JPS63130685A - Pressure-sensitive adhesive composition - Google Patents
Pressure-sensitive adhesive compositionInfo
- Publication number
- JPS63130685A JPS63130685A JP27518386A JP27518386A JPS63130685A JP S63130685 A JPS63130685 A JP S63130685A JP 27518386 A JP27518386 A JP 27518386A JP 27518386 A JP27518386 A JP 27518386A JP S63130685 A JPS63130685 A JP S63130685A
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- acrylic copolymer
- adhesive composition
- crosslinking agent
- 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.)
- Pending
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 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
- -1 amine compound Chemical class 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 125000004069 aziridinyl group Chemical group 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000035945 sensitivity Effects 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
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-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
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FYAMXEPQQLNQDM-UHFFFAOYSA-N Tris(1-aziridinyl)phosphine oxide Chemical compound C1CN1P(N1CC1)(=O)N1CC1 FYAMXEPQQLNQDM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000002075 main ingredient 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 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
- YVOQADGLLJCMOE-UHFFFAOYSA-N n-[6-(aziridine-1-carbonylamino)hexyl]aziridine-1-carboxamide Chemical compound C1CN1C(=O)NCCCCCCNC(=O)N1CC1 YVOQADGLLJCMOE-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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-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
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の目的〕
（産業上の利用分野）
本発明はアクリル系の溶剤型感圧性接着剤組成物に関し
、より詳しくは、速硬化性の優れた硬化剤を配合し、か
つポットライフの長い作業特性に優れた感圧性接着剤組
成物に関する。[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention relates to an acrylic solvent-based pressure-sensitive adhesive composition, and more specifically, it relates to an acrylic solvent-based pressure-sensitive adhesive composition, and more specifically, to an acrylic solvent-based pressure-sensitive adhesive composition containing a curing agent having excellent fast curing properties. The present invention relates to a pressure-sensitive adhesive composition having a long pot life and excellent working properties.
（従来の技術）
アクリル系共重合体からなる感圧性接着剤は、凝集性お
よび感温性が悪く、これを改良するために官能基を導入
したアクリル系樹脂を、インシアネート化合物、メラミ
ン系樹脂、エポキシ系樹脂、アジリジニル化合物等の架
橋剤で架橋処理する手法が知られている。このように架
橋剤を配合したアクリル系感圧性接着剤は、凝集力が増
大し感温特性も向上するが、イソシアネート化合物、メ
ラミン系樹脂、エポキシ系樹脂のような架橋剤は１反応
性が低いために長い硬化処理時間を必要とし、しかも得
られた感圧性接着剤層には未反応の架橋剤が残存しやす
く。(Prior art) Pressure-sensitive adhesives made of acrylic copolymers have poor cohesiveness and temperature sensitivity. , epoxy resins, aziridinyl compounds, and other crosslinking agents are known. Acrylic pressure-sensitive adhesives containing crosslinking agents have increased cohesive force and improved temperature sensitivity, but crosslinking agents such as isocyanate compounds, melamine resins, and epoxy resins have low reactivity. Therefore, a long curing time is required, and unreacted crosslinking agent tends to remain in the resulting pressure-sensitive adhesive layer.
これが接着剤の性能に経時的な性能低下を招く傾向があ
る。また、イソシアネート化合物は反応性は高いが、空
気中の水分とも反応するので接着剤組成物のポットライ
フが短く接着剤組成物を支持体に塗布する際の作業性に
おいて良好であるとは言い難い。This tends to cause the performance of the adhesive to deteriorate over time. In addition, although isocyanate compounds have high reactivity, they also react with moisture in the air, so the pot life of the adhesive composition is short and it cannot be said that they are good in terms of workability when applying the adhesive composition to a support. .
アジリジニル化合物も反応性が高（粘着剤の経時性能劣
化がないが、ポットライフが短く実用的な使用は不可能
であった。Aziridinyl compounds also have high reactivity (no deterioration of adhesive performance over time), but their short pot life makes them impossible to use for practical purposes.
（発明が解決しようとする問題点）
本発明は上記架橋剤の配合に伴う欠点を全て解消したも
のであり、ポットライフが長く作業性に優れ。(Problems to be Solved by the Invention) The present invention eliminates all the drawbacks associated with the above-mentioned combination of crosslinking agents, and has a long pot life and excellent workability.
感圧性接着剤の経時の性能劣化のない感圧性接着剤組成
物を提供するものである。The object of the present invention is to provide a pressure-sensitive adhesive composition that does not deteriorate in performance over time.
（問題点を解決するための手段） すなわち９本発明は。 (Means for solving problems) In other words, the present invention is as follows.
炭素数４〜１２のアルキル基を有する（メタ）アクリル
酸アルキルエステル（ａ）
６０〜９９．８重量％
重合性不飽和カルボン酸（ｂ）
０．２〜１０重量％
上記以外の共重合可能なビニル系モノマー（ｃ）Ｏ〜３
９．８重量％
を有機溶剤中で共重合させて得られるアクリル系共重杏
体溶液に、揮発性アミン化合物と、架橋剤としてのアジ
リジニル化合物とを配合してなる感圧性接着剤組成物で
ある。(Meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms (a) 60 to 99.8% by weight Polymerizable unsaturated carboxylic acid (b) 0.2 to 10% by weight Copolymerizable with other than the above Vinyl monomer (c) O~3
A pressure-sensitive adhesive composition prepared by blending a volatile amine compound and an aziridinyl compound as a crosslinking agent into an acrylic copolymer solution obtained by copolymerizing 9.8% by weight in an organic solvent. be.
本発明において、炭素数４〜１２のアルキル基を有する
（メタ）アクリル酸エステル（ａ）としては。In the present invention, as the (meth)acrylic ester (a) having an alkyl group having 4 to 12 carbon atoms.
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２−エチルヘキシル等の直鎖または
分岐した脂肪族アルコールのアクリル酸エステルまたは
相当するメタアクリル酸エステルがある。Examples include acrylic esters of linear or branched aliphatic alcohols, such as butyl acrylate, hexyl acrylate, octyl acrylate, and 2-ethylhexyl acrylate, or corresponding methacrylic esters.
重合性不飽和カルボン酸（ｂ）としては、アクリル酸、
メタアクリル酸、クロトン酸、イタコン酸。As the polymerizable unsaturated carboxylic acid (b), acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid.
マレイン酸、フマール酸等の七ツマ−がある。重合性不
飽和カルボン酸（ｂ）は、アジリジニル化合物との架橋
点を形成するものであり、アクリル系共重合体中０．２
〜１０重量％の範囲で有効である。There are seven acids such as maleic acid and fumaric acid. The polymerizable unsaturated carboxylic acid (b) forms a crosslinking point with the aziridinyl compound, and contains 0.2% of the acrylic copolymer.
It is effective in the range of ~10% by weight.
上記（ａ）（ｂ）以外のビニル系モノマー（ｃ）として
は１例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビ
ニルのようなカルボン酸ビニル七ツマ−。Vinyl monomers (c) other than the above (a) and (b) include, for example, vinyl carboxylate monomers such as vinyl acetate, vinyl propionate, and vinyl butyrate.
アクリル酸β−ヒドロキシルエチル、アクリル酸β−ヒ
ドロキシルプロピルのような水酸基含有アクリル酸エス
テルおよび対応するメタクリル酸エステル。Hydroxyl group-containing acrylic esters such as β-hydroxyethyl acrylate, β-hydroxylpropyl acrylate, and the corresponding methacrylic esters.
スチレンおよびその誘導体等がある。これらの共重合可
能なモノマー（ｃ）は、アクリル系共重合体中θ〜３’
９．８重量％の範囲で使用することができる。Examples include styrene and its derivatives. These copolymerizable monomers (c) are θ~3' in the acrylic copolymer.
It can be used in a range of 9.8% by weight.
本発明においてアクリル系共重合体は通常の溶液重合の
手法を用いて合成することができる。すなわち、上記（
ａ）（ｂ）及び必要に応じて（ｃ）からなる七ツマ−の
混合物を有機溶剤中でラジカル発生剤の存在下に共重合
させれば良い。In the present invention, the acrylic copolymer can be synthesized using a conventional solution polymerization method. That is, the above (
A mixture of a), (b) and optionally (c) may be copolymerized in an organic solvent in the presence of a radical generator.
本発明におけるアミン化合物は、有機溶剤中でアクリル
系共重合体中のカルボキシル基をブロックし。The amine compound in the present invention blocks carboxyl groups in the acrylic copolymer in an organic solvent.
アジリジニル化合物とカルボキシル基との反応を阻害す
るが、接着剤組成物の塗布、乾燥過程では速やかに揮発
して架橋反応を有効に進行させる。このようなアミン化
合物としては９例えば、エチルアミン。Although it inhibits the reaction between the aziridinyl compound and the carboxyl group, it quickly volatilizes during the coating and drying process of the adhesive composition, allowing the crosslinking reaction to proceed effectively. Examples of such amine compounds include ethylamine.
ジエチルアミン、トリエチルアミン、プロピルアミン、
ジプロとルアミノ。イソプロピルアミン、ジイソプロピ
ルアミン、ブチルアミン、２−エチルヘキシルアミン、
ジー２−エチルヘキシルアミン、ジメチルアミノプロと
ルアミノ。エチレンジアミン、ジエチレントリアミン、
トリエチレンテトラミン、テトラエチレンペンタミン、
プロピレンジアミン、ジメチルアミノエタノール等があ
げられる。diethylamine, triethylamine, propylamine,
Zipro and Ruamino. Isopropylamine, diisopropylamine, butylamine, 2-ethylhexylamine,
Di-2-ethylhexylamine, dimethylaminopro and ruamino. Ethylenediamine, diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
Examples include propylene diamine and dimethylaminoethanol.
揮発性アミン化合物はアクリル系共重合体のカルボキシ
ル基よりモル的に過剰な量が配合され９通常アクリル系
共重合体１００重量部に対して０．０５〜１．０重量部
が適当である。The volatile amine compound is blended in an amount in molar excess relative to the carboxyl groups of the acrylic copolymer, and is usually 0.05 to 1.0 parts by weight per 100 parts by weight of the acrylic copolymer.
本発明における架橋剤としてのアジリジニル化合物は、
１分子中に少なくともアジリジニル基を２個以上有する
化合物であり９例えば、トリー１−アジリジニルホスフ
ィンオキサイド、Ｎ、Ｎ’−へキサメチレン−１，６−
ビス（１−アジリジンカルボキシアマイド）、Ｎ、Ｎ’
−ジフェニルエタン−４゜４′−ビス（１−アジリジン
カルボキシルアマイド）、トリメチロールプロパン−ト
リーβ−アジリジニルプロピオネート、Ｎ、Ｎ’−）ル
エンー２．４−ビス（１−アジリジンカルボキシアミド
）、ビスイソフタロイル−１−（２−メチルアジリジン
）。The aziridinyl compound as a crosslinking agent in the present invention is
It is a compound having at least two or more aziridinyl groups in one molecule.9 For example, tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-
Bis(1-aziridinecarboxamide), N, N'
-diphenylethane-4゜4'-bis(1-aziridinecarboxylamide), trimethylolpropane-triβ-aziridinylpropionate, N,N'-)luene-2,4-bis(1-aziridinecarboxylamide) ), bisisophthaloyl-1-(2-methylaziridine).
トリス−１−（２−メチルアジリジン）ホスフィン。Tris-1-(2-methylaziridine)phosphine.
トリメチロールプロパン−トリーβ−（２−メチルアジ
リジン）プロピオネート等がある。これらの１種もしく
は２種以上を併用してもよい。Examples include trimethylolpropane-triβ-(2-methylaziridine)propionate. One or more of these may be used in combination.
上記アジリジニル化合物はアクリル系共重合体１ｄＯ重
量部に対して、０．０１〜２．０重量部好ましくは、０
．０５〜１．５重量部の範囲で使用される。The above aziridinyl compound is preferably 0.01 to 2.0 parts by weight per 1 dO part by weight of the acrylic copolymer.
．． It is used in an amount of 0.05 to 1.5 parts by weight.
本発明の感圧性接着剤組成物は９通常、アクリル系共重
合体溶液からなる主剤と、架橋剤成分とからなる２液型
感圧性接着剤として使用されるが、アミン化合物は、ア
クリル系共重合体溶液に配合しても。The pressure-sensitive adhesive composition of the present invention is usually used as a two-component pressure-sensitive adhesive consisting of a main ingredient made of an acrylic copolymer solution and a crosslinking agent component. Even if it is blended into a polymer solution.
架橋剤成分中に配合しても良い。It may also be blended into the crosslinking agent component.
以下、実施例について説明する。例中「重量部」は「部
」を示す。Examples will be described below. In the examples, "parts by weight" refers to "parts".
（実施例）
実施例１
アクリル酸−２−エチルヘキシル ４７． Ｏｓアク
リル酸ブチル ３３．０部酢酸ビニル
１９．０部アクリル酸
１．０部過酸化ベンゾイル
０．１部上記組成物を酢酸エチルの還
流温度で反応させ。(Example) Example 1 2-ethylhexyl acrylate 47. Os Butyl acrylate 33.0 parts Vinyl acetate 19.0 parts Acrylic acid
1.0 part benzoyl peroxide
0.1 part of the above composition was reacted at the reflux temperature of ethyl acetate.
アクリル系共重合体を得た。このアクリル系共重合体を
含む３５％酢酸エチル溶液１００部に対し、ジメチルア
ミノエタノール０．３部を添加し、十分に混合した。こ
の混合物にトリメチロールプロパントリアジリジニルプ
ロビオネートを０．３部添加し、感圧性接着剤組成物を
得た。この感圧性接着剤組成物の配合直後の液温４０℃
の粘度は１３００ｃｐｓ、４部℃で８時間保存後の粘度
は１５００ｃｐｓで塗工可能であった。An acrylic copolymer was obtained. To 100 parts of a 35% ethyl acetate solution containing this acrylic copolymer, 0.3 part of dimethylaminoethanol was added and thoroughly mixed. 0.3 parts of trimethylolpropane triaziridinylprobionate was added to this mixture to obtain a pressure-sensitive adhesive composition. The liquid temperature immediately after blending this pressure-sensitive adhesive composition is 40°C.
The viscosity of 4 parts was 1300 cps, and after storage at 4 parts for 8 hours, the viscosity was 1500 cps, allowing coating.
この感圧性接着剤組成物をポリエステルフィルム上に塗
工し、２５ｇ／ｒｒｒの感圧性接着剤層を形成した。こ
の感圧性接着剤の２４時間後の接着力は、３５０ ｇ
／ ２５ｍｍ ’（対ステンレス）であり、保持力、粘
着力ともに優れていた。This pressure-sensitive adhesive composition was coated on a polyester film to form a 25 g/rrr pressure-sensitive adhesive layer. The adhesive strength of this pressure sensitive adhesive after 24 hours is 350 g
/ 25 mm' (vs. stainless steel), and both holding power and adhesive strength were excellent.
比較例１
実施例１においてアミン化合物を添加しないでアジリジ
ニル化合物を配合した感圧性接着剤組成物の配合直後の
粘度は１３００ｃｐｓであったが、２時間後では１６０
０ｃｐｓ、４時間後にはゲル化して塗工できなかった。Comparative Example 1 The viscosity of the pressure-sensitive adhesive composition in Example 1 in which an aziridinyl compound was blended without adding an amine compound was 1300 cps immediately after blending, but after 2 hours it was 160 cps.
After 0 cps and 4 hours, it gelled and could not be coated.
実施例２
アクリル酸−２−エチルヘキシル ６３．０ 部アク
リル酸ブチル ３０．０部アクリル酸
７．０部過酸化ベンゾイル
０．１部上記組成物を酢酸エチル
の還流温度で反応させ。Example 2 63.0 parts of 2-ethylhexyl acrylate 30.0 parts of butyl acrylate 7.0 parts of acrylic acid 0.1 part of benzoyl peroxide The above composition was reacted at the reflux temperature of ethyl acetate.
アクリル系共重合体を得た。このアクリル系共重合体を
含む４０％酢酸エチル溶液１００部に対し、プロピルア
ミン０．５部を添加し、十分に混合した。この混合物に
トリメチロールプロパントリアジリジニルプロビオネー
トを０．３部添加し、感圧性接着剤組成物を得た。この
感圧性接着剤組成物の配合直後の液温４０℃の粘度は２
５００ｃｐｓ、４０℃で８時間保存後の粘度は２８００
ｃｐｓで塗工可能であった。An acrylic copolymer was obtained. To 100 parts of a 40% ethyl acetate solution containing this acrylic copolymer, 0.5 part of propylamine was added and thoroughly mixed. 0.3 parts of trimethylolpropane triaziridinylprobionate was added to this mixture to obtain a pressure-sensitive adhesive composition. The viscosity of this pressure-sensitive adhesive composition at a liquid temperature of 40°C immediately after blending is 2.
500cps, viscosity after storage at 40℃ for 8 hours is 2800
It was possible to coat with cps.
この感圧性接着剤組成物をポリエステルフィルム上に塗
工し、２５ｇ／ｒｒｒの感圧性接着剤層を形成した。こ
の感圧性接着剤の２４時間後の接着力は、２３０ ｇ／
２５ｍｍ （対ステンレス）であり、保持力、粘着力と
もに優れていた。This pressure-sensitive adhesive composition was coated on a polyester film to form a 25 g/rrr pressure-sensitive adhesive layer. The adhesive strength of this pressure sensitive adhesive after 24 hours is 230 g/
It was 25 mm (vs. stainless steel) and had excellent holding power and adhesive strength.
比較例２
実施例２においてアミン化合物を添加しないでアジリジ
ニル化合物を配合した感圧性接着剤組成物の配合直後の
粘度は２５００ｃｐｓであったが、２時間後にはゲル化
して塗工できなかった。Comparative Example 2 The pressure-sensitive adhesive composition of Example 2, in which an aziridinyl compound was blended without adding an amine compound, had a viscosity of 2500 cps immediately after blending, but it gelled after 2 hours and could not be coated.
実施例３
実施例１のアクリル系共重合体の溶液１００部にプロピ
ルアミン０．５部とビスイソフタロイル−１−（２−メ
チルアジリジン）１．０部を配合した感圧性接着剤組成
物の配合直後の液温４０℃の粘度は１３ＱＱｃｐｓ、４
０℃で８時間保存後の粘度は１３５Ｑｃｐｓで塗工可能
であった。Example 3 A pressure-sensitive adhesive composition containing 0.5 parts of propylamine and 1.0 parts of bisisophthaloyl-1-(2-methylaziridine) in 100 parts of the solution of the acrylic copolymer of Example 1. The viscosity at a liquid temperature of 40℃ immediately after blending is 13QQcps, 4
After storage at 0° C. for 8 hours, the viscosity was 135 Qcps and coating was possible.
この感圧性接着剤組成物をポリエステルフィルム上に塗
工し、２５ｇ１０ｆの感圧性接着剤層を形成した。この
感圧性接着剤の２４時間後の接着力は、７００ｇ／２５
鰭（対ステンレス）であり、保持力、粘着力ともに優れ
ていた。This pressure-sensitive adhesive composition was coated on a polyester film to form a pressure-sensitive adhesive layer of 25 g and 10 f. The adhesive strength of this pressure sensitive adhesive after 24 hours is 700g/25
It has a fin (vs. stainless steel) and has excellent holding power and adhesive strength.
比較例３
実施例３においてアミン化合物を添加しないでアジリジ
ニル化合物を配合した感圧性接着剤組成物の配合直後の
粘度は７３ ＱＱｃｐ！であったが、４時間後にはゲ
ル化して塗工できなかった。Comparative Example 3 The viscosity of the pressure-sensitive adhesive composition of Example 3 in which an aziridinyl compound was blended without adding an amine compound was 73 QQcp! However, it gelled after 4 hours and could not be coated.
本発明の感圧性接着剤組成物は、架橋点としてカルボキ
シル基を導入したアクリル系共重合体に反応性の高い架
橋剤を配合することによって、感圧性接着剤の凝集力を
高め、かつ未反応の架橋剤による感圧性接着剤の経時性
能劣化が防止される。さらに。The pressure-sensitive adhesive composition of the present invention increases the cohesive strength of the pressure-sensitive adhesive by blending a highly reactive crosslinking agent into an acrylic copolymer into which carboxyl groups are introduced as crosslinking points, and Deterioration of the performance of the pressure sensitive adhesive over time due to the crosslinking agent is prevented. moreover.
アミン化合物を配合したので組成物溶液のポットライフ
が伸び、粘着テープ、粘着ラベル等の製造工程において
作業に特別な配慮をすることもなく使用できるので実用
的価値が高い。Since the amine compound is blended, the pot life of the composition solution is extended, and it can be used without special consideration in the production process of adhesive tapes, adhesive labels, etc., so it has high practical value.
Claims (1)
リル酸アルキルエステル（ａ） ６０〜９９．８重量％ 重合性不飽和カルボン酸（ｂ） ０．２〜１０重量％ 上記以外の共重合可能なビニル系モノマー（ｃ）０〜３
９．８重量％ を有機溶剤中で共重合させて得られるアクリル系共重合
体溶液に、揮発性アミン化合物と、架橋剤としてのアジ
リジニル化合物とを配合してなる感圧性接着剤組成物。[Claims] 1. (meth)acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms (a) 60 to 99.8% by weight Polymerizable unsaturated carboxylic acid (b) 0.2 to 10% by weight % Copolymerizable vinyl monomer other than the above (c) 0-3
A pressure-sensitive adhesive composition comprising a volatile amine compound and an aziridinyl compound as a crosslinking agent mixed with an acrylic copolymer solution obtained by copolymerizing 9.8% by weight in an organic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27518386A JPS63130685A (en) | 1986-11-20 | 1986-11-20 | Pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27518386A JPS63130685A (en) | 1986-11-20 | 1986-11-20 | Pressure-sensitive adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63130685A true JPS63130685A (en) | 1988-06-02 |
Family
ID=17551833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27518386A Pending JPS63130685A (en) | 1986-11-20 | 1986-11-20 | Pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63130685A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270780A (en) * | 1988-09-06 | 1990-03-09 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
| JPH03281586A (en) * | 1990-03-29 | 1991-12-12 | Sekisui Chem Co Ltd | Acrylic pressure-sensitive adhesive composition |
| JP2017149837A (en) * | 2016-02-24 | 2017-08-31 | 旭ファイバーグラス株式会社 | Production method of thermosetting aqueous binder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5087433A (en) * | 1973-12-07 | 1975-07-14 | ||
| JPS5089430A (en) * | 1973-12-13 | 1975-07-17 | ||
| JPS5147458A (en) * | 1974-10-01 | 1976-04-23 | Nordberg Carl Eric Bertil | |
| JPS60120777A (en) * | 1983-12-02 | 1985-06-28 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
-
1986
- 1986-11-20 JP JP27518386A patent/JPS63130685A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5087433A (en) * | 1973-12-07 | 1975-07-14 | ||
| JPS5089430A (en) * | 1973-12-13 | 1975-07-17 | ||
| JPS5147458A (en) * | 1974-10-01 | 1976-04-23 | Nordberg Carl Eric Bertil | |
| JPS60120777A (en) * | 1983-12-02 | 1985-06-28 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0270780A (en) * | 1988-09-06 | 1990-03-09 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
| JPH03281586A (en) * | 1990-03-29 | 1991-12-12 | Sekisui Chem Co Ltd | Acrylic pressure-sensitive adhesive composition |
| JP2017149837A (en) * | 2016-02-24 | 2017-08-31 | 旭ファイバーグラス株式会社 | Production method of thermosetting aqueous binder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5869568A (en) | One-part cold crosslinking emulsion composition and method of manufacturing the same | |
| JP2782991B2 (en) | Adhesive composition | |
| JPS63130685A (en) | Pressure-sensitive adhesive composition | |
| JPH07157741A (en) | Repeelable type aqueous pressure-sensitive composition | |
| JPS60166366A (en) | One-pack type aqueous emulsion adhesive composition | |
| GB897726A (en) | A process for the manufacture of hardened artificial resin materials and compositions therefor | |
| JPH09176603A (en) | Self-adhesive for polarizing and phase-contrast plates | |
| JP3029707B2 (en) | Curable resin composition | |
| JPH0270780A (en) | Pressure-sensitive adhesive composition | |
| JPH03111471A (en) | Water-based adhesive composition | |
| JPH02178379A (en) | Acrylic pressure-sensitive adhesive | |
| JPH06122859A (en) | Pressure-sensitive adhesive composition | |
| JP3029708B2 (en) | Curable resin composition | |
| JPH05186758A (en) | Pressure-sensitive adhesive composition | |
| JPH03265678A (en) | Water-base pressure-sensitive adhesive composition | |
| JP3237024B2 (en) | Self-crosslinking pressure-sensitive adhesive composition | |
| JPH0551566A (en) | Acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive tape, label or sheet | |
| JPH02178381A (en) | Tacky agent and tacky sheet using same tacky agent | |
| JPS5822059B2 (en) | Water-based pressure-sensitive adhesive composition for surface protection | |
| JP2993722B2 (en) | Adhesive paper | |
| JPH03128985A (en) | Solvent-base adhesive | |
| JPS6011568A (en) | Pressure-sensitive adhesive composition having anaerobic curability | |
| JPH03119086A (en) | Pressure-sensitive adhesive composition | |
| JPH06329978A (en) | Water-base coating composition | |
| JPS62100571A (en) | Water-dispersed pressure-sensitive adhesive composition |