JPH0794649B2 - Pressure sensitive adhesive composition - Google Patents
Pressure sensitive adhesive compositionInfo
- Publication number
- JPH0794649B2 JPH0794649B2 JP63222992A JP22299288A JPH0794649B2 JP H0794649 B2 JPH0794649 B2 JP H0794649B2 JP 63222992 A JP63222992 A JP 63222992A JP 22299288 A JP22299288 A JP 22299288A JP H0794649 B2 JPH0794649 B2 JP H0794649B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- weight
- pressure
- adhesive composition
- parts
- 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
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，速硬化性に優れた硬化剤を配合し，
かつ，ポットライフの長い作業性に優れ，経時性能の安
定した感圧接着剤組成物に関する。The present invention relates to an acrylic solvent-based pressure-sensitive adhesive composition, and more specifically, it contains a curing agent excellent in quick-curing property. Then
In addition, the present invention relates to a pressure-sensitive adhesive composition having a long pot life, excellent workability, and stable performance over time.
（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，イソシアネート化合物，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，エポキシ化合物のような架橋剤は，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，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
イプ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。更にエポキシ化合物
は，硬化処理を完全に行なった後の接着性組成物の基材
に対する密着性が充分であるとは言い難い。アジニジニ
ル化合物は比較的ポットライフが短く，硬化処理後の基
材に対する密着性も良好であるため，一部実用化されて
いるが，粘着剤の高温高湿時による経時性能安定性が充
分とは言い難い。(Prior Art) A pressure-sensitive adhesive made of an acrylic copolymer has poor cohesiveness and temperature sensitivity. To improve the pressure-sensitive adhesive, an acrylic resin introduced with a functional group is used as an isocyanate compound, a melamine resin, A method of performing a crosslinking treatment with a crosslinking agent such as an epoxy resin or an aziridinyl compound is known. Acrylic pressure-sensitive adhesives containing a cross-linking agent in this way have increased cohesive strength and improved temperature-sensitive properties, but cross-linking agents such as isocyanate compounds, melamine-based resins, and epoxy compounds have low reactivity. It requires a long curing time, and the unreacted cross-linking agent is likely to remain in the obtained pressure-sensitive adhesive layer, which tends to deteriorate the performance of the adhesive over time. Also, isocyanate compounds are highly reactive,
Since it also reacts with moisture in the air, pot potion of the adhesive composition is short, and workability in applying the adhesive composition to a support is not good. Furthermore, it is hard to say that the epoxy compound has sufficient adhesion to the base material of the adhesive composition after the curing treatment is completed. Azinidinyl compounds have a relatively short pot life and have good adhesion to the base material after curing treatment, so they have been partially put into practical use, but the stability of the performance of the pressure-sensitive adhesive over time at high temperature and high humidity is not sufficient. Hard to say.
（発明が解決しようとする課題） 本発明は上記架橋剤の配合に伴う欠点をすべて解消した
ものであり，ポットライフが長く，作業性に優れ，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。(Problems to be Solved by the Invention) The present invention solves all the drawbacks associated with the incorporation of the above-mentioned crosslinking agent, has a long pot life, is excellent in workability, and has a feeling that the pressure-sensitive adhesive does not deteriorate in performance over time. A pressure-sensitive adhesive composition is provided.
（課題を解決するための手段） 本発明は，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）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
可能なビニルモノマー（ｃ）０〜39.8重量％を有機溶媒
中で共重合させて得られるアクリル系共重合体固形分10
0重量部に対して，アジリジニル系化合物0.01〜10.0重
量部及びエポキシ系化合物0.01〜10.0重量部とを配合し
てなる感圧性接着剤組成物である。(Means for Solving the Problem) The present invention has an alkyl group having 4 to 12 carbon atoms (meth).
Acrylic ester (a) 60 to 99.8% by weight, polymerizable unsaturated carboxylic acid (b) 0.2 to 10% by weight, and copolymerizable vinyl monomer (c) 0 to 39.8% by weight other than the above in an organic solvent. Acrylic copolymer solids obtained by polymerization 10
A pressure-sensitive adhesive composition comprising 0.01 to 10.0 parts by weight of an aziridinyl compound and 0.01 to 10.0 parts by weight of an epoxy compound with respect to 0 part by weight.
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，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枝した
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
メタクリル酸エステルがある。In the present invention, the (meth) acrylic acid ester (a) having an alkyl group having 4 to 12 carbon atoms includes butyl acrylate, hexyl acrylate, octyl acrylate,
There are acrylic or corresponding methacrylic acid esters of linear or branched aliphatic alcohols such as 2-ethylhexyl acrylate.
重合性不飽和カルボン酸（ｂ）としては，アクリル酸，
メタクリル酸，クロトン酸，イタコン酸，マレイン酸，
フマール酸等のモノマーがある。As the polymerizable unsaturated carboxylic acid (b), acrylic acid,
Methacrylic acid, crotonic acid, itaconic acid, maleic acid,
There are monomers such as fumaric acid.
重合性不飽和カルボン酸（ｂ）は，アジリジニル化合物
及びエポキシ化合物との架橋点を形成するものであり，
アクリル系重合体中それぞれ0.2〜50重量％の範囲で有
効である。The polymerizable unsaturated carboxylic acid (b) forms a cross-linking point with the aziridinyl compound and the epoxy compound,
It is effective within the range of 0.2 to 50% by weight in the acrylic polymer.
上記（ａ）（ｂ）以外のビニル系モノマー（ｃ）として
は，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モノマー，アクリルβ−ヒ
ドロキシエチル，アクリル酸β−ヒドロキシプロピルの
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，スチレン，アクリロニトリルまた
その誘導体がある。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０〜39.8重量％の範囲で
使用することができる。Examples of vinyl-based monomers (c) other than the above (a) and (b) include vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl butyrate, β-hydroxyethyl acrylate and β-hydroxypropyl acrylate. There are various hydroxyl group-containing acrylic acid esters and corresponding methacrylic acid esters, styrene, acrylonitrile and their derivatives. The copolymerizable monomer (c) can be used in the range of 0 to 39.8% by weight of the acrylic copolymer.
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）からなるモノマー
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
合させればよい。In the present invention, the acrylic copolymer can be synthesized by using a usual solution polymerization method. That is, a mixture of the monomers (a) and (b) and optionally (c) may be copolymerized in an organic solvent in the presence of a radical generator.
本発明における架橋剤としてのアリジニル化合物は,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，例えば，トリ−１−アジリジニルホスフィン
オキサイド,N,N′−ヘキサメチレン−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−β−アジリジ
ニルプロピオネート,N,N′−トルエン−2,4−2,4−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）ホスフィン，トリ
メチロールプロパン−トリ−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
種以上の併用してもよい。The aridinyl compound as a cross-linking agent in the present invention is a compound having at least two aziridinyl groups in one molecule. For example, tri-1-aziridinylphosphine oxide, N, N′-hexamethylene-1,6 -Bis (1-
Aziridinecarboxyamide), N, N'-diphenylethane-4,4'-bis (1-aziridinecarboxyamide), trimethylolpropane-tri-β-aziridinylpropionate, N, N'-toluene-2 , 4-2,4-bis (1-aziridinecarboxamide), bisisophthaloyl-1- (2-methylaziridine) phosphine, trimethylolpropane-tri-β- (2-methylaziridine) propionate and the like. One or two of these
You may use together 1 or more types.
上記アジリジニル化合物はアクリル系共重合体100重量
部に対して,0.01〜10.0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 aziridinyl compound is used in an amount of 0.01 to 10.0 parts by weight, preferably 0.05 to 1.5 parts by weight, based on 100 parts by weight of the acrylic copolymer.
本発明におけるエポキシ化合物は,1分子中に少なくとも
グリシジニ基を１個以上有する化合物であり，例えばビ
スフェノールＡ系エポキシ樹脂，ビスフェノールＦ系エ
ポキシ樹脂，またはその変性タイプや，フロログリシノ
ールトリグリシジルエーテル，トリヒドロキシビフェニ
ルトリグリシジルエーテル，テトラグリシジルベンゾフ
ェノン，ビスレゾルシノールテラグリシジルエーテル，
ビスフェノールＡジグリシジルエーテル，ビスフェノー
ルヘキサフルオロアセトンジグリシジルエーテル，レゾ
ルシノールジグリシジルエーテル,1,3−ビス〔１−（2,
3−エポキシプロパキシ）−１−トリフルオロメチル−
2,2,2−トリフルオロメチル〕ベンゼン等のグリシジル
エーテル，またシクロヘキセンオキサイド基，トリシク
ロデセンオキサイド基，シクロペンテンオキサイド基等
を有する環式脂肪族エポキシ樹脂，更に，フタル酸ジグ
リシジルエステル，テトラヒドロフタル酸ジグリシジル
エステル，ヘキサヒドロフタル酸ジグリシジルエステ
ル，ジグリシジルｐ−オキシ安息香酸，ダイマー酸グリ
シジルエステル等のグリシジルエステルや，ジグリシジ
ルヒダントイン，グリシジルグリシドオキシアルキルヒ
ダントイン，トリグリシジルイソシアヌレート等の複素
環式エポキシ樹脂，またその他脂肪族及び芳香族，無機
系エポキシ化合物がある。これらの１種もしくは２種以
上を併用してもよい。The epoxy compound in the present invention is a compound having at least one glycidinyl group in one molecule. For example, a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a modified type thereof, a phloroglicinol triglycidyl ether, and a triglycidyl ether Hydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol teraglycidyl ether,
Bisphenol A diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, resorcinol diglycidyl ether, 1,3-bis [1- (2,
3-epoxypropoxy) -1-trifluoromethyl-
Glycidyl ethers such as 2,2,2-trifluoromethyl] benzene, cycloaliphatic epoxy resins having cyclohexene oxide group, tricyclodecene oxide group, cyclopentene oxide group, etc., and further diphthalic acid diglycidyl ester, tetrahydrophthale Glycidyl esters such as acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester, etc., and heterocyclic systems such as diglycidyl hydantoin, glycidyl glycidoxyalkyl hydantoin, triglycidyl isocyanurate, etc. There are epoxy resins and other aliphatic, aromatic and inorganic epoxy compounds. You may use together 1 type (s) or 2 or more types.
上記エポキシ化合物はアクリル系共重合体100重量部に
対して,0.01〜10.0重量部，好ましくは0.05〜5.0重量部
の範囲で使用される。The epoxy compound is used in an amount of 0.01 to 10.0 parts by weight, preferably 0.05 to 5.0 parts by weight, based on 100 parts by weight of the acrylic copolymer.
本発明の感圧性接着剤組成物は，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，
あるいは３液型感圧性接着剤として使用されるが，エポ
キシ化合物の一部はアクリル系共重合体溶液に配合して
も，架橋剤成分に配合しても良く,2液型感圧接着剤とし
て使用される。The pressure-sensitive adhesive composition of the present invention is usually a two-pack type composed of a main agent composed of an acrylic copolymer solution and a cross-linking agent component,
Alternatively, it is used as a three-pack type pressure-sensitive adhesive, but a part of the epoxy compound may be blended in the acrylic copolymer solution or the cross-linking agent component. used.
（実 施 例） 以下，実施例により本発明を説明する。例中，部とは重
量部を，％とは重量％をそれぞれ表わす。(Examples) The present invention will be described below with reference to examples. In the examples, "part" means "part by weight" and "%" means "% by weight".
実施例 １ アクリル酸−２−エチルヘキシル 47.0部 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，アクリ
ル共重合体を得た。このアクリル共重合体を含む35％酢
酸エチル溶液100部に対し，ビスフェノールＡ型エポキ
シ（エピコート828;油化シェルエポキシ社製）1.0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ピオネートを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1500cps,40℃で８時間
保存後の粘度は1900cpsで塗工可能であった。Example 1 2-Ethylhexyl acrylate 47.0 parts Butyl acrylate 33.0 parts Vinyl acetate 19.0 parts Acrylic acid 1.0 parts Benzoyl peroxide 0.1 parts The above composition was reacted at the reflux temperature of ethyl acetate to obtain an acrylic copolymer. To 100 parts of a 35% ethyl acetate solution containing this acrylic copolymer, 1.0 part of bisphenol A type epoxy (Epicoat 828; manufactured by Yuka Shell Epoxy Co., Ltd.) was added and mixed sufficiently. 0.3 part of trimethylolpropane triaziridinyl propionate was added to this mixture to obtain a pressure-sensitive adhesive composition. Immediately after the pressure-sensitive adhesive composition was mixed, the viscosity at a liquid temperature of 40 ° C. was 1500 cps, and the viscosity after storage at 40 ° C. for 8 hours was 1900 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/m2の感圧性接着剤層を形成した。塗工後の硬
化に要する時間０℃の雰囲気下で測定したところ,3日間
と良好であった。This pressure-sensitive adhesive composition was coated on a polyester film to form a 25 g / m 2 pressure-sensitive adhesive layer. Time required for curing after coating When measured in an atmosphere of 0 ° C., it was good at 3 days.
この感圧性接着剤の24時間後の接着力は300g/25mm（対
ステンレス）であり，保持力，粘着力とも優れていた。
また，この感圧性接着剤の塗布されたポリエステルフィ
ルムを70℃以上で１ケ月間加熱処理をした後，貼着24時
間後の接着力は305g/25mmであり，加熱経時の影響を受
けず，耐熱性が非常に良好であることを認めた。The adhesive strength of this pressure-sensitive adhesive after 24 hours was 300 g / 25 mm (against stainless steel), and the holding power and adhesive strength were excellent.
In addition, the polyester film coated with this pressure-sensitive adhesive was heat-treated at 70 ° C or higher for 1 month, and the adhesive force after sticking for 24 hours was 305g / 25mm, which was not affected by heating. It was confirmed that the heat resistance was very good.
比較例 １ 実施例１において硬化剤としてエポキシ化合物を添加し
ないでアジリジニル化合物のみを配合した感圧性接着剤
組成物について実施例１と同様にして塗工した。塗工後
の硬化に有する時間を０℃の雰囲気下で測定したとこ
ろ,5日間と良好であった。Comparative Example 1 A pressure-sensitive adhesive composition prepared by adding only an aziridinyl compound without adding an epoxy compound as a curing agent in Example 1 was coated in the same manner as in Example 1. When the time required for curing after coating was measured in an atmosphere of 0 ° C., it was good at 5 days.
この感圧接着剤の24時間後の接着力は380g/25mm（対ス
テンレス）であったが,70℃以上で１ケ月間加熱処理を
した後の24時間後の接着力は650g/25mmであり熱経時安
定性が不良であった。The adhesive strength of this pressure-sensitive adhesive after 24 hours was 380 g / 25 mm (against stainless steel), but the adhesive strength after 24 hours after heat treatment at 70 ° C or higher for 1 month was 650 g / 25 mm. The thermal aging stability was poor.
比較例 ２ 実施例１においてアジリジニル化合物を添加しないでエ
ポキシ化合物のみを配合した感圧性接着剤組成物につい
て実施例１と同様にして塗工した。塗工後の硬化に有す
る時間を０℃の雰囲気下で測定したところ,14日を要
し，さらに表面基材ポリエステルフィルムとの密着性は
著しく不良であった。Comparative Example 2 A pressure-sensitive adhesive composition prepared by mixing only the epoxy compound without adding the aziridinyl compound in Example 1 was coated in the same manner as in Example 1. When the time required for curing after coating was measured in an atmosphere of 0 ° C., it took 14 days, and the adhesiveness with the surface-based polyester film was remarkably poor.
実施例 ２ アクリル酸−２−エチルヘキシル 66.0部 アクリル酸ブチル 30.0部 アクリル酸 4.0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，アクリ
ル共重合体を得た。このアクリル共重合体を含む40％酢
酸エチル溶液100重量部に対し,2,2′4,4′−テトラグリ
シドキシビフェニル0.2部を添加し，十分に混合した。
この混合物にビスイソフタロイル−１−（２−メチルア
ジリジン）0.1部を添加し，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℃での
粘度は2800cps,40℃で８時間の保存後の粘度は3200cps
で塗工可能であった。Example 2 2-Ethylhexyl acrylate 66.0 parts Butyl acrylate 30.0 parts Acrylic acid 4.0 parts Benzoyl peroxide 0.1 parts The above composition was reacted at the reflux temperature of ethyl acetate to obtain an acrylic copolymer. To 100 parts by weight of a 40% ethyl acetate solution containing this acrylic copolymer, 0.2 part of 2,2'4,4'-tetraglycidoxybiphenyl was added and mixed well.
To this mixture was added 0.1 part of bisisophthaloyl-1- (2-methylaziridine) to obtain a pressure sensitive adhesive composition. Immediately after the composition of this pressure-sensitive adhesive composition, the viscosity at a liquid temperature of 40 ° C. is 2800 cps, and the viscosity after storage at 40 ° C. for 8 hours is 3200 cps.
It was possible to coat with.
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/m2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330g/25mm（対ステンレ
ス）であり，硬化処理時間も０℃で３日と良好であっ
た。尚，表面基材ポリエステルフィルムとの密着性も優
れていることを認めた。This pressure-sensitive adhesive composition was coated on a polyester film to form a 25 g / m 2 pressure-sensitive adhesive layer. The adhesive strength of this pressure-sensitive adhesive after 24 hours was 330 g / 25 mm (against stainless steel), and the curing treatment time was good at 0 ° C. for 3 days. In addition, it was confirmed that the adhesiveness with the surface-based polyester film was also excellent.
比較例 ３ 実施例２においてアジリジニル化合物を添加しないでエ
ポキシ化合物を配合した感圧性接着剤組成物において
は，ポリエステルフィルムに塗工した後の硬化処理時間
は０℃で14日間必要であった。尚，表面基材ポリエステ
ルフィルムとの密着性は著しく不良であることを認め
た。Comparative Example 3 In the pressure-sensitive adhesive composition containing the epoxy compound without adding the aziridinyl compound in Example 2, the curing treatment time after coating on the polyester film was required to be 14 days at 0 ° C. In addition, it was confirmed that the adhesiveness with the surface-based polyester film was extremely poor.
実施例 ３ アクリル酸ブチル 70.0部 酢酸ビニル 25.0部 アクリル酸 5.0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重量部に対し，ビスフェノールＦエ
ポキシ（エポコート801,油化シェルエポキシ）1.0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−β−（２−メチルアジリジン）プロピ
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℃を粘度は
3500cps,40℃で８時間保存の5.の粘度は,3800cpsで塗工
可能であった。Example 3 Butyl acrylate 70.0 parts Vinyl acetate 25.0 parts Acrylic acid 5.0 parts Benzoyl peroxide 0.1 parts The above composition was reacted at the reflux temperature of ethyl acetate to obtain an acrylic copolymer. 35% including this acrylic copolymer
To 100 parts by weight of the ethyl acetate solution, 1.0 part of bisphenol F epoxy (Epocoat 801, oiled shell epoxy) was added and mixed well. To this mixture was added 0.3 part of trimethylolpropane-tri-β- (2-methylaziridine) propionate to obtain a pressure sensitive adhesive composition.
Immediately after compounding this pressure-sensitive adhesive composition, the viscosity at 40 ° C
The viscosity of 5 stored at 3500 cps at 40 ° C for 8 hours was 3800 cps 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に塗工
し,25g/m2の感圧性接着剤層を形成した。この感圧性接
着剤24時間後の接着力は250g/25mm（対ステンレス）で
あり，保持力，粘着力とも優れていた。またこの感圧性
接着剤の塗布されたポリエステルフィルムを70℃以上で
１ケ月間加熱処理をした後，貼着24時間後の接着力は24
5g/25mmであり，加熱経時の影響を受けず，耐熱性が非
常に良好であることを認めた。This pressure-sensitive adhesive composition was applied to a polyester film to form a 25 g / m 2 pressure-sensitive adhesive layer. The adhesive strength of this pressure-sensitive adhesive after 24 hours was 250 g / 25 mm (against stainless steel), and the holding power and adhesive strength were excellent. Also, the polyester film coated with this pressure-sensitive adhesive was heat-treated at 70 ° C or higher for 1 month, and the adhesive strength after 24 hours of adhesion was 24.
It was 5 g / 25 mm, and it was confirmed that the heat resistance was very good without being affected by the aging of heating.
比較例 ４ 実施例３においてエポキシ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については
ポリエステルフィルムに塗工した後,24時間後の接着力
は280g/25mm（対ステンレス）であったが,70℃以上で一
ケ月加熱処理をした後の24時間後の接着力は530g/25mm
であり塗工物の耐熱性は不良であった。Comparative Example 4 The pressure-sensitive adhesive composition of Example 3 containing the aziridinyl compound without adding the epoxy compound had an adhesive force of 280 g / 25 mm (against stainless steel) after being applied to a polyester film for 24 hours. However, the adhesive strength after 24 hours after heat treatment at 70 ° C or more for one month is 530g / 25mm.
The heat resistance of the coated product was poor.
本発明の感圧性接着剤組成物は，架橋点としてエルボキ
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
橋剤と低い架橋剤を併用配合したので，感圧性接着剤の
凝集力が高まり，かつ，架橋剤の結合力も高くなるの
で，熱経時性能劣化を防止される。更に，硬化処理時間
の短縮や，表面基材との密着性の向上し，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。In the pressure-sensitive adhesive composition of the present invention, since an acrylic copolymer having an erboxyl group introduced as a cross-linking point is used in combination with a highly reactive cross-linking agent and a low-reactivity cross-linking agent, the cohesive force of the pressure-sensitive adhesive is increased. In addition, since the bonding strength of the cross-linking agent also becomes high, deterioration with time due to heat is prevented. Furthermore, shortening the curing time and improving the adhesion with the surface substrate,
It can be used without any special consideration in the manufacturing process of adhesive labels, etc., so it has high practical value.
Claims (1)
タ）アクルリ酸エステル（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
重合可能なビニルモノマー（ｃ）０〜39.8重量％を有機
溶媒中で共重合させて得られるアクリル系共重合体固形
分100重量部に対して、アジリジニル系化合物0.01〜10
重量部およびエポキシ系化合物0.01〜10重量部とを配合
してなる感圧性接着剤において、 配合後40℃、８時間保存した後の溶液の粘度が3800cps
以内であることを特徴とする感圧性接着剤組成物。1. A (meth) acrylic acid ester (a) having an alkyl group having 4 to 12 carbon atoms (a) (60 to 99.8% by weight), a polymerizable unsaturated carboxylic acid (b) (0.2 to 10% by weight), and a copolymer other than the above. 0.01 to 10 of aziridinyl-based compound to 100 parts by weight of solid content of acrylic copolymer obtained by copolymerizing 0 to 39.8% by weight of possible vinyl monomer (c) in an organic solvent.
In a pressure sensitive adhesive prepared by blending 1 part by weight and 0.01 to 10 parts by weight of an epoxy compound, the viscosity of the solution after storage at 40 ° C. for 8 hours after blending is 3800 cps.
A pressure-sensitive adhesive composition characterized by being within the range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63222992A JPH0794649B2 (en) | 1988-09-06 | 1988-09-06 | Pressure sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63222992A JPH0794649B2 (en) | 1988-09-06 | 1988-09-06 | Pressure sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0270780A JPH0270780A (en) | 1990-03-09 |
| JPH0794649B2 true JPH0794649B2 (en) | 1995-10-11 |
Family
ID=16791109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63222992A Expired - Lifetime JPH0794649B2 (en) | 1988-09-06 | 1988-09-06 | Pressure sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794649B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8420214B2 (en) | 2008-06-09 | 2013-04-16 | 3M Innovative Properties Company | Acrylic pressure-sensitive adhesives with aziridine crosslinking agents |
| CN102405267A (en) | 2009-03-09 | 2012-04-04 | 3M创新有限公司 | Aziridine crosslinking agents for acrylic adhesives |
| US8148471B2 (en) | 2009-11-23 | 2012-04-03 | 3M Innovative Properties Company | Acrylic pressure-sensitive adhesives with aziridinyl-epoxy crosslinking system |
| CN102127183B (en) | 2010-01-20 | 2014-08-20 | 3M创新有限公司 | Crosslinkable acrylate adhesive polymer composite |
| US20160311967A1 (en) * | 2013-12-19 | 2016-10-27 | Dic Corporation | Epoxy resin, method for producing the same, epoxy resin composition, and cured product thereof |
| CN106471035B (en) * | 2014-07-02 | 2019-04-16 | Dic株式会社 | Electronic material composition epoxy resin, its solidfied material and electronic component |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5137930A (en) * | 1974-09-27 | 1976-03-30 | Cemedine Co Ltd | SETSUCHAKUSEISOSEIBUTSU |
| JPS5915465A (en) * | 1982-07-19 | 1984-01-26 | Sumitomo Naugatuck Co Ltd | Carpet backing adhesive composition |
| JPS6119677A (en) * | 1984-07-09 | 1986-01-28 | Toyo Kohan Co Ltd | Adhesive for polyester film |
| JPS63130685A (en) * | 1986-11-20 | 1988-06-02 | Toyo Ink Mfg Co Ltd | Pressure-sensitive adhesive composition |
-
1988
- 1988-09-06 JP JP63222992A patent/JPH0794649B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0270780A (en) | 1990-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5639811A (en) | Tackified dual cure pressure-sensitive adhesive | |
| US4987186A (en) | Pressure sensitive adhesive composition | |
| US6277481B1 (en) | Adhesive composition and adhesive sheet | |
| US4812541A (en) | High performance pressure-sensitive adhesive polymers | |
| CA1103395A (en) | Pressure sensitive adhesives | |
| EP0412152B1 (en) | Siliconized emulsion based pressure-sensitive adhesives | |
| JP6204633B2 (en) | Adhesive composition and adhesive sheet | |
| US3563953A (en) | Curable copolymer of an alkyl acrylate,a glycidyl acrylate or methacrylate and diketene | |
| JPH01178567A (en) | Pressure-sensitive adhesive | |
| JPH0794649B2 (en) | Pressure sensitive adhesive composition | |
| US5869568A (en) | One-part cold crosslinking emulsion composition and method of manufacturing the same | |
| JP3997268B2 (en) | Adhesive composition and transparent adhesive film using the same | |
| US4769410A (en) | Crosslinkable compositions dissolved or dispersed in an organic solvent and having a long shelf life, their preparation and their use | |
| JP2782991B2 (en) | Adhesive composition | |
| JP3846471B2 (en) | Adhesive and adhesive processed product using the adhesive | |
| US3189480A (en) | Pressure sensitive adhesive sheet material with diketene-acrylic acid ester copolymer coating | |
| JPH07278498A (en) | Low-hydroxyl-value modified rosin, method for reducing hydroxyl value of rosin derivative, tackifier for pressure-sensitive adhesive, and pressure-sensitive adhesive composition | |
| JP2734607B2 (en) | Resin composition for adhesive | |
| JPS63130686A (en) | Tacky composition | |
| JPS617369A (en) | Adhesive composition | |
| JP4437631B2 (en) | Adhesive composition for gas float prevention film and adhesive sheet | |
| JPS6121980B2 (en) | ||
| JPS63130685A (en) | Pressure-sensitive adhesive composition | |
| JP4577739B2 (en) | Adhesive composition and adhesive sheet using the same | |
| JPS601277A (en) | Pressure-sensitive adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |