JP2582875B2 - Removable adhesive - Google Patents
Removable adhesiveInfo
- Publication number
- JP2582875B2 JP2582875B2 JP63276892A JP27689288A JP2582875B2 JP 2582875 B2 JP2582875 B2 JP 2582875B2 JP 63276892 A JP63276892 A JP 63276892A JP 27689288 A JP27689288 A JP 27689288A JP 2582875 B2 JP2582875 B2 JP 2582875B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- silicone
- graft copolymer
- 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.)
- Expired - Lifetime
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は表面保護材などに好適な非シリコーン系の
再剥離型粘着剤に関する。Description: TECHNICAL FIELD The present invention relates to a non-silicone removable pressure-sensitive adhesive suitable for a surface protective material and the like.
従来、表面保護材などの粘着剤として、粘着剤中にリ
ン酸エステル系やアミン系の界面活性剤を配合して被着
体に対する接着力の経日上昇を抑制し、これにより被着
体よりの再剥離を容易としたものが知られている。Conventionally, as a pressure-sensitive adhesive such as a surface protective material, a phosphate ester-based or amine-based surfactant is blended into the pressure-sensitive adhesive to suppress the aging of the adhesive force with respect to the adherend. Is known which facilitates the re-peeling of the film.
また、上記の界面活性剤を粘着剤中に配合する方式で
はその剥離特性がバラツキやすいことなどから、界面活
性剤が粘着剤層の表面を占めることとなるように、支持
基材の背面側に界面活性剤層を設けるようにしたものも
知られている。In addition, in the method in which the above surfactant is incorporated into the pressure-sensitive adhesive, since the peeling characteristics are likely to vary, the surfactant occupies the surface of the pressure-sensitive adhesive layer. There is also known one provided with a surfactant layer.
〔発明が解決しようとする課題〕 しかるに、上記従来の方式では、再剥離性に好結果が
得られても、界面活性剤により被着体が汚染されるとい
う問題点があつた。[Problems to be Solved by the Invention] However, in the above-mentioned conventional method, there is a problem that the adherend is contaminated by the surfactant even if a good result is obtained in the removability.
そこで、この発明は、再剥離性と非汚染性とに共にす
ぐれた界面保護材などとして好適な粘着剤を提供するこ
とを目的としている。Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive which is suitable as an interface protective material having excellent removability and non-staining properties.
この発明者らは、上記の目的を達成するために鋭意研
究を重ねた結果、粘着剤中に架橋性を有する特定のシリ
コーン系グラフト共重合体を含有させることにより、再
剥離性と非汚染性とに共にすぐれた再剥離型粘着剤が得
られることを見い出し、この発明をなすに至つた。The present inventors have conducted intensive studies to achieve the above object, and as a result, by including a specific silicone-based graft copolymer having crosslinkability in the adhesive, removability and non-staining property The present inventors have found that an excellent re-peelable pressure-sensitive adhesive can be obtained at the same time, and have accomplished the present invention.
すなわち、この発明は、非シリコーン系粘着剤に、こ
の粘着剤のベースポリマーと架橋反応しうる官能基を持
つた架橋性モノマーおよびシリコーンマクロモノマーを
必須成分としたシリコーン系グラフト共重合体を含有さ
せたことを特徴とする再剥離型粘着剤に係るものであ
る。That is, the present invention provides a non-silicone-based pressure-sensitive adhesive containing a cross-linkable monomer having a functional group capable of cross-linking with the base polymer of the pressure-sensitive adhesive and a silicone-based graft copolymer containing a silicone macromonomer as essential components. The present invention relates to a removable pressure-sensitive adhesive.
このように、この発明においては、上記の如き特定の
シリコーン系グラフト共重合体を用いたことにより、再
剥離性と非汚染性とを共に改善しえたものであるが、こ
れはこの共重合体が接着力の上昇に対する抑制効果にす
ぐれる一方、粘着剤から分離しにくいためである、つま
りこの共重合体が非シリコーン系の粘着剤より疎外され
やすいために粘着剤層の表面に位置しやすく、一方この
共重合体に含まれる架橋性の官能基が粘着剤を構成する
ベースポリマーの官能基との間で架橋反応を起こし、粘
着剤との分離が起こらないためである、と考えられる。As described above, in the present invention, both the removability and the non-staining property can be improved by using the specific silicone-based graft copolymer as described above. Is excellent in the effect of suppressing the increase in adhesive strength, but is difficult to separate from the adhesive, that is, the copolymer is more likely to be alienated than the non-silicone adhesive, so it is easily located on the surface of the adhesive layer. On the other hand, it is considered that the cross-linkable functional group contained in the copolymer causes a cross-linking reaction with the functional group of the base polymer constituting the pressure-sensitive adhesive, thereby preventing separation from the pressure-sensitive adhesive.
この発明において用いられる非シリコーン系粘着剤と
は、ベースポリマーとして非シリコーン系のポリマーを
用いた粘着剤を意味し、これにはアクリル系粘着剤やゴ
ム系粘着剤などで代表されるようなシリコーン系粘着剤
以外の粘着剤が広く包含されるものである。The non-silicone-based pressure-sensitive adhesive used in the present invention means a pressure-sensitive adhesive using a non-silicone-based polymer as a base polymer, such as a silicone represented by an acrylic-based pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive. Adhesives other than the system-based adhesive are widely included.
このような粘着剤の中でも、耐候性などの点より、ア
クリル酸またはメタクリル酸のアルキルエステルを主モ
ノマーとした、つまり通常50重量％以上使用したアクリ
ル系ポリマーをベースポリマーとして含むアクリル系粘
着剤が、特に好適なものとして挙げられる。Among such pressure-sensitive adhesives, acrylic pressure-sensitive adhesives containing, as a main polymer, an alkyl ester of acrylic acid or methacrylic acid as a main monomer, that is, an acrylic polymer usually used in an amount of 50% by weight or more, from the viewpoint of weather resistance, etc. Are particularly preferred.
この発明において用いられるシリコーン系グラフト共
重合体は、シリコーンマクロモノマーと架橋性モノマー
とを必須成分として含む単量体混合物を共重合させるこ
とにより得られる、重量平均分子量が通常20,000〜500,
000程度の共重合体である。The silicone-based graft copolymer used in the present invention is obtained by copolymerizing a monomer mixture containing a silicone macromonomer and a crosslinkable monomer as essential components, and has a weight average molecular weight of usually 20,000 to 500,
About 000 copolymer.
シリコーンマクロモノマーとしては、分子鎖中にシロ
キサン結合を有するとともに、その分子鎖末端に重合性
不飽和結合を有する、通常1,000〜20,000程度の重量平
均分子量を有するものが好ましく用いられる。その代表
例としては、下記の一般式で表されるものが挙げられ
る。As the silicone macromonomer, those having a siloxane bond in the molecular chain and a polymerizable unsaturated bond at the terminal of the molecular chain and generally having a weight average molecular weight of about 1,000 to 20,000 are preferably used. Typical examples include those represented by the following general formula.
CH2＝CR−COO−C3H6−Si(OX)3 なお、上記の各式中のＲは水素またはメチル基であ
り、Ｘはつぎの式； で表される基である。また、上記の各式中、Si原子に結
合するメチル基は、エチル基やフエニル基などであつて
もよいし、またメトキシ基やエトキシ基などであつても
よく、上記のものに特に限定されない。 CH 2 = CR—COO—C 3 H 6 —Si (OX) 3 In the above formulas, R is hydrogen or a methyl group, and X is the following formula: Is a group represented by In each of the above formulas, the methyl group bonded to the Si atom may be an ethyl group, a phenyl group, or the like, or may be a methoxy group, an ethoxy group, or the like, and is not particularly limited to the above. .
一方、架橋性モノマーとしては、粘着剤のベースポリ
マーに含まれる官能基と反応しうる官能基として、たと
えばエポキシ基、イソシアナート基、カルボキシル基、
水酸基、アミド基などを有するモノマーが用いられる。
その代表例としては、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−イソシアナートエチ
ル、メタクリル酸２−イソシアナートエチル、アクリル
酸、メタクリル酸、イタコン酸、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、アクリルアミド、メタクリルアミドな
どが挙げられる。On the other hand, as the crosslinkable monomer, as a functional group capable of reacting with a functional group contained in the base polymer of the pressure-sensitive adhesive, for example, an epoxy group, an isocyanate group, a carboxyl group,
A monomer having a hydroxyl group, an amide group, or the like is used.
Representative examples thereof include glycidyl acrylate, glycidyl methacrylate, 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate. Examples include hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide and the like.
この発明においては、これらのシリコーンマクロモノ
マーおよび架橋性モノマーのほかに、これらのモノマー
と共重合可能でかつ架橋反応を阻害しないモノマーを任
意成分として用いることもできる。その具体例として
は、アクリル酸やメタクリル酸のアルキルエステル、ス
チレンまたはその誘導体、酢酸ビニル、アクリロニトリ
ル、メタクリロニトリルなどが挙げられる。In the present invention, in addition to the silicone macromonomer and the crosslinkable monomer, a monomer that can be copolymerized with these monomers and does not inhibit the crosslinking reaction can be used as an optional component. Specific examples thereof include alkyl esters of acrylic acid and methacrylic acid, styrene or derivatives thereof, vinyl acetate, acrylonitrile, methacrylonitrile, and the like.
これらの単量体混合物における各モノマーの割合とし
ては、全モノマー中、シリコーンマクロモノマーが通常
１〜50重量％、好適には５〜30重量％、架橋性モノマー
が通常0.5〜50重量％、好適には２〜20重量％、任意成
分としての前記共重合可能なモノマーが通常０〜90重量
％、好適には30〜80重量％となるようにするのがよい。As the ratio of each monomer in these monomer mixtures, the silicone macromonomer is usually 1 to 50% by weight, preferably 5 to 30% by weight, and the crosslinkable monomer is usually 0.5 to 50% by weight, preferably The amount of the copolymerizable monomer as an optional component is usually 0 to 90% by weight, preferably 30 to 80% by weight.
このような単量体混合物を用いた共重合は、たとえば
公知の溶液重合方式、エマルジヨン重合方式、懸濁重合
方式、バルク重合方式などにより行うことができる。こ
れらの中でも、溶液重合方式が簡便性の点より特に好ま
しい。Copolymerization using such a monomer mixture can be performed by, for example, a known solution polymerization system, emulsion polymerization system, suspension polymerization system, bulk polymerization system, or the like. Among these, the solution polymerization method is particularly preferred from the viewpoint of simplicity.
この発明においては、このようにして得られるシリコ
ーン系グラフト共重合体を前記した非シリコーン系粘着
剤に含有させることにより、再剥離性および非汚染性に
すぐれる再剥離型粘着剤を調製する。ここで、シリコー
ン系グラフト共重合体の含有量は、粘着剤（の固形分）
中のシリコーンマクロモノマー単位が0.05〜20重量％と
なるような割合が適当であり、特に0.1〜10重量％とな
るような割合が好ましい。この含有量が過少では満足で
きる再剥離性が得られず、過多となると支持基材などに
対する密着性に乏しくなり、また被着体に対する汚染が
起こりやすくなる。In the present invention, a re-peelable pressure-sensitive adhesive having excellent re-peelability and non-staining properties is prepared by incorporating the silicone-based graft copolymer thus obtained into the above-mentioned non-silicone-based pressure-sensitive adhesive. Here, the content of the silicone-based graft copolymer is determined by (solid content of the pressure-sensitive adhesive).
An appropriate ratio is such that the silicone macromonomer unit therein is 0.05 to 20% by weight, and particularly preferably a ratio such that it is 0.1 to 10% by weight. If the content is too low, satisfactory removability cannot be obtained. If the content is too high, adhesion to a supporting substrate or the like becomes poor, and contamination of an adherend is likely to occur.
この発明の再剥離型粘着剤は、加工中や運搬中などで
の傷付防止を目的とする表面保護材やマスキング材など
のように、被着体に一旦貼着したのち再剥離する必要の
ある用途に好ましく使用されるが、その際、紙糸、布
糸、プラスチツク糸、金属箔糸などの適宜の支持基材に
付設した状態で用いるのが一般的である。The removable pressure-sensitive adhesive of the present invention needs to be once adhered to an adherend and then removed again, such as a surface protective material or a masking material for the purpose of preventing damage during processing or transportation. Although it is preferably used for a certain application, it is generally used in such a state that it is attached to an appropriate supporting base material such as paper thread, cloth thread, plastic thread, metal foil thread and the like.
貼着の対象である被着体としては、金属板、プラスチ
ツク板、ガラス板、シリコン板、半導体ウエハなどが挙
げられる。また、被着体への粘着剤の貼着は、ロール圧
着方式などの通常方式で容易に行うことができる。Examples of the adherend to be adhered include a metal plate, a plastic plate, a glass plate, a silicon plate, and a semiconductor wafer. Further, the sticking of the pressure-sensitive adhesive to the adherend can be easily performed by a normal method such as a roll pressure bonding method.
この発明の再剥離型粘着剤は、シリコーン系グラフト
共重合体を含有するので再剥離性にずぐれている。ま
た、そのシリコーン系グラフト共重合体は粘着剤と架橋
反応により結合しているため、粘着剤との分離がおこら
ず、これにより被着体に対する非汚染性にもすぐれてい
る。The removable pressure-sensitive adhesive of the present invention is excellent in removability since it contains a silicone-based graft copolymer. In addition, since the silicone-based graft copolymer is bonded to the pressure-sensitive adhesive by a crosslinking reaction, the silicone-based graft copolymer does not separate from the pressure-sensitive adhesive, thereby being excellent in non-staining property to the adherend.
つぎに、この発明の実施例を記載してより具体的に説
明する。なお、以下部とあるのは重量部を意味し、また
アクリル系粘着剤（Ｉ），（II）とシリコーン系グラフ
ト共重合体（１）〜（III）は、下記の方法で調製した
ものである。Next, an embodiment of the present invention will be described in more detail. The parts below mean parts by weight, and the acrylic pressure-sensitive adhesives (I) and (II) and the silicone-based graft copolymers (1) to (III) were prepared by the following method. is there.
＜アクリル系粘着剤（Ｉ）＞ アクリル酸ブチル80部とアクリル酸エチル15部とアク
リル酸２−ヒドロキシエチル５部とを、トルエン中で過
酸化ベンゾイル0.4部の存在下に、70℃で12時間重合処
理して、アクリル系粘着剤（Ｉ）のトルエン溶液を得
た。<Acrylic pressure-sensitive adhesive (I)> 80 parts of butyl acrylate, 15 parts of ethyl acrylate and 5 parts of 2-hydroxyethyl acrylate in toluene in the presence of 0.4 parts of benzoyl peroxide at 70 ° C for 12 hours. By carrying out the polymerization treatment, a toluene solution of the acrylic pressure-sensitive adhesive (I) was obtained.
＜アクリル系粘着剤（II）＞ アクリル酸２−エチルヘキシル70部とメタクリル酸ブ
チル28部とアクリル酸２部とを、酢酸エチル中で２・
２′−アゾビスイソブチロニトリル0.5部の存在下に、7
0℃で16時間重合処理して、アクリル系粘着剤（II）の
酢酸エチル溶液を得た。<Acrylic pressure-sensitive adhesive (II)> 70 parts of 2-ethylhexyl acrylate, 28 parts of butyl methacrylate, and 2 parts of acrylic acid were mixed in ethyl acetate for 2 times.
In the presence of 0.5 part of 2'-azobisisobutyronitrile, 7
Polymerization treatment was performed at 0 ° C. for 16 hours to obtain a solution of acrylic pressure-sensitive adhesive (II) in ethyl acetate.
＜シリコーン系グラフト共重合体（Ｉ）＞ で表されるシリコーンマクロモノマー（式中のｎ≒70）
20部とアクリル酸ブチル60部とメタクリル酸２−イソシ
アナートエチル20部とを、トルエン中で２・２′−アゾ
ビスイソブチロニトリル0.6部の存在下に70℃で12時間
反応させて、重量平均分子量12万のシリコーン系グラフ
ト重合体（Ｉ）のトルエン溶液を得た。<Silicone graft copolymer (I)> A silicone macromonomer represented by the formula (n ≒ 70 in the formula)
20 parts, 60 parts of butyl acrylate and 20 parts of 2-isocyanatoethyl methacrylate were reacted in toluene at 70 ° C. for 12 hours in the presence of 0.6 part of 2.2′-azobisisobutyronitrile in toluene, A toluene solution of the silicone-based graft polymer (I) having a weight average molecular weight of 120,000 was obtained.
＜シリコーン系グラフト共重合体（II）＞ で表されるシリコーンマクロモノマー（式中のｎ≒30）
20部とアクリル酸２−エチルヘキシル60部とメタクリル
酸グリシジル20部とを、トルエン中で２・２′−アゾビ
スイソブチロニトリル0.8部の存在下に70℃で10時間反
応させて、重量平均分子量15万のシリコーン系グラフト
共重合体（II）のトルエン溶液を得た。<Silicone graft copolymer (II)> (N マ ク ロ 30 in the formula)
20 parts of 2-ethylhexyl acrylate and 60 parts of glycidyl methacrylate were reacted in toluene in the presence of 0.8 part of 2.2′-azobisisobutyronitrile at 70 ° C. for 10 hours to obtain a weight average. A toluene solution of the silicone-based graft copolymer (II) having a molecular weight of 150,000 was obtained.
＜シリコーン系グラフト共重合体（III）＞ メタクリル酸２−イソシアナートエチル20部の代わり
にメタクリル酸ブチルを20部用いた以外は、シリコーン
系グラフト共重合体（Ｉ）の場合と同様に重合処理し
て、重量平均分子量10万のシリコーン系グラフト共重合
体（III）のトルエン溶液を得た。<Silicone graft copolymer (III)> A polymerization treatment was performed in the same manner as the silicone graft copolymer (I) except that 20 parts of butyl methacrylate was used instead of 20 parts of 2-isocyanatoethyl methacrylate. Thus, a toluene solution of the silicone-based graft copolymer (III) having a weight average molecular weight of 100,000 was obtained.
実施例１ アクリル系粘着剤（Ｉ）のトルエン溶液とシリコーン
系グラフト共重合体（Ｉ）のトルエン溶液とを、前者対
後者の固形分重量比が80:20となるように混合して、粘
着剤溶液を得た。なお、粘着剤中のシリコーンマクロモ
ノマーの含有率は計算値で4.0重量％であつた。Example 1 A toluene solution of an acrylic pressure-sensitive adhesive (I) and a toluene solution of a silicone-based graft copolymer (I) were mixed such that the weight ratio of the former to the latter was 80:20, and adhesion was performed. An agent solution was obtained. The content of the silicone macromonomer in the pressure-sensitive adhesive was calculated to be 4.0% by weight.
実施例２ アクリル系粘着剤（II）の酢酸エチル溶液とシリコー
ン系グラフト共重合体（II）のトルエン溶液とを、前者
対後者の固形分重量比が90:10となるように混合し、こ
の混合物の固形分100部に対してさらにトリエチルアミ
ン0.5部を混合して、粘着剤溶液を得た。なお、粘着剤
中のシリコーンマクロモノマーの含有率は計算値で1.0
重量％であつた。Example 2 An ethyl acetate solution of the acrylic pressure-sensitive adhesive (II) and a toluene solution of the silicone-based graft copolymer (II) were mixed so that the weight ratio of the former to the latter was 90:10. 0.5 part of triethylamine was further mixed with 100 parts of the solid content of the mixture to obtain an adhesive solution. The content of the silicone macromonomer in the adhesive was 1.0
% By weight.
実施例３ アクリル系粘着剤（Ｉ）のトルエン溶液とシリコーン
系グラフト共重合体（Ｉ）のトルエン溶液とを、前者対
後者の固形分重量比が65:35となるように混合して、粘
着剤溶液を得た。なお、粘着剤中のシリコーンマクロモ
ノマーの含有率は計算値で7.0重量％であつた。Example 3 A toluene solution of an acrylic pressure-sensitive adhesive (I) and a toluene solution of a silicone-based graft copolymer (I) were mixed so that the weight ratio of the former to the latter was 65:35, and adhesion was performed. An agent solution was obtained. The content of the silicone macromonomer in the pressure-sensitive adhesive was calculated to be 7.0% by weight.
比較例１ アクリル系粘着剤（Ｉ）のトルエン溶液とシリコーン
系グラフト共重合体（III）のトルエン溶液とを、前者
対後者の固形分重量比が78:20となるように混合し、こ
の混合物の固形分98部に対してさらにポリイソシアネー
ト系架橋剤２部を混合して、粘着剤溶液を得た。なお、
シリコーンマクロモノマーの含有率は計算値で4.0重量
％であつた。Comparative Example 1 A toluene solution of the acrylic pressure-sensitive adhesive (I) and a toluene solution of the silicone-based graft copolymer (III) were mixed such that the weight ratio of the former to the latter was 78:20, and this mixture was used. Was further mixed with 2 parts of a polyisocyanate-based crosslinking agent with respect to 98 parts of the solid content to obtain an adhesive solution. In addition,
The calculated content of silicone macromonomer was 4.0% by weight.
比較例２ アクリル系粘着剤（Ｉ）のトルエン溶液に、その固形
分98部に対して２部となる割合のポリイソシアネート系
架橋剤を混合して、粘着剤溶液を得た。Comparative Example 2 A toluene solution of the acrylic pressure-sensitive adhesive (I) was mixed with a polyisocyanate-based crosslinking agent in a ratio of 2 parts to 98 parts of the solid content to obtain a pressure-sensitive adhesive solution.
以上の実施例１〜３および比較例1,2で得た各粘着剤
溶液を、表面をコロナ処理した厚さ60μｍのポリエチレ
ンフイルムに塗布し、加熱乾燥処理して、厚さ10μｍの
粘着剤層を有する表面保護シートを得、以下の試験に供
した。試験結果は、後記の表に示されるとおりであつ
た。Each of the adhesive solutions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 was applied to a polyethylene film having a thickness of 60 μm having a corona-treated surface, dried by heating, and subjected to a 10 μm-thick adhesive layer. Was obtained and subjected to the following tests. The test results were as shown in the table below.
＜初期接着力＞ 表面保護シートを厚さ0.4mmのステンレス板（SUS 304
BA仕上げ）に23℃下で貼着し、30分後の接着力（180度
ピール、引張速度300mm/分）を測定した。<Initial adhesive strength> A surface protection sheet is made of a 0.4 mm thick stainless steel plate (SUS 304
BA finish) at 23 ° C., and the adhesive force (180 ° peel, tensile speed 300 mm / min) after 30 minutes was measured.
＜接着力上昇性＞ 初期接着力の試験に準じ、表面保護シートをステンレ
ス板に貼着したのち50℃下に７日間放置し、23℃に冷却
後その接着力を測定した。<Adhesive strength increasing property> According to the initial adhesive strength test, the surface protective sheet was stuck to a stainless steel plate, left at 50 ° C for 7 days, cooled to 23 ° C, and the adhesive strength was measured.
＜非汚染性＞ 表面保護シートをガラス板に貼着し、50℃下に24時間
放置後取り出して表面保護シートを引き剥がし、第１図
の如くそのガラス板１の剥がし面に水滴２を落として接
触角計によりその角度（θ）を測定し、接触角が10度以
下の場合を○、11℃以上の場合を×として評価した。<Non-contaminating property> A surface protection sheet was stuck on a glass plate, left at 50 ° C. for 24 hours, taken out, peeled off the surface protection sheet, and dropped water droplets 2 on the peeled surface of the glass plate 1 as shown in FIG. The angle (θ) was measured by a contact angle meter, and evaluated when the contact angle was 10 ° or less as 、, and when the contact angle was 11 ° C. or more as ×.
＜加工性＞ 初期接着力の試験に準じ、表面保護シートを貼着した
ステンレス板４を、第２図の如きポンチ３と金型５を用
いて絞り加工した際に、加工後の表面保護シートにシ
ワ，破れ，浮きなどの問題がなく、良好な貼着状態を維
持している場合を○、シワ，破れ，浮きなどが部分的に
発生している場合を△、シワや破れが著しかつたり、全
面が浮いている場合を×として評価した。<Workability> According to the initial adhesion test, when the stainless steel plate 4 to which the surface protection sheet was adhered was drawn using the punch 3 and the mold 5 as shown in FIG. When there is no problem such as wrinkles, tears, or floats, and when a good adhered state is maintained, ○ indicates when wrinkles, tears, or floats are partially generated, and wrinkles or tears are significant. Once, the case where the whole surface was floating was evaluated as x.
上記表の結果から明らかなように、この発明の再剥離
型粘着剤は、接着力の変化が少なくて再剥離性にすぐれ
るうえに、非汚染性にもすぐれており、しかも良好な加
工性をも備えていることが判る。 As is evident from the results in the above table, the removable pressure-sensitive adhesive of the present invention has a small change in adhesive force and excellent removability, is excellent in non-staining properties, and has good workability. It can be seen that it also has.
第１図は非汚染性の試験における接触角を測定する方法
を示す説明図、第２図は加工性の試験方法を示す説明図
である。FIG. 1 is an explanatory view showing a method for measuring a contact angle in a test for non-contamination, and FIG. 2 is an explanatory view showing a test method for workability.
Claims (3)
ースポリマーと架橋反応しうる官能基を持つた架橋性モ
ノマーおよびシリコーンマクロモノマーを必須成分とし
たシリコーン系グラフト共重合体を含有させたことを特
徴とする再剥離型粘着剤。1. A non-silicone pressure-sensitive adhesive containing a crosslinkable monomer having a functional group capable of undergoing a cross-linking reaction with a base polymer of the pressure-sensitive adhesive and a silicone-based graft copolymer containing a silicone macromonomer as essential components. A removable pressure-sensitive adhesive, characterized in that:
が、粘着剤中のシリコーンマクロモノマー単位で0.05〜
20重量％となる割合とされた請求項（１）に記載の再剥
離型粘着剤。2. The content of the silicone-based graft copolymer is from 0.05 to 0.05 based on silicone macromonomer units in the pressure-sensitive adhesive.
The removable pressure-sensitive adhesive according to claim 1, wherein the amount is 20% by weight.
はメタクリル酸のアルキルエステルを主モノマーとする
アクリル系ポリマーをベースポリマーとして含むアクリ
ル系粘着剤である請求項（１）または（２）に記載の再
剥離型粘着剤。3. The non-silicone pressure-sensitive adhesive according to claim 1, wherein the non-silicone pressure-sensitive adhesive is an acrylic pressure-sensitive adhesive containing, as a base polymer, an acrylic polymer having an alkyl ester of acrylic acid or methacrylic acid as a main monomer. Removable adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63276892A JP2582875B2 (en) | 1988-11-01 | 1988-11-01 | Removable adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63276892A JP2582875B2 (en) | 1988-11-01 | 1988-11-01 | Removable adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02123182A JPH02123182A (en) | 1990-05-10 |
| JP2582875B2 true JP2582875B2 (en) | 1997-02-19 |
Family
ID=17575851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63276892A Expired - Lifetime JP2582875B2 (en) | 1988-11-01 | 1988-11-01 | Removable adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2582875B2 (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04117475A (en) * | 1990-09-07 | 1992-04-17 | Toyo Ink Mfg Co Ltd | Re-releasable pressure sensitive adhesive composition |
| JP3911790B2 (en) * | 1997-09-29 | 2007-05-09 | 東洋インキ製造株式会社 | Release agent and release liner using the same |
| JP4247818B2 (en) * | 2003-01-07 | 2009-04-02 | 株式会社リコー | Heat sensitive adhesive material |
| JP5087910B2 (en) * | 2005-12-13 | 2012-12-05 | 東レ株式会社 | Adhesive composition for electronic device, adhesive sheet for electronic device, and electronic component using the same |
| JP5178732B2 (en) * | 2007-10-16 | 2013-04-10 | 電気化学工業株式会社 | Pressure-sensitive adhesive, pressure-sensitive adhesive sheet, multilayer pressure-sensitive adhesive sheet, and electronic component manufacturing method |
| JP5765303B2 (en) * | 2012-08-20 | 2015-08-19 | 信越化学工業株式会社 | Optical pressure-sensitive adhesive composition |
| JP6045892B2 (en) * | 2012-11-30 | 2016-12-14 | 東洋化学株式会社 | Composite film for coating material used by coating an object subject to bending deformation |
| JP6223836B2 (en) | 2013-04-15 | 2017-11-01 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP6373458B2 (en) * | 2013-04-15 | 2018-08-15 | 日東電工株式会社 | Adhesive composition, adhesive layer, and adhesive sheet |
| US10894904B2 (en) | 2013-04-15 | 2021-01-19 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet and pressure sensitive adhesive composition |
| WO2015076612A1 (en) * | 2013-11-21 | 2015-05-28 | 주식회사 엘지화학 | Protection film |
| KR102394517B1 (en) * | 2014-03-03 | 2022-05-06 | 린텍 가부시키가이샤 | Sheet for semiconductor-related-member processing and process for producing chip using said sheet |
| CN105555895B (en) * | 2014-04-22 | 2017-10-27 | 日东电工株式会社 | Bonding sheet |
| JP6316686B2 (en) * | 2014-07-04 | 2018-04-25 | 旭化成株式会社 | Pellicle, photomask with pellicle, and method for manufacturing semiconductor device |
| JP7348838B2 (en) * | 2018-06-05 | 2023-09-21 | 積水化学工業株式会社 | Adhesive tape |
| CN112218926A (en) * | 2018-06-06 | 2021-01-12 | 积水化学工业株式会社 | Adhesive tape |
| JP7512192B2 (en) * | 2019-03-08 | 2024-07-08 | 積水化学工業株式会社 | Adhesive composition and adhesive tape |
| CN111748302A (en) * | 2020-05-15 | 2020-10-09 | 明基材料有限公司 | (meth) acrylate adhesive composition |
| TWI785849B (en) | 2021-10-18 | 2022-12-01 | 明基材料股份有限公司 | (meth)acrylate adhesive composition |
| CN113913135A (en) * | 2021-10-26 | 2022-01-11 | 明基材料有限公司 | (meth) acrylate adhesive composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60197780A (en) * | 1984-03-19 | 1985-10-07 | Daicel Chem Ind Ltd | Restrippable pressure-sensitive adhesive |
| US4728571A (en) * | 1985-07-19 | 1988-03-01 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer release coating sheets and adhesive tapes |
| US4693935A (en) * | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
| JP2680342B2 (en) * | 1988-04-06 | 1997-11-19 | 日本油脂株式会社 | Peelable adhesive composition |
-
1988
- 1988-11-01 JP JP63276892A patent/JP2582875B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02123182A (en) | 1990-05-10 |
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