JPH03244685A - Pressure-sensitive adhesive - Google Patents
Pressure-sensitive adhesiveInfo
- Publication number
- JPH03244685A JPH03244685A JP4121590A JP4121590A JPH03244685A JP H03244685 A JPH03244685 A JP H03244685A JP 4121590 A JP4121590 A JP 4121590A JP 4121590 A JP4121590 A JP 4121590A JP H03244685 A JPH03244685 A JP H03244685A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- parts
- sensitive adhesive
- acrylate
- 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.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 150000004820 halides Chemical class 0.000 claims abstract description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 14
- 230000001070 adhesive effect Effects 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 9
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 abstract description 6
- -1 dimethyldiallylammonium halide Chemical class 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052571 earthenware Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940061607 dibasic sodium phosphate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- CXPOFJRHCFPDRI-UHFFFAOYSA-N dodecylbenzene;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1 CXPOFJRHCFPDRI-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 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
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明は感圧性接着剤、詳しくはアクリル系エマルショ
ン感圧性接着剤に関し、ガラス、陶器及びプラスチック
製の容器外面に貼布したり、流通産業における各種ケー
スの封緘用に使用されるシール、ラベル等に有用な感圧
性接着剤に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Application Field) The present invention relates to a pressure-sensitive adhesive, specifically an acrylic emulsion pressure-sensitive adhesive, which can be applied to the outer surface of glass, ceramic and plastic containers. The present invention relates to pressure-sensitive adhesives useful for seals, labels, etc. used for sealing various cases in the distribution industry.
（従来の技術）
近年、アクリル系感圧性接着剤は、その優れた接着物性
、耐久性から従来の天然ゴム系、合成ゴム系の感圧性接
着剤に代り、広範に普及しつつある。また省資源、環境
衛生、製品コストのかねあいから水系の感圧性接着剤か
研究開発されている。(Prior Art) In recent years, acrylic pressure-sensitive adhesives have been widely used in place of conventional natural rubber-based and synthetic rubber-based pressure-sensitive adhesives due to their excellent adhesive properties and durability. Additionally, water-based pressure-sensitive adhesives are being researched and developed from the standpoint of resource conservation, environmental hygiene, and product cost.
天然ゴム系、合成ゴム系の感圧性接着剤は低温下におけ
る粘着性の低下、高温における凝集力の不足等、各種の
耐久性かアクリル系感圧性接着剤に劣るにもかかわらず
常態時での剪断力か優れている。Natural rubber-based and synthetic rubber-based pressure-sensitive adhesives are inferior to acrylic-based pressure-sensitive adhesives in terms of durability, such as decreased tackiness at low temperatures and lack of cohesive strength at high temperatures. Excellent shearing force.
このため感圧接着剤を紙等の基材に塗工してラベル、シ
ール等として容器の曲面や屈曲した個所、あるいは各種
ケースの封緘用に使用する場合のように基材の復元力に
抗しうるような耐反発性か求められる用途には依然とし
て天然ゴム系、合成ゴム系の感圧性接着剤か主流となっ
ている。For this reason, when pressure-sensitive adhesives are applied to a base material such as paper and used for labels, stickers, etc. on curved or bent parts of containers, or for sealing various cases, it is difficult to resist the restoring force of the base material. Natural rubber-based or synthetic rubber-based pressure-sensitive adhesives are still the mainstream for applications that require high repulsion resistance.
従来のアクリル系感圧性接着剤は、高度の剪断力か望ま
れる用途に適用する場合には満足てきるものとはいえな
い。そこで、この種の感圧性接着剤の剪断力をさらに向
上させるために乳化重合で得られたアクリル系エマルジ
ョンに架橋剤、たとえばアジリジン化合物、メラミン化
合物、エポキシ化合物、金属塩なとを配合する試みがさ
れてきた。ところか、このような手段では凝集力のみか
大きくなり、それに供なって接着力や粘着性の低下かみ
られ、結局高接着力、高粘着性でかつ、高剪断力を有す
るような感圧性接着剤組成物を得ることは難しかった。Conventional acrylic pressure sensitive adhesives are unsatisfactory for applications where high shear forces are desired. Therefore, in order to further improve the shear strength of this type of pressure-sensitive adhesive, attempts have been made to incorporate crosslinking agents such as aziridine compounds, melamine compounds, epoxy compounds, and metal salts into the acrylic emulsion obtained by emulsion polymerization. It has been. However, with such a method, only the cohesive force increases, resulting in a decrease in adhesion and tack, resulting in a pressure-sensitive adhesive that has high adhesive strength, high tack, and high shear force. It was difficult to obtain a drug composition.
（発明か解決しようとする課題）
本発明は耐久性、高剪断力を併せもつ感圧性接着剤を提
供するものである。さらに本発明は高接着力、高粘着性
の水系感圧性接着剤を提供するものである。(Problems to be Solved by the Invention) The present invention provides a pressure-sensitive adhesive having both durability and high shear strength. Furthermore, the present invention provides a water-based pressure-sensitive adhesive with high adhesive strength and high tack.
（課題を解決するための手段〕
本発明は、
（ａ）アルキル基の炭素数か４〜１２であるアクリル酸
アルキルエステル ５０〜９９．８９重量％（ｂ）
α、β−不飽和カルホン酸 ０．１〜１５重量％（Ｃ）
ジアルキルジアリルアンモニウムハライド０、Ｏ１〜２
０重量９６
（ｄ）上記以外のビニル系モノマー
０〜４９．８９重量９６
を共重合してなることを特徴とする感圧性接着剤である
。(Means for Solving the Problems) The present invention provides: (a) 50 to 99.89% by weight of an acrylic acid alkyl ester whose alkyl group has 4 to 12 carbon atoms;
α, β-unsaturated carbonic acid 0.1-15% by weight (C)
Dialkyl diallylammonium halide 0, O1-2
(d) A pressure-sensitive adhesive characterized by being copolymerized with 0 to 49.89 weight 96 of a vinyl monomer other than the above.
本発明の共重合体に使用されるアルキル基の炭酸数か４
〜１２であるアクリル酸アルキルエステル（ａ）は、ア
クリル酸ブチル、アクリル酸ヘキシル、アクリル酸オク
チル、アクリル酸ラウリル、アクリル酸２−エチルヘキ
シル等の直鎖または分岐脂肪族アルコールのアクリル酸
エステルを挙げることかできる。特に好ましいものはア
クリル酸２−エチルヘキシルである。感圧性接着剤とし
ての基本物性を得るためこれらのアクリル酸アルキルエ
ステルの使用量は全共重合体のの５０〜９９．９重量％
か好ましい。The carbon number of the alkyl group used in the copolymer of the present invention is 4.
-12, acrylic acid alkyl ester (a), includes acrylic esters of linear or branched aliphatic alcohols such as butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, etc. I can do it. Particularly preferred is 2-ethylhexyl acrylate. In order to obtain the basic physical properties as a pressure-sensitive adhesive, the amount of these acrylic acid alkyl esters used is 50 to 99.9% by weight of the total copolymer.
Or preferable.
本発明のα、β−不飽和カルボン酸（ｂ）は、アクリル
酸、メタクリル酸、無水マレイン酸、クロトン酸、イタ
コン酸、フマール酸等を挙げることかできる。α、β−
不飽和カルホン酸（ｂ）は共重合体を基準としてＯ，１
〜１５重ｆｉ ％を他の必要なモノマーと共重合させる
ことにより感圧性接着剤の接着性と凝集力のバランスを
図ることができる。Examples of the α,β-unsaturated carboxylic acid (b) of the present invention include acrylic acid, methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, and fumaric acid. α, β−
Unsaturated carbonic acid (b) is O,1 based on the copolymer.
By copolymerizing ~15 wt. fi % with other necessary monomers, the adhesiveness and cohesive strength of the pressure sensitive adhesive can be balanced.
本発明の感圧接着剤となる共重合体の一成分となるジア
ルキルジアリルアンモニウムハライド（Ｃ）は、下記−
数式て表されるものである。The dialkyl diallylammonium halide (C) that is one component of the copolymer that is the pressure-sensitive adhesive of the present invention is as follows -
It is expressed as a mathematical formula.
はメチル基、エチル基、プロピル基、ブチル基等の低級
アルキノＬ基、Ｘは塩素、臭素等のハロゲン原子である
。これらのジアルキルジアリルアンモニウムハライドは
水溶液として得ることかできる。is a lower alkino L group such as a methyl group, ethyl group, propyl group or butyl group, and X is a halogen atom such as chlorine or bromine. These dialkyl diallylammonium halides can be obtained as an aqueous solution.
ジアルキルシアリルアンモニウムハライドは共重体に対
して、０．０１〜２０重量部を使用することか好ましく
、２０重量％より多い場合は乳化重合法により共重合体
を製造する際凝集物か発生しやすくなるので好ましくな
く、０．Ｏ１重量？６より少ない場合は感圧接着剤の凝
集力か低下して本発明の効果を達成できない。また、ジ
メチルジアルキマハライドの使用量は用途によっても異
なり、接着力か重視される用途においては０．１〜５重
量％か好ましく、再剥離用と称される用途においては２
〜１５重量％か好ましい。It is preferable to use dialkylsialyl ammonium halide in an amount of 0.01 to 20 parts by weight based on the copolymer; if it is more than 20% by weight, aggregates are likely to occur when producing the copolymer by emulsion polymerization. Therefore, it is not preferable and 0. O1 weight? If it is less than 6, the cohesive force of the pressure sensitive adhesive will decrease and the effects of the present invention cannot be achieved. In addition, the amount of dimethyl dialkymahalide used varies depending on the application, and in applications where adhesive strength is important, it is preferably 0.1 to 5% by weight, and in applications called removable, it is preferably 0.1 to 5% by weight.
~15% by weight is preferred.
本発明の共重合体に使用できる上記以外のビニルモノマ
ー（ｄ）としては、アルキル基の炭素数か３以下のアク
リル酸アルキルエステル、例えば、アクリル酸メチル、
アクリル酸エチル、アクリル酸プロピル等、アルキル基
の炭素数か１〜１２のメタクリル酸エステル、例えば、
メタクリル酸メチル、メタクリル酸ブチル、メタクリル
酸２−エチルヘキシル等があり、その他に、酢酸ビニル
、スチレン、ビニルトルエン、アクリロニトリル等かあ
る。Vinyl monomers (d) other than those mentioned above that can be used in the copolymer of the present invention include acrylic acid alkyl esters having an alkyl group having 3 or less carbon atoms, such as methyl acrylate,
Methacrylic acid esters having an alkyl group of 1 to 12 carbon atoms, such as ethyl acrylate and propyl acrylate, for example,
Examples include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and others such as vinyl acetate, styrene, vinyltoluene, and acrylonitrile.
本発明の共重合体は一般的な乳化重合て製造することが
できるが、溶液重合で製造することか可能である。乳化
重合として製造する場合には上記（ａ）〜（ｄ）成分の
モノマー類を混合物として乳化剤と重合開始剤の存在下
、水系で乳化重合させればよい。The copolymer of the present invention can be produced by general emulsion polymerization, but it is also possible to produce it by solution polymerization. When producing by emulsion polymerization, the monomers of components (a) to (d) above may be mixed and emulsion polymerized in an aqueous system in the presence of an emulsifier and a polymerization initiator.
（実施例）
実施例 １
純 水 ６５部
第２リン酸ソーダ ０．６部ドデシルベ
ンセンスルフすネート １部を計量し、１５０ Ｐ
ＰＭの撹拌下に８０°Ｃに加熱しておく次いて、
アクリル酸２−エチルヘキシル ７９部酢 酸
ピ ニ゛ル １５部ア り リ ル
酸 ５部ジメチ
ルジアリルアンモニウム
クロライド １部の混合物
と５％過硫酸カリウム水溶液６部を８０℃に保たれた反
応系中に３時間にわたって均等に滴下し、重合させた。(Example) Example 1 Pure water 65 parts Sodium phosphate 0.6 part Weighed 1 part dodecylbenzene sulfurate, 150 P
Heat the PM to 80°C with stirring, then add 2-ethylhexyl acrylate 79 parts acetic acid
A mixture of 15 parts of pineyl, 5 parts of arylic acid, 1 part of dimethyldiallylammonium chloride and 6 parts of a 5% potassium persulfate aqueous solution were added dropwise evenly over a period of 3 hours into the reaction system kept at 80°C, and polymerization was carried out. I let it happen.
モノマーをすへて滴下した後、８０’Ｃて２時間反応を
続行し、重合を完結させた。After the monomer was completely added dropwise, the reaction was continued at 80'C for 2 hours to complete the polymerization.
この組成物をクリスタルコート紙（日本加工製紙（株）
製）に塗布し、１００℃−２分間（塗布量ドライ３０〜
４０ ｇ７ｍ２）加熱乾燥して試料片を得た。This composition was applied to crystal coated paper (Nippon Kako Paper Co., Ltd.).
(manufactured by) and 100℃ for 2 minutes (coating amount dry 30 ~
40g7m2) was dried by heating to obtain a sample piece.
次に上記試料をステンレス板に貼合せ、ＪＩＳ法に準じ
てロール圧着し、ショパー型剥離試験機にて１８０度剥
離強度、ポールタック及び剪断力を測定し、曲面を有す
る各種容器に貼付及び市販段ホールケースの封緘に供し
た。Next, the above sample was laminated to a stainless steel plate, roll pressure bonded according to JIS method, 180 degree peel strength, pole tack and shear force were measured using a Schopper type peel tester, and the sample was laminated to various curved containers and sold. It was used to seal a corrugated hole case.
結果を表１に示す。The results are shown in Table 1.
実施例 ２
純 水 ７０
部酢酸ソーダ ０．６部を
計量し、１５ＰＰＭの撹拌下に８０℃に加熱しておく。Example 2 Pure water 70
Measure out 0.6 parts of sodium acetate and heat to 80° C. while stirring at 15 PPM.
次いて
アクリル酸２−エチルヘキシル ５８ 部アクリル
酸ブチル ２７ 部酢酸ビニル
ＩＯ部アクリル酸
３ 部ジブチルジアリルアンモニウム
クロライド ２ 部の混合物
と１０％過硫酸アンモニウム水溶液６部を８０°Ｃに保
たれた反応系中に３時間にわたって均等に滴下し重合さ
せる。モノマーかすべて滴下した後、８０°Ｃて２時間
反応を続行して重合を完結させた。この組成物を実施例
１と同様に操作して試料片を作成、試験を行った。結果
を表１に示す。Next, 2-ethylhexyl acrylate 58 parts butyl acrylate 27 parts vinyl acetate
IO part acrylic acid
A mixture of 3 parts dibutyldiallylammonium chloride and 2 parts and 6 parts of a 10% ammonium persulfate aqueous solution are uniformly dropped into a reaction system maintained at 80°C over 3 hours to polymerize. After all the monomers were added dropwise, the reaction was continued at 80°C for 2 hours to complete the polymerization. This composition was operated in the same manner as in Example 1 to prepare sample pieces and tested. The results are shown in Table 1.
比較例 ｌ
実施例１においてジメチルジアリルアンモニウムクロラ
イドを配合しないで、実施例１と同様に操作して組成物
を得、これより試料片を作成、評価を行った。測定結果
を表１に示す。Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that dimethyldiallylammonium chloride was not blended, and sample pieces were prepared from this and evaluated. The measurement results are shown in Table 1.
実施例 ３
純 水 ６８ 部
第２リン酸ソーダ ０．６部ドデシル
ベンセンスルホネート １ 部を計量し、１５０
ＰＰＭの撹拌下に８０°Ｃに加熱しておく次いて、
アクリル酸２エチルヘキノル ８０ 部酢酸ビニ
ル ５部
アクリル酸 ５ 部
ジメチルジアリルアンモニウム
クロライド １０ 部の混合物
と５％過硫酸カリウム水溶液６部を８０°Ｃに保たれた
反応系中に３時間にわたって均等に滴下し重合させた。Example 3 Weigh out 68 parts of pure water, 0.6 parts of dibasic sodium phosphate, and 1 part of dodecyl benzene sulfonate.
PPM was heated to 80°C with stirring, and then a mixture of 80 parts of 2-ethylhexynol acrylate, 5 parts of vinyl acetate, 5 parts of acrylic acid, and 10 parts of dimethyldiallylammonium chloride and 6 parts of a 5% aqueous potassium persulfate solution were heated at 80°C. The mixture was evenly added dropwise over 3 hours into the reaction system maintained at a temperature of 40°C for polymerization.
モノマーかすへて滴下した後、８０°Ｃて２時間反応を
続行し、重合を完結させた。After the monomer was added dropwise, the reaction was continued at 80°C for 2 hours to complete the polymerization.
この組成物を上質紙（４５ｋｇ）に塗布し、１００°Ｃ
−２分間（塗布量ドライ２０ｇ／ｍ２）加熱乾燥して試
料片を得た。This composition was applied to high-quality paper (45 kg) and heated to 100°C.
A sample piece was obtained by heating and drying for -2 minutes (dry coating amount: 20 g/m2).
次に上記試料片をステンレス板に貼合せ、ＪＩＳ法に準
してロール圧着し、ショパー型剥離試験機にて１８０度
剥離強度を測定し、各種被着体に対する汚染性を調へた
。結果を下記の表に示す。Next, the above-mentioned sample piece was laminated to a stainless steel plate, roll-pressed according to the JIS method, and the 180 degree peel strength was measured using a Schopper type peel tester to check the contamination of various adherends. The results are shown in the table below.
実施例 ４
純 水 ７０
部酢酸ソーダ ０．６部を計
量し、１５０ ＰＰＭの撹拌下に８０°Ｃに加熱してお
く。次いて、
アクリル酸２−エチルヘキシル ６５ 部アクリル
酸ブチル １７ 部酢酸ビニル
ｌＯ部アクリル酸
２ 部ジメチルジアリルアンモニウム
クロライド ５ 部の混合物
と１０％過硫酸アンモニウム水溶液６部を８０℃に保た
れた反応系中に３時間にわたって均等に滴下し重合させ
る。モノマーかすへて滴下した後、８０’Ｃて２時間反
応を続行して重合を完結させた。Example 4 Pure water 70
Weigh out 0.6 parts of sodium acetate and heat to 80°C while stirring at 150 PPM. Next, 65 parts of 2-ethylhexyl acrylate, 17 parts of butyl acrylate, and vinyl acetate.
lO part acrylic acid
A mixture of 2 parts and 5 parts of dimethyldiallylammonium chloride and 6 parts of a 10% ammonium persulfate aqueous solution are uniformly dropped into a reaction system maintained at 80° C. over a period of 3 hours to polymerize. After the monomer was added dropwise, the reaction was continued at 80'C for 2 hours to complete the polymerization.
この組成物を実施例３と同様に操作して試料片を作成し
、同様に接着力と各種被着体に対する汚染性を調へた結
果を表２に示す。Sample pieces were prepared using this composition in the same manner as in Example 3, and the adhesive strength and staining properties on various adherends were similarly examined. Table 2 shows the results.
比較例 ２
実施例４においてジブチルジアリルアンモニウムクロラ
イドを配合しないで、実施例４と同様に操作して試料片
を作成、比較を行なった。測定結果を表２に示す。Comparative Example 2 Sample pieces were prepared and compared in the same manner as in Example 4, except that dibutyl diallylammonium chloride was not blended. The measurement results are shown in Table 2.
本発明の感圧性接着剤組成物は、高接着力、高粘着性で
かつ高剪断力であるため、金属、ガラス、陶器、塩ビ、
ポリエチレン、等の被着体の種類を選ばす適用すること
かできる。特に容器の曲面や屈曲した個所、ケースの封
緘用等ラベル、シール等の基材の復元力か働くような個
所に貼着しても時間の経過とともにラベル、シールか部
分的に剥れてくるようなことかない。The pressure-sensitive adhesive composition of the present invention has high adhesive strength, high tackiness, and high shearing force, so it can be applied to metals, glass, ceramics, PVC, etc.
It can be applied to any type of adherend such as polyethylene. In particular, labels and stickers may partially peel off over time even if they are applied to curved or bent areas of containers, cases used for sealing, etc., where the restoring force of the base material acts. That doesn't happen.
また、本発明の感圧性接着剤組成物は、ジアルキルジア
リルアンモニウムハライドの配合量により再剥離性の感
圧接着剤から接着強度を重視する用途まで、巾広く設計
することかできる。Further, the pressure-sensitive adhesive composition of the present invention can be designed in a wide range of applications, from removable pressure-sensitive adhesives to applications where adhesive strength is important, depending on the amount of dialkyl diallylammonium halide.
書（方
許庁
事件の表示
平成
２年特許願第
２１、
発明の名称
感圧性接着剤
補正をする者
事件との関係 特許出願人
住 所 東京都中央区京橋二丁目３番１３号
４、補正命令の日付
平成２年５月１４日（発送日平成２年５月２９日）補正
の対象(Representation of Patent Office Case No. 21 of 1990, Name of the Invention Relationship with the Pressure Sensitive Adhesive Amendment Case Patent Applicant Address 2-3-13-4, Kyobashi, Chuo-ku, Tokyo, Amendment) Date of order: May 14, 1990 (Date of dispatch: May 29, 1990) Subject to amendment
Claims (1)
ル酸アルキルエステル５０〜９９．８９重量％（ｂ）α
，β−不飽和カルボン酸０．１〜１５重量％（ｃ）ジア
ルキルジアリルアンモニウムハライド０．０１〜２０重
量％ （ｄ）上記以外のビニル系モノマー ０〜４９．８９重量％ を共重合してなることを特徴とする感圧性接着剤。[Claims] 1. (a) 50 to 99.89% by weight of an acrylic acid alkyl ester whose alkyl group has 4 to 12 carbon atoms (b) α
, β-unsaturated carboxylic acid 0.1 to 15% by weight (c) dialkyl diallylammonium halide 0.01 to 20% by weight (d) vinyl monomer other than the above 0 to 49.89% by weight copolymerized A pressure-sensitive adhesive characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4121590A JPH0786189B2 (en) | 1990-02-23 | 1990-02-23 | Pressure sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4121590A JPH0786189B2 (en) | 1990-02-23 | 1990-02-23 | Pressure sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03244685A true JPH03244685A (en) | 1991-10-31 |
| JPH0786189B2 JPH0786189B2 (en) | 1995-09-20 |
Family
ID=12602178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4121590A Expired - Fee Related JPH0786189B2 (en) | 1990-02-23 | 1990-02-23 | Pressure sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0786189B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076040C (en) * | 1997-09-19 | 2001-12-12 | 中国科学院化学研究所 | Adhesive for cell and its preparation method and use |
| CN1077910C (en) * | 1997-09-19 | 2002-01-16 | 中国科学院化学研究所 | Method for preparing self-thickening adhesive |
| JP2007513240A (en) * | 2003-12-02 | 2007-05-24 | スリーエム イノベイティブ プロパティズ カンパニー | Cationic microsphere and method for producing cationic microsphere |
| WO2010044232A1 (en) * | 2008-10-14 | 2010-04-22 | 日本化薬株式会社 | Polarizing plate |
-
1990
- 1990-02-23 JP JP4121590A patent/JPH0786189B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076040C (en) * | 1997-09-19 | 2001-12-12 | 中国科学院化学研究所 | Adhesive for cell and its preparation method and use |
| CN1077910C (en) * | 1997-09-19 | 2002-01-16 | 中国科学院化学研究所 | Method for preparing self-thickening adhesive |
| JP2007513240A (en) * | 2003-12-02 | 2007-05-24 | スリーエム イノベイティブ プロパティズ カンパニー | Cationic microsphere and method for producing cationic microsphere |
| WO2010044232A1 (en) * | 2008-10-14 | 2010-04-22 | 日本化薬株式会社 | Polarizing plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0786189B2 (en) | 1995-09-20 |
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