JPH05247410A - Radiation-curable hot pressure-sensitive adhesive and adhesive tape made therefrom - Google Patents
Radiation-curable hot pressure-sensitive adhesive and adhesive tape made therefromInfo
- Publication number
- JPH05247410A JPH05247410A JP4081535A JP8153592A JPH05247410A JP H05247410 A JPH05247410 A JP H05247410A JP 4081535 A JP4081535 A JP 4081535A JP 8153592 A JP8153592 A JP 8153592A JP H05247410 A JPH05247410 A JP H05247410A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- radiation
- parts
- sensitive
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、短時間の低温加熱で強
固な接着力が発現する放射線硬化型の熱時感圧接着剤、
及びそれを用いてなる接着テープに関する。FIELD OF THE INVENTION The present invention relates to a radiation-curable heat-sensitive pressure-sensitive adhesive that exhibits a strong adhesive force by heating at low temperature for a short time.
And an adhesive tape using the same.
【０００２】[0002]
【従来の技術】従来、室温で強固な接着力を示す粘着剤
に熱溶融性樹脂を配合してクリープ特性等の保持力を改
良した感圧接着剤が知られていた（特公昭５６−１３０
４０号公報）。しかしながら、大量の有機溶剤に溶解さ
せて接着テープ等に加工する必要があり、環境衛生や安
全性などの点で難点がある問題点があった。2. Description of the Related Art Conventionally, a pressure-sensitive adhesive has been known in which a heat-melting resin is blended with a pressure-sensitive adhesive showing a strong adhesive force at room temperature to improve the holding power such as creep characteristics (Japanese Patent Publication No. 56-130).
No. 40). However, it is necessary to dissolve it in a large amount of an organic solvent and process it into an adhesive tape or the like, and there is a problem in that it is difficult in terms of environmental hygiene and safety.
【０００３】一方、前記の如く使用溶剤の減量要求に応
えて無溶剤、ないし少量の溶剤使用で塗工できる無溶剤
塗工型で、放射線硬化型の感圧接着剤が提案されてい
る。かかる放射線硬化型の感圧接着剤は、エマルジョン
型やホットメルト型のものに比べて耐水性や耐熱性に優
れる利点を有している。しかしながら、従来の放射線硬
化型感圧接着剤において、ベースポリマーの低分子量化
で無溶剤塗工型としたものにあっては凝集力の低下を招
いて保持力に乏しく、反応性モノマーで希釈した無溶剤
塗工型のものにあっては接着力に乏しい問題点があっ
た。On the other hand, as described above, there has been proposed a radiation-curable pressure-sensitive adhesive which is a solventless coating type which can be coated with a solvent or using a small amount of solvent in response to the demand for reducing the amount of solvent used. Such a radiation-curable pressure-sensitive adhesive has the advantage of being superior in water resistance and heat resistance as compared with emulsion-type and hot-melt type adhesives. However, in the conventional radiation-curable pressure-sensitive adhesive, a base polymer having a low molecular weight and a solventless coating type causes a decrease in cohesive force and poor holding power, and is diluted with a reactive monomer. The solventless coating type has a problem of poor adhesive strength.
【０００４】また、従来の放射線硬化型感圧接着剤に熱
溶融性樹脂を配合した場合、放射線による架橋処理が阻
害されて凝集力が低下する問題点があった。従って、い
ずれの場合にも無溶剤塗工を満足させつつ接着力と保持
力を両立させることが困難であった。When a conventional radiation-curable pressure-sensitive adhesive is blended with a heat-melting resin, there is a problem that the crosslinking treatment by radiation is hindered and the cohesive force is lowered. Therefore, in either case, it was difficult to satisfy both the adhesive force and the holding force while satisfying the solventless coating.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、無溶剤塗工
型で、接着力と保持力に優れる放射線硬化型の感圧接着
性を示す接着剤、ないし接着テープの開発を課題とす
る。SUMMARY OF THE INVENTION An object of the present invention is to develop a solventless coating type adhesive agent or adhesive tape which exhibits radiation-curable pressure-sensitive adhesiveness and is excellent in adhesive strength and holding power.
【０００６】[0006]
【課題を解決するための手段】本発明は、一般式：ＣＨ
2＝Ｃ（Ｒ1）ＣＯＯＲ2（ただし、Ｒ1は水素又はメチル
基、Ｒ2は炭素数が２〜１４のアルキル基である。）で
表されるアクリル系モノマー単位を５０重量％以上含有
するアクリル系重合体１００重量部と、融点が７０〜２
００℃の熱溶融性樹脂５０〜１５０重量部と、分子中に
放射線反応性不飽和結合を２個以上有する多官能モノマ
ー１〜３０重量部を含有することを特徴とする放射線硬
化型熱時感圧接着剤、及びかかる放射線硬化型熱時感圧
接着剤からなる層を支持体の片面、又は両面に有するこ
とを特徴とする接着テープを提供するものである。The present invention has the general formula: CH
2 = C (R 1 ) COOR 2 (provided that R 1 is hydrogen or a methyl group, and R 2 is an alkyl group having 2 to 14 carbon atoms) is contained in an amount of 50% by weight or more. 100 parts by weight of an acrylic polymer having a melting point of 70 to 2
50 to 150 parts by weight of a heat-meltable resin at 00 ° C. and 1 to 30 parts by weight of a polyfunctional monomer having two or more radiation-reactive unsaturated bonds in a molecule, and a radiation-curable heat-sensitive material. A pressure-sensitive adhesive, and a layer comprising the radiation-curable heat-sensitive pressure-sensitive adhesive are provided on one side or both sides of a support, which provides an adhesive tape.
【０００７】[0007]
【作用】上記の組成とすることにより、無溶剤ないし少
量の溶剤使用で塗工できる無溶剤塗工型の熱時感圧接着
剤を得ることができる。かかる熱時感圧接着剤は、放射
線の照射で硬化し、加熱処理前の室温では容易に貼直し
や位置修正等ができる弱い接着力を示し、加熱により強
固な接着力を発現して接着力と保持力のバランスに優れ
る接着特性を示す。With the above composition, it is possible to obtain a solventless coating type heat-sensitive pressure-sensitive adhesive which can be coated with no solvent or using a small amount of solvent. Such a heat-sensitive pressure-sensitive adhesive is hardened by irradiation of radiation and exhibits weak adhesive force that can be easily re-attached or position-corrected at room temperature before heat treatment. It exhibits excellent adhesive properties with a good balance of holding power.
【０００８】[0008]
【発明の構成要素の例示】本発明の放射線硬化型熱時感
圧接着剤は、一般式：ＣＨ2＝Ｃ（Ｒ1）ＣＯＯＲ2（た
だし、Ｒ1は水素又はメチル基、Ｒ2は炭素数が２〜１４
のアルキル基である。）で表されるアクリル系モノマー
単位を５０重量％以上含有するアクリル系重合体を成分
とする。凝集力等の接着特性や無溶剤塗工性などの点よ
り好ましく用いうるアクリル系重合体は、重量平均分子
量が５万〜４０万、就中１０万〜３０万のものである。Illustrative of the constituent elements of the invention The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention has the general formula: CH 2 ═C (R 1 ) COOR 2 (wherein R 1 is hydrogen or a methyl group, and R 2 is carbon). Number is 2-14
Is an alkyl group. ) An acrylic polymer containing 50% by weight or more of an acrylic monomer unit represented by (4) is used as a component. The acrylic polymer that can be preferably used in terms of adhesive properties such as cohesive force and solventless coating properties has a weight average molecular weight of 50,000 to 400,000, and particularly 100,000 to 300,000.
【０００９】前記のアクリル系モノマー単位の具体例と
しては、エチル基、プルピル基、ブチル基、イソブチル
基、イソアミル基、ヘキシル基、２−エチルヘキシル
基、イソオクチル基、イソノニル基、イソデシル基の如
きアルキル基を有するアクリル酸やメタクリル酸のエス
テルなどがあげられる。Specific examples of the acrylic monomer unit include an alkyl group such as ethyl group, propyl group, butyl group, isobutyl group, isoamyl group, hexyl group, 2-ethylhexyl group, isooctyl group, isononyl group and isodecyl group. Examples thereof include esters of acrylic acid and methacrylic acid having
【００１０】アクリル系重合体は、１種又は２種以上の
アクリル系モノマーを５０〜１００重量％用いて調製し
たものであってよい。アクリル系重合体が接着特性等の
調節のため含有することのある他のモノマー単位の例と
しては、アクリル酸、メタクリル酸、アクリルアミド、
メタクリルアミド、アクリロニトリル、酢酸ビニル、ス
チレン、Ｎ−ビニルピロリドン、Ｎ−メチロールアクリ
ルアミド、アクリル酸グリシジル、メタクリル酸グリシ
ジル、アクリル酸２−ヒドロキシエチル、メタクリル酸
２−ヒドロキシエチル、アクリル酸２−ヒドロキシプロ
ピル、メタクリル酸２−ヒドロキシプロピルなどがあげ
られる。The acrylic polymer may be prepared by using 50 to 100% by weight of one or more acrylic monomers. Examples of other monomer units that the acrylic polymer may contain for the purpose of controlling adhesive properties and the like include acrylic acid, methacrylic acid, acrylamide,
Methacrylamide, acrylonitrile, vinyl acetate, styrene, N-vinylpyrrolidone, N-methylolacrylamide, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methacryl Examples thereof include 2-hydroxypropyl acid.
【００１１】またアクリル系重合体は、架橋性の向上等
を目的に放射線反応性不飽和結合を有していてもよい。
その放射線反応性不飽和結合の導入は、例えばアクリル
系の重合体におけるヒドロキシル基やカルボキシル基、
アミノ基等の官能基と反応しうる官能基と放射線反応性
不飽和結合を有するモノマー、例えばアクリル酸グリシ
ジル、メタクリル酸グリシジル、２−メタクリロイルオ
キシエチルイソシアネート等をアクリル系の重合体と反
応させる方法、あるいはラジカル反応性ないし放射線反
応性不飽和結合を２個以上有する化合物を併用してアク
リル系重合体をラジカル重合法で調製する方法などによ
り行うことができる。The acrylic polymer may have a radiation-reactive unsaturated bond for the purpose of improving crosslinkability.
The introduction of the radiation-reactive unsaturated bond is, for example, a hydroxyl group or a carboxyl group in an acrylic polymer,
A method of reacting a monomer having a functional group capable of reacting with a functional group such as an amino group and a radiation-reactive unsaturated bond, for example, glycidyl acrylate, glycidyl methacrylate, 2-methacryloyloxyethyl isocyanate with an acrylic polymer, Alternatively, it can be carried out by a method of preparing an acrylic polymer by a radical polymerization method in combination with a compound having two or more radical-reactive or radiation-reactive unsaturated bonds.
【００１２】本発明の放射線硬化型熱時感圧接着剤は、
融点が７０〜２００℃の熱溶融性樹脂を成分とする。そ
の融点が７０℃未満では得られる接着剤が耐熱性に乏し
く、２００℃を超えると得られる接着剤が低温加熱での
接着力発現性に乏しくなる。好ましく用いうる熱溶融性
樹脂は、ロジン系樹脂、クマロンインデン系樹脂、テル
ペン系樹脂、石油系樹脂などである。熱溶融性樹脂は、
１種又は２種以上を用いうる。The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention comprises
A heat-meltable resin having a melting point of 70 to 200 ° C. is used as a component. When the melting point is less than 70 ° C, the obtained adhesive has poor heat resistance, and when the melting point exceeds 200 ° C, the obtained adhesive has poor adhesive force expression at low temperature heating. Preferable heat-melting resins are rosin-based resins, coumarone-indene-based resins, terpene-based resins, petroleum-based resins and the like. Thermofusible resin is
One kind or two or more kinds may be used.
【００１３】前記のロジン系樹脂の具体例としては、ロ
ジンエステル、水添ロジンエステル、不均化ロジンエス
テル、重合ロジンエステルなどがあげられる。クマロン
インデン系樹脂の具体例としては、クマロンインデン樹
脂、水添クマロンインデン樹脂、フェノール変性クマロ
ンインデン樹脂、エポキシ変性クマロンインデン樹脂な
どがあげられる。テルペン系樹脂の具体例としては、ポ
リテルペン樹脂、スチレン変性テルペン樹脂、フェノー
ル変性テルペン樹脂などがあげられる。石油系樹脂の具
体例としては、脂肪族系石油樹脂、芳香族系石油樹脂、
芳香族変性脂肪族系石油樹脂、芳香族系純モノマー樹脂
などがあげられる。Specific examples of the rosin-based resin include rosin ester, hydrogenated rosin ester, disproportionated rosin ester and polymerized rosin ester. Specific examples of the coumarone-indene resin include coumarone-indene resin, hydrogenated coumarone-indene resin, phenol-modified coumarone-indene resin, and epoxy-modified coumarone-indene resin. Specific examples of the terpene-based resin include polyterpene resin, styrene-modified terpene resin, and phenol-modified terpene resin. Specific examples of petroleum-based resins include aliphatic petroleum resins, aromatic petroleum resins,
Examples thereof include aromatic modified aliphatic petroleum resin and aromatic pure monomer resin.
【００１４】熱溶融性樹脂の配合量は、アクリル系重合
体１００重量部あたり５０〜１５０重量部とされる。そ
の配合量が５０重量部未満では、得られる接着剤が接着
力に乏しくなり、１５０重量部を超えると得られる接着
剤が被着体に対する濡れ性に乏しくなる。The amount of the hot-melt resin blended is 50 to 150 parts by weight per 100 parts by weight of the acrylic polymer. If the content is less than 50 parts by weight, the adhesive obtained will have poor adhesive strength, and if it exceeds 150 parts by weight, the adhesive obtained will have poor wettability with respect to the adherend.
【００１５】本発明の放射線硬化型熱時感圧接着剤は、
分子中にビニル基、アクリロイル基、メタクリロイル
基、ビニルベンジル基の如き放射線の照射で架橋処理
（硬化）しうる１種又は２種以上の放射線反応性不飽和
結合を２個以上有する多官能モノマーを成分とする。好
ましい多官能モノマーは、アクリロイル基又は／及びメ
タクリロイル基を有するものである。放射線反応性不飽
和結合が２個未満のものでは得られる接着剤の保持力や
接着力等の接着特性をバランスさせにくい。なお一般に
は、含有の放射線反応性不飽和結合が１０個以下のもの
が用いられるが、これに限定するものではない。The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention comprises
A polyfunctional monomer having two or more one or more radiation-reactive unsaturated bonds capable of undergoing a crosslinking treatment (curing) upon irradiation with radiation such as a vinyl group, an acryloyl group, a methacryloyl group and a vinylbenzyl group in a molecule. As an ingredient. Preferred polyfunctional monomers are those having an acryloyl group and / or a methacryloyl group. When the number of the radiation-reactive unsaturated bonds is less than 2, it is difficult to balance the adhesive properties such as holding power and adhesive force of the obtained adhesive. Generally, those containing 10 or less radiation-reactive unsaturated bonds are used, but the number is not limited to this.
【００１６】前記した好ましく用いうる多官能モノマー
の具体例としては、ジエチレングリコールジアクリレー
ト、ジエチレングリコールジメタクリレート、トリエチ
レングリコールジアクリレート、トリエチレングリコー
ルジメタクリレート、テトラエチレングリコールジアク
リレート、テトラエチレングリコールジメタクリレー
ト、トリプロピレングリコールジアクリレート、トリプ
ロピレングリコールジメタクリレート、１，６−ヘキサ
ンジオールジアクリレート、ネオペンチルグリコールジ
アクリレート、ネオペンチルグリコールジメタクリレー
ト、トリメチロールプロパントリアクリレート、トリメ
チロールプロパントリメタクリレート、ペンタエリスリ
トールトリアクリレート、ペンタエリスリトールトリメ
タクリレート、ジペンタエリスリトールヘキサアクリレ
ート、ジペンタエリスリトールヘキサメタクリレートな
どがあげられる。Specific examples of the above-mentioned polyfunctional monomers that can be preferably used include diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and triethylene glycol dimethacrylate. Propylene glycol diacrylate, tripropylene glycol dimethacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, penta Erythritol trimethacrylate, dipe Data hexaacrylate, dipentaerythritol hexa methacrylate, and the like.
【００１７】多官能モノマーの配合量は、アクリル系重
合体１００重量部あたり１〜３０重量部とされる。その
配合量が１重量部未満では、得られる接着剤が凝集力に
乏しくなり、３０重量部を超えると得られる接着剤が接
着力に乏しくなる。The compounding amount of the polyfunctional monomer is 1 to 30 parts by weight per 100 parts by weight of the acrylic polymer. If the blending amount is less than 1 part by weight, the adhesive obtained will be poor in cohesive force, and if it exceeds 30 parts by weight, the adhesive obtained will be poor in adhesive force.
【００１８】本発明の放射線硬化型熱時感圧接着剤は、
配合成分を混合することにより調製することができる。
その際、感圧接着剤に通常使用される添加剤、例えばガ
ラス繊維や金属粉の如き充填剤、顔料、着色剤、可塑剤
なども通常量添加することができる。The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention comprises
It can be prepared by mixing the ingredients.
At that time, additives usually used for pressure-sensitive adhesives, for example, fillers such as glass fibers and metal powders, pigments, colorants, plasticizers and the like can be added in usual amounts.
【００１９】本発明の放射線硬化型熱時感圧接着剤は、
活性エネルギー線、例えばα線、β線、γ線、中性子
線、電子線の如き電離性放射線や紫外線などの照射で硬
化するものである。照射線量は、電離性放射線の場合、
通例０.５〜２０Ｍrad程度あり、就中１〜１０Ｍradが
好ましい。紫外線の場合には、通例４００〜３０００mj
／cm2程度である。The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention comprises
It is cured by irradiation with active energy rays such as α-rays, β-rays, γ-rays, neutron rays and electron beams, and ionizing radiation such as ultraviolet rays. For ionizing radiation, the irradiation dose is
It is usually about 0.5 to 20 Mrad, and preferably 1 to 10 Mrad. In the case of ultraviolet rays, it is usually 400-3000 mj
It is about / cm 2 .
【００２０】なお紫外線としては１８０〜４６０nmの波
長範囲が好ましく、その発生源としては水銀ランプ、メ
タルハライドランプが好ましい。また紫外線照射により
硬化させる場合、光反応開始剤(光増感剤)の併用が望ま
しい。光反応開始剤の例としては、ベンゾイン、ベンゾ
インメチルエーテル、ベンゾインエチルエーテル、ジベ
ンジル、ベンジルジメチルケタールなどがあげられる。The wavelength of ultraviolet rays is preferably in the range of 180 to 460 nm, and a mercury lamp or a metal halide lamp is preferable as a source of the ultraviolet rays. When curing by ultraviolet irradiation, it is desirable to use a photoreaction initiator (photosensitizer) together. Examples of the photoreaction initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, dibenzyl, benzyl dimethyl ketal and the like.
【００２１】本発明の接着テープは、支持体の片面、又
は両面に上記した放射線硬化型熱時感圧接着剤からなる
層を有するものである。その熱時感圧接着剤層は、支持
体に固定されたものであってもよいし、支持体より剥離
できるようにしたものであってもよい。剥離可能なタイ
プは、例えば剥離剤で処理した支持体を用いる方法など
により形成することができる。支持体には、例えばプラ
スチックフィルム、紙、不織布、金属箔など、適宜なも
のを用いてよい。支持体に設ける熱時感圧接着剤層の厚
さは１〜５００μmが一般的であるが、これに限定され
ず適宜な厚さとしてよい。The adhesive tape of the present invention has a layer comprising the above radiation-curable heat-sensitive pressure-sensitive adhesive on one side or both sides of the support. The heat-sensitive pressure-sensitive adhesive layer may be fixed to the support or may be peelable from the support. The peelable type can be formed by, for example, a method using a support treated with a release agent. As the support, an appropriate material such as a plastic film, paper, non-woven fabric, or metal foil may be used. The thickness of the heat-sensitive pressure-sensitive adhesive layer provided on the support is generally 1 to 500 μm, but is not limited to this and may be an appropriate thickness.
【００２２】[0022]
【発明の効果】本発明の放射線硬化型熱時感圧接着剤
は、無溶剤、ないし少ない溶剤使用量で塗工できて、放
射線の照射で硬化させることができる。また加熱処理前
の室温では弱い接着力を示して容易に貼直しや位置修正
などを行うことができ、１００℃以下程度の比較的低温
の、かつ短時間の加熱処理で強固な接着力が発現して、
接着力と保持力のバランスに優れた接着特性を発揮す
る。The radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention can be applied with no solvent or with a small amount of solvent, and can be cured by irradiation with radiation. In addition, it shows weak adhesion at room temperature before heat treatment, and can be easily re-attached or position-corrected, and a strong adhesion can be obtained by heat treatment at a relatively low temperature of about 100 ° C or less for a short time. do it,
Exhibits excellent adhesive properties with a good balance between adhesive strength and holding power.
【００２３】[0023]
参考例１ 冷却管、窒素導入管、温度計、撹拌装置を備えた反応容
器に、アクリル酸２−エチルヘキシル８５部（重量部、
以下同じ）、アクリル酸メチル１０部、アクリルアミド
５部、アクリル酸２−ヒドロキシエチル０．２部、２−
メルカプトエタノール０．１部、２，２'−アゾビス−
２−シアノプロパノール０.２部、トルエン５０部を入
れ、窒素気流中で重合処理して重量平均分子量２５万の
アクリル系重合体を得た。Reference Example 1 In a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer, and a stirrer, 85 parts of 2-ethylhexyl acrylate (parts by weight,
The same shall apply hereinafter), 10 parts of methyl acrylate, 5 parts of acrylamide, 0.2 parts of 2-hydroxyethyl acrylate, 2-
Mercaptoethanol 0.1 part, 2,2'-azobis-
0.2 parts of 2-cyanopropanol and 50 parts of toluene were added, and the mixture was polymerized in a nitrogen stream to obtain an acrylic polymer having a weight average molecular weight of 250,000.
【００２４】参考例２ 冷却管、窒素導入管、温度計、撹拌装置を備えた反応容
器にアクリル酸ブチル７０部、アクリル酸イソノニル２
０部、酢酸ビニル７部、アクリル酸３部、２，２'−ア
ゾビスイソブチルニトリル０.３部、ラウリルメルカプ
タン０．１５部、酢酸エチル５０部を入れ、窒素気流中
で重合処理して重量平均分子量１８万のアクリル系重合
体を得た。Reference Example 2 70 parts of butyl acrylate and 2 parts of isononyl acrylate were placed in a reaction vessel equipped with a cooling pipe, a nitrogen introducing pipe, a thermometer and a stirrer.
0 parts, 7 parts of vinyl acetate, 3 parts of acrylic acid, 0.3 parts of 2,2'-azobisisobutyl nitrile, 0.15 parts of lauryl mercaptan and 50 parts of ethyl acetate were added, and the mixture was polymerized in a nitrogen stream and weighed. An acrylic polymer having an average molecular weight of 180,000 was obtained.
【００２５】参考例３ 参考例１で得たアクリル系重合体と、２−メタクリロイ
ルオキシエチルイソシアネート０．６部をジブチルスズ
ジラウレート０．１部の使用下に反応させて、メタクリ
ロイル基を有するアクリル系重合体を得た。Reference Example 3 The acrylic polymer obtained in Reference Example 1 was reacted with 0.6 parts of 2-methacryloyloxyethylisocyanate using 0.1 part of dibutyltin dilaurate to give an acrylic polymer having a methacryloyl group. Got united.
【００２６】実施例１ 参考例１で得たアクリル系重合体１００部、重合ロジン
のペンタエリスリトールエステル（融点１２０℃）７０
部、水添クマロンインデン樹脂（融点１００℃）２０
部、及びペンタエリスリトールトリメタクリレート１０
部を混合して放射線硬化型熱時感圧接着剤を調製した。
ついで、前記の放射線硬化型熱時感圧接着剤をセパレー
ター上に塗工し、８０℃で３分間乾燥後、電子線を３Ｍ
rad照射して硬化処理し、厚さ約５０μmの硬化層を有す
る接着テープを得た。Example 1 100 parts of the acrylic polymer obtained in Reference Example 1, pentaerythritol ester of polymerized rosin (melting point 120 ° C.) 70
Part, hydrogenated coumarone indene resin (melting point 100 ° C.) 20
Parts and pentaerythritol trimethacrylate 10
The parts were mixed to prepare a radiation-curable heat-sensitive pressure-sensitive adhesive.
Then, the radiation-curable heat-sensitive pressure-sensitive adhesive was applied onto the separator, dried at 80 ° C. for 3 minutes, and then irradiated with an electron beam of 3M.
Curing treatment was performed by rad irradiation to obtain an adhesive tape having a cured layer having a thickness of about 50 μm.
【００２７】実施例２ 重合ロジンのペンタエリスリトールエステル及び水添ク
マロンインデン樹脂に代えて、フェノール変性テルペン
樹脂（融点１３０℃）５０部、及びスチレン系樹脂（融
点９０℃）２０部を用いたほかは、実施例１に準じて放
射線硬化型熱時感圧接着剤及び接着テープを得た。Example 2 In place of the pentaerythritol ester of polymerized rosin and hydrogenated coumarone indene resin, 50 parts of phenol-modified terpene resin (melting point 130 ° C.) and 20 parts of styrene resin (melting point 90 ° C.) were used. A radiation-curable heat-sensitive pressure-sensitive adhesive and adhesive tape were obtained in the same manner as in Example 1.
【００２８】実施例３ 参考例２で得たアクリル系重合体１００部、水添ロジン
のペンタエリスリトールエステル（融点１００℃）８０
部、芳香族変性脂肪族系石油樹脂（融点９０℃）３０
部、及びトリメチロールプロパントリメタクリレート１
５部を混合して放射線硬化型熱時感圧接着剤を調製し、
それを用いて実施例１に準じ接着テープを得た。Example 3 100 parts of the acrylic polymer obtained in Reference Example 2 and pentaerythritol ester of hydrogenated rosin (melting point 100 ° C.) 80
Parts, aromatic modified aliphatic petroleum resin (melting point 90 ° C) 30
Parts and trimethylolpropane trimethacrylate 1
Prepare a radiation-curable heat-sensitive pressure-sensitive adhesive by mixing 5 parts,
Using it, an adhesive tape was obtained according to Example 1.
【００２９】実施例４ 参考例１で得たアクリル系重合体に代えて参考例３で得
たアクリル系重合体を用い、ペンタエリスリトールトリ
メタクリレートに代えてテトラエチレングリコールジメ
タクリレート５部を用いたほかは、実施例１に準じて放
射線硬化型熱時感圧接着剤及び接着テープを得た。Example 4 The acrylic polymer obtained in Reference Example 3 was used in place of the acrylic polymer obtained in Reference Example 1, and 5 parts of tetraethylene glycol dimethacrylate was used in place of pentaerythritol trimethacrylate. A radiation-curable heat-sensitive pressure-sensitive adhesive and adhesive tape were obtained in the same manner as in Example 1.
【００３０】比較例１ 重合ロジンのペンタエリスリトールエステルの使用量を
２０部とし、水添クマロンインデン樹脂の使用量を１０
部としたほかは、実施例１に準じて放射線硬化型の組成
物及び接着テープを得た。Comparative Example 1 The amount of pentaerythritol ester of polymerized rosin used was 20 parts, and the amount of hydrogenated coumarone indene resin used was 10 parts.
A radiation curable composition and an adhesive tape were obtained in the same manner as in Example 1 except that the parts were used.
【００３１】比較例２ 重合ロジンのペンタエリスリトールエステルに代えて、
融点が−１８℃の水添ロジンのトリエチレングリコール
エステル（７０部）を用いたほかは、実施例１に準じて
放射線硬化型の組成物及び接着テープを得た。Comparative Example 2 Instead of the pentaerythritol ester of polymerized rosin,
A radiation curable composition and an adhesive tape were obtained in the same manner as in Example 1 except that hydrogenated rosin triethylene glycol ester (70 parts) having a melting point of -18 ° C was used.
【００３２】評価試験 実施例、比較例で得た接着テープについて、下記の試験
を行った。 剪断接着力 接着テープより分離した熱時感圧接着剤層又は組成物層
を介して厚さ０．５mmのアルミニウム板を１０mm×１０
mmの接着面積で仮着後、２３℃、６０℃又は１００℃、
１kg／cm2の条件で１分間、圧着し、その試験片の剪断
接着力をインストロン型万能引張り試験機にて測定した
（引張り速度５０mm／分、２３℃、６５％R.H.）。Evaluation Test The adhesive tapes obtained in Examples and Comparative Examples were subjected to the following tests. Shearing adhesiveness An aluminum plate having a thickness of 0.5 mm is 10 mm × 10 through a pressure-sensitive adhesive layer under heat or a composition layer separated from an adhesive tape.
After temporary attachment with a bonding area of mm, 23 ℃, 60 ℃ or 100 ℃,
The test piece was pressure-bonded for 1 minute under the condition of 1 kg / cm 2 , and the shear adhesive strength of the test piece was measured by an Instron type universal tensile tester (pulling speed 50 mm / minute, 23 ° C., 65% RH).
【００３３】保持力 前記と同様に作製した試験片（１００℃で加熱圧着した
もの）を８０℃の雰囲気下に２０分間放置したのち試験
片を垂下し、その自由端に５００ｇの均一荷重を負荷
し、８０℃においてアルミニウム板が落下するまでの時
間を測定した。Holding power A test piece prepared in the same manner as described above (heat-pressed at 100 ° C.) was left in an atmosphere of 80 ° C. for 20 minutes, and then the test piece was hung down, and a uniform load of 500 g was applied to its free end. Then, the time until the aluminum plate fell at 80 ° C. was measured.
【００３４】結果を表１に示した。The results are shown in Table 1.
【表１】 [Table 1]
【００３５】表１より、本発明の放射線硬化型熱時感圧
接着剤は、加熱処理前の室温では弱い接着力を示し、比
較的低温の、かつ短時間の加熱処理で強固な接着力が発
現して接着力と保持力に優れており、それらがバランス
よく両立していることがわかる。From Table 1, it can be seen that the radiation-curable heat-sensitive pressure-sensitive adhesive of the present invention shows a weak adhesive force at room temperature before heat treatment, and shows a strong adhesive force by a heat treatment at a relatively low temperature for a short time. It can be seen that they are manifested and have excellent adhesive strength and holding power, and they are well balanced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 157/00 ＪＤＫ 6770−4Ｊ (72)発明者 諸石 裕 大阪府茨木市下穂積１丁目１番２号 日東 電工株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical indication location C09J 157/00 JDK 6770-4J (72) Inventor Yutaka Moroishi 1-1-1 Shimohozumi, Ibaraki-shi, Osaka No. 2 Nitto Denko Corporation
Claims (2)
2（ただし、Ｒ1は水素又はメチル基、Ｒ2は炭素数が２
〜１４のアルキル基である。）で表されるアクリル系モ
ノマー単位を５０重量％以上含有するアクリル系重合体
１００重量部と、融点が７０〜２００℃の熱溶融性樹脂
５０〜１５０重量部と、分子中に放射線反応性不飽和結
合を２個以上有する多官能モノマー１〜３０重量部を含
有することを特徴とする放射線硬化型熱時感圧接着剤。1. A general formula: CH 2 ═C (R 1 ) COOR
2 (However, R 1 is hydrogen or a methyl group, and R 2 has 2 carbon atoms.
~ 14 alkyl groups. ) 100 parts by weight of an acrylic polymer containing 50% by weight or more of an acrylic monomer unit, 50 to 150 parts by weight of a heat-meltable resin having a melting point of 70 to 200 ° C., and a radiation-reactive A radiation-curable heat-sensitive pressure-sensitive adhesive containing 1 to 30 parts by weight of a polyfunctional monomer having two or more saturated bonds.
載の放射線硬化型熱時感圧接着剤からなる層を有するこ
とを特徴とする接着テープ。2. An adhesive tape having a layer comprising the radiation-curable heat-sensitive pressure-sensitive adhesive according to claim 1 on one side or both sides of the support.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08153592A JP3281026B2 (en) | 1992-03-03 | 1992-03-03 | Radiation-curable hot pressure-sensitive adhesive and its adhesive tape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08153592A JP3281026B2 (en) | 1992-03-03 | 1992-03-03 | Radiation-curable hot pressure-sensitive adhesive and its adhesive tape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05247410A true JPH05247410A (en) | 1993-09-24 |
| JP3281026B2 JP3281026B2 (en) | 2002-05-13 |
Family
ID=13749005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08153592A Expired - Fee Related JP3281026B2 (en) | 1992-03-03 | 1992-03-03 | Radiation-curable hot pressure-sensitive adhesive and its adhesive tape |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3281026B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001337443A (en) * | 2000-05-25 | 2001-12-07 | Kimoto & Co Ltd | Protective film transferring sheet for photomask and method for transferring protective film |
| WO2008029768A1 (en) * | 2006-09-04 | 2008-03-13 | Nitto Denko Corporation | Ultraviolet-curable adhesive composition, ultraviolet-curable adhesive sheet and method for producing the same |
| US7641966B2 (en) | 1999-06-14 | 2010-01-05 | Nitto Denko Corporation | Re-release adhesive and re-release adhesive sheet |
| US8598250B2 (en) | 2008-01-22 | 2013-12-03 | Nitto Denko Corporation | Photocurable acrylic viscoelastic material composition, acrylic viscoelastic material, acrylic viscoelastic material layer tape or sheet and proceed for producing the same |
| WO2022230027A1 (en) * | 2021-04-26 | 2022-11-03 | リンテック株式会社 | Energy ray-crosslinkable adhesive agent composition, crosslinked adhesive agent, adhesive sheet, and methods for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574703B (en) * | 2009-06-05 | 2011-02-16 | 中国第一重型机械股份公司 | Shell course rolling technology |
-
1992
- 1992-03-03 JP JP08153592A patent/JP3281026B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7641966B2 (en) | 1999-06-14 | 2010-01-05 | Nitto Denko Corporation | Re-release adhesive and re-release adhesive sheet |
| JP2001337443A (en) * | 2000-05-25 | 2001-12-07 | Kimoto & Co Ltd | Protective film transferring sheet for photomask and method for transferring protective film |
| JP4601769B2 (en) * | 2000-05-25 | 2010-12-22 | 株式会社きもと | Protective film transfer sheet for photomask and protective film transfer method |
| WO2008029768A1 (en) * | 2006-09-04 | 2008-03-13 | Nitto Denko Corporation | Ultraviolet-curable adhesive composition, ultraviolet-curable adhesive sheet and method for producing the same |
| JP2008088408A (en) * | 2006-09-04 | 2008-04-17 | Nitto Denko Corp | Ultraviolet-curable adhesive composition, ultraviolet-curable adhesive sheet, and method for producing the same |
| US8598250B2 (en) | 2008-01-22 | 2013-12-03 | Nitto Denko Corporation | Photocurable acrylic viscoelastic material composition, acrylic viscoelastic material, acrylic viscoelastic material layer tape or sheet and proceed for producing the same |
| WO2022230027A1 (en) * | 2021-04-26 | 2022-11-03 | リンテック株式会社 | Energy ray-crosslinkable adhesive agent composition, crosslinked adhesive agent, adhesive sheet, and methods for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3281026B2 (en) | 2002-05-13 |
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