中に２個以上有する架橋剤(C)
0.001〜５重量部とよりなる再剥離型粘着剤組成
物である。
本発明で重合球体(A)に使用される(a)成分の（メ
タ）アクリル酸アルキルエステルとしてはブチル
アクリレート、２−エチルヘキシルアクリレー
ト、イソオクチルアクリレート、イソノニルアク
リレート、ラウリルアクリレート、ブチルメタク
リレート、ラウリルメタクリレートなどが挙げら
れる。
(b)成分のα−モノオレインカルボン酸としては
アクリル酸、メタクリル酸、イタコン酸、マレイ
ン酸、クロトン酸などがあり、これらのアンモニ
ウム塩も同様に使用できる。
また(c)成分のビニル系単量体は懸濁重合安定性
及び粘着力と凝集力の調整を図るために用いられ
るもので、前者としてナトリウムアクリレート、
ナトリウムメタクリレートなどがあり、後者とし
てメチル（メタ）アクリレート、エチル（メタ）
アクリレート、酢酸ビニル、プロピオン酸ビニ
ル、スチレン、アクリロニトリル、（メタ）アク
リル酸ヒドロキシエチル、（メタ）アクリル酸ヒ
ドロキシプロピル、Ｎ，Ｎ−ジメチルアミノエチ
ルアクリレート、アクリル酸アミド、Ｎ−メトキ
シメチルアクリルアミド、Ｎ−メトキシメチルア
クリルアミド、Ｎ−ｎ−ブトキシメチルアクリル
＊アミドなどがあり、これらのビニル系単量体は
重合球体(A)の構成成分の19.9重量％までを単独で
または併用して用いる。
(a)成分の（メタ）アクリレートは粘着性を与え
る成分であり、少なくとも80％は必要であり、こ
れ以下では粘着性に欠除する。
(b)成分のα−モノオレフインカルボン酸もしく
はそのアンモニウム塩は、架橋剤(C)と結合する反
応部位となるものであり、その使用量は0.1〜５
重量％である。その使用量が５重量％を越えると
内部凝集力が高くなり過ぎ、粘着力が弱くなるた
め接着不能になる。また、使用量が0.1重量％よ
り少ないと重合反応時に粒子の凝固が生じやす
く、重合体(B)との密着性あるいは架橋剤(C)との反
応性に欠け、その結果、重合球体(A)が転移しやす
くなり被着体を汚す。好ましい使用量は0.5〜５
重量％である。
重合体(B)の主成分である（メタ）アクリル酸ア
ルキルエステル系単量体としては、炭素数が１〜
12までのアルキル基を有する（メタ）アクリル酸
のアルキルエステルがあり、重合体(B)はこの単量
体を少なくとも50重量％以上で含むものであるこ
とが好ましい。また、共重合可能で反応性基を有
する単量体としてはカルボキシル基、水酸基、エ
ポキシ基などの反応性基を有する共重合可能な単
量体をいい、0.1〜15％の範囲で単独または併用
することができる。好ましくはα−モノオレフイ
ンカルボン酸でアクリル酸、メタクリル酸、イタ
コン酸、マレイン酸、クロトン酸などがある。
また、重合体(B)の構成成分として、上記以外の
ビニル系単量体、例えば、酢酸ビニル、プロピオ
ン酸ビニル、スチレン、アクリロニトリルなどを
使用することができ、これらのビニル系単量体
は、粘着力と凝集力の調整を図り、微粘着性を保
持するため使用することが好ましい。
架橋剤(C)は、重合球体(A)中に含まれるカルボキ
シル基及び重合体(B)中に含まれる反応性基と反応
する基を一分子中に二個以上有するものをいい、
官能基としてアジリニル基
[Object of the Invention] (Industrial Application Field) The present invention relates to a removable pressure-sensitive adhesive composition that can be repeatedly applied and peeled off to various types of adherends without staining the adherends. Adhesives have the characteristic of being easy to adhere to, and are used in a wide variety of applications due to their workability and advantages in the working environment, and there is a demand for adhesives to be designed according to each application and resistance. Under these circumstances, there is a growing demand for the development of adhesives with removability. Sheets and tapes using conventional adhesives are attached to paper, plastic, metal, glass, and other adherends, and when they are removed, the adhesive remains and stains the adherend, or the paper, etc. The adherend or the base material such as paper often breaks.
It also had the disadvantage that it could not be used repeatedly by pasting and peeling. Unlike these conventional adhesives, removable adhesives can be applied and peeled off repeatedly by being used in sheets, tapes, etc., and there is no glue transfer and there is no need to stain the adherend. It disappears. (Prior Art) A removable pressure-sensitive adhesive sheet is disclosed in Japanese Patent Application Laid-Open No. 50-2736. This technology uses polymerized spheres obtained by aqueous suspension polymerization of a monomer consisting of an acrylic acid alkyl ester and an ionic monomer.
It consists of a bonding agent used to hold it together and prevent the sphere from peeling off from the adhesive surface. It is said that the binder must not act chemically on the polymer spheres, in other words, the binder that has a fixing effect should be inert towards the polymer spheres, and the adhesive obtained in this way It is said that by using the agent, repeated application and peeling can be performed. In addition, since the binder is inert to the polymer spheres, the adhesion between the binder and the polymer spheres is poor, and during repeated application and peeling, the polymer spheres may transfer to the adherend, etc., and the back surface of the adherend or tape may be It often gets dirty. (Problems to be Solved by the Invention) As a result of research to eliminate the above-mentioned defects, the present inventors found that it is extremely easy to manufacture industrially, has good storage stability, good adhesion between the binder and the polymerized spheres, Adhesive polymer spheres obtained through aqueous suspension polymerization that have excellent adhesion and coating properties and do not stain the adherend or the back of the tape are stably and uniformly dispersed in the binder system as an aqueous suspension. The inventors have discovered that a removable pressure-sensitive adhesive can be obtained, leading to the present invention. [Structure of the Invention] (Means for Solving the Problems) That is, the present invention provides (a) an alkyl ester of (meth)acrylic acid having an alkyl group having 4 to 12 carbon atoms;
80 to 99.9% by weight, (b) α-monoolefincarboxylic acid or its ammonium salt 0.1 to 10% by weight,
and (c) the average particle diameter obtained by aqueous suspension polymerization of a monomer component consisting of 0 to 19.9% by weight of a copolymerizable monomer other than both components (a) and (b) above.
100 parts by weight of ~120 μ sticky polymer spheres (A) and (Meta)
The main component is an acrylic acid alkyl ester monomer, and 0.1% of a monomer that is copolymerizable and has a reactive group.
Polymer (B)20 obtained by polymerizing a vinyl monomer mixture containing ~15% by weight in an aqueous medium
~150 parts by weight, and a crosslinking agent (C) having two or more groups in one molecule that react with the carboxyl group contained in the polymer sphere (A) and the reactive group contained in the polymer (B).
This is a removable adhesive composition comprising 0.001 to 5 parts by weight. Examples of the (meth)acrylic acid alkyl ester used in the polymer sphere (A) in the present invention include butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, lauryl acrylate, butyl methacrylate, and lauryl methacrylate. Examples include. Examples of the α-monooleic carboxylic acid of component (b) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid, and ammonium salts of these can also be used. In addition, the vinyl monomer (c) component is used to adjust suspension polymerization stability and adhesive force and cohesive force, and the former includes sodium acrylate,
These include sodium methacrylate, and the latter include methyl (meth)acrylate and ethyl (meth)acrylate.
Acrylate, vinyl acetate, vinyl propionate, styrene, acrylonitrile, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl acrylate, acrylamide, N-methoxymethylacrylamide, N- Examples include methoxymethylacrylamide and N-n-butoxymethylacryl*amide, and these vinyl monomers are used alone or in combination in an amount of up to 19.9% by weight of the constituent components of the polymer sphere (A). Component (a) (meth)acrylate is a component that provides tackiness, and at least 80% is required; anything less than this will result in a lack of tackiness. The α-monoolefincarboxylic acid or ammonium salt thereof, which is the component (b), serves as a reaction site for bonding with the crosslinking agent (C), and the amount used is 0.1 to 5.
Weight%. If the amount used exceeds 5% by weight, the internal cohesive force becomes too high and the adhesive strength becomes weak, making it impossible to bond. In addition, if the amount used is less than 0.1% by weight, the particles tend to coagulate during the polymerization reaction, resulting in poor adhesion with the polymer (B) or reactivity with the crosslinking agent (C), resulting in polymer spheres (A ) can easily transfer and stain the adherend. The preferred usage amount is 0.5-5
Weight%. The (meth)acrylic acid alkyl ester monomer, which is the main component of the polymer (B), has 1 to 1 carbon atoms.
There are alkyl esters of (meth)acrylic acid having up to 12 alkyl groups, and the polymer (B) preferably contains at least 50% by weight of this monomer. In addition, monomers that can be copolymerized and have reactive groups refer to monomers that can be copolymerized and have reactive groups such as carboxyl groups, hydroxyl groups, and epoxy groups, and can be used alone or in combination in the range of 0.1 to 15%. can do. Preferable α-monoolefin carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and crotonic acid. In addition, vinyl monomers other than those mentioned above, such as vinyl acetate, vinyl propionate, styrene, acrylonitrile, etc., can be used as constituent components of the polymer (B). It is preferable to use it in order to adjust the adhesive force and cohesive force and maintain slight tackiness. The crosslinking agent (C) has two or more groups in one molecule that react with the carboxyl group contained in the polymer sphere (A) and the reactive group contained in the polymer (B),
Azilinyl group as a functional group
【式】（ただ
しＲはＨまたは低級アルキル基）、エポキシ基
[Formula] (R is H or lower alkyl group), epoxy group
【式】などがあり、これらの基を一種類で
二つ以上の基をまたは二種類以上の基を併用して
二つ以上の基を持つた架橋剤を一種または二種以
上使用することも可能である。
架橋剤(C)しては、アジリジニル基を二個以上有
するものとして、例えば、１，６−ヘキサメチレ
ンジエチレン尿素、１，５−ペンタメチレンジエ
チレン尿素、ジフエニルメタン−ビス−４，４−
Ｎ，Ｎ−ジエチレン尿素、２，４−ジエチレン尿
素トルイジンなどがあり、エポキシ基を二個以上
有するものとして、例えば、エチレングリコール
ジグリシジルエーテル、ポリエチレングリコール
グリシジルエーテル、プロピレングリコールジグ
リシジルエーテル、ポリプロピレングリコールグ
リシジルエーテル、ネオペンチルグリコールジグ
リシジルエーテル、グリセロールポリグリシジル
エーテル、トリメチロールプロパンポリグリシジ
ルエーテル、ジグリセロールポリグリシジルエー
テル、ソルビトールポリグリシジルエーテル、ペ
ンタエリスリトールポリグリシジルエーテルなど
がある。
本発明の粘着性重合球体(A)は、単量体混合物を
水性媒体中で界面活性剤と重合開始剤必要ならば
懸濁安定剤などの存在下に懸濁重合することによ
つて得ることができる。界面活性剤としてはアニ
オン性あるいはノニオン性界面活性剤を使用する
が、特にアニオン性界面活性剤が好ましい。重合
開始剤は油溶性開始剤を用い、例えばベンゾイル
パーオキサイドなどを使用する。その他、重合調
節剤を使用しても差しつかえない。
水性懸濁重合で得られる粘着性重合球体(A)の粒
子径は３〜150μのものが良く、その平均粒系は
６〜120μのものが良い。6μ以下の平均粒系のも
のは非常な高速撹拌か、多量の分散剤を必要とし
非常な高速撹拌は機械上、工業的な安定製造は難
しく、多量の分散剤の使用は物性上問題がある。
120μ以上の平均粒径のものは重合球体が転移し、
被着体を汚す。
また、高濃度化を実現するために水性懸濁重合
体の下層の水層部分を必要に応じ適宜抜いて65％
程度までの高濃度にしてもよく、その状態でも本
水性懸濁重合体は凝集することなく安定である。
本発明の重合体(B)は、重合球体(A)を物理的に固
着する結合剤としての機能を有しており、重合球
体(A)100重量部に対し、固形分として20〜150重量
部添加する必要があり、重合球体(A)を安定、均一
に分散することができる。また、重合体(B)は重合
球体(A)を少なくとも部分的には覆つており、再剥
離機能を具備させるためには微粘着性を有するこ
とが好ましい。重合体(B)は、構成成分となる単量
体混合物を、水性媒体中で乳化重合させることに
より得ることができる。
粘着性重合球体(A)が被着体などへの転移を防ぐ
ためには、重合体(B)だけでは十分ではなく、架橋
剤(C)が必要となる。この架橋剤(C)により化学的に
重合球体(A)と重合体(B)を結びつけ重合球体の転移
を防ぐことができる。架橋剤の添加量は架橋剤の
種類により異なるが重合球体100重量部に対し
0.001〜５重量部が良く、好ましくは0.01〜３重
量部の範囲である。
この再剥離型粘着剤を基材に塗布するにあた
り、必要に応じ、下塗り剤を用いることが好まし
く、またテープ状、剥離紙を用いず粘着シートな
どを重ねた状態で使用する場合、適当な剥離処理
剤を用いることも使用基材、用途により施すこと
ができる。
以下に実施例を挙げて説明する。尚、実施例中
「部」、「％」とあるのはそれぞれ重量部、重量％
を示す。
（実施例）
実施例 １
温度計、還流冷却器、変速機付撹拌機及び窒素
導入管を備えた１の４つ口フラスコを用いて下
記なる成分を全量投入する。
２−エチルヘキシルアクリレート 85部
ｎ−ブチルアクリレート 35部
アクリル酸 3.5部
アニオン性界面活性剤 1.5部
過酸化ベンゾイル 0.5部
水 360部
窒素ガスパージをし、撹拌速度400回転前後で
撹拌する。その後徐々に昇温すると70〜75℃で重
合反応が始まり、80〜82℃位から急に激しくな
り、88〜90℃まで発熱する。その後、冷却し80℃
を保持させ、６時間重合反応させる。
その後、生成した水性懸濁液を30℃まで冷却さ
せ、その蒸発残分、粘度及び粒子径を確認した。
蒸発残分25％、粘度35cps／25℃、粒子径は小さ
い方で３〜5μ、大きい方で70〜90μで平均的には
約50〜60μであつた。
更に別の同様の装置を用い、アニオン性界面活
性剤7.5部、ノニオン性界面活性剤7.5部、水390
部、過硫酸アンモニウム２部、アクリル酸15部、
２−エチルヘキシルアクリレート170部、エチル
アクリレート190部を通常の乳化重合を行い蒸発
残分50％、粘度50cps／25℃のエマルジヨン液を
得た。このエマルジヨン液を先に生成した水性懸
濁液100部に対し、30部添加し、混合液を得た。
得られた混合液は蒸発残分30％、粘度3500cps／
25℃であつた。この混合液にソルビトールポリグ
リシジルエーテルを架橋剤として混合液100重量
部に対し0.5部添加し、得られた再剥離型粘着剤
を上質紙（55K）に乾燥後10〜15ｇ／m2になるよ
うに直接塗布乾燥させた。このようにして用意さ
れた粘着シートを作成した。
実施例 ２
実施例１に記述した装置及び手続きを用いて水
性懸濁重合を下記の成分により行つた。
２−エチルヘキシルアクリレート 120部
アクリル酸 2.0部
ナトリウムアクリレート 2.0部
アニオン性界面活性剤 1.5部
過酸化ベンゾイル 0.5部
水 360部
生成した水性懸濁液の蒸発残分25.5％、粘度
30cps／25℃、粒子径は平均で40〜50μであつた。
次いで実施例１に記述したエマルジヨン液を用い
上記水性懸濁重合液100部に対しエマルジヨン液
を25部添加し、更に架橋剤ジフエニルメタン−ビ
ス−４，４−Ｎ，Ｎジエチレン尿素の５％水性分
散体を固形分にして0.1部添加した混合液を得た。
得られた混合液は蒸発残分29％、粘度3500cps／
25℃であつた。次いで実施例１と同様に粘着シー
トを作成した。
実施例 ３
実施例１に記述した装置及び手続きを用いて水
性懸濁重合を下記の成分により行つた。
２−エチルヘキシルアクリレート 120部
イタコン酸 2.0部
ナトリウムアクリレート 2.0部
アニオン性界面活性剤 1.0部
ノニオン性界面活性剤 1.0部
過酸化ベンゾイル 0.5部
水 360部
生成した水性懸濁液の蒸発残分は26.0％、粘度
50cps／25℃、粒子径は平均で50〜60μであつた。
更に下記に記述する成分により実施例１に記述し
た通常のエマルジヨン重合方法を行いエマルジヨ
ン液を得た。
アニオン性界面活性剤7.5部、ノニオン性界面
活性剤7.5部、水390部、過硫酸アンモニウム２
部、メタクリル酸15部、２−エチルヘキシルアク
リレート150部、イソブチルアクリレート210部、
を用いて生成したエマルジヨン液は蒸発残分50.0
％、粘度45CP／25℃であつた。このエマルジヨ
ン液を先に生成した水性懸濁液100部に対し25部
添加し更に架橋剤ジフエニルメタン−ビス−４，
４−Ｎ，Ｎジエチレン尿素の５％水性分散体を固
形分にして0.1部添加し混合液を得た。得られた
混合液は蒸発残分は29％、粘度3500cps／25℃で
あつた。このようにして得られた再剥離型粘着剤
を実施例１と同様の手続きで粘着シートを作成し
た。
比較例 １
実施例１と同様な操作を行い、架橋剤ソルビト
ールポリグリシジルエーテルを添加せず、粘着シ
ートを作成した。
比較例 ２
実施例２と同様な操作を行い、架橋剤ジフエニ
ルメタン−ビス−４，４−Ｎ，Ｎ−ジエチレン尿
素を添加せずに、粘着シートを作成した。
比較例 ３
実施例３と同様な操作を行い、架橋剤ジフエニ
ルメタン−ビス−４，４−Ｎ，Ｎ−ジエチレン尿
素を添加せずに、粘着シートを作成した。
以上の操作より作成した粘着シートを用いJIS
−Ｚ−0237に準拠してステンレス板、及び上質紙
に対する接着力（ｇ／25mm）、粘着性を測定し上
質紙に繰り返し貼付−剥離を行つた時の糊の転移
状態などを観察した。
結果を表に示す。[Formula] etc., and it is also possible to use one or more types of crosslinking agents that have two or more groups in one type or two or more groups in combination. It is possible. Examples of the crosslinking agent (C) having two or more aziridinyl groups include 1,6-hexamethylene diethylene urea, 1,5-pentamethylene diethylene urea, diphenylmethane-bis-4,4-
N,N-diethylene urea, 2,4-diethylene urea toluidine, etc., and those having two or more epoxy groups include, for example, ethylene glycol diglycidyl ether, polyethylene glycol glycidyl ether, propylene glycol diglycidyl ether, and polypropylene glycol glycidyl. Examples include ether, neopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol polyglycidyl ether. The adhesive polymer spheres (A) of the present invention can be obtained by suspension polymerizing a monomer mixture in an aqueous medium in the presence of a surfactant, a polymerization initiator, and if necessary a suspension stabilizer. I can do it. As the surfactant, anionic or nonionic surfactants are used, and anionic surfactants are particularly preferred. As the polymerization initiator, an oil-soluble initiator is used, such as benzoyl peroxide. Other polymerization regulators may also be used. The particle diameter of the adhesive polymer spheres (A) obtained by aqueous suspension polymerization is preferably 3 to 150 μm, and the average particle size is preferably 6 to 120 μm. Products with an average particle size of 6μ or less require very high-speed stirring or a large amount of dispersant, and very high-speed stirring is mechanically difficult to produce stably on an industrial scale, and the use of large amounts of dispersant poses problems in terms of physical properties. .
For those with an average particle size of 120 μ or more, polymer spheres are transferred,
Contaminates the adherend. In addition, in order to achieve high concentration, the lower aqueous layer of the aqueous suspension polymer is removed as necessary to achieve a 65%
Even in such a high concentration, the aqueous suspension polymer is stable without agglomeration. The polymer (B) of the present invention has a function as a binder to physically fix the polymer spheres (A), and has a solid content of 20 to 150 parts by weight per 100 parts by weight of the polymer spheres (A). Polymer spheres (A) can be stably and uniformly dispersed. Further, the polymer (B) at least partially covers the polymer spheres (A), and preferably has slight adhesiveness in order to provide removability. Polymer (B) can be obtained by emulsion polymerizing a monomer mixture as a constituent component in an aqueous medium. In order to prevent the adhesive polymer spheres (A) from transferring to adherends, etc., the polymer (B) alone is not sufficient, and a crosslinking agent (C) is required. This crosslinking agent (C) can chemically link the polymer spheres (A) and the polymer (B) to prevent the polymer spheres from transferring. The amount of crosslinking agent added varies depending on the type of crosslinking agent, but is based on 100 parts by weight of polymer spheres.
The amount is preferably from 0.001 to 5 parts by weight, preferably from 0.01 to 3 parts by weight. When applying this removable adhesive to a base material, it is preferable to use a primer if necessary, and if it is used in the form of a tape or in a layered state such as an adhesive sheet without using release paper, an appropriate peeling agent may be used. A treatment agent may also be used depending on the substrate used and the purpose. Examples will be described below. In addition, "parts" and "%" in the examples refer to parts by weight and % by weight, respectively.
shows. (Examples) Example 1 Using a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer with a variable speed gear, and a nitrogen inlet tube, the following components were added in their entirety. 2-ethylhexyl acrylate 85 parts n-butyl acrylate 35 parts Acrylic acid 3.5 parts Anionic surfactant 1.5 parts Benzoyl peroxide 0.5 part Water 360 parts Purify with nitrogen gas and stir at a stirring speed of around 400 rpm. Thereafter, when the temperature is gradually raised, the polymerization reaction starts at 70-75°C, and suddenly becomes more intense from around 80-82°C, generating heat up to 88-90°C. Then cool to 80℃
was maintained and the polymerization reaction was carried out for 6 hours. Thereafter, the resulting aqueous suspension was cooled to 30°C, and its evaporation residue, viscosity, and particle size were confirmed.
The evaporation residue was 25%, the viscosity was 35 cps/25°C, and the particle size was 3 to 5 μ on the small side, 70 to 90 μ on the large side, and about 50 to 60 μ on average. Using another similar device, add 7.5 parts of anionic surfactant, 7.5 parts of nonionic surfactant, and 390 parts of water.
parts, ammonium persulfate 2 parts, acrylic acid 15 parts,
170 parts of 2-ethylhexyl acrylate and 190 parts of ethyl acrylate were subjected to conventional emulsion polymerization to obtain an emulsion liquid with an evaporation residue of 50% and a viscosity of 50 cps/25°C. 30 parts of this emulsion liquid was added to 100 parts of the previously produced aqueous suspension to obtain a mixed liquid.
The resulting mixed liquid has an evaporation residue of 30% and a viscosity of 3500 cps/
It was 25℃. Add 0.5 parts of sorbitol polyglycidyl ether as a crosslinking agent to this mixed solution per 100 parts by weight of the mixed solution, and dry the resulting removable adhesive on high-quality paper (55K) so that the weight becomes 10 to 15 g/ m2 . Apply directly to dry. An adhesive sheet prepared in this way was created. Example 2 Aqueous suspension polymerizations were carried out using the equipment and procedures described in Example 1 with the following components. 2-Ethylhexyl acrylate 120 parts Acrylic acid 2.0 parts Sodium acrylate 2.0 parts Anionic surfactant 1.5 parts Benzoyl peroxide 0.5 parts Water 360 parts Evaporation residue of the resulting aqueous suspension 25.5%, viscosity
The temperature was 30cps/25°C, and the average particle size was 40-50μ.
Next, using the emulsion solution described in Example 1, 25 parts of the emulsion solution was added to 100 parts of the above aqueous suspension polymerization solution, and a 5% aqueous dispersion of the crosslinking agent diphenylmethane-bis-4,4-N,N diethylene urea was added. A mixed solution was obtained in which 0.1 part of the solid content was added.
The resulting mixed liquid had an evaporation residue of 29% and a viscosity of 3500 cps/
It was 25℃. Next, a pressure-sensitive adhesive sheet was created in the same manner as in Example 1. Example 3 Aqueous suspension polymerizations were carried out using the equipment and procedures described in Example 1 with the following components. 2-Ethylhexyl acrylate 120 parts Itaconic acid 2.0 parts Sodium acrylate 2.0 parts Anionic surfactant 1.0 parts Nonionic surfactant 1.0 parts Benzoyl peroxide 0.5 parts Water 360 parts The evaporation residue of the aqueous suspension produced was 26.0%. viscosity
The temperature was 50cps/25°C, and the average particle size was 50-60μ.
Further, the usual emulsion polymerization method described in Example 1 was carried out using the components described below to obtain an emulsion liquid. 7.5 parts of anionic surfactant, 7.5 parts of nonionic surfactant, 390 parts of water, 2 parts of ammonium persulfate
parts, 15 parts of methacrylic acid, 150 parts of 2-ethylhexyl acrylate, 210 parts of isobutyl acrylate,
The emulsion liquid produced using this method has an evaporation residue of 50.0
%, and the viscosity was 45CP/25°C. 25 parts of this emulsion liquid was added to 100 parts of the previously produced aqueous suspension, and further a crosslinking agent diphenylmethane-bis-4,
A mixed solution was obtained by adding 0.1 part of a 5% aqueous dispersion of 4-N,N diethylene urea as a solid content. The resulting mixed solution had an evaporation residue of 29% and a viscosity of 3500 cps/25°C. A pressure-sensitive adhesive sheet was prepared using the removable pressure-sensitive adhesive thus obtained in the same manner as in Example 1. Comparative Example 1 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 without adding the crosslinking agent sorbitol polyglycidyl ether. Comparative Example 2 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 2 without adding the crosslinking agent diphenylmethane-bis-4,4-N,N-diethyleneurea. Comparative Example 3 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 3 without adding the crosslinking agent diphenylmethane-bis-4,4-N,N-diethyleneurea. JIS using the adhesive sheet created through the above operations.
In accordance with -Z-0237, the adhesion (g/25 mm) and tackiness to a stainless steel plate and high-quality paper were measured, and the state of adhesive transfer when repeatedly applied and peeled from the high-quality paper was observed. The results are shown in the table.
【表】
（発明の効果）
本発明の再剥離型粘着剤組成物は、重合球体(A)
とその結合剤である重合体(B)とが、架橋剤(C)によ
り、化学的に強固に結合しているため、貼付−剥
離を多数回繰り返しても粘着性重合球体(A)の被着
体への転移がなく、したがつて、剥離後の被着体
を汚すことがない。また、粘着性重合球体(A)は、
繰り返し使用しても粘着面から無くならないた
め、粘着力が低下しない。[Table] (Effects of the invention) The removable pressure-sensitive adhesive composition of the present invention has polymer spheres (A)
and its binder, the polymer (B), are chemically strongly bonded by the crosslinking agent (C), so even if the adhesive polymer sphere (A) is repeatedly pasted and peeled off many times, the adhesive polymer sphere (A) will not be covered. There is no transfer to the adherend, so the adherend will not be contaminated after peeling. In addition, the adhesive polymer sphere (A) is
Even after repeated use, it does not disappear from the adhesive surface, so the adhesive strength does not decrease.
Claims (1)
タ）アクリル酸のアルキルエステル80〜99.9重
量％、 (b) α−モノオレフインカルボン酸もしくはその
アンモニウム塩0.1〜10重量％、および (c) 上記(a)、(b)両成分以外の共重合可能な単量体
０〜19.9重量％ とからなる単量体成分を水性懸濁重合することに
より得られる平均粒子径が６〜120μの粘着性重
合球体(A)100重量部と、 （メタ）アクリル酸アルキルエステル系単量体
を主成分とし、共重合可能で反応性基を有する単
量体を0.1〜15重量％含有するビニル系単量体混
合物を水性媒体中で重合することにより得られる
重合体(B)20〜150重量部と、 重合球体(A)中に含まれるカルボキシル基および
重合体(B)中に含まれる反応性基と反応する基を一
分子中に２個以上有する架橋剤(C)0.001〜５重量
部 とよりなる再剥離型粘着剤組成物。 ２ 重合球体(A)が微粘着性を有するものである特
許請求の範囲第１項記載の再剥離型粘着剤組成
物。[Scope of Claims] 1 (a) 80 to 99.9% by weight of an alkyl ester of (meth)acrylic acid having an alkyl group having 4 to 12 carbon atoms, (b) 0.1 to 10% by weight of α-monoolefincarboxylic acid or its ammonium salt % by weight, and (c) 0 to 19.9% by weight of a copolymerizable monomer other than both components (a) and (b) above. Average particles obtained by aqueous suspension polymerization of a monomer component. 100 parts by weight of adhesive polymer spheres (A) with a diameter of 6 to 120μ and a (meth)acrylic acid alkyl ester monomer as main components, and 0.1 to 15 parts of a copolymerizable monomer having a reactive group. 20 to 150 parts by weight of a polymer (B) obtained by polymerizing a vinyl monomer mixture containing % by weight in an aqueous medium, and the carboxyl group and polymer (B) contained in the polymer spheres (A). A removable pressure-sensitive adhesive composition comprising 0.001 to 5 parts by weight of a crosslinking agent (C) having two or more groups in one molecule that react with reactive groups contained therein. 2. The removable pressure-sensitive adhesive composition according to claim 1, wherein the polymer spheres (A) have slight tackiness.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27385784A JPS61152779A (en) | 1984-12-27 | 1984-12-27 | Repeatedly releasable type pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27385784A JPS61152779A (en) | 1984-12-27 | 1984-12-27 | Repeatedly releasable type pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61152779A JPS61152779A (en) | 1986-07-11 |
| JPH0527669B2 true JPH0527669B2 (en) | 1993-04-21 |
Family
ID=17533518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27385784A Granted JPS61152779A (en) | 1984-12-27 | 1984-12-27 | Repeatedly releasable type pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61152779A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0684490B2 (en) * | 1985-05-15 | 1994-10-26 | ニチバン株式会社 | Removable adhesive composition |
| JPS63260973A (en) * | 1987-04-17 | 1988-10-27 | Sekisui Chem Co Ltd | Production of microspherical pressure-sensitive adhesive |
| JP3838808B2 (en) * | 1999-03-30 | 2006-10-25 | 日本カーバイド工業株式会社 | Re-peelable pressure-sensitive adhesive composition |
| JP2000281996A (en) * | 1999-03-30 | 2000-10-10 | Nippon Carbide Ind Co Inc | Re-releasable pressure-sensitive adhesive composition |
| JP4572007B2 (en) * | 1999-11-02 | 2010-10-27 | 日東電工株式会社 | Water-dispersible pressure-sensitive adhesive for re-peeling and its adhesive sheets |
| JP4705233B2 (en) * | 2000-09-22 | 2011-06-22 | 日本合成化学工業株式会社 | Re-peelable pressure-sensitive adhesive composition |
| JP5230879B2 (en) * | 2000-09-29 | 2013-07-10 | 株式会社日本触媒 | Adhesive products |
| US7442438B2 (en) * | 2005-05-04 | 2008-10-28 | 3M Innovative Properties Company | Wet and dry stick adhesive, articles, and methods |
| JP6896439B2 (en) * | 2017-02-07 | 2021-06-30 | リンテック株式会社 | Adhesives and packaging materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787481A (en) * | 1980-11-20 | 1982-05-31 | Toagosei Chem Ind Co Ltd | Removable adhesive mass composition |
| JPS59159869A (en) * | 1983-03-03 | 1984-09-10 | Enomoto Toshio | Repeelable pressure-sensitive adhesive composition and production thereof |
-
1984
- 1984-12-27 JP JP27385784A patent/JPS61152779A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5787481A (en) * | 1980-11-20 | 1982-05-31 | Toagosei Chem Ind Co Ltd | Removable adhesive mass composition |
| JPS59159869A (en) * | 1983-03-03 | 1984-09-10 | Enomoto Toshio | Repeelable pressure-sensitive adhesive composition and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61152779A (en) | 1986-07-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |