JP2000265137A - Pressure-sensitive adhesive composition and its bonding sheets - Google Patents
Pressure-sensitive adhesive composition and its bonding sheetsInfo
- Publication number
- JP2000265137A JP2000265137A JP11071442A JP7144299A JP2000265137A JP 2000265137 A JP2000265137 A JP 2000265137A JP 11071442 A JP11071442 A JP 11071442A JP 7144299 A JP7144299 A JP 7144299A JP 2000265137 A JP2000265137 A JP 2000265137A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymer
- sensitive adhesive
- pressure
- adhesive composition
- 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.)
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高固形分濃度に調
製可能な感圧性接着剤組成物と、これを用いたテ―プ状
やシ―ト状などの接着シ―ト類とに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition which can be adjusted to a high solid content, and to tape- or sheet-like adhesive sheets using the same.
【０００２】[0002]
【従来の技術】感圧性接着剤は、重合体溶液に粘着付与
樹脂や架橋剤を混合することにより、調製され、これを
支持体上に塗布し乾燥させて、テ―プ状やシ―ト状など
の接着シ―ト類とされている。近年、乾燥効率や省エネ
ルギ―性、作業環境の面から、溶剤の使用量をできるだ
け削減することが要望されている。2. Description of the Related Art A pressure-sensitive adhesive is prepared by mixing a tackifying resin or a crosslinking agent with a polymer solution, and then applying the resulting mixture on a support and drying it to form a tape or sheet. Adhesive sheets such as shapes. In recent years, it has been demanded to reduce the amount of solvent used as much as possible from the viewpoint of drying efficiency, energy saving, and work environment.
【０００３】この要望に対し、重合体溶液を高固形分濃
度にすると、重合体溶液の粘度が上昇して、支持体上に
塗布する際の作業性に問題を生じたり、塗布面が荒れる
などの不都合を生じる。重合体の分子量を下げることに
より、低粘度で高固形分濃度にする試みもあるが、この
場合、架橋後の凝集力が不足し、とくに耐熱性（高温下
での接着力および保持力）に問題が生じる。これを回避
するために架橋しすぎると、接着力やタツクが不足する
などの問題を生じる。[0003] In response to this demand, if the polymer solution is made to have a high solid content, the viscosity of the polymer solution increases, which causes a problem in workability when applying the solution on a support and a roughened surface to be applied. Causes inconvenience. Attempts have been made to lower the molecular weight of the polymer to lower the viscosity and increase the solids concentration. However, in this case, the cohesive strength after crosslinking is insufficient, and the heat resistance (adhesive strength and holding power at high temperatures) is particularly low. Problems arise. Excessive crosslinking to avoid this causes problems such as insufficient adhesive strength and tack.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、このような
事情に照らして、低粘度で高固形分濃度に調製可能で、
しかも接着特性、とくに高温下での接着特性にすぐれ
る、耐熱性の良好な感圧性接着剤組成物と、その接着シ
―ト類を得ることを目的とする。SUMMARY OF THE INVENTION In view of such circumstances, the present invention can be adjusted to a low viscosity and a high solid content.
In addition, an object of the present invention is to obtain a pressure-sensitive adhesive composition having excellent adhesive properties, particularly excellent adhesive properties at high temperatures, and excellent heat resistance, and adhesive sheets thereof.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために、鋭意検討した結果、重合体の分子
鎖末端に所定量の官能基を導入するとともに、この重合
体にさらにアルコ―ル性水酸基を持つ粘着付与樹脂を混
合すると、上記重合体の分子量を下げて低粘度で高固形
分濃度の溶液としても、これを架橋剤で架橋処理したと
きに、上記重合体の分子鎖末端同士の反応確率が高くな
つて、しかも上記粘着付与樹脂がアルコ―ル性水酸基の
反応性により架橋剤を介して上記重合体と結合する結
果、分子鎖長の長い架橋重合体が生成して、かつこの架
橋重合体の分子鎖中に通常高軟化点を示す上記粘着付与
樹脂が取り込まれることにより、接着特性とくに高温下
での接着特性にすぐれ、耐熱性の非常に良好な感圧性接
着剤組成物とその接着シ―ト類が得られることを知り、
本発明を完成するに至つた。Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have introduced a predetermined amount of a functional group into the molecular chain terminal of the polymer, Furthermore, when a tackifying resin having an alcoholic hydroxyl group is mixed, the molecular weight of the polymer is lowered to obtain a solution having a low viscosity and a high solid content, and when this is cross-linked with a cross-linking agent, As the probability of reaction between the molecular chain ends increases, and the tackifying resin is bonded to the polymer via a crosslinking agent due to the reactivity of the alcoholic hydroxyl group, a crosslinked polymer having a long molecular chain length is formed. And by incorporating the tackifying resin, which usually shows a high softening point, into the molecular chain of the crosslinked polymer, it has excellent adhesive properties, especially at high temperatures, and has very good heat resistance and pressure sensitivity. Adhesive composition and its connection Shi - to know that the door acids can be obtained,
The present invention has been completed.
【０００６】すなわち、本発明は、一般式；ＣＨ2 ＝Ｃ
（Ｒ1 ）ＣＯＯＲ2 （式中、Ｒ1 は水素またはメチル
基、Ｒ2 は炭素数２〜１４のアルキル基である）で表さ
れるアクリル系単量体を５０重量％以上含む単量体の重
合体で、数平均分子量が６万以上、重量平均分子量が１
０万以上、分子鎖末端の官能基導入率が５０％以上であ
る重合体を主剤とし、この主剤１００重量部あたり、ア
ルコ―ル性水酸基を持つ粘着付与樹脂１０〜７０重量部
を含むことを特徴とする感圧性接着剤組成物（請求項
１）と、支持体上に上記の感圧性接着剤組成物を架橋処
理した接着剤層を有することを特徴とする接着シ―ト類
（請求項６）とに係るものである。That is, the present invention provides a compound represented by the general formula: CH 2 ＝ C
(R 1 ) a monomer containing 50% by weight or more of an acrylic monomer represented by COOR 2 (wherein R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 2 to 14 carbon atoms) Having a number average molecular weight of 60,000 or more and a weight average molecular weight of 1
A polymer having a molecular chain terminal functional group introduction ratio of 50,000 or more, wherein the main component is 100,000 or more, and 10 to 70 parts by weight of a tackifying resin having an alcoholic hydroxyl group is contained per 100 parts by weight of the main component. A pressure-sensitive adhesive composition (Claim 1) characterized by having an adhesive layer obtained by crosslinking the above-described pressure-sensitive adhesive composition on a support (Claim 1). 6).
【０００７】また、本発明は、上記の感圧性接着剤組成
物として、とくに、アルコ―ル性水酸基を持つ粘着付与
樹脂の水酸基価が１０〜１００ＫＯＨmg／ｇである感圧
性接着剤組成物（請求項２）、アルコ―ル性水酸基を持
つ粘着付与樹脂がロジン系エステルである感圧性接着剤
組成物（請求項３）、アルコ―ル性水酸基を持つ粘着付
与樹脂の軟化点が９０℃以上である感圧性接着剤組成物
（請求項４）、さらに主剤としての重合体１００重量部
あたり、架橋剤を０．０５〜７重量部含む感圧性接着剤
組成物（請求項５）を、提供できるものである。Further, the present invention provides a pressure-sensitive adhesive composition as described above, wherein the hydroxyl value of the tackifying resin having an alcoholic hydroxyl group is 10 to 100 KOH mg / g. Item 2), a pressure-sensitive adhesive composition wherein the tackifying resin having an alcoholic hydroxyl group is a rosin ester (Claim 3), wherein the tackifying resin having an alcoholic hydroxyl group has a softening point of 90 ° C. or more. A certain pressure-sensitive adhesive composition (Claim 4), and a pressure-sensitive adhesive composition containing 0.05 to 7 parts by weight of a crosslinking agent per 100 parts by weight of a polymer as a main component (Claim 5) can be provided. Things.
【０００８】[0008]
【発明の実施の形態】本発明におけるアクリル系単量体
は、一般式；ＣＨ2 ＝Ｃ（Ｒ1 ）ＣＯＯＲ2（式中、Ｒ
1 は水素またはメチル基、Ｒ2 は炭素数２〜１４のアル
キル基である）で表される単量体であり、とくに、アク
リル系ブチル、アクリル酸２−エチルヘキシル、アクリ
ル酸イソオクチル、アクリル酸イソノニルなどの炭素数
４〜１２のアルキル基を有するアクリル酸エステルが好
ましく用いられる。このアクリル系単量体とともに、こ
れと共重合可能な改質用単量体を併用してもよく、この
場合、良好な接着特性を得るために、上記アクリル系単
量体が単量体全体の５０重量％以上、好ましくは７０重
量％以上、さらに好ましくは８０重量％以上となるよう
にするのがよい。また、重合体のガラス転移点が２５０
Ｋ以下となるように、単量体組成を選択するのが望まし
い。BEST MODE FOR CARRYING OUT THE INVENTION The acrylic monomer in the present invention has the general formula: CH 2 ＣC (R 1 ) COOR 2 (wherein R
1 is hydrogen or a methyl group, and R 2 is an alkyl group having 2 to 14 carbon atoms), particularly, acrylic butyl, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate Acrylic esters having an alkyl group having 4 to 12 carbon atoms, such as, for example, are preferably used. Along with this acrylic monomer, a modifying monomer copolymerizable therewith may be used.In this case, in order to obtain good adhesive properties, the acrylic monomer is used as a whole monomer. The content is preferably 50% by weight or more, preferably 70% by weight or more, and more preferably 80% by weight or more. Further, the glass transition point of the polymer is 250
It is desirable to select the monomer composition so as to be K or less.
【０００９】上記の改質用単量体としては、酢酸ビニ
ル、プロピオン酸ビニル、スチレン、（メタ）アクリル
アミド、マレイン酸のモノまたはジエステル、Ｎ−メチ
ロ―ル（メタ）アクリルアミド、グリシジル（メタ）ア
クリレ―ト、Ｎ，Ｎ−ジメチルアミノエチル（メタ）ア
クリレ―ト、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）
アクリルアミド、２−ヒドロキシプロピル（メタ）アク
リレ―ト、（メタ）アクリル酸、オリゴエステル（メ
タ）アクリレ―ト、ε−カプロラクトン（メタ）アクリ
レ―トなどが挙げられる。The above-mentioned modifying monomers include vinyl acetate, vinyl propionate, styrene, (meth) acrylamide, mono- or diesters of maleic acid, N-methylol (meth) acrylamide, glycidyl (meth) acryl -N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth)
Examples include acrylamide, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, oligoester (meth) acrylate, and ε-caprolactone (meth) acrylate.
【００１０】本発明においては、このようなアクリル系
単量体を５０重量％以上含む単量体を用いて、数平均分
子量が６万以上、重量平均分子量が１０万以上、分子鎖
末端の官能基導入率が５０％以上である重合体を生成す
る。ここで、上記の「数平均分子量」と「重量平均分子
量」は、ゲルパ―ミエ―シヨンクロマトグラフイ―法
（ＧＰＣ法）により、測定される。また、上記の「分子
鎖末端の官能基導入率」とは、分子鎖末端に官能基が導
入された重合体の量が重合体全体に対して５０％以上で
あることを意味し、ＧＰＣ法による数平均分子量と核磁
気共鳴スペクトル（ＮＭＲ）での分子鎖末端の官能基量
とより、計算される。In the present invention, a monomer containing 50% by weight or more of such an acrylic monomer has a number average molecular weight of 60,000 or more, a weight average molecular weight of 100,000 or more, A polymer having a group introduction ratio of 50% or more is produced. Here, the “number average molecular weight” and “weight average molecular weight” are measured by a gel permeation chromatography (GPC method). The term “functional group introduction rate at the molecular chain end” means that the amount of the polymer having a functional group introduced at the molecular chain end is 50% or more based on the whole polymer, and the GPC method. Is calculated from the number average molecular weight according to the above formula and the amount of functional group at the end of the molecular chain in nuclear magnetic resonance spectrum (NMR).
【００１１】このような分子鎖末端の官能基導入率が５
０％以上（通常、９０％まで）の重合体によると、この
重合体の分子量を上記のように小さくして、低粘度で高
固形分濃度の重合体溶液としても、これにアルコ―ル性
水酸基を含有する粘着付与樹脂を混合して架橋処理した
ときに、上記重合体の分子鎖末端同士の反応確率が高く
なつて、分子鎖長の長い架橋重合体を生成し、しかもこ
の架橋重合体の分子鎖中に通常高軟化点を示す粘着付与
樹脂が取り込まれることにより、接着特性、とくに高温
下での接着特性にすぐれる、耐熱性の改善された感圧性
接着剤組成物が得られる。これに対し、分子鎖末端の官
能基導入率が５０％に満たない重合体や側鎖にしか官能
基を持たない重合体などでは、架橋処理により上記のよ
うな分子鎖長の長い架橋構造体を生成できず、また上記
高軟化点の粘着付与樹脂を重合体の分子鎖中に取り込み
にくく、良好な耐熱性が得られない。The functional group introduction rate at the end of the molecular chain is 5
According to the polymer of 0% or more (usually up to 90%), the molecular weight of the polymer is reduced as described above, and even if a polymer solution having a low viscosity and a high solid content is used, the alcoholic property can be reduced. When a hydroxyl group-containing tackifier resin is mixed and cross-linked, the probability of reaction between the molecular chain ends of the polymer is increased to produce a cross-linked polymer having a longer molecular chain length. By incorporating a tackifier resin which usually shows a high softening point into the molecular chain of the above, a pressure-sensitive adhesive composition having improved heat resistance and excellent adhesive properties, in particular, adhesive properties at high temperatures can be obtained. On the other hand, in a polymer having a functional group introduction rate of less than 50% at a molecular chain terminal or a polymer having a functional group only in a side chain, a crosslinked structure having a long molecular chain as described above due to the crosslinking treatment. And it is difficult to incorporate the tackifying resin having a high softening point into the molecular chain of the polymer, and good heat resistance cannot be obtained.
【００１２】また、分子鎖末端の官能基導入率が５０％
以上あつても、この重合体の分子量があまりに低すぎる
と、上記のような架橋重合体をやはり生成しにくい。こ
のため、本発明に用いる上記分子鎖末端の官能基導入率
が５０％以上の重合体としては、既述のとおり、数平均
分子量が６万以上、重量平均分子量が１０万以上である
ことが必要とされる。分子量の上限としては、塗布性な
どに支障をきたさない低粘度で高固形分濃度が得られる
限り、できるだけ高い分子量に設定でき、重合体の組成
や溶剤の種類などに応じて、適宜決定される。通常は、
数平均分子量が１５万以下、重量平均分子量が４０万以
下であるのがよい。The functional group introduction rate at the molecular chain end is 50%.
Even with the above, if the molecular weight of this polymer is too low, it is still difficult to produce the above-mentioned crosslinked polymer. For this reason, as described above, the polymer having a functional group introduction rate at the molecular chain terminal of 50% or more used in the present invention may have a number average molecular weight of 60,000 or more and a weight average molecular weight of 100,000 or more. Needed. As the upper limit of the molecular weight, the molecular weight can be set as high as possible as long as a high solid content can be obtained at a low viscosity that does not hinder the coatability, and is appropriately determined according to the composition of the polymer or the type of the solvent. . Normally,
The number average molecular weight is preferably 150,000 or less, and the weight average molecular weight is preferably 400,000 or less.
【００１３】本発明において、このように分子鎖末端の
官能基導入率および分子量がそれぞれ特定された重合体
は、たとえば、前記アクリル系単量体を５０重量％以上
含む単量体を、官能基を有する連鎖移動剤の存在下で溶
液重合することにより、またその際に上記連鎖移動剤の
溶解性、連鎖移動定数、消費速度などを考慮して、適宜
の重合条件を選択する、とくに重合系内の上記連鎖移動
剤の濃度が重合初期から終期までほぼ一定となるように
上記連鎖移動剤を重合の進行に伴つて滴下法で加えて重
合処理することにより、生成することができる。In the present invention, the polymer whose molecular chain terminal functional group introduction rate and molecular weight are specified as described above is, for example, a monomer containing 50% by weight or more of the acrylic monomer described above, By performing solution polymerization in the presence of a chain transfer agent having the above, and at that time, considering the solubility of the above chain transfer agent, the chain transfer constant, the consumption rate, etc., select appropriate polymerization conditions, especially the polymerization system The chain transfer agent can be produced by adding the chain transfer agent by a dropping method with the progress of polymerization so as to make the concentration of the chain transfer agent substantially constant from the beginning to the end of the polymerization.
【００１４】官能基を有する連鎖移動剤は、重合体の分
子鎖末端に官能基を導入して、架橋剤を介して分子鎖末
端同士および粘着付与樹脂と反応させるためのものであ
り、２−メルカプトエタノ―ル、１−メルカプト−２−
プロパノ―ル、３−メルカプト−１−プロパノ―ルなど
の水酸基を有する連鎖移動剤が好ましく用いられる。こ
れらは、溶解性や連鎖移動定数により異なるが、通常、
単量体１００重量部あたり、０．０１〜５重量部の割合
で使用する。多すぎると、分子量が低下しすぎたり、不
純物として未反応の連鎖移動剤が残存して、架橋反応を
阻害する場合があり、少なすぎると、前記した所定の分
子量が得られなくなる。The chain transfer agent having a functional group is for introducing a functional group to the molecular chain terminal of the polymer and reacting the molecular chain terminals with each other and the tackifier resin via a crosslinking agent. Mercaptoethanol, 1-mercapto-2-
Chain transfer agents having a hydroxyl group such as propanol and 3-mercapto-1-propanol are preferably used. These vary depending on solubility and chain transfer constant, but usually
It is used in a ratio of 0.01 to 5 parts by weight per 100 parts by weight of the monomer. If the amount is too large, the molecular weight may be too low, or an unreacted chain transfer agent may remain as an impurity to inhibit the crosslinking reaction. If the amount is too small, the above-mentioned predetermined molecular weight may not be obtained.
【００１５】本発明における粘着付与樹脂は、架橋剤を
介して上記重合体の分子鎖末端と結合させるために、ア
ルコ―ル性水酸基を持つものが用いられ、とくに水酸基
価が１０〜１００ＫＯＨmg／ｇの範囲にあるものが好ま
しく用いられる。上記「水酸基価」は、ＪＩＳ Ｋ−０
０７０により、測定される値である。このような粘着付
与樹脂に代えて、フエノ―ル性水酸基を持つ粘着付与樹
脂などを用いると、架橋剤を介して上記重合体と反応せ
ず、耐熱性を改善できなくなる。As the tackifying resin in the present invention, a resin having an alcoholic hydroxyl group is used for bonding to the molecular chain terminal of the above-mentioned polymer via a crosslinking agent, and a hydroxyl value is preferably 10 to 100 KOH mg / g. Are preferably used. The above “hydroxyl value” is JIS K-0
070 is the value measured. When a tackifying resin having a phenolic hydroxyl group is used instead of such a tackifying resin, the resin does not react with the polymer via a cross-linking agent, and the heat resistance cannot be improved.
【００１６】アルコ―ル性水酸基を持つ粘着付与樹脂と
して、とくに好ましいものは、ロジン、不均化ロジン、
水添ロジン、またはロジンの二量化物（重合ロジン）な
どをグリセリンやペンタエリスリト―ルなどのアルコ―
ルとエステル化反応させることにより得られる、ロジン
系エステルである。このようなロジン系エステルは、軟
化点が９０℃以上であるのがよく、このように高軟化点
を有する粘着付与樹脂を前記重合体に混合して架橋処理
すると、架橋重合体の分子鎖中に高軟化点の樹脂成分が
取り込まれ、耐熱性の向上に好結果が得られる。Particularly preferred tackifying resins having an alcoholic hydroxyl group include rosin, disproportionated rosin,
Hydrogenated rosin or rosin dimer (polymerized rosin) can be converted to alcohol such as glycerin or pentaerythritol.
A rosin ester obtained by an esterification reaction with Such a rosin-based ester preferably has a softening point of 90 ° C. or higher. When a tackifier resin having such a high softening point is mixed with the polymer and subjected to crosslinking treatment, the molecular chain of the crosslinked polymer is reduced. The resin component having a high softening point is taken in, and good results can be obtained in improving the heat resistance.
【００１７】このようなロジン系エステルの市販品とし
ては、荒川化学工業（株）製の「ス―パ―エステルＡ−
１００」（軟化点１００℃）、「ス―パ―エステルＳ−
１００」（軟化点１００℃）、「ス―パ―エステルＡ１
２５」（軟化点１２５℃）、「ＫＥ−３１１」（軟化点
９５℃）、「ＫＥ−３４０−１Ｂ」（軟化点１０８
℃）、「ペンセルＤ−１２５」（軟化点１２５℃）、
「ペンセルＤ−１３５」（軟化点１３５℃）、「ペンセ
ルＤ−１６０」（軟化点１６０℃）などや、理化ハ―キ
ユレス（株）製の「ペンタリンＨ」（軟化点９３〜１０
１℃）、「エステルガム１０Ｄ」（軟化点１０９℃）、
「ペンタリンＫ」（軟化点１６５〜１７５℃）、「ペン
タリンＣＪ」（軟化点１１８〜１２８℃）、「フオ―ラ
ル１０５」（軟化点９３〜１０１℃）などが挙げられ
る。Commercial products of such rosin-based esters include "Super Ester A-A" manufactured by Arakawa Chemical Industries, Ltd.
100 ”(softening point 100 ° C),“ Super Ester S-
100 ”(softening point 100 ° C),“ Super Ester A1
25 "(softening point 125 ° C)," KE-311 "(softening point 95 ° C)," KE-340-1B "(softening point 108
° C), "Pencel D-125" (softening point 125 ° C),
“Pencel D-135” (softening point 135 ° C.), “Pencel D-160” (softening point 160 ° C.), and “Pentalin H” (softening point 93 to 10) manufactured by Rika Hakires Co., Ltd.
1 ° C), “Ester gum 10D” (softening point 109 ° C),
“Pentalin K” (softening point 165 to 175 ° C.), “Pentalin CJ” (softening point 118 to 128 ° C.), “Fural 105” (softening point 93 to 101 ° C.) and the like can be mentioned.
【００１８】本発明の感圧性接着剤組成物は、上記の分
子鎖末端の官能基導入率および分子量がそれぞれ特定さ
れた重合体を主剤とし、これに上記のアルコ―ル性水酸
基を持つ粘着付与樹脂を含ませたことを特徴とする。こ
こで、アルコ―ル性水酸基を持つ粘着付与樹脂の含有量
としては、上記重合体からなる主剤１００重量部あた
り、１０〜７０重量部、好適には２０〜６０重量部とな
る割合とするのがよい。アルコ―ル性水酸基を持つ粘着
付与樹脂が１０重量部未満となると、高温下での接着特
性が悪くなり、耐熱性の改善効果が十分に得られず、ま
た７０重量部を超えると、接着力などの低下が起こり、
いずれも好ましくない。The pressure-sensitive adhesive composition of the present invention comprises, as a main component, a polymer having the above-described functional group introduction ratio and molecular weight at the molecular chain terminal, and a tackifier having the above-mentioned alcoholic hydroxyl group. It is characterized by including a resin. Here, the content of the tackifying resin having an alcoholic hydroxyl group should be 10 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight of the base material composed of the polymer. Is good. When the amount of the tackifying resin having an alcoholic hydroxyl group is less than 10 parts by weight, the adhesive properties at high temperatures are deteriorated, and the effect of improving the heat resistance cannot be sufficiently obtained. Such as drop,
Neither is preferred.
【００１９】本発明の感圧性接着剤組成物は、上記の重
合体およびアルコ―ル性水酸基を持つ粘着付与樹脂のほ
かに、本発明の効果を損なわない範囲内で、必要に応じ
て、上記以外の粘着付与樹脂やその他充填剤、顔料など
の一般の感圧性接着剤組成物に配合される各種の添加剤
を含ませることができる。The pressure-sensitive adhesive composition of the present invention may further comprise, in addition to the polymer and the tackifying resin having an alcoholic hydroxyl group, the above-mentioned adhesive within the range that does not impair the effects of the present invention. Various additives, such as tackifier resins and other fillers and pigments, which are blended in general pressure-sensitive adhesive compositions can be included.
【００２０】本発明の感圧性接着剤組成物は、一般に、
上記の重合体およびアルコ―ル性水酸基を持つ粘着付与
樹脂などからなる固形分の濃度が４０重量％以上、好ま
しくは５０重量％以上、さらに好ましくは６０重量％以
上（通常７０重量％まで）となる高固形分濃度の溶液と
して、取り扱われる。このときの溶液粘度としては、塗
布性、その他の取り扱い性に支障をきたすことのない、
室温で５００ポイズ以下、好ましくは３００ポイズ以
下、さらに好ましくは２００ポイズ以下（通常５０ポイ
ズまで）に調整されているのが望ましい。The pressure-sensitive adhesive composition of the present invention generally comprises
When the solid content of the above polymer and the tackifying resin having an alcoholic hydroxyl group is 40% by weight or more, preferably 50% by weight or more, more preferably 60% by weight or more (usually up to 70% by weight). It is handled as a solution having a high solid content. At this time, the viscosity of the solution does not impair coatability and other handling properties.
At room temperature, it is desirably adjusted to 500 poise or less, preferably 300 poise or less, more preferably 200 poise or less (usually up to 50 poise).
【００２１】本発明の感圧性接着剤組成物は、最終的に
架橋処理して、高温下での接着特性を向上させ、耐熱性
の改善をはかる。架橋処理は、重合体の分子鎖末端に導
入された官能基の反応性により、また粘着付与樹脂のア
ルコ―ル性水酸基の反応性により、重合体の分子鎖長を
長くし、かつその分子鎖中に上記粘着付与樹脂を取り込
むとともに、適度に架橋構造化させるものである。この
目的を達成するため、感圧性接着剤組成物の調製に際
し、あらかじめ重合体の分子鎖末端の官能基などと反応
する多官能性化合物を架橋剤として含ませておくのがよ
い。The pressure-sensitive adhesive composition of the present invention is finally subjected to a crosslinking treatment to improve the adhesive properties at high temperatures and to improve the heat resistance. The crosslinking treatment increases the molecular chain length of the polymer due to the reactivity of the functional group introduced into the molecular chain terminal of the polymer and the reactivity of the alcoholic hydroxyl group of the tackifying resin, and increases the molecular chain length. The above-mentioned tackifying resin is incorporated therein, and a crosslinked structure is appropriately formed. In order to achieve this object, it is preferable that a polyfunctional compound which reacts with a functional group at the molecular chain end of the polymer is previously contained as a crosslinking agent in preparing the pressure-sensitive adhesive composition.
【００２２】架橋剤としては、トリレンジイソシアネ―
ト、ジフエニルメタンジイソシアネ―ト、ｐ−フエニレ
ンジイソシアネ―ト、１，５−ナフタレンジイソシアネ
―ト、多価アルコ―ルとジイソシアネ―トの付加物など
のポリイソシアネ―ト化合物が、とくに好ましく用いら
れる。使用量としては、前記の重合体１００重量部に対
し、通常０．０５〜７重量部とするのがよく、多すぎる
と、接着力が低下し、少なすぎると凝集力が不足し、い
ずれも好ましくない。また、このようなポリイソシアネ
―ト化合物とともに、必要に応じて、エポキシ樹脂など
の他の多官能性化合物を一緒に含ませるようにしてもよ
い。As the crosslinking agent, tolylene diisocyanate
Polyisocyanate compounds such as diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalenediisocyanate, and adducts of polyvalent alcohol and diisocyanate Is particularly preferably used. The amount to be used is preferably 0.05 to 7 parts by weight, based on 100 parts by weight of the polymer. If the amount is too large, the adhesive force is reduced, and if the amount is too small, the cohesive force is insufficient. Not preferred. Further, other polyfunctional compounds such as an epoxy resin may be included together with such a polyisocyanate compound, if necessary.
【００２３】本発明においては、このような感圧性接着
剤組成物を支持体上に塗布し、乾燥して、また前記した
架橋処理を施して、支持体の片面または両面に厚さが片
面で通常１０〜２００μｍとなる架橋処理した接着剤層
を有するテ―プ状やシ―ト状などの接着シ―ト類とす
る。支持体としては、各種のプラスチツクフイルム、
紙、ラミネ―ト紙、不織布、金属箔、発泡シ―トなどが
用いられる。In the present invention, such a pressure-sensitive adhesive composition is coated on a support, dried, and subjected to the above-mentioned crosslinking treatment, so that one side or both sides of the support have a thickness of one side. Adhesive sheets such as tapes and sheets having a cross-linked adhesive layer usually having a thickness of 10 to 200 μm are obtained. As the support, various plastic films,
Paper, laminated paper, non-woven fabric, metal foil, foam sheet, and the like are used.
【００２４】[0024]
【実施例】つぎに、本発明の実施例を記載して、より具
体的に説明する。なお、以下において、部とあるのは重
量部を意味する。Next, an embodiment of the present invention will be described in more detail. In the following, “parts” means “parts by weight”.
【００２５】実施例１ 冷却管、窒素導入管、温度計、撹拌機を備えた反応容器
に、酢酸エチル６６部を溶剤として、アクリル酸２−エ
チルヘキシル４５部、アクリル酸ブチル５０部、アクリ
ル酸５部、２，２′−アゾビスイソブチロニトリル０．
１部、２−メルカプトエタノ―ル０．０３部を入れ、窒
素置換を行つたのち、昇温して、重合反応を行つた。重
合途中でサンプリングし、ガスクロマトグラフイ―法に
より２−メルカプトエタノ―ルの消費量を測定し、残存
するモノマ―に対し２−メルカプトエタノ―ルが重合初
期と同じ濃度となるように滴下法で追加して、重合さ
せ、全２−メルカプトエタノ―ル使用量を０．１部とし
た。重合温度は開始から４時間は６０℃に保ち、その後
２時間７０℃とした。このようにして、重量平均分子量
が１５万、数平均分子量が７万（ＧＰＣ法によるポリス
チレン換算）、分子鎖末端の水酸基導入率が６０％であ
る重合体を生成し、この重合体を６０重量％含有する溶
液（常温での粘度：１００ポイズ）を得た。Example 1 In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 45 parts of 2-ethylhexyl acrylate, 50 parts of butyl acrylate, and 5 parts of acrylic acid were used, using 66 parts of ethyl acetate as a solvent. Part, 2,2'-azobisisobutyronitrile 0.
1 part and 0.03 part of 2-mercaptoethanol were added, and after purging with nitrogen, the temperature was raised to carry out a polymerization reaction. Sampled during the polymerization, the consumption of 2-mercaptoethanol was measured by gas chromatography, and the remaining monomer was dropped by the dropping method so that 2-mercaptoethanol had the same concentration as in the initial stage of polymerization. It was additionally polymerized to make the total amount of 2-mercaptoethanol used 0.1 part. The polymerization temperature was kept at 60 ° C. for 4 hours from the start and then at 70 ° C. for 2 hours. In this way, a polymer having a weight average molecular weight of 150,000, a number average molecular weight of 70,000 (in terms of polystyrene by the GPC method), and a hydroxyl group introduction ratio of a molecular chain terminal of 60% is produced. % (Viscosity at room temperature: 100 poise).
【００２６】この重合体溶液に、その固形分１００部あ
たり、アルコ―ル性水酸基を持つ粘着付与樹脂〔荒川化
学工業（株）製の「ス―パ―エステルＡ１２５」、水酸
基価２５ＫＯＨmg／ｇの不均化ロジンエステル樹脂〕３
０部、トリメチロ―ルプロパンのトリレンジイソシアネ
―ト付加物３．２部、エポキシ系架橋剤０．５部を加え
て、感圧性接着剤組成物を調製した。これをセパレ―タ
上に厚さが７５μｍとなるように塗布し、１００℃で３
分間加熱処理したのち、不織布の両面に貼り合わせ、両
面に架橋処理した接着剤層を有する接着テ―プを作製し
た。To 100 parts of the solid content of the polymer solution, a tackifier resin having an alcoholic hydroxyl group ["Super Ester A125" manufactured by Arakawa Chemical Industry Co., Ltd., having a hydroxyl value of 25 KOH mg / g. Disproportionated rosin ester resin] 3
0 parts, 3.2 parts of a tolylene diisocyanate adduct of trimethylolpropane, and 0.5 part of an epoxy crosslinking agent were added to prepare a pressure-sensitive adhesive composition. This was applied on a separator so as to have a thickness of 75 μm.
After heat treatment for a minute, the nonwoven fabric was stuck on both sides to prepare an adhesive tape having a crosslinked adhesive layer on both sides.
【００２７】実施例２ トルエン３３部と酢酸エチル３３部を溶剤とし、アクリ
ル酸２−エチルヘキシル８０部、アクリル酸エチル１５
部、アクリルアミド５部、２，２′−アゾビスイソブチ
ロニトリル０．１部、２−メルカプトエタノ―ル０．０
９部（全量）を用い、実施例１と同様にして、重量平均
分子量が２４万、数平均分子量が１２万、分子鎖末端の
水酸基導入率が５６％である重合体を生成し、この重合
体を６０重量％含有する溶液（常温での粘度：１３０ポ
イズ）を得た。Example 2 80 parts of 2-ethylhexyl acrylate and 15 parts of ethyl acrylate were used as a solvent with 33 parts of toluene and 33 parts of ethyl acetate.
Part, acrylamide 5 parts, 2,2'-azobisisobutyronitrile 0.1 part, 2-mercaptoethanol 0.0
Using 9 parts (total amount), a polymer having a weight average molecular weight of 240,000, a number average molecular weight of 120,000, and a hydroxyl group introduction ratio of molecular chain terminal of 56% was produced in the same manner as in Example 1. A solution (viscosity at room temperature: 130 poise) containing 60% by weight of the union was obtained.
【００２８】この重合体溶液に、その固形分１００部あ
たり、アルコ―ル性水酸基を持つ粘着付与樹脂〔荒川化
学工業（株）製の「ペンセルＤ１３５」、水酸基価４８
ＫＯＨmg／ｇの重合ロジンエステル樹脂〕１０部、トリ
メチロ―ルプロパンのヘキサメチレンジイソシアネ―ト
付加物２．６部、エポキシ系架橋剤０．５部を加え、感
圧性接着剤組成物を調製した。これを用いて、以下、実
施例１と同様にして、両面に架橋処理した接着剤層を有
する接着テ―プを作製した。To this polymer solution, a tackifying resin having an alcoholic hydroxyl group [“Pencel D135” manufactured by Arakawa Chemical Industries, Ltd .;
10 parts of a polymerized rosin ester resin of KOH mg / g], 2.6 parts of a hexamethylene diisocyanate adduct of trimethylolpropane, and 0.5 part of an epoxy crosslinking agent were added to prepare a pressure-sensitive adhesive composition. . Using this, an adhesive tape having a cross-linked adhesive layer on both surfaces was produced in the same manner as in Example 1.
【００２９】実施例３ 酢酸エチル６６部を溶剤とし、アクリル酸イソノニル９
０部、アクリロイルモルホリン１０部、２，２′−アゾ
ビスイソブチロニトリル０．１部、３−メルカプト−１
−プロパノ―ル０．０５部（全量）を用いて、実施例１
と同様にして、重量平均分子量が２２万、数平均分子量
が１０万、分子鎖末端の水酸基導入率が５５％である重
合体を生成し、この重合体を６０重量％含有する溶液
（常温での粘度：１２０ポイズ）を得た。Example 3 Using 66 parts of ethyl acetate as a solvent, isononyl acrylate 9
0 parts, acryloylmorpholine 10 parts, 2,2'-azobisisobutyronitrile 0.1 part, 3-mercapto-1
Example 1 using 0.05 parts (total amount) of propanol
In the same manner as described above, a polymer having a weight average molecular weight of 220,000, a number average molecular weight of 100,000, and a hydroxyl group introduction ratio of molecular chain terminal of 55% is produced, and a solution containing this polymer at 60% by weight (at room temperature). Of 120 poise.
【００３０】この重合体溶液に、その固形分１００部あ
たり、アルコ―ル性水酸基を持つ粘着付与樹脂〔理化ハ
―キユレス（株）製の「ペンタリンＣＪ」、水酸基価４
０ＫＯＨmg／ｇの重合ロジンエステル樹脂〕５０部、ト
リメチロ―ルプロパンのトリレンジイソシアネ―ト付加
物４部、エポキシ系架橋剤０．５部を加えて、感圧性接
着剤組成物を調製した。これを用いて、以下、実施例１
と同様にして、両面に架橋処理した接着剤層を有する接
着テ―プを作製した。To 100 parts of the solid content of this polymer solution, a tackifying resin having an alcoholic hydroxyl group [“Pentalin CJ” manufactured by Rika Hakuures Co., Ltd.
(0 KOH mg / g polymerized rosin ester resin), 50 parts of a trimethylolpropane tolylene diisocyanate adduct, and 0.5 part of an epoxy crosslinking agent were added to prepare a pressure-sensitive adhesive composition. Using this, the following Example 1
In the same manner as in the above, an adhesive tape having a cross-linked adhesive layer on both surfaces was produced.
【００３１】比較例１ 冷却管、窒素導入管、温度計、撹拌機を備えた反応容器
に、酢酸エチル６６部を溶剤として、アクリル酸２−エ
チルヘキシル４５部、アクリル酸ブチル５０部、２−ヒ
ドロキシエチルアクリレ―ト０．１部、２，２′−アゾ
ビスイソブチロニトリル０．１部、ラウリルメルカプタ
ン０．２３３部（全量）を入れ、窒素置換を行つたの
ち、昇温して、重合反応を行つた。その際、重合の最初
から連鎖移動剤を全量入れた。重合温度は、開始から４
時間は６０℃に保ち、その後２時間７０℃とした。この
ようにして、重量平均分子量が２４万、数平均分子量が
１２万で、分子末端ではなく分子側鎖に水酸基を有する
重合体を生成し、この重合体を６０重量％含有する溶液
（常温での粘度：１３０ポイズ）を得た。COMPARATIVE EXAMPLE 1 A reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer was charged with 66 parts of ethyl acetate as a solvent, 45 parts of 2-ethylhexyl acrylate, 50 parts of butyl acrylate, 0.1 part of ethyl acrylate, 0.1 part of 2,2'-azobisisobutyronitrile, 0.233 part of lauryl mercaptan (total amount) were added, and after purging with nitrogen, the temperature was increased. The polymerization reaction was performed. At that time, the whole amount of the chain transfer agent was charged from the beginning of the polymerization. The polymerization temperature is 4
The time was kept at 60 ° C. and then at 70 ° C. for 2 hours. In this way, a polymer having a weight average molecular weight of 240,000 and a number average molecular weight of 120,000, having a hydroxyl group not in the molecular terminal but in the molecular side chain is produced, and a solution containing this polymer at 60% by weight (at room temperature). Of 130 poise).
【００３２】この重合体溶液に、その固形分１００部あ
たり、アルコ―ル性水酸基を持つ粘着付与樹脂〔荒川化
学工業（株）製の「ペンセルＤ１２５」、水酸基価３０
ＫＯＨmg／ｇの重合ロジンエステル樹脂〕３０部、トリ
メチロ―ルプロパンのトリレンジイソシアネ―ト付加物
３部、エポキシ系架橋剤０．５部を加えて、感圧性接着
剤組成物を調製した。これを用いて、以下、実施例１と
同様にして、両面に架橋処理した接着剤層を有する接着
テ―プを作製した。To this polymer solution, a tackifying resin having an alcoholic hydroxyl group [“Pencel D125” manufactured by Arakawa Chemical Industries, Ltd.
30 parts of a polymerized rosin ester resin of KOH mg / g], 3 parts of a tolylene diisocyanate adduct of trimethylolpropane, and 0.5 part of an epoxy crosslinking agent were added to prepare a pressure-sensitive adhesive composition. Using this, an adhesive tape having a cross-linked adhesive layer on both surfaces was produced in the same manner as in Example 1.
【００３３】比較例２ 実施例３で得た重合体を６０重量％含有する溶液（常温
での粘度：１２０ポイズ）に、その固形分１００部あた
り、フエノ―ル性水酸基を持つ粘着付与樹脂〔ヤスハラ
ケミカル（株）製の「ＹＳポリスタ―Ｔ１３０」、水酸
基価５０ＫＯＨmg／ｇのテルペンフエノ―ル樹脂〕３０
部、トリメチロ―ルプロパンのトリレンジイソシアネ―
ト付加物３．２部、エポキシ系架橋剤０．５部を加え
て、感圧性接着剤組成物を調製した。これを用いて、以
下、実施例１と同様にして、両面に架橋処理した接着剤
層を有する接着テ―プを作製した。Comparative Example 2 A tackifying resin having a phenolic hydroxyl group was added to a solution containing 60% by weight of the polymer obtained in Example 3 (viscosity at room temperature: 120 poise) per 100 parts of the solid content. "YS Polystar T130" manufactured by Yashara Chemical Co., Ltd., terpene phenol resin having a hydroxyl value of 50 KOH mg / g] 30
Part, tolylene diisocyanate of trimethylolpropane
Then, 3.2 parts of the adduct and 0.5 part of an epoxy crosslinking agent were added to prepare a pressure-sensitive adhesive composition. Using this, an adhesive tape having a cross-linked adhesive layer on both surfaces was produced in the same manner as in Example 1.
【００３４】比較例３ 酢酸エチル６６部を溶剤とし、アクリル酸２−エチルヘ
キシル４５部、アクリル酸ブチル５０部、アクリル酸５
部、２，２′−アゾビスイソブチロニトリル０．１部、
２−メルカプトエタノ―ル０．２３５部（全量）を用い
て、実施例１と同様にして、重量平均分子量が６万、数
平均分子量が３万、分子鎖末端の水酸基導入率が７７％
である重合体を生成し、この重合体を６０重量％含有す
る溶液（常温での粘度：４０ポイズ）を得たComparative Example 3 Using 66 parts of ethyl acetate as a solvent, 45 parts of 2-ethylhexyl acrylate, 50 parts of butyl acrylate, and 5 parts of acrylic acid
Parts, 2,2'-azobisisobutyronitrile 0.1 part,
Using 0.235 parts (total amount) of 2-mercaptoethanol, in the same manner as in Example 1, the weight average molecular weight was 60,000, the number average molecular weight was 30,000, and the introduction ratio of hydroxyl groups at the molecular chain terminals was 77%.
And a solution (viscosity at room temperature: 40 poise) containing 60% by weight of this polymer was obtained.
【００３５】この重合体溶液に、その固形分１００部あ
たり、フエノ―ル性水酸基を持つ粘着付与樹脂〔新日鉄
化学（株）製の「エスクロンＶ１２０」、水酸基価３０
ＫＯＨmg／ｇのクマロンインデン樹脂〕３０部、トリメ
チロ―ルプロパンのトリレンジイソシアネ―ト付加物
３．２部を加えて、感圧性接着剤組成物を調製した。こ
れを用いて、以下、実施例１と同様にして、両面に架橋
処理した接着剤層を有する接着テ―プを作製した。Into this polymer solution, a tackifying resin having a phenolic hydroxyl group [“Escron V120” manufactured by Nippon Steel Chemical Co., Ltd .;
30 parts of a coumarone indene resin of KOH mg / g] and 3.2 parts of a tolylene diisocyanate adduct of trimethylolpropane were added to prepare a pressure-sensitive adhesive composition. Using this, an adhesive tape having a cross-linked adhesive layer on both surfaces was produced in the same manner as in Example 1.
【００３６】上記の実施例１〜３および比較例１〜３で
作製した各接着テ―プについて、以下の方法により、高
温剥離接着力および高温保持力を測定した。これらの測
定結果は、表１に示されるとおりであつた。For each of the adhesive tapes prepared in Examples 1 to 3 and Comparative Examples 1 to 3, the adhesive strength at high temperature and the adhesive strength at high temperature were measured by the following methods. The results of these measurements were as shown in Table 1.
【００３７】＜高温剥離接着力＞２０mm×１００mmの接
着テ―プを、その片面のセパレ―タを剥がし、他面側は
セパレ―タを剥がしたのち厚さが２５μｍのポリエチレ
ンテレフタレ―トフイルム（以下、ＰＥＴフイルムとい
う）で裏打ちした状態で、被着体として＃２８０のサン
ドペ―パでサンデイングしたステンレス板に、２Kgのロ
―ラを１往復させる方式で室温で圧着した。８０℃下で
２０分間経過後、８０℃の雰囲気下、引張り速度３００
mm／分の条件で、１８０度剥離に要する力を測定した。<High Temperature Peeling Adhesive Strength> A 20 mm × 100 mm adhesive tape was peeled off on one side and the other side was peeled off, and then a 25 μm thick polyethylene terephthalate film ( In the state of backing with a PET film), a 2 kg roller was pressure-bonded at room temperature to a stainless steel plate sanded with # 280 sandpaper as an adherend at room temperature. After a lapse of 20 minutes at 80 ° C., a tensile speed of 300 in an atmosphere of 80 ° C.
The force required for 180-degree peeling was measured under the condition of mm / min.
【００３８】＜高温保持力＞接着テ―プを、その片面の
セパレ―タを剥がし、他面側はセパレ―タを剥がしたの
ち厚さが２５μｍのＰＥＴフイルムで裏打ちした状態
で、フエノ―ル樹脂板に１０mm×２０mmの接着面積で室
温で接着し、２０分経過後、８０℃下に３０分放置し
た。ついで、フエノ―ル樹脂板を垂下し、接着テ―プの
自由末端に５００ｇの均一荷重を負荷し、８０℃におい
て接着テ―プが落下するまでの時間（分）を測定した。<Hot holding power> The adhesive tape was peeled off on one side and the other side was peeled off, and then backed with a PET film having a thickness of 25 μm. It was bonded to a resin plate at a bonding area of 10 mm × 20 mm at room temperature, and after 20 minutes, it was left at 80 ° C. for 30 minutes. Then, the phenol resin plate was hung down, a uniform load of 500 g was applied to the free end of the adhesive tape, and the time (min) until the adhesive tape dropped at 80 ° C. was measured.
【００３９】 [0039]
【００４０】上記表１の結果より明らかなように、本発
明の実施例１〜３では、重合体の分子量を小さくして高
固形分濃度（６０重量％）で低粘度な重合体溶液を調製
し、これにアルコ―ル性水酸基を持つ粘着付与樹脂を加
えて感圧性接着剤組成物を構成させるようにしたことに
より、高温下で高接着力および高保持力を示す、耐熱性
にすぐれた接着テ―プを作製できるものであることがわ
かる。As is clear from the results shown in Table 1, in Examples 1 to 3 of the present invention, the molecular weight of the polymer was reduced to prepare a polymer solution having a high solid content (60% by weight) and a low viscosity. Then, by adding a tackifying resin having an alcoholic hydroxyl group to the pressure-sensitive adhesive composition, it shows high adhesive strength and high holding power at high temperatures, and has excellent heat resistance. It can be seen that an adhesive tape can be produced.
【００４１】これに対して、感圧性接着剤組成物の調製
に際し、重合体として分子鎖末端ではなく分子側鎖に水
酸基を有するものを用いた比較例１、フエノ―ル性水酸
基を持つ粘着付与樹脂を用いた比較例２、重合体として
分子量が低すぎるものを使用し、かつこれにフエノ―ル
性水酸基を持つ粘着付与樹脂を加えた比較例３では、い
ずれも、耐熱性にすぐれた接着テ―プを作製することが
できない。On the other hand, in the preparation of the pressure-sensitive adhesive composition, Comparative Example 1 in which a polymer having a hydroxyl group in a molecular side chain instead of a molecular chain terminal was used as a polymer, and a tackifier having a phenolic hydroxyl group was used. In Comparative Example 2 using a resin and Comparative Example 3 in which a polymer having a too low molecular weight was used and a tackifier resin having a phenolic hydroxyl group was added, all of the adhesives having excellent heat resistance were used. Unable to make tape.
【００４２】[0042]
【発明の効果】以上のように、本発明においては、分子
鎖末端の官能基導入率および分子量が特定された重合体
を主剤として、これにアルコ―ル性水酸基を持つ粘着付
与樹脂を加える構成としたことにより、低粘度で高固形
分濃度の感圧性接着剤溶液を容易に調製できるととも
に、これを架橋処理することにより分子鎖長が長くてか
つ上記の粘着付与樹脂が重合体の分子鎖中に取り込まれ
た架橋重合体を生成でき、これにより接着特性、とくに
高温下での接着特性にすぐれ、耐熱性の改善された感圧
性接着剤組成物とその接着シ―ト類を得ることができ
る。As described above, in the present invention, a polymer having a specified functional group introduction ratio and molecular weight at the molecular chain terminal is used as a main component, and a tackifier resin having an alcoholic hydroxyl group is added thereto. As a result, a low-viscosity, high-solids-concentration pressure-sensitive adhesive solution can be easily prepared, and a cross-linking treatment of the pressure-sensitive adhesive solution has a long molecular chain length and the tackifying resin has a polymer molecular chain. A crosslinked polymer entrapped in the polymer can be formed, whereby it is possible to obtain a pressure-sensitive adhesive composition having excellent adhesive properties, particularly excellent adhesive properties at high temperatures, and improved heat resistance, and adhesive sheets thereof. it can.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J004 AA04 AA10 AA14 AB01 CA01 CA08 CB01 CB04 CC02 CC03 4J040 BA202 DF041 DF051 EF181 HC16 HD03 JA09 JB09 KA16 KA18 KA26 LA01 LA02 LA08 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J004 AA04 AA10 AA14 AB01 CA01 CA08 CB01 CB04 CC02 CC03 4J040 BA202 DF041 DF051 EF181 HC16 HD03 JA09 JB09 KA16 KA18 KA26 LA01 LA02 LA08
Claims (6)
（式中、Ｒ1 は水素またはメチル基、Ｒ2 は炭素数２〜
１４のアルキル基である）で表されるアクリル系単量体
を５０重量％以上含む単量体の重合体で、数平均分子量
が６万以上、重量平均分子量が１０万以上、分子鎖末端
の官能基導入率が５０％以上である重合体を主剤とし、
この主剤１００重量部あたり、アルコ―ル性水酸基を持
つ粘着付与樹脂１０〜７０重量部を含むことを特徴とす
る感圧性接着剤組成物。1. General formula; CH 2 ＣC (R 1 ) COOR 2
(Wherein, R 1 is hydrogen or a methyl group, and R 2 is C 2 -C 2
Is an alkyl group represented by the formula (14): a monomer polymer containing 50% by weight or more of an acrylic monomer represented by the following formula, having a number average molecular weight of 60,000 or more, a weight average molecular weight of 100,000 or more, A polymer having a functional group introduction rate of 50% or more as a main component,
A pressure-sensitive adhesive composition comprising 10 to 70 parts by weight of a tackifier resin having an alcoholic hydroxyl group per 100 parts by weight of the main agent.
は、水酸基価が１０〜１００ＫＯＨmg／ｇである請求項
１に記載の感圧性接着剤組成物。2. The pressure-sensitive adhesive composition according to claim 1, wherein the tackifier resin having an alcoholic hydroxyl group has a hydroxyl value of 10 to 100 KOH mg / g.
は、ロジン系エステルである請求項１または２に記載の
感圧性接着剤組成物。3. The pressure-sensitive adhesive composition according to claim 1, wherein the tackifying resin having an alcoholic hydroxyl group is a rosin ester.
は、軟化点が９０℃以上である請求項１〜３のいずれか
に記載の感圧性接着剤組成物。4. The pressure-sensitive adhesive composition according to claim 1, wherein the tackifying resin having an alcoholic hydroxyl group has a softening point of 90 ° C. or higher.
り、架橋剤を０．０５〜７重量部含む請求項１〜４のい
ずれかに記載の感圧性接着剤組成物。5. The pressure-sensitive adhesive composition according to claim 1, which comprises 0.05 to 7 parts by weight of a crosslinking agent per 100 parts by weight of a polymer as a main agent.
載の感圧性接着剤組成物を架橋処理した接着剤層を有す
ることを特徴とする接着シ―ト類。6. An adhesive sheet comprising a support and an adhesive layer obtained by subjecting the pressure-sensitive adhesive composition according to claim 1 to a crosslinking treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11071442A JP2000265137A (en) | 1999-03-17 | 1999-03-17 | Pressure-sensitive adhesive composition and its bonding sheets |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11071442A JP2000265137A (en) | 1999-03-17 | 1999-03-17 | Pressure-sensitive adhesive composition and its bonding sheets |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000265137A true JP2000265137A (en) | 2000-09-26 |
Family
ID=13460670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11071442A Pending JP2000265137A (en) | 1999-03-17 | 1999-03-17 | Pressure-sensitive adhesive composition and its bonding sheets |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000265137A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002146301A (en) * | 2000-11-17 | 2002-05-22 | Nitto Denko Hoso System Kk | Adhesive sheet |
| JP2002285114A (en) * | 2001-03-26 | 2002-10-03 | Sekisui Chem Co Ltd | Tape for abrasive fixing |
| JP2003049144A (en) * | 2001-08-08 | 2003-02-21 | Sekisui Chem Co Ltd | Heat-conductive pressure-sensitive adhesive and heat- conductive pressure-sensitive adhesive sheet |
| JP2007291299A (en) * | 2006-04-27 | 2007-11-08 | Sekisui Chem Co Ltd | Acrylic adhesive composition |
| JP2008024818A (en) * | 2006-07-21 | 2008-02-07 | Toray Fine Chemicals Co Ltd | Tacky adhesive composition |
| WO2013146650A1 (en) * | 2012-03-30 | 2013-10-03 | 昭和電工株式会社 | Adhesive agent composition and removable adhesive double-faced sheet using same |
| JP2015028130A (en) * | 2013-01-31 | 2015-02-12 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP2015110724A (en) * | 2013-11-07 | 2015-06-18 | 積水化学工業株式会社 | Adhesive tape |
-
1999
- 1999-03-17 JP JP11071442A patent/JP2000265137A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002146301A (en) * | 2000-11-17 | 2002-05-22 | Nitto Denko Hoso System Kk | Adhesive sheet |
| JP2002285114A (en) * | 2001-03-26 | 2002-10-03 | Sekisui Chem Co Ltd | Tape for abrasive fixing |
| JP2003049144A (en) * | 2001-08-08 | 2003-02-21 | Sekisui Chem Co Ltd | Heat-conductive pressure-sensitive adhesive and heat- conductive pressure-sensitive adhesive sheet |
| JP2007291299A (en) * | 2006-04-27 | 2007-11-08 | Sekisui Chem Co Ltd | Acrylic adhesive composition |
| JP2008024818A (en) * | 2006-07-21 | 2008-02-07 | Toray Fine Chemicals Co Ltd | Tacky adhesive composition |
| WO2013146650A1 (en) * | 2012-03-30 | 2013-10-03 | 昭和電工株式会社 | Adhesive agent composition and removable adhesive double-faced sheet using same |
| JP2015028130A (en) * | 2013-01-31 | 2015-02-12 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP2015110724A (en) * | 2013-11-07 | 2015-06-18 | 積水化学工業株式会社 | Adhesive tape |
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