JP2548970B2 - Adhesive member - Google Patents
Adhesive memberInfo
- Publication number
- JP2548970B2 JP2548970B2 JP63227954A JP22795488A JP2548970B2 JP 2548970 B2 JP2548970 B2 JP 2548970B2 JP 63227954 A JP63227954 A JP 63227954A JP 22795488 A JP22795488 A JP 22795488A JP 2548970 B2 JP2548970 B2 JP 2548970B2
- Authority
- JP
- Japan
- Prior art keywords
- pressure
- sensitive adhesive
- weight
- adhesive layer
- crosslinking
- 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 - Fee Related
Links
Landscapes
- Adhesive Tapes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、紫外線硬化により架橋度を部分的に相違さ
せて接着力と凝集力とを両立させた粘着部材に関する。Description: TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive member that has both adhesive strength and cohesive strength by partially differentiating the degree of crosslinking by ultraviolet curing.
従来の技術及び課題 感圧接着層にあっては、タック等の接着力と、保持性
に関係する凝集力とをバランスさせることが基本的重要
事項である。2. Description of the Related Art Conventional Problems and Problems In the pressure-sensitive adhesive layer, it is a fundamentally important matter to balance the adhesive force such as tack and the cohesive force related to the holding property.
従来、かかるバランスを調節する手段としては過酸化
物、金属系化合物、多官能性化合物の如き架橋剤を用い
たり、紫外線や電子線等の放射線を照射して、感圧接着
層の全体を均一に架橋処理する方式が知られていた。Conventionally, as a means for adjusting such a balance, a crosslinking agent such as a peroxide, a metal compound or a polyfunctional compound is used, or radiation such as an ultraviolet ray or an electron beam is irradiated to make the entire pressure sensitive adhesive layer uniform. A method of cross-linking was known.
しかしながら、得られる感圧接着層の接着力と凝集力
とを高度にバランスさせることが困難な問題点があっ
た。すなわち、タック等の接着力を低下させずに凝集力
を増大させることができず、架橋度の上昇による凝集力
の増大には、接着力の低下が不可避であった。また、架
橋度の上昇に伴い耐反発性が低下する問題もあった。従
って、従来の架橋方式では、いずれの場合も接着力と凝
集力を両立させることができなかった。However, there is a problem that it is difficult to highly balance the adhesive force and the cohesive force of the obtained pressure-sensitive adhesive layer. That is, the cohesive force cannot be increased without lowering the adhesive force such as tack, and in order to increase the cohesive force by increasing the degree of cross-linking, it is unavoidable that the adhesive force is decreased. Further, there is also a problem that the repulsion resistance decreases with an increase in the degree of crosslinking. Therefore, the conventional cross-linking method cannot achieve both the adhesive force and the cohesive force in any case.
一方、粘着部材の主要な用途に、金属板、樹脂板、塗
装板、化粧板等の表面に貼着して保存時、輸送時、加工
時等における保護を目的とした表面保護シートの如く、
貼着目的達成後に被着体より容易に剥離できるようにし
たものがある。かかる再剥離用途の粘着部材、特に表面
保護シートには、被着体への貼着が容易で切断やプレス
等の加工時に浮き等の剥がれを生じることがなく、しか
も目的達成後は簡単に剥離できること、という性能が要
求される。つまり経時上昇しにくい接着力と、糊残りを
生じにくい凝集力が要求される。On the other hand, the main use of the adhesive member is to attach it to the surface of a metal plate, a resin plate, a coating plate, a decorative plate, etc., and to protect it during storage, transportation, processing, etc.
There is one that can be peeled off easily from the adherend after the purpose of attachment is achieved. Such an adhesive member for re-peeling, particularly a surface protection sheet, can be easily attached to an adherend and does not peel off when processed such as cutting or pressing, and can be easily peeled off after achieving the purpose. The ability to do is required. That is, an adhesive force that is unlikely to rise with time and a cohesive force that is unlikely to cause adhesive residue are required.
従来、かかる要求性能に応える粘着部材としては、ガ
ラス転移点の高いホモポリマを形成する単量体を共重合
させた感圧接着性ポリマを用いたもの、乳化剤を添加し
たもの、上記した架橋方式を併用したものが提案されて
いるが、その調製に高度な技術を要する問題点のほか、
被着体や支持基材の種類によりその性能が大きく変化
し、要求性能をバランスよくマッチングさせることが困
難な問題点があった。Conventionally, as an adhesive member that responds to such required performance, one using a pressure-sensitive adhesive polymer obtained by copolymerizing a monomer forming a high glass transition homopolymer, one using an emulsifier, and the above-mentioned crosslinking method A combination of them has been proposed, but in addition to the problems that require advanced technology for their preparation,
The performance varies greatly depending on the type of adherend and the supporting base material, and there is a problem that it is difficult to match the required performance in a well-balanced manner.
課題を解決するための手段 本発明は、架橋度を部分的に相違させる方式により上
記の課題を克服したものである。Means for Solving the Problems The present invention overcomes the above problems by a method in which the degree of crosslinking is partially different.
すなわち、本発明は、支持基材に感圧接着層を設けて
なる粘着部材において、その感圧接着層を紫外線硬化型
感圧接着剤で形成し、かつ紫外線硬化により架橋度に部
分的な相違をもたせて接着力と凝集力とをバランスさせ
たことを特徴とする粘着部材を提供するものである。That is, the present invention relates to a pressure-sensitive adhesive member comprising a support substrate and a pressure-sensitive adhesive layer formed on the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer is formed of a UV-curable pressure-sensitive adhesive, and the degree of crosslinking is partially different by UV curing. The present invention provides a pressure-sensitive adhesive member characterized by balancing adhesive force and cohesive force.
作用 紫外線硬化型感圧接着剤を用いることにより、パター
ンマスク等を介して紫外線を照射するなどの簡単な処理
操作で、容易にかつ精度よく架橋度に部分的な相違をも
たせることができる。一方、架橋度に部分的な相違をも
たせることにより、高架橋域に基づく高凝集力と、低架
橋域ないし未架橋域に基づく高接着力を付与することが
できて、接着力を維持させたまま凝集力を高めることが
できる。その接着力と凝集力のバランスは、架橋度相違
領域の配置や占有面積割合、架橋度差等の制御で調節す
ることができる。その結果、被着体や支持基材の種類に
応じた性能バランスを容易に付与することができる。Action By using the UV-curable pressure-sensitive adhesive, it is possible to easily and accurately make a partial difference in the cross-linking degree by a simple processing operation such as irradiating UV rays through a pattern mask or the like. On the other hand, by giving a partial difference in the degree of cross-linking, it is possible to impart high cohesive force based on the high cross-linking region and high adhesive force based on the low cross-linking region or the non-cross-linking region, while maintaining the adhesive force. The cohesive force can be increased. The balance between the adhesive force and the cohesive force can be adjusted by controlling the arrangement of the cross-linking degree different regions, the occupied area ratio, the cross-linking degree difference, and the like. As a result, it is possible to easily give a performance balance according to the types of the adherend and the supporting base material.
発明の構成要素の例示 本発明においては紫外線硬化型感圧接着剤が用いられ
る。その種類につき特に限定はない。好ましく用いうる
ものは、ゴム系やアクリル系などの種々のポリマからな
るガラス転移点が250K以下の感圧接着性ポリマに、重合
性二重結合を２個以上有する架橋性単量体と、光開始剤
を配合したものである。就中、紫外線による硬化処理前
後における感圧接着性ポリマの溶剤不溶分の差が５重量
％以上となるよう調製したものが好ましい。特に、再剥
離用途の場合には、紫外線による硬化処理後における感
圧接着性ポリマの良溶媒に対する不溶分が60重量％以上
となるよう調製したものが好ましい。Exemplary Components of the Invention In the present invention, a UV-curable pressure-sensitive adhesive is used. There is no particular limitation on the type. Preferable ones are pressure-sensitive adhesive polymers having a glass transition point of 250 K or less made of various polymers such as rubber-based or acrylic-based, and a crosslinkable monomer having two or more polymerizable double bonds, It contains an initiator. In particular, it is preferable that the difference between the solvent-insoluble content of the pressure-sensitive adhesive polymer and the solvent-insoluble content before and after the curing treatment with ultraviolet rays is 5% by weight or more. In particular, in the case of re-peeling use, it is preferable that the content of the pressure-sensitive adhesive polymer after the curing treatment with ultraviolet rays is adjusted to 60% by weight or more in the good solvent.
なお、前記の感圧接着性ポリマとしては、ガラス転移
点の調節性、アクリル酸やアクリロニトリル等の共重合
による極性基の導入性、酢酸ビニルやスチレン等の共重
合による改質性などの点より、アクリル酸やメタクリル
酸のアルキルエステルを主成分とするアクリル系ポリマ
が適当である。As the pressure-sensitive adhesive polymer, from the viewpoint of controllability of glass transition point, introduction of polar group by copolymerization of acrylic acid, acrylonitrile, etc., modification property by copolymerization of vinyl acetate, styrene, etc. Acrylic polymers containing an acrylic acid or methacrylic acid alkyl ester as a main component are suitable.
また、架橋性単量体としては通例、エチレングリコー
ルジアクリレート、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、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、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、
ジビニルベンゼンなどが用いられる。架橋性単量体は、
感圧接着性ポリマが架橋性二重結合を有する場合には配
合されないときもあるなど、その配合量は他の併用成分
の種類や量、架橋性単量体そのものの種類などにより適
宜に決定される。架橋性単量体の配合量が過少では架橋
による凝集力の増大に乏しくて糊残りする場合があり、
過多では接着力の低下が大きい。一般には、感圧接着性
ポリマ100重量部あたり0.01〜20重量部の配合量とさ
れ、再剥離用途の場合には0.05〜10重量部の配合量とさ
れる。Further, as the crosslinkable monomer, usually ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate. , Dipentaerythritol hexamethacrylate,
Divinylbenzene or the like is used. The crosslinkable monomer is
When the pressure-sensitive adhesive polymer has a crosslinkable double bond, it may not be blended, and the blending amount is appropriately determined depending on the types and amounts of other concomitant components, the type of the crosslinkable monomer itself, and the like. It If the amount of the crosslinkable monomer is too small, the increase in cohesive force due to crosslinkage may be poor and adhesive residue may remain.
If the amount is too large, the adhesive strength will be greatly reduced. Generally, the amount is 0.01 to 20 parts by weight per 100 parts by weight of the pressure-sensitive adhesive polymer, and the amount is 0.05 to 10 parts by weight for re-peeling use.
用いる光開始剤の一般的なものとしては、ベンゾフェ
ノン、ベンゾイン、ベンゾインアルキルエーテル、ベン
ジルジメチルケタールの如き、光開裂型ないし水素引抜
き型のものなどがあげられる。光開始剤の配合量は、感
圧接着性ポリマ100重量部あたり0.01〜５重量部が適当
である。その配合量が過多であると、残存物が耐候性の
低下や黄変の原因となるので必要最少量の配合が望まし
い。Typical photoinitiators used include photocleavable or hydrogen-abstractable ones such as benzophenone, benzoin, benzoin alkyl ether, and benzyl dimethyl ketal. A suitable amount of the photoinitiator is 0.01 to 5 parts by weight per 100 parts by weight of the pressure-sensitive adhesive polymer. If the blending amount is too large, the residue may cause deterioration of weather resistance and yellowing, so that the minimum necessary blending amount is desirable.
なお、本発明において用いる紫外線硬化型感圧接着剤
は、溶液型、水分散型、バルク型等のいずれの形態に調
製されたものであってもよい。紫外線による硬化処理に
より５％以上、再剥離用途の場合には20％以上の架橋度
の差を形成できる範囲において、加熱型架橋剤など通例
の架橋剤を含有していてもよい。また、必要に応じ各種
の可塑剤や充填剤等の添加剤を含有していてもよい。通
例の架橋剤を含有する場合、その架橋剤はこれに基づき
予め全体を均一に架橋処理するなどして、感圧接着層の
ベースの形成などに利用される。The ultraviolet-curable pressure-sensitive adhesive used in the present invention may be prepared in any form such as a solution type, a water dispersion type and a bulk type. A usual crosslinking agent such as a heating type crosslinking agent may be contained in an amount capable of forming a difference in crosslinking degree of 5% or more by curing treatment with ultraviolet rays, and 20% or more in the case of re-peeling use. In addition, additives such as various plasticizers and fillers may be contained if necessary. When a usual crosslinking agent is contained, the crosslinking agent is preliminarily subjected to uniform crosslinking treatment based on this, and is used for forming the base of the pressure-sensitive adhesive layer.
本発明の粘着部材は、紫外線硬化型感圧接着剤を架橋
度が部分的に相違するよう紫外線硬化させてなる感圧接
着層を、支持基材に設けたものである。The pressure-sensitive adhesive member of the present invention comprises a support substrate provided with a pressure-sensitive adhesive layer obtained by ultraviolet-curing an ultraviolet-curable pressure-sensitive adhesive so that the degree of crosslinking partially differs.
その製造は例えば、紫外線硬化型感圧接着剤を支持基
材上に塗布乾燥後、パターンマスクを介するなどして紫
外線を照射し、架橋度が部分的に相違する感圧接着層が
形成されるよう硬化処理する方法などにより行うことが
できる。形成する高架橋域の割合は10〜80％が適当であ
る。特に、再剥離用途の場合には40〜70％が適当であ
る。凝集力は高架橋域を増すことにより高めることがで
き、接着力は低架橋域ないし未架橋域を増すことにより
大きくすることができる。接着力と凝集力のバランス
は、前記した架橋度相違領域の占有面積割合の調節のほ
か、その配置パターンや、架橋度差などを制御すること
によっても調節することができる。なお、高架橋域の割
合が前記範囲における下限未満では満足できる凝集力が
発現しにくく、上限を超えると満足できる接着力が発現
しにくい。In the production, for example, a UV-curable pressure-sensitive adhesive is applied on a supporting substrate and dried, and then ultraviolet rays are irradiated through a pattern mask or the like to form a pressure-sensitive adhesive layer having a partially different degree of crosslinking. It can be performed by a method of curing treatment. The proportion of the high cross-linking area to be formed is appropriately 10 to 80%. In particular, 40 to 70% is suitable for re-peeling use. The cohesive strength can be increased by increasing the high crosslinked area, and the adhesive strength can be increased by increasing the low crosslinked area or the uncrosslinked area. The balance between the adhesive force and the cohesive force can be adjusted not only by adjusting the occupied area ratio of the cross-linking degree different regions, but also by controlling the arrangement pattern, the cross-linking degree difference, and the like. If the proportion of the highly crosslinked region is less than the lower limit of the above range, a satisfactory cohesive force is unlikely to be exhibited, and if it exceeds the upper limit, a satisfactory adhesive force is unlikely to be exhibited.
感圧接着層にもたせる架橋度の相違パターンは適宜に
決定される。一般には、所定架橋度のベースに、その架
橋度とは相違する架橋度の部分が点在するか、モザイク
状に分布するパターンなどとされる。好ましいパターン
は、低架橋ないし未架橋のベースに、高架橋域を点在さ
せるか、モザイク状に分布させたものである。なお、再
剥離用途にあっては、ベースの架橋度が比較的高めに設
定され、良溶媒に対する不溶分が60重量％以上、就中70
重量％以上の高架橋域と、40重量％以下の低架橋域の組
合せとなるよう調節することが好ましい。The pattern of difference in the degree of crosslinking given to the pressure-sensitive adhesive layer is appropriately determined. Generally, a base having a predetermined degree of crosslinking is dotted with portions having a degree of crosslinking different from the degree of crosslinking, or has a mosaic pattern. A preferred pattern is a low-crosslinked or uncrosslinked base with scattered high-crosslinked regions or a mosaic distribution. For re-peel applications, the degree of crosslinking of the base is set to be relatively high, and the content of insolubles in good solvents is 60% by weight or more, especially 70%.
It is preferable to adjust so as to be a combination of a high cross-linking area of not less than wt% and a low cross-linking area of not more than 40 wt%.
支持基材としては、紙、布、プラスチックフィルム、
発泡体、金属箔などの公知物のいずれも用いることがで
きる。また、剥離剤で表面処理したものなどからなるセ
パレータなどを用いて、両面粘着テープの如き粘着部材
とすることもできる。その場合、感圧接着層を紙や不織
布等の繊維で補強してもよい。再剥離用途の粘着部材の
形成には作業性や加工性等の点より、厚さが20〜150μ
ｍ、伸び60〜700％の可とう性フィルムからなる支持基
材が好ましく用いられる。可とう性フィルムの材質とし
てはポリエチレン、エチレン・酢酸ビニル共重合体、軟
質塩化ビニルなどが一般であるが、特に限定はない。As the supporting substrate, paper, cloth, plastic film,
Any known material such as foam and metal foil can be used. Further, a pressure sensitive adhesive member such as a double-sided pressure sensitive adhesive tape can be prepared by using a separator or the like which is surface-treated with a release agent. In that case, the pressure-sensitive adhesive layer may be reinforced with fibers such as paper and nonwoven fabric. In terms of workability and workability, the thickness of the adhesive material for re-peeling is 20-150μ.
A supporting base material made of a flexible film having m and an elongation of 60 to 700% is preferably used. The material of the flexible film is generally polyethylene, ethylene-vinyl acetate copolymer, soft vinyl chloride, etc., but is not particularly limited.
なお、紫外線の照射による硬化処理は、高圧水銀灯、
メタルハライドランプ、カーボンカーク灯、キセノン灯
などの適宜な紫外線照射装置を用いて行ってよい。照射
光量は感圧接着剤の紫外線硬化特性に応じ決定される。
例示した装置を光源に用いた場合、通例0.3秒以上、就
中３秒以上の照射処理が施される。Incidentally, the curing treatment by irradiation of ultraviolet rays is performed by a high pressure mercury lamp,
It may be carried out using an appropriate ultraviolet irradiation device such as a metal halide lamp, a carbon Kirk lamp, a xenon lamp. The irradiation light amount is determined according to the ultraviolet curing characteristics of the pressure sensitive adhesive.
When the exemplified device is used as a light source, the irradiation treatment is usually performed for 0.3 seconds or longer, and especially for 3 seconds or longer.
発明の効果 本発明によれば、感圧接着層を紫外線硬化型感圧接着
剤で形成し、これを架橋度が部分的に相違するよう架橋
処理したので、タック等の接着力を良好に維持させたま
ま凝集力を向上させることができ、接着力と凝集力が良
好にバランスした感圧接着層を有する粘着部材を得るこ
とができる。EFFECTS OF THE INVENTION According to the present invention, the pressure-sensitive adhesive layer is formed of an ultraviolet-curable pressure-sensitive adhesive and subjected to a crosslinking treatment so that the degree of crosslinking is partially different. It is possible to improve the cohesive force while keeping it, and it is possible to obtain an adhesive member having a pressure-sensitive adhesive layer in which the adhesive force and the cohesive force are well balanced.
また、接着力と凝集力のバランスを、架橋度の部分的
な相違のパターンや割合等を変えることにより制御する
ことができ、その制御をマスクパターンの変更など紫外
線照射条件の変更で容易に行うことができる。従って、
使用目的に応じた接着力と凝集力のバランスを有する幅
広い粘着部材を容易に形成できる利点を有している。そ
の場合、接着力が経時上昇しにくい特性も容易に付与で
きる。その結果、表面保護シートの如き再剥離用途に好
適な粘着部材も容易に得ることができる。Further, the balance between the adhesive force and the cohesive force can be controlled by changing the pattern or the ratio of the partial difference in the crosslinking degree, and the control can be easily performed by changing the ultraviolet irradiation conditions such as changing the mask pattern. be able to. Therefore,
It has an advantage that a wide range of pressure-sensitive adhesive members having a balance of adhesive force and cohesive force according to the purpose of use can be easily formed. In that case, it is possible to easily provide the property that the adhesive force is unlikely to increase with time. As a result, it is possible to easily obtain an adhesive member suitable for re-peel use such as a surface protection sheet.
特に再剥離用途の粘着部材の場合、剥離に際して紫外
線を再照射することにより被着体に対する接着力を低下
させることができ、剥離がより容易になる利点なども有
している。In particular, in the case of an adhesive member for re-peeling use, it is possible to reduce the adhesive force to an adherend by re-irradiating with ultraviolet rays at the time of peeling, and there is an advantage that peeling becomes easier.
実施例 実施例１ アクリル酸ｎ−ブチル95重量％とアクリル酸５重量％
からなるガラス転移点が224kの感圧接着性ポリマ100部
（重量部、以下同じ）、テトラエチレングリコールジメ
タクリレート５部、ベンゾフェノン１部をトルエン200
部に溶解させてなる紫外線硬化型感圧接着剤を、厚さ25
μｍのポリエステルフィルムに乾燥後の厚さが50μｍと
なるよう塗布し、乾燥させた。Examples Example 1 95% by weight of n-butyl acrylate and 5% by weight of acrylic acid
Consisting of 100 parts of a pressure-sensitive adhesive polymer having a glass transition point of 224 k (parts by weight, the same applies hereinafter), 5 parts of tetraethylene glycol dimethacrylate, 1 part of benzophenone and 200 parts of toluene.
UV curable pressure-sensitive adhesive dissolved in
It was applied to a polyester film of μm so that the thickness after drying would be 50 μm, and dried.
次に、形成された感圧接着層を、直径1mmの孔を多数
有する全孔面積の占有割合が55％のマスクを介し、高圧
水銀灯にて1500mj/cm2の紫外線を照射し、架橋度が部分
的に相違する感圧接着層を有する粘着シートを得た。そ
の感圧接着層の溶剤不溶分は15.5重量％であった。Next, the pressure-sensitive adhesive layer formed, through a mask having a total hole area of 55% having a large number of holes with a diameter of 1 mm 55%, is irradiated with ultraviolet rays of 1500 mj / cm 2 with a high pressure mercury lamp, and the degree of crosslinking is A pressure-sensitive adhesive sheet having partially different pressure-sensitive adhesive layers was obtained. The solvent-insoluble content of the pressure-sensitive adhesive layer was 15.5% by weight.
実施例２ アクリル酸２−エチルヘキシル92重量％と酢酸ビニル
６重量％とアクリル酸２重量％からなるガラス転移点が
210kの感圧接着性ポリマ100部、トリメチロールプロパ
ントリアクリレート３部、ジフェニルメタン4,4′−ジ
イソシアネート２部、ベンジルジメチルケタール0.5部
をトルエン200部に溶解させてなる紫外線硬化型感圧接
着剤を、厚さ25μｍのポリエステルフィルムに乾燥後の
厚さが50μｍとなるよう塗布し、100℃で３分間乾燥硬
化処理した。Example 2 A glass transition point composed of 92% by weight of 2-ethylhexyl acrylate, 6% by weight of vinyl acetate and 2% by weight of acrylic acid was obtained.
A UV-curable pressure-sensitive adhesive prepared by dissolving 100 parts of 210 k pressure-sensitive adhesive polymer, 3 parts of trimethylolpropane triacrylate, 2 parts of diphenylmethane 4,4'-diisocyanate and 0.5 part of benzyldimethylketal in 200 parts of toluene. It was applied to a polyester film having a thickness of 25 μm so that the thickness after drying would be 50 μm, and dried and cured at 100 ° C. for 3 minutes.
次に、形成された感圧接着層を、1mm角の孔のモザイ
クパターンを有する全孔面積の占有割合が50％のマスク
を介し、メタルハライドランプにて1200mj/cm2の紫外線
を照射し、架橋度が部分的に相違する感圧接着層を有す
る粘着シートを得た。その感圧接着層の溶剤不溶分は3
1.7重量％であった。Next, the pressure-sensitive adhesive layer formed is irradiated with 1200 mj / cm 2 of ultraviolet light by a metal halide lamp through a mask having a 50% occupancy rate of the total hole area having a mosaic pattern of 1 mm square holes, and crosslinking. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a partially different degree was obtained. Solvent insoluble content of the pressure sensitive adhesive layer is 3
It was 1.7% by weight.
実施例３ アクリル酸ｎ−ブチル66.6重量％とアクリロニトリル
31重量％とアクリル酸2.4重量％からなるガラス転移点
が235kの感圧接着性ポリマ100部、トリメチロールプロ
パントリアクリレート５部、ベンジルジメチルケタール
0.3部をトルエンに溶解させてなる10重量％の濃度の紫
外線硬化型感圧接着剤を、厚さ60μｍのポリエチレンフ
ィルムに乾燥後の厚さが10μｍとなるよう塗布し、乾燥
させた。Example 3 66.6% by weight of n-butyl acrylate and acrylonitrile
100 parts of a pressure-sensitive adhesive polymer composed of 31% by weight and 2.4% by weight of acrylic acid and having a glass transition point of 235 k, 5 parts of trimethylolpropane triacrylate, benzyl dimethyl ketal
An ultraviolet-curable pressure-sensitive adhesive having a concentration of 10% by weight dissolved in 0.3 part of toluene was applied to a polyethylene film having a thickness of 60 μm so that the thickness after drying was 10 μm, and dried.
次に、形成された感圧接着層を、1mm角の孔のモザイ
クパターンを有する全孔面積の占有割合が50％のマスク
を介し、高圧水銀灯にて1500mj/cm2の紫外線を照射し、
架橋度が部分的に相違する感圧接着層を有する表面保護
シートを得た。その感圧接着層の溶剤不溶分は75重量％
であった。Next, the formed pressure-sensitive adhesive layer, through a mask having an occupancy rate of 50% of the total hole area having a mosaic pattern of 1 mm square holes, irradiating 1500 mj / cm 2 ultraviolet rays with a high-pressure mercury lamp,
A surface protective sheet having a pressure-sensitive adhesive layer having partially different degrees of crosslinking was obtained. Solvent insoluble content of the pressure sensitive adhesive layer is 75% by weight
Met.
実施例４ アクリル酸ｎ−ブチル66.6重量％とアクリロニトリル
31重量％とアクリル酸2.4重量％からなるガラス転移点
が235kの感圧接着性ポリマ100部、ジペンタエリスリト
ールヘキサメタクリレート２部、ベンゾフェノン２部、
ジフェニルメタン4,4′−ジイソシアネート0.5部をトル
エンに溶解させてなる10重量％濃度の紫外線硬化型感圧
接着剤を、厚さ60μｍのポリエチレンフィルムに乾燥後
の厚さが10μｍとなるよう塗布し、100℃で５分間乾燥
硬化処理した。Example 4 66.6% by weight of n-butyl acrylate and acrylonitrile
100 parts of pressure-sensitive adhesive polymer consisting of 31% by weight and 2.4% by weight of acrylic acid and having a glass transition point of 235 k, 2 parts of dipentaerythritol hexamethacrylate, 2 parts of benzophenone,
A 10% by weight concentration UV-curable pressure-sensitive adhesive prepared by dissolving 0.5 parts of diphenylmethane 4,4′-diisocyanate in toluene was applied to a polyethylene film having a thickness of 60 μm so that the thickness after drying would be 10 μm. It was dried and cured at 100 ° C. for 5 minutes.
次に、形成された感圧接着層を、直径1mmの孔を有す
る全孔面積の占有割合が55％のマスクを介し、高圧水銀
灯にて1500mj/cm2の紫外線を照射し、架橋度が部分的に
相違する感圧接着層を有する表面保護シートを得た。そ
の感圧接着層における高架橋域の溶剤不溶分は89重量％
であり、低架橋域のそれは25重量％であった。Next, the formed pressure-sensitive adhesive layer is irradiated with ultraviolet rays of 1500 mj / cm 2 with a high-pressure mercury lamp through a mask having a hole area of 1 mm and occupying the entire hole area of 55%. A surface protective sheet having different pressure sensitive adhesive layers was obtained. The solvent-insoluble content in the highly crosslinked area of the pressure-sensitive adhesive layer is 89% by weight.
And that in the low cross-linking area was 25% by weight.
比較例１ 実施例１における紫外線硬化処理前の粘着シートをそ
のまま用いた。その感圧接着層の溶剤不溶分は０重量％
であった。Comparative Example 1 The pressure-sensitive adhesive sheet before the ultraviolet curing treatment in Example 1 was used as it was. Solvent insoluble content of the pressure sensitive adhesive layer is 0% by weight
Met.
比較例２ マスクを用いずに紫外線を全面照射して硬化処理した
以外は実施例１に準じて粘着シートを得た。その感圧接
着層の溶剤不溶分は35.2重量％であった。Comparative Example 2 An adhesive sheet was obtained in the same manner as in Example 1 except that the entire surface was irradiated with ultraviolet rays without using a mask for curing treatment. The solvent-insoluble content of the pressure-sensitive adhesive layer was 35.2% by weight.
比較例３ 実施例２における紫外線硬化処理前の粘着シートをそ
のまま用いた。その感圧接着層の溶剤不溶分は22.5重量
％であった。Comparative Example 3 The pressure-sensitive adhesive sheet before the ultraviolet curing treatment in Example 2 was used as it was. The solvent-insoluble content of the pressure-sensitive adhesive layer was 22.5% by weight.
比較例４ マスクを用いずに紫外線を全面照射して硬化処理した
以外は実施例２に準じて粘着シートを得た。その感圧接
着層の溶剤不溶分は53.1重量％であった。Comparative Example 4 An adhesive sheet was obtained in the same manner as in Example 2 except that the whole surface was irradiated with ultraviolet rays without using a mask to carry out curing treatment. The solvent-insoluble content of the pressure-sensitive adhesive layer was 53.1% by weight.
評価試験 実施例1,2及び比較例１〜４で得た粘着シートにつき
下記の試験を行った。Evaluation Test The following tests were conducted on the pressure-sensitive adhesive sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 4.
［接着力］ JIS Z 1528に準じてステンレス板に対する接着力（18
0度ピール）を測定した。[Adhesive strength] Adhesive strength (18
0 degree peel) was measured.
［タック］ 20℃、65％R.H.下、傾斜角30度の斜面で粘着シートの
粘着面上に直径の異なるステンレスボールを助走距離10
cmでころがし、粘着面の10cmのところで停止する直径が
最大のボールを調べた。なお表にはボールNo.で示した
が、その直径は次式で算出される。[Tack] At 20 ℃, 65% RH, stainless steel balls with different diameters are run on the adhesive surface of the adhesive sheet with a slope angle of 30 degrees.
We examined the ball with the largest diameter that rolled at 10 cm and stopped at 10 cm on the adhesive surface. Although the ball number is shown in the table, its diameter is calculated by the following formula.
直径（インチ）＝ボールNo./36 ［保持力］ 粘着シートの試験片を10mm幅×20mm長の接着面積でベ
ークライト板に貼着し、その試験片の自由端に500gの荷
重を吊り下げ、40℃又は80℃の恒温機中で試験片が凝集
破壊により落下するまでの時間を測定した。Diameter (inch) = Ball No./36 [Holding power] Adhesive sheet test pieces were attached to a bakelite plate with an adhesive area of 10 mm width x 20 mm length, and a 500 g load was hung on the free end of the test pieces. The time until the test piece dropped due to cohesive failure was measured in a thermostat of 40 ° C or 80 ° C.
上記の結果を第１表に示した。 The above results are shown in Table 1.
第１表より、実施例の粘着シートにあっては、接着
力、タックを損なうことなく、凝集力が大幅に向上し
て、接着力と凝集力が良好なバランスで両立しているこ
とがわかる。 From Table 1, it can be seen that in the pressure-sensitive adhesive sheets of Examples, the cohesive force is significantly improved without impairing the adhesive force and the tack, and the adhesive force and the cohesive force are well balanced. .
［経時接着力］ 実施例3,4で得た表面保護シートを厚さ0.6mmのステン
レス板に常温で貼着し、30分経過後及び１ヶ月経過後の
接着力（180度ピール、剥離速度300mm/分）を調べた。
また、剥離後のステンレス板における糊残りの有無を調
べた。[Adhesive strength with time] The surface protective sheets obtained in Examples 3 and 4 were adhered to a stainless steel plate having a thickness of 0.6 mm at room temperature, and the adhesive strength (180 degree peeling, peeling speed after 30 minutes and 1 month) was passed. 300 mm / min).
Moreover, the presence or absence of adhesive residue on the stainless steel plate after peeling was examined.
［加工性］ 実施例3,4で得た表面保護シートを厚さ0.5mmのステン
レス板に常温で貼着し、深さ5mmのエリクセン絞り加工
を施し、表面保護シートの浮きの有無調べた。また、剥
離後のステンレス板における糊残りの有無を調べた。[Workability] The surface protection sheets obtained in Examples 3 and 4 were attached to a stainless steel plate having a thickness of 0.5 mm at room temperature, subjected to Erichsen drawing processing with a depth of 5 mm, and the presence or absence of floating of the surface protection sheet was examined. Moreover, the presence or absence of adhesive residue on the stainless steel plate after peeling was examined.
上記の結果を第２表に示した。 The above results are shown in Table 2.
第２表より、実施例の表面保護シートは、加工時に浮
き等の剥がれを生じない接着力を示し、接着力の経時上
昇が小さくて被着体よりの剥離が容易であることがわか
る。また、経時や加工によっても糊残りを生じず、充分
な凝集力も有していることがわかる。 From Table 2, it can be seen that the surface protective sheets of the examples show an adhesive force that does not cause peeling such as floating during processing, and the adhesive force does not increase with time so that it can be easily peeled from the adherend. Further, it can be seen that the adhesive residue is not generated even with the passage of time and processing, and that it has a sufficient cohesive force.
なお、実施例４の表面保護シートを１ヶ月放置後、再
度紫外線で照射処理するとそのステンレス板に対する接
着力は50g/20mmとなった。When the surface protective sheet of Example 4 was left for one month and then irradiated again with ultraviolet rays, the adhesive strength to the stainless steel plate was 50 g / 20 mm.
Claims (2)
材において、その感圧接着層を紫外線硬化型感圧接着剤
で形成し、かつ紫外線硬化により架橋度に部分的な相違
をもたせて接着力と凝集力とをバランスさせたことを特
徴とする粘着部材。1. A pressure-sensitive adhesive member comprising a support substrate and a pressure-sensitive adhesive layer formed on the support substrate, wherein the pressure-sensitive adhesive layer is formed of a UV-curable pressure-sensitive adhesive, and a partial difference in crosslinking degree is caused by UV-curing. An adhesive member characterized in that it has a balance between adhesive force and cohesive force.
離を容易とした請求項１に記載の粘着部材。2. The pressure-sensitive adhesive member according to claim 1, wherein a flexible film is used as the supporting substrate to facilitate re-peeling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63227954A JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63227954A JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0275679A JPH0275679A (en) | 1990-03-15 |
| JP2548970B2 true JP2548970B2 (en) | 1996-10-30 |
Family
ID=16868867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63227954A Expired - Fee Related JP2548970B2 (en) | 1988-09-12 | 1988-09-12 | Adhesive member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2548970B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010021505A3 (en) * | 2008-08-20 | 2010-06-17 | (주)Lg화학 | Adhesive agent having hard and |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19743014A1 (en) * | 1997-09-29 | 1999-04-01 | Basf Ag | Process for crosslinking radiation-crosslinkable pressure-sensitive adhesive layers |
| US6338901B1 (en) * | 1999-05-03 | 2002-01-15 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
| US6524675B1 (en) | 1999-05-13 | 2003-02-25 | 3M Innovative Properties Company | Adhesive-back articles |
| JP5596262B2 (en) * | 2007-08-22 | 2014-09-24 | 三菱樹脂株式会社 | Adhesive sheet |
| JP5405758B2 (en) * | 2008-03-25 | 2014-02-05 | 三菱樹脂株式会社 | Adhesive sheet |
| JP2009292893A (en) * | 2008-06-03 | 2009-12-17 | Seiko Epson Corp | Joining method and joined body |
-
1988
- 1988-09-12 JP JP63227954A patent/JP2548970B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010021505A3 (en) * | 2008-08-20 | 2010-06-17 | (주)Lg화학 | Adhesive agent having hard and |
| KR101114361B1 (en) * | 2008-08-20 | 2012-03-13 | 주식회사 엘지화학 | Pressure-sensitive adhesive |
| CN102131881B (en) * | 2008-08-20 | 2016-01-20 | Lg化学株式会社 | Tackiness agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0275679A (en) | 1990-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3281490B2 (en) | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet or sheet using the composition | |
| JPH04114075A (en) | Hot melt pressure-sensitive adhesive based on acrylate | |
| JPH06218879A (en) | Self-adhesive capable of partial reduction of adhesion by radioactive ray | |
| JP2018109102A (en) | Adhesive composition, adhesive, adhesive sheet, method for producing laminate with adhesive layer, image display device, and touch panel | |
| JPS5846235B2 (en) | Method for producing a pressure-sensitive heat-melt adhesive that can be cured by exposure to electron beam irradiation | |
| JPH11199832A (en) | Pressure-sensitive adhesive sheets and their production | |
| JPH0753849B2 (en) | Acrylic adhesive tape or sheet manufacturing method | |
| WO1996033247A1 (en) | Radiation-cured adhesive film having differential surface adhesion | |
| JPH02187478A (en) | Releasable tacky adhesive | |
| JP2548970B2 (en) | Adhesive member | |
| JPH02248482A (en) | Photocurable pressure-sensitive adhesive composition | |
| JP4936908B2 (en) | Active energy ray polymerizable composition, pressure-sensitive adhesive, and pressure-sensitive adhesive tape | |
| JPH0431480A (en) | Acrylic pressure-sensitive adhesive composition | |
| JP3078362B2 (en) | Radiation-curable adhesive and its adhesive tape | |
| JP3014203B2 (en) | Active energy ray-curable pressure-sensitive adhesive composition | |
| JPS63268784A (en) | Substrate-less double-sided tacky tape | |
| JP2003253224A (en) | Double-sided adhesive tape | |
| JP2686303B2 (en) | Radiation-curable pressure-sensitive adhesive composition | |
| JPH0848944A (en) | Radiation-curable self-adhesive composition and self-adhesive tape or sheet produced therefrom | |
| JP2789236B2 (en) | Active energy ray-curable pressure-sensitive adhesive for hot melt | |
| JPH05311130A (en) | Tape for setting electronic components side by side | |
| JP3444423B2 (en) | UV curable acrylic pressure-sensitive adhesive compositions containing carbamate-functional monomers and adhesives prepared therefrom | |
| JP3191176B2 (en) | Adhesive composition | |
| JPH06152099A (en) | Method for eliminating resist film image in image forming process of printed wiring board and adhesive or adhesion sheet used for it | |
| JPH05247410A (en) | Radiation-curable hot pressure-sensitive adhesive and adhesive tape made therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |