JPH0579273B2 - - Google Patents
Info
- Publication number
- JPH0579273B2 JPH0579273B2 JP62096027A JP9602787A JPH0579273B2 JP H0579273 B2 JPH0579273 B2 JP H0579273B2 JP 62096027 A JP62096027 A JP 62096027A JP 9602787 A JP9602787 A JP 9602787A JP H0579273 B2 JPH0579273 B2 JP H0579273B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- acrylate
- meth
- soluble
- reaction
- 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
- 239000000178 monomer Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 18
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 description 43
- 239000000853 adhesive Substances 0.000 description 40
- 238000006243 chemical reaction Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- -1 2-ethylhexyl Chemical group 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate 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
- 238000006276 transfer reaction Methods 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Description
（産業上の利用分野）
本発明は、優れた性質の再剥離性感圧性接着剤
を短時間のうちに再現性よく製造する方法に関す
る。
（従来の技術）
上質紙などの基材の一部に感圧性粘着剤層が形
成された再剥離性メモ用紙パツドや開閉自在封筒
がオフイスなどで利用されている。例えば感圧性
接着剤層を有する上記メモ用紙は、再剥離性が良
好であり、接着対象物から剥離後再び他の接着対
象物に接着させることも可能である。このような
用途に使用される接着剤は、初期接着性に優れ、
かつ再剥離性の良好であることが必要である。つ
まり、基材に該接着剤の層が形成されたシートを
接着対象物に軽く押しつけて接着させたときの接
着力が比較的高く、かつ強く押しつけて接着させ
たときにも接着力がそれほど上昇しないため比較
的小さな力で剥離され得ることが望まれる。さら
に、いわゆる糊残りがなく、かつ再び他の接着対
象物に良好な接着性をもつて接着しうることが望
まれる。
このような再剥離・再接着性を有する接着剤
（以下再剥離性接着剤という）およびこの接着剤
の層が形成されたシートが、例えば米国特許第
3691140号、米国特許第3857731号、米国特許第
4166152号、特開昭50−2736号公報および特開昭
60−11569号公報に開示されている。ここに記載
された接着剤は、いずれもアルキルアクリレート
モノマーと極性モノマーと水性懸濁重合して得ら
れる微球状の接着剤である。接着剤の形状を微球
状としたため比較的良好に再剥離がなされる。し
かし、例えば特開昭50−2736号公報に記載のモノ
マー組成物を水性懸濁重合させると、重合反応時
の温度、時間、攪拌状態により得られる微球状接
着剤の品質が一定しない。このような接着剤を用
いて、例えば粘着シートを調製すると、得られる
シートの接着力などにバラツキを生じ、一定した
品質のシートが得られない。上記懸濁重合時に
は、生じたラジカルにより（メタ）アクリレート
モノマーが重合し主鎖を形成すると同時に、生じ
た（メタ）アクリレートポリマーとラジカルとの
間のラジカル連鎖移動反応により架橋反応が起こ
ると考えられる。しかし、このラジカルの連鎖移
動反応は、不確定性要素が大きく、ラジカル反応
の結果常に一定の架橋状態を有する安定した品質
のポリマーは得られない。その結果、上記のよう
な品質のバラツキがもたらされると考えられる。
このように、安定した反応条件下で優れた性質の
再剥離性感圧性接着剤を再現性よく製造する方法
は開発されていないのが現状である。
（発明が解決しようとする問題点）
本発明は上記従来の欠点を解決するものであり
その目的とするところは、初期接着性および再剥
離性に優れた感圧性接着剤を安定した反応条件下
で再現性よく製造する方法を提供することにあ
る。本発明の他の目的は、アクリル系モノマーの
重合反応により安定した品質の微球状再剥離性接
着剤の製造方法を提供することにある。
（問題点を解決するための手段および作用）
本発明の微球状感圧性接着剤の製造方法は、
（メタ）アクリレート、該（メタ）アクリレート
と共重合性を有する水溶性モノマー、および分子
内に２個以上の重合性不飽和基を有する油溶性の
多官能性モノマーを含有する組成物を油溶性重合
開始剤および界面活性剤の存在下で、水性懸濁重
合し、そのことにより上記目的が達成される。
本発明の微球状感圧性接着剤に使用される（メ
タ）アクリレート（アクリレートおよび／または
メタクリレートという）は、
(Industrial Application Field) The present invention relates to a method for producing removable pressure-sensitive adhesives with excellent properties in a short period of time and with good reproducibility. (Prior Art) Removable memo pads and removable envelopes, which have a pressure-sensitive adhesive layer formed on a portion of a base material such as high-quality paper, are used in offices and the like. For example, the memo paper having a pressure-sensitive adhesive layer has good removability, and after being peeled off from an object to be bonded, it can be reattached to another object to be bonded. Adhesives used for such applications have excellent initial adhesion and
In addition, it is necessary to have good removability. In other words, the adhesive strength is relatively high when a sheet with a layer of the adhesive formed on the base material is lightly pressed against the object to be adhered, and the adhesive strength increases significantly even when it is strongly pressed and adhered. Therefore, it is desirable to be able to peel off with a relatively small force. Furthermore, it is desired that there is no so-called adhesive residue and that it can be bonded to other objects to be bonded again with good adhesive properties. An adhesive having such removable and readhesive properties (hereinafter referred to as a removable adhesive) and a sheet on which a layer of this adhesive is formed are disclosed in, for example, US Patent No.
3691140, U.S. Patent No. 3857731, U.S. Patent No.
No. 4166152, JP-A-50-2736 and JP-A-Sho
It is disclosed in Publication No. 60-11569. All of the adhesives described herein are microspherical adhesives obtained by aqueous suspension polymerization of an alkyl acrylate monomer and a polar monomer. Since the adhesive has a microspherical shape, it can be re-peeled relatively well. However, when the monomer composition described in, for example, JP-A-50-2736 is subjected to aqueous suspension polymerization, the quality of the resulting microspherical adhesive varies depending on the temperature, time, and stirring conditions during the polymerization reaction. For example, when a pressure-sensitive adhesive sheet is prepared using such an adhesive, the adhesive strength of the resulting sheet varies, making it impossible to obtain a sheet of consistent quality. During the above suspension polymerization, it is thought that the generated radicals polymerize the (meth)acrylate monomer to form a main chain, and at the same time, a crosslinking reaction occurs due to a radical chain transfer reaction between the generated (meth)acrylate polymer and the radicals. . However, this radical chain transfer reaction has large uncertainties, and as a result of the radical reaction, a polymer of stable quality that always has a constant crosslinked state cannot be obtained. As a result, it is thought that the above-mentioned variations in quality are brought about.
Thus, at present, no method has been developed for producing removable pressure-sensitive adhesives with excellent properties under stable reaction conditions with good reproducibility. (Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional drawbacks, and its purpose is to produce a pressure-sensitive adhesive with excellent initial adhesion and removability under stable reaction conditions. The objective is to provide a method for manufacturing with good reproducibility. Another object of the present invention is to provide a method for producing a microspherical removable adhesive of stable quality through a polymerization reaction of acrylic monomers. (Means and effects for solving the problems) The method for producing a microspherical pressure-sensitive adhesive of the present invention includes:
A composition containing a (meth)acrylate, a water-soluble monomer copolymerizable with the (meth)acrylate, and an oil-soluble polyfunctional monomer having two or more polymerizable unsaturated groups in the molecule is made into an oil-soluble composition. In the presence of a polymerization initiator and a surfactant, aqueous suspension polymerization is carried out, thereby achieving the above object. The (meth)acrylate (referred to as acrylate and/or methacrylate) used in the microspherical pressure-sensitive adhesive of the present invention is
【式】で示
され、R1は炭素数４〜９の飽和炭化水素基、そ
してR2はＨまたはCH3を表す。このような（メ
タ）アクリレートとしては、ｎ−ブチル（メタ）
アクリレート、２−エチルヘキシル（メタ）アク
リレート、イソオクチル（メタ）アクリレート，
イソノニル（メタ）アクリレートなどが挙げられ
る。
上記（メタ）アクリレートと共重合性を有する
水溶性モノマーとしては、例えば、（メタ）アク
リル酸、フマル酸、マレイン酸、イタコン酸およ
びそれらの塩が挙げられる。
分子内に２個以上の重合性不飽和基を有する油
溶性の多官能性モノマーとしては、実質的に水に
不溶であり、かつ上記（メタ）アクリレートと相
溶する性質を有する化合物が好ましい。そのよう
な多官能性モノマーとしては、ジビニルベンゼ
ン、トリアリルイソシアヌレートなどが挙げられ
る。
本発明の接着剤の原料組成物は、上記（メタ）
アクリレート100重量部に対して、上記水溶性モ
ノマーが1.0〜10.0重量部の割合で、そして多官
能性モノマーが0.01〜0.5重量部の割合で含有さ
れる。上記組成物中で、水溶性モノマーの量が過
少であると微球が凝集しやすく、逆に過剰である
と適度な粘着性、柔軟性が得られない。多官能性
モノマーの量が過少であると製造時の架橋反応が
安定して起こらないため再現性が悪く、品質にバ
ラツキを生じる。逆に過少であると架橋の度合が
高くなり粘着性が発現されない。
開始剤（重合反応開始剤）は熱などにより分解
してラジカルを発生する性質を有する。本発明で
は、この開始剤としては、実質的に水に不溶であ
り（油溶性であり）、アクリル系モノマーに可溶
なものが使用される。例えば、アゾビスイソブチ
ロニトリルなどのアゾ化合物、ベンゾイルパーオ
キシドなどの過酸化物が好適に利用される。油溶
性開始剤は全モノマー成分100重量部に対し、
0.05〜0.5重量部の割合で使用される。
界面活性剤としては、ドデシルベンゼンスルホ
ン酸ナトリウムなどのイオン性界面活性剤、ポリ
オキシエチレンラウリルアルコールエーテルなど
の非イオン性界面活性剤が利用され得る。界面活
性剤は、臨界ミセル濃度以上で使用される。
本発明の微球状感圧性接着剤を得るには、上記
（メタ）アクリレート、多官能性モノマー、界面
活性剤および油溶性開始剤を水もしくは水性溶媒
に加えて攪拌しながら重合反応を行う、重合条件
は通常の水性懸濁重合反応に準じる。例えば75℃
前後で約１時間攪拌を行う。本発明方法に用いら
れる組成物は、（メタ）アクリレート、水溶性モ
ノマーおよび油溶性の多官能性モノマーを適当な
割合で含有するため、安定した反応条件で重合反
応が進行する。特に多官能性モノマーが油溶性で
あるため（メタ）アクリレートと充分に相溶し、
その結果架橋速度にバラツキがなく安定して反応
が進行する。このような反応により比較的短時間
で重合・架橋反応が終了する。重合反応により平
均粒径が10〜150μmの粒径の揃つた微球状ポリマ
ーが得られる。得られた微球状ポリマーは、良好
な接着性を示し、かつ適度な架橋度を有するため
再剥離性に優れる。この接着剤を用いて、例え
ば、粘着シートを調製するには、例えば、紙、プ
ラスチツクフイルムなどの基材にニトロセルロー
スなどのバインダーで下塗処理を行い、この上に
上記接着剤の有機溶媒分散液を塗工・乾燥させ
る。接着剤とバインダーとを混合して基材上に塗
工してもよい。
架橋構造を有する接着剤組成物としては、特開
昭57−111368号公報にエマルジヨン系ポリマー
100重量部に架橋剤が２重量部以下の割合で配合
された組成物が開示されている。架橋剤として
は、多官能エポキシ化合物、メラミン化合物、イ
ソシアネート化合物などが用いられる。しかし、
基材上に塗布後、加熱することにより架橋反応が
起こるという点で本発明の接着剤とは異なる。さ
らに、この接着剤を基材上に塗布して架橋反応を
起こさせるべく加熱すると球状のポリマーの型が
くずれフイルム状となるため、本発明のような再
剥離性接着剤としては適当とはいえない。この
他、架橋構造を有する微球体のポリマーとして
は、スチレン系の微粒子がクロマトグラフイー用
に製造されているが、これはTgが高いため接着
性を有していないことから、本発明の接着剤とは
全く異なる。
（実施例）
以下に本発明を実施例につき説明する。
実施例 １
２−エチルヘキシルアクリレート291ｇ、アク
リル酸９ｇ、ジビニルベンゼン0.09ｇ（0.043モ
ル％）およびベンゾイルパーオキシド0.9ｇを２
のセパラブルフラスコに入れ、これに純水1000
ｇ、界面活性剤としてドデシルベンゼンスルホン
酸ナトリウム6.66ｇ、およびPH調整用に水酸化ナ
トリウム5.4ｇを加えた。この懸濁液を40℃にて
１時間、回転速度270rpmで攪拌した後、液温を
75℃に上昇させて反応を開始させた。液温が75℃
に上昇してから、１時間、３時間、６時間そして
12時間に反応液の一部を取り出し、それぞれメタ
ノールを加えた。それぞれの固型分を分別し、乾
燥させた。平均粒子径はいずれも約30μmであつ
た。このポリマーをトルエン中に濃度が８％にな
るように加え、このトルエン分散液をニトロセル
ロースで下塗処理を施した上質紙に10ｇ／m2の割
合で塗布し乾燥させることによつて、各々の反応
時間に対応する４種の紙粘着シートを得た。
上記工程で得られた接着剤および紙粘着シート
を次の方法により評価した。その結果を下表に示
す。実施例２および比較例１〜２の結果もあわせ
て下表に示す。
(1) ゲル分率
反応により得られた固型分を８％の割合でトル
エンと混合し、このトルエン分散液を遠心分離器
にかけ、沈降したトルエン不溶分の重量から算出
する。
(2) 対紙接着力
得られた紙粘着シートをステンレススチール板
に２Kg接着ロールによつて押しつけた場合の20℃
における180°剥離接着力を求める。別に、200ｇ
接着ロールを用いて同様の試験を行う。
実施例 ２
実施例１の工程を繰り返して行い、再現性を評
価した。
比較例 １
ジビニルベンゼンを用いなかつたこと以外は、
実施例１と同様である。
比較例 ２
比較例１の工程を繰り返して行い、再現性を評
価した。[Formula], R 1 represents a saturated hydrocarbon group having 4 to 9 carbon atoms, and R 2 represents H or CH 3 . Such (meth)acrylates include n-butyl (meth)
Acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate,
Examples include isononyl (meth)acrylate. Examples of the water-soluble monomer copolymerizable with the above (meth)acrylate include (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, and salts thereof. The oil-soluble polyfunctional monomer having two or more polymerizable unsaturated groups in the molecule is preferably a compound that is substantially insoluble in water and compatible with the above (meth)acrylate. Such polyfunctional monomers include divinylbenzene, triallylisocyanurate, and the like. The raw material composition of the adhesive of the present invention is the above (meth)
The water-soluble monomer is contained in an amount of 1.0 to 10.0 parts by weight, and the polyfunctional monomer is contained in an amount of 0.01 to 0.5 parts by weight, based on 100 parts by weight of acrylate. If the amount of the water-soluble monomer in the composition is too small, the microspheres will tend to aggregate, whereas if it is in excess, appropriate tackiness and flexibility will not be obtained. If the amount of the polyfunctional monomer is too small, the crosslinking reaction during production will not occur stably, leading to poor reproducibility and resulting in variations in quality. On the other hand, if the amount is too low, the degree of crosslinking will be high and no adhesiveness will be developed. The initiator (polymerization reaction initiator) has the property of generating radicals when decomposed by heat or the like. In the present invention, the initiator used is one that is substantially insoluble in water (oil-soluble) and soluble in the acrylic monomer. For example, azo compounds such as azobisisobutyronitrile and peroxides such as benzoyl peroxide are preferably used. The oil-soluble initiator should be added to 100 parts by weight of all monomer components.
It is used in a proportion of 0.05 to 0.5 parts by weight. As the surfactant, ionic surfactants such as sodium dodecylbenzenesulfonate and nonionic surfactants such as polyoxyethylene lauryl alcohol ether can be used. Surfactants are used above the critical micelle concentration. In order to obtain the microspherical pressure-sensitive adhesive of the present invention, the above-mentioned (meth)acrylate, polyfunctional monomer, surfactant, and oil-soluble initiator are added to water or an aqueous solvent, and a polymerization reaction is carried out with stirring. The conditions are similar to those for ordinary aqueous suspension polymerization reactions. For example 75℃
Stir for about 1 hour before and after. Since the composition used in the method of the present invention contains (meth)acrylate, a water-soluble monomer, and an oil-soluble polyfunctional monomer in appropriate proportions, the polymerization reaction proceeds under stable reaction conditions. In particular, since the polyfunctional monomer is oil-soluble, it is sufficiently compatible with (meth)acrylate.
As a result, there is no variation in crosslinking rate and the reaction proceeds stably. Due to such a reaction, the polymerization/crosslinking reaction is completed in a relatively short time. The polymerization reaction yields a uniformly spherical polymer with an average particle size of 10 to 150 μm. The obtained microspherical polymer exhibits good adhesion and has an appropriate degree of crosslinking, so it has excellent removability. To prepare a pressure-sensitive adhesive sheet using this adhesive, for example, a base material such as paper or plastic film is undercoated with a binder such as nitrocellulose, and then an organic solvent dispersion of the adhesive Coat and dry. The adhesive and binder may be mixed and coated onto the substrate. As an adhesive composition having a crosslinked structure, an emulsion-based polymer is disclosed in JP-A-57-111368.
A composition is disclosed in which a crosslinking agent is blended in a ratio of 2 parts by weight or less to 100 parts by weight. As the crosslinking agent, polyfunctional epoxy compounds, melamine compounds, isocyanate compounds, etc. are used. but,
It differs from the adhesive of the present invention in that a crosslinking reaction occurs by heating after coating on a substrate. Furthermore, when this adhesive is applied onto a base material and heated to cause a crosslinking reaction, the spherical polymer shape collapses and forms a film, so although it is not suitable as a removable adhesive as in the present invention. do not have. In addition, styrene-based microparticles are manufactured for chromatography as microspherical polymers with a crosslinked structure, but these do not have adhesive properties due to their high Tg. It is completely different from the agent. (Example) The present invention will be described below with reference to Examples. Example 1 291 g of 2-ethylhexyl acrylate, 9 g of acrylic acid, 0.09 g (0.043 mol%) of divinylbenzene and 0.9 g of benzoyl peroxide were
Put it in a separable flask and add 1000ml of pure water to it.
g, 6.66 g of sodium dodecylbenzenesulfonate as a surfactant, and 5.4 g of sodium hydroxide for pH adjustment. After stirring this suspension at 40°C for 1 hour at a rotation speed of 270 rpm, the liquid temperature was lowered.
The reaction was started by increasing the temperature to 75°C. Liquid temperature is 75℃
1 hour, 3 hours, 6 hours and then
A portion of the reaction solution was taken out after 12 hours, and methanol was added to each portion. Each solid component was separated and dried. The average particle diameter was about 30 μm in all cases. This polymer was added to toluene to a concentration of 8%, and the toluene dispersion was applied to high-quality paper primed with nitrocellulose at a rate of 10 g/m 2 and dried. Four types of paper adhesive sheets corresponding to reaction times were obtained. The adhesive and paper adhesive sheet obtained in the above steps were evaluated by the following method. The results are shown in the table below. The results of Example 2 and Comparative Examples 1 and 2 are also shown in the table below. (1) Gel fraction The solid content obtained by the reaction is mixed with toluene at a ratio of 8%, the toluene dispersion is centrifuged, and the gel fraction is calculated from the weight of the toluene-insoluble content that precipitates. (2) Adhesive strength to paper At 20°C when the obtained paper adhesive sheet is pressed onto a stainless steel plate with a 2 kg adhesive roll
Find the 180° peel adhesive strength at . Separately, 200g
A similar test is performed using adhesive rolls. Example 2 The steps of Example 1 were repeated and the reproducibility was evaluated. Comparative Example 1 Except that divinylbenzene was not used,
This is the same as in Example 1. Comparative Example 2 The process of Comparative Example 1 was repeated and the reproducibility was evaluated.
【表】【table】
【表】
表から明らかなように、油溶性多官能性モノマ
ーをラジカル共重合性架橋剤として用いる本発明
の方法により、短時間のうちに再剥離性接着剤と
して好適な架橋構造を有する微球状の接着剤が得
られる。このような感圧性接着剤の接着性は、重
合反応時間により大きなバラツキがなく１時間以
上の反応で得られるポリマーは、その架橋度が一
定するため接着力も安定していることがわかる。
対紙接着力から、この接着剤は再剥離性接着剤と
して好適な性質を有することがわかる。重合反応
の再現性もよく、常に安定した品質の再剥離性接
着剤の得られることがわかる。
これに対して油溶性多官能性モノマーを用いず
に重合反応を行うと、重合速度が遅く、かつ安定
した品質の接着剤が得られず、反応の再現性に乏
しい。特に同様の条件で反応を行つても反応時間
による架橋の度合が一定しないため、所定の品質
の接着剤が得られない。
（発明の効果）
本発明方法によれば、このように、アクリル系
モノマーおよび油溶性の多官能性モノマーを含む
特定の組成物を使用し、初期接着性および再剥離
性に優れた感圧性接着剤を安定した反応条件下で
再現性よく短時間で製造する方法が提供される。
得られた感圧性接着剤は、接着層を有するメモ用
紙パツドや開閉自在の封筒などの用途に好適に利
用され得る。[Table] As is clear from the table, by the method of the present invention using an oil-soluble polyfunctional monomer as a radical copolymerizable crosslinking agent, microspherical particles with a crosslinked structure suitable as a removable adhesive can be formed in a short time. of adhesive is obtained. It can be seen that the adhesive properties of such pressure-sensitive adhesives do not vary greatly depending on the polymerization reaction time, and that polymers obtained by reaction for one hour or more have stable adhesive strength because the degree of crosslinking is constant.
The adhesive strength to paper indicates that this adhesive has properties suitable as a removable adhesive. It can be seen that the reproducibility of the polymerization reaction is good and that a removable adhesive of consistently stable quality can be obtained. On the other hand, when a polymerization reaction is carried out without using an oil-soluble polyfunctional monomer, the polymerization rate is slow, an adhesive of stable quality cannot be obtained, and the reproducibility of the reaction is poor. In particular, even if the reaction is carried out under similar conditions, the degree of crosslinking is not constant depending on the reaction time, making it impossible to obtain an adhesive of a predetermined quality. (Effects of the Invention) According to the method of the present invention, a pressure-sensitive adhesive with excellent initial adhesion and removability is obtained by using a specific composition containing an acrylic monomer and an oil-soluble polyfunctional monomer. Provided is a method for producing reproducible agents in a short time under stable reaction conditions.
The obtained pressure-sensitive adhesive can be suitably used for memo paper pads having an adhesive layer, openable and closable envelopes, and the like.
Claims (1)
ートと共重合性を有する水溶性モノマー、および
分子内に２個以上の重合性不飽和基を有する油溶
性の多官能性モノマーを含有する組成物を油溶性
重合開始剤および界面活性剤の存在下で、水性懸
濁重合する工程を包含する微球状感圧性接着剤の
製造方法。 ２ 前記（メタ）アクリレート100重量部に対し、
前記水溶性モノマーが10.1〜1.0重量部の割合で、
そして前記多官能性モノマーが0.01〜0.5重量部
の割合で含有される特許請求の範囲第１項に記載
の製造方法。 ３ 前記微球状感圧性接着剤の粒径が10〜150μm
である特許請求の範囲第１項に記載の製造方法。[Claims] 1. A (meth)acrylate, a water-soluble monomer copolymerizable with the (meth)acrylate, and an oil-soluble polyfunctional monomer having two or more polymerizable unsaturated groups in the molecule. A method for producing a microspherical pressure-sensitive adhesive comprising the step of aqueous suspension polymerization of a composition containing the same in the presence of an oil-soluble polymerization initiator and a surfactant. 2 For 100 parts by weight of the above (meth)acrylate,
The water-soluble monomer is in a proportion of 10.1 to 1.0 parts by weight,
The manufacturing method according to claim 1, wherein the polyfunctional monomer is contained in a proportion of 0.01 to 0.5 parts by weight. 3 The particle size of the microspherical pressure-sensitive adhesive is 10 to 150 μm.
The manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9602787A JPS63260973A (en) | 1987-04-17 | 1987-04-17 | Production of microspherical pressure-sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9602787A JPS63260973A (en) | 1987-04-17 | 1987-04-17 | Production of microspherical pressure-sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63260973A JPS63260973A (en) | 1988-10-27 |
| JPH0579273B2 true JPH0579273B2 (en) | 1993-11-01 |
Family
ID=14153893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9602787A Granted JPS63260973A (en) | 1987-04-17 | 1987-04-17 | Production of microspherical pressure-sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63260973A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT394779B (en) * | 1988-12-20 | 1992-06-25 | Universale Grundbau | INCLINATION MEASURING SYSTEM FOR SLOT WALLS |
| JPH04117478A (en) * | 1990-09-07 | 1992-04-17 | Sekisui Chem Co Ltd | Sprayable pressure-sensitive adhesive composition |
| US5719247A (en) * | 1991-12-17 | 1998-02-17 | Minnesota Mining And Manufacturing Company | Tack-free elastomeric acrylate microspheres |
| US5714237A (en) | 1996-01-16 | 1998-02-03 | Minnesota Mining Manufacturing Company | Partially crosslinked microspheres |
| US6296932B1 (en) | 1998-12-14 | 2001-10-02 | 3M Innovative Properties Company | Microsphere adhesive coated article for use with coated papers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61148278A (en) * | 1984-12-22 | 1986-07-05 | Hoechst Gosei Kk | Aqueous suspension of adhesive microsphere |
| JPS61148279A (en) * | 1984-12-22 | 1986-07-05 | Hoechst Gosei Kk | Adhesive microsphere suspension in solvent, and pressure-sensitive adhesive sheet material utilizing characteristics thereof |
| JPS61152779A (en) * | 1984-12-27 | 1986-07-11 | Toyo Ink Mfg Co Ltd | Repeatedly releasable type pressure-sensitive adhesive composition |
-
1987
- 1987-04-17 JP JP9602787A patent/JPS63260973A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61148278A (en) * | 1984-12-22 | 1986-07-05 | Hoechst Gosei Kk | Aqueous suspension of adhesive microsphere |
| JPS61148279A (en) * | 1984-12-22 | 1986-07-05 | Hoechst Gosei Kk | Adhesive microsphere suspension in solvent, and pressure-sensitive adhesive sheet material utilizing characteristics thereof |
| JPS61152779A (en) * | 1984-12-27 | 1986-07-11 | Toyo Ink Mfg Co Ltd | Repeatedly releasable type pressure-sensitive adhesive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63260973A (en) | 1988-10-27 |
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