JP2003192899A - Nonsolvent-type addition reaction curable organopolysiloxane composition - Google Patents
Nonsolvent-type addition reaction curable organopolysiloxane compositionInfo
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- JP2003192899A JP2003192899A JP2001399739A JP2001399739A JP2003192899A JP 2003192899 A JP2003192899 A JP 2003192899A JP 2001399739 A JP2001399739 A JP 2001399739A JP 2001399739 A JP2001399739 A JP 2001399739A JP 2003192899 A JP2003192899 A JP 2003192899A
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- viscosity
- addition reaction
- curable organopolysiloxane
- organopolysiloxane composition
- component
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、硬化後の皮膜が特
定の物理強度を有する無溶剤型付加反応硬化性オルガノ
ポリシロキサン組成物に関する。詳しくは、各種紙，ラ
ミネート紙，合成樹脂フィルム，金属箔などの各種基材
の表面に、特定の物理強度を有する剥離性硬化皮膜を形
成する無溶剤型付加反応硬化性オルガノポリシロキサン
組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solventless addition reaction curable organopolysiloxane composition in which a cured film has a specific physical strength. More specifically, the present invention relates to a solvent-free addition reaction curable organopolysiloxane composition that forms a peelable cured film having specific physical strength on the surface of various substrates such as various papers, laminated papers, synthetic resin films, and metal foils. .
【０００２】[0002]
【従来の技術】アルケニル基含有オルガノポリシロキサ
ン、オルガノハイドロジェンポリシロキサンおよび白金
系触媒からなる付加反応硬化型オルガノポリシロキサン
組成物は、硬化後の皮膜が粘着性物質に対して剥離性を
示すことから、粘着テープや粘着シートの剥離ライナー
として使用されている。このような剥離性硬化皮膜形成
用オルガノポリシロキサン組成物としては、例えば、分
子鎖両末端トリメチルシロキシ基封鎖メチルビニルポリ
シロキサンを主剤とする無溶剤型付加反応硬化性組成物
（特開平７―２５８６０６号公報参照）、分子中に炭素
数6以上の高級アルケニル基を有するポリジオルガノシ
ロキサンを主剤とする無溶剤型付加反応硬化性組成物
（特開昭６２−８６０６１号公報参照）、分子鎖両末端
トリメチルシロキシ基封鎖メチルヘキセニルシロキサン
・ジメチルシロキサン共重合体と分子鎖両末端ジメチル
ビニルシロキシ基封鎖ジメチルポリシロキサンの混合物
を主剤とする無溶剤型付加反応硬化性組成物（特開２０
００−１６０１０２号公報参照）が提案されている。し
かしながらこのような無溶剤タイプの剥離剤は、一般
に、使用されるオルガノポリシロキサンが低粘度である
ため硬化後の皮膜の強度が低く、その結果、強い摩擦が
かかると皮膜表面が破壊することがあるという欠点があ
った。また剥離ライナーには、通常、粘着性物質を高速
度（約５０m/分以上）で剥離した場合の剥離抵抗値が小
さいことが要求されるが、無溶剤型付加反応硬化性オル
ガノポリシロキサン組成物においてこれを達成すること
は困難であった。2. Description of the Related Art An addition reaction-curable organopolysiloxane composition comprising an alkenyl group-containing organopolysiloxane, an organohydrogenpolysiloxane and a platinum-based catalyst is such that the cured film shows releasability from an adhesive substance. Therefore, it is used as a release liner for adhesive tapes and sheets. As such an organopolysiloxane composition for forming a releasable cured film, for example, a solventless addition reaction curable composition mainly composed of methylvinylpolysiloxane endcapped with trimethylsiloxy groups at both terminals of the molecular chain (JP-A-7-258606). JP-A-62-86061), a solventless addition reaction curable composition containing a polydiorganosiloxane having a higher alkenyl group having 6 or more carbon atoms in the molecule as a main component, and both ends of a molecular chain. Solvent-free addition-curable composition mainly composed of a mixture of a trimethylsiloxy group-blocked methylhexenylsiloxane / dimethylsiloxane copolymer and a dimethylvinylsiloxy group-blocked dimethylpolysiloxane at both molecular chain terminals (JP 20
No. 00-160102) has been proposed. However, such a solvent-free type release agent generally has a low viscosity after curing because the organopolysiloxane used has a low viscosity, and as a result, the surface of the coating may be destroyed when strong friction is applied. There was a drawback. Further, the release liner is usually required to have a small release resistance value when an adhesive substance is released at a high speed (about 50 m / min or more), but a solventless addition reaction curable organopolysiloxane composition It was difficult to achieve this in.
【０００３】一方、物理強度の高い硬化皮膜を形成する
剥離性硬化皮膜形成性オルガノポリシロキサン組成物と
しては、例えば、生ゴム状ヘキセニル基含有オルガノポ
リシロキサン、オルガノハイドロジェンポリシロキサ
ン、白金系触媒、付加反応抑制剤および有機溶剤からな
る組成物（特開平２−１４５６４９号公報参照）や、ビ
ニル基含有オルガノポリシロキサンをトルエンに溶解し
た後、オルガノハイドロジェンポリシロキサンと白金系
触媒を配合した組成物（特開平６−３３６５７４号公報
参照）が提案されている。しかしながらこれらの組成物
は、主剤のアルケニル基含有オルガノポリシロキサンが
生ゴム状の高分子量物であるために大量の有機溶剤を必
要とし、その結果、大気汚染や作業者の健康への悪影
響、溶剤回収装置に多額の費用がかかる等の問題点があ
った。また、硬化皮膜の硬度が高いだけでは、強い摩擦
がかかった場合に皮膜表面が破壊することがある上、こ
れらの組成物は一般に剥離抵抗値が大きく、粘着性物質
の残留接着率が低下する等の欠点があり、用途によって
は必ずしも満足できるものではなかった。On the other hand, examples of the peelable cured film-forming organopolysiloxane composition which forms a cured film having high physical strength include, for example, raw rubber-like hexenyl group-containing organopolysiloxane, organohydrogenpolysiloxane, platinum catalyst and addition. A composition comprising a reaction inhibitor and an organic solvent (see JP-A-2-145649), or a composition in which a vinyl group-containing organopolysiloxane is dissolved in toluene and then an organohydrogenpolysiloxane and a platinum-based catalyst are blended ( JP-A-6-336574) is proposed. However, these compositions require a large amount of organic solvent because the main ingredient alkenyl group-containing organopolysiloxane is a raw rubber-like high molecular weight substance, and as a result, air pollution, adverse effects on worker health, and solvent recovery. There is a problem that the device costs a lot of money. Further, if the hardness of the cured film is high only, the surface of the film may be destroyed when strong friction is applied, and these compositions generally have a large peel resistance value and the residual adhesion ratio of the sticky substance decreases. However, it is not always satisfactory depending on the application.
【０００４】[0004]
【発明が解決しようとする課題】本発明者らは上記欠点
を解消するために鋭意検討した結果、硬化後の皮膜が特
定の硬度と引裂強度と伸びを有することにより、強い摩
擦がかかった場合にも皮膜表面が破壊しにくく、また、
粘着性物質を高速度で剥離した場合の剥離抵抗値が小さ
い剥離性硬化皮膜が得られることを見出し、本発明に到
達した。即ち、本発明の目的は、強い摩擦がかかった場
合に皮膜表面が破壊しにくく、かつ、粘着性物質を高速
度で剥離した場合の剥離抵抗値が小さい剥離性硬化皮膜
を形成し得る無溶剤型付加反応硬化性オルガノポリシロ
キサン組成物を提供することにある。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, when a film after curing has specific hardness, tear strength and elongation, a strong friction is applied. Also, the surface of the film is hard to break, and
The present inventors have found that a peelable cured film having a small peel resistance value when a tacky substance is peeled at a high speed can be obtained, and thus reached the present invention. That is, the object of the present invention is a solvent-free solvent capable of forming a peelable cured film having a small peeling resistance when the surface of the coating is less likely to be broken when strong friction is applied, and the adhesive substance is peeled at a high speed. A mold addition reaction curable organopolysiloxane composition is provided.
【０００５】[0005]
【課題を解決するための手段】本発明は、硬化後の皮膜
が、
JIS K 6253に規定されたJISタイプA硬度計による硬度
が３５以上であり、
JIS K 6252に規定された切り込み無しアングル形試験
片の引裂強度が１．５Ｎ／ｍｍ以上であり、
JIS K 6251に規定された3号ダンベル試験片の切断時
伸びが１００％以上であることを特徴とする、無溶剤型
付加反応硬化性オルガノポリシロキサン組成物に関す
る。[Means for Solving the Problems] The present invention provides a cured film having a hardness of 35 or more as measured by a JIS type A hardness meter specified in JIS K 6253, and a non-cutting angle type specified in JIS K 6252. Tear strength of the test piece is 1.5 N / mm or more, and elongation at break of the No. 3 dumbbell test piece specified in JIS K 6251 is 100% or more, solvent-free addition reaction curability It relates to organopolysiloxane compositions.
【０００６】[0006]
【発明の実施の形態】本発明組成物は、アルケニル官能
性ジオルガノポリシロキサン、オルガノハイドロジェン
ポリシロキサンおよび付加反応促進触媒からなる無溶剤
型付加反応硬化性オルガノポリシロキサン組成物であ
り、硬化後の皮膜が
JIS K 6253に規定されたJISタイプA硬度計による硬度
が３５以上であり、
JIS K 6252に規定された切り込み無しアングル形試験
片の引裂強度が１．５Ｎ／ｍｍ以上であり、かつ、
JIS K 6251に規定された3号ダンベル試験片の切断時
伸びが１００％以上であることを特徴とする。これによ
り、強い摩擦がかかった場合にも皮膜表面が破壊しにく
く、摩耗性に優れた剥離性硬化皮膜が得られる。主剤の
アルケニル官能性ジオルガノポリシロキサンとしては、
２種類のアルケニル官能性ジオルガノポリシロキサンを
使用することが好ましく、さらにその内の一方のアルケ
ニル官能性ジオルガノポリシロキサンが、（ａ）２５℃
における粘度が３０〜３００ｍＰａ・ｓの低粘度物と
（ｂ）２５℃における粘度が３００〜５０００ｍＰａ・
ｓの高粘度物の混合物であることが好ましい。さらに
（ａ）低粘度物の粘度は３０〜２００ｍＰａ・ｓである
ことが好ましく、（ｂ）高粘度物の粘度は、３００〜３
０００ｍＰａ・ｓであることが好ましく、３００〜１５
００ｍＰａ・ｓであることがより好ましい。また、
（ａ）低粘度物と（ｂ）高粘度物の粘度差は３０ｍPa・
ｓ以上であり、５０〜４７００ｍＰａ・ｓであることが
好ましく、１００〜２７００ｍＰａ・ｓであることがよ
り好ましい。該混合物中、（ａ）低粘度物の比率は３０
重量％以下であり、（ａ）低粘度物と（ｂ）高粘度物の
混合比率は、５〜３０：９５〜７０重量％の範囲である
ことが好ましい。これは、（ａ）低粘度物の比率が３０
重量％を越えると硬化後の皮膜に十分な引裂強度と伸び
が得られず、また５重量％未満であると硬化皮膜の硬度
が低くなることがあるためである。本発明で言うアルケ
ニル官能性ジオルガノポリシロキサンとしては、分子鎖
末端にのみアルケニル基を有するジオルガノポリシロキ
サン、分子鎖末端と側鎖にアルケニル基を有するジオル
ガノポリシロキサン、側鎖にのみアルケニル基を有する
ジオルガノポリシロキサンが挙げられるが、中でも、
（Ａ）分子鎖末端にのみアルケニル基を有するジオルガ
ノポリシロキサンと（Ｂ）分子鎖末端と側鎖にアルケニ
ル基を有するジオルガノポリシロキサンの組合わせが好
ましく、（Ａ）成分が前記したような（ａ）低粘度物と
（ｂ）高粘度物の混合物であることが好ましい。また、
これらのアルケニル官能性ジオルガノポリシロキサン
中、アルケニル基以外のケイ素原子に結合する有機基と
しては、アルキル基、アリール基、アラルキル基が挙げ
られる。BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention is a solvent-free addition-curable organopolysiloxane composition comprising an alkenyl-functional diorganopolysiloxane, an organohydrogenpolysiloxane and an addition reaction accelerating catalyst. Has a hardness of 35 or more by a JIS type A hardness tester specified in JIS K 6253, and a tear strength of an uncut angle type test piece specified in JIS K 6252 of 1.5 N / mm or more, and The JIS No. 3 dumbbell test piece specified in JIS K 6251 has an elongation at break of 100% or more. This makes it possible to obtain a peelable cured film having excellent abrasion resistance, because the surface of the film is not easily broken even when strong friction is applied. The alkenyl-functional diorganopolysiloxane of the main component,
It is preferable to use two kinds of alkenyl-functional diorganopolysiloxane, and one of the alkenyl-functional diorganopolysiloxane is (a) 25 ° C.
Viscosity of 30 to 300 mPa · s at (b) Viscosity at 25 ° C. of 300 to 5000 mPa · s
It is preferably a mixture of high viscosity substances of s. Furthermore, the viscosity of (a) the low-viscosity product is preferably 30 to 200 mPa · s, and the viscosity of (b) the high-viscosity product is 300 to 3
000 mPa · s is preferable, 300 to 15
More preferably, it is 00 mPa · s. Also,
The viscosity difference between (a) low viscosity product and (b) high viscosity product is 30 mPa.
s or more, preferably 50 to 4700 mPa · s, and more preferably 100 to 2700 mPa · s. In the mixture, the ratio of (a) low viscosity product is 30
It is preferable that the mixing ratio of the low-viscosity substance (a) and the high-viscosity substance (b) is 5 to 30:95 to 70% by weight. This is because the ratio of (a) low viscosity substances is 30.
This is because if the content exceeds 5% by weight, the cured film may not have sufficient tear strength and elongation, and if it is less than 5% by weight, the hardness of the cured film may decrease. The alkenyl-functional diorganopolysiloxane referred to in the present invention includes a diorganopolysiloxane having an alkenyl group only at the molecular chain end, a diorganopolysiloxane having an alkenyl group at the molecular chain end and a side chain, and an alkenyl group only at the side chain. Among them are diorganopolysiloxanes having
A combination of (A) a diorganopolysiloxane having an alkenyl group only at the molecular chain end and (B) a diorganopolysiloxane having an alkenyl group at the molecular chain end and a side chain are preferable, and the component (A) is as described above. A mixture of (a) a low viscosity product and (b) a high viscosity product is preferable. Also,
In these alkenyl-functional diorganopolysiloxanes, examples of the organic group bonded to a silicon atom other than the alkenyl group include an alkyl group, an aryl group and an aralkyl group.
【０００７】上記した〜の物理強度は、例えば、
（Ａ）分子鎖末端にのみアルケニル基を有するジオルガ
ノポリシロキサンの（ａ）低粘度物と（ｂ）高粘度物の
混合物、（Ｂ）分子鎖末端と側鎖にアルケニル基を有す
るジオルガノポリシロキサン、［（Ａ）成分：（Ｂ）成
分＝７０〜２０：３０〜８０重量％である。］
（Ｃ）ケイ素原子結合水素原子含有オルガノハイドロジ
ェンポリシロキサン（Ａ）成分と（Ｂ）成分の合計１０
０重量部に対して３〜５０重量部、（Ｄ）付加反応促進
触媒 触媒
量からなり、２５℃における粘度が３０〜５０００ｍＰ
ａ・ｓである無溶剤型付加反応硬化性オルガノポリシロ
キサン組成物によって達成される。The physical strengths of the above-mentioned are, for example,
(A) A mixture of (a) a low-viscosity product and (b) a high-viscosity product of a diorganopolysiloxane having an alkenyl group only at the molecular chain end, (B) a diorganopolysiloxane having an alkenyl group at the molecular chain end and the side chain Siloxane, [(A) component: (B) component = 70 to 20:30 to 80% by weight. ] (C) Silicon hydrogen atom-containing hydrogen atom-containing organohydrogenpolysiloxane (A) component and (B) component total 10
3 to 50 parts by weight relative to 0 parts by weight, (D) addition reaction accelerating catalyst consisting of a catalytic amount, and a viscosity at 25 ° C. of 30 to 5000 mP
This is achieved by a solventless addition reaction curable organopolysiloxane composition that is a · s.
【０００８】（Ａ）分子鎖末端にのみアルケニル基を有
するジオルガノポリシロキサンの混合物において、
（ａ）低粘度物と（ｂ）高粘度物の粘度、粘度差、比率
は前記と同様である。このようなジオルガノポリシロキ
サンの具体例としては、一般式：(A) In a mixture of diorganopolysiloxanes having an alkenyl group only at the terminal of the molecular chain,
The viscosity, viscosity difference, and ratio of the (a) low-viscosity product and the (b) high-viscosity product are the same as above. Specific examples of such a diorganopolysiloxane include those represented by the general formula:
【化１】
で表される分子鎖両末端ジメチルアルケニルシロキシ基
封鎖ジメチルポリシロキサンが挙げられる。上式中、Ｒ
はアルケニル基であり、ビニル基，ブテニル基，ヘキセ
ニル基，オクテニル基，デセニル基が例示される。これ
らの中でもビニル基が好ましい。ｘは（Ａ）成分の２５
℃における粘度が３０〜５０００ｍＰａ・ｓとなるよう
な値であり、好ましくは５０〜２０００ｍＰａ・ｓとな
るような値である。このような（Ａ）成分は、例えば、
ジメチルシロキサン環状体と低粘度のジメチルビニルシ
ロキシ基封鎖ジメチルポリシロキサンを、酸性触媒もし
くはアルカリ性触媒の存在下に平衡化重合させる方法に
より製造できる。[Chemical 1] A dimethylpolysiloxane having a dimethylalkenylsiloxy group blocked at both ends of the molecular chain represented by In the above formula, R
Is an alkenyl group, and examples thereof include a vinyl group, a butenyl group, a hexenyl group, an octenyl group and a decenyl group. Of these, vinyl groups are preferred. x is 25 of the (A) component
It is a value such that the viscosity at 30 ° C. is 30 to 5000 mPa · s, preferably 50 to 2000 mPa · s. Such component (A) is, for example,
It can be produced by a method of equilibrating and polymerizing a dimethylsiloxane cyclic compound and a low-viscosity dimethylvinylsiloxy group-capped dimethylpolysiloxane in the presence of an acidic catalyst or an alkaline catalyst.
【０００９】（Ｂ）分子鎖末端と側鎖にアルケニル基を
有するジオルガノポリシロキサンの具体例としては、一
般式：Specific examples of the diorganopolysiloxane (B) having an alkenyl group at the terminal and side chain of the molecular chain are represented by the general formula:
【化２】
で表されるジメチルシロキサン・メチルアルケニルシロ
キサン共重合体が挙げられる。上式中、Ｒはアルケニル
基であり、ビニル基，ブテニル基，ヘキセニル基，オク
テニル基，デセニル基が例示される。これらの中でも、
ビニル基もしくはヘキセニル基であることが好ましく、
特に、分子鎖末端に結合するアルケニル基がビニル基で
あり、側鎖に結合するアルケニル基がヘキセニル基であ
ることが好ましい。またこのアルケニル基の含有量は、
ケイ素原子に結合する全有機基の０．２〜１０．０モル
％の範囲であることが好ましい。ｙは１以上の正数であ
り、ｚは２以上の正数であり、０.０１＜ｚ／（ｙ+ｚ）
≦０.２５である。これは、ｚ／（ｙ+ｚ）が０.０１以
下では、高速度で剥離した場合の剥離抵抗値が大きくな
り、また０.２５を越えると、低速度で剥離した場合も
高速度で剥離した場合も剥離抵抗値が大きくなるためで
ある。ここで、ｚ／（ｙ+ｚ）は０.０３〜０.０６の範
囲であることが好ましい。尚、（ｙ+ｚ）は（Ｂ）成分
の２５℃における粘度が５０〜５０００ｍＰａ・ｓとな
るような値であり、１００〜２０００ｍＰａ・ｓとなる
ような値であることが好ましい。このような（Ｂ）成分
は、例えば、メチルヘキセニルシロキサン環状体とジメ
チルシロキサン環状体と低粘度のジメチルビニルシロキ
シ基封鎖ジメチルポリシロキサンを、酸性触媒もしくは
アルカリ性触媒の存在下に平衡化重合させる方法により
製造することができる。[Chemical 2] A dimethyl siloxane / methyl alkenyl siloxane copolymer represented by In the above formula, R is an alkenyl group, and examples thereof include a vinyl group, a butenyl group, a hexenyl group, an octenyl group, and a decenyl group. Among these,
It is preferably a vinyl group or a hexenyl group,
Particularly, it is preferable that the alkenyl group bonded to the terminal of the molecular chain is a vinyl group and the alkenyl group bonded to the side chain is a hexenyl group. The content of this alkenyl group is
It is preferably in the range of 0.2 to 10.0 mol% of all organic groups bonded to silicon atoms. y is a positive number of 1 or more, z is a positive number of 2 or more, and 0.01 <z / (y + z)
≦ 0.25. This is because when z / (y + z) is 0.01 or less, the peeling resistance value when peeling at high speed becomes large, and when z / (y + z) exceeds 0.25, peeling at high speed occurs even when peeling at low speed. This is because the peeling resistance value becomes large even in the case of doing so. Here, z / (y + z) is preferably in the range of 0.03 to 0.06. In addition, (y + z) is a value such that the viscosity of the component (B) at 25 ° C. is 50 to 5000 mPa · s, and preferably 100 to 2000 mPa · s. Such component (B) can be obtained, for example, by a method in which a methylhexenyl siloxane cyclic compound, a dimethyl siloxane cyclic compound, and a low-viscosity dimethylvinylsiloxy group-capped dimethylpolysiloxane are equilibrated and polymerized in the presence of an acidic catalyst or an alkaline catalyst. It can be manufactured.
【００１０】（Ａ）成分と（Ｂ）成分の混合比率は、７
０〜２０：３０〜８０重量％であり、７０〜４０：３０
〜６０重量％が好ましい。これは、（Ａ）成分が７０重
量％を越えると高速度で剥離した場合の剥離抵抗が大き
くなるためであり、２０重量％未満であると十分な物理
強度が得られなくなるためである。The mixing ratio of the components (A) and (B) is 7
0 to 20:30 to 80% by weight, 70 to 40:30
-60% by weight is preferred. This is because if the component (A) exceeds 70% by weight, the peeling resistance when peeling at a high speed becomes large, and if it is less than 20% by weight, sufficient physical strength cannot be obtained.
【００１１】（Ｃ）ケイ素原子結合水素原子含有オルガ
ノハイドロジェンポリシロキサンは架橋剤として作用す
る成分であり、一分子中に少なくとも３個のケイ素原子
結合水素原子を有することが必要であり、その結合位置
は特に限定されない。水素原子以外のケイ素原子に結合
する有機基としては、メチル基，エチル基，プロピル
基，ブチル基，ペンチル基，ヘキシル基等のアルキル
基；フェニル基，トリル基，キシリル基等のアリール
基；ベンジル基，フェネチル基等のアラルキル基のよう
な脂肪族不飽和結合を含有しない一価炭化水素基が挙げ
られる。本成分の２５℃における粘度は、１〜１０００
ｍＰａ・ｓである。本成分は周知の製造方法により製造
できる（特開平３−１７０５３１号公報、特開平８−３
１１２０４号公報参照）。本成分の配合量は、（Ａ）成
分と（Ｂ）成分の合計１００重量部に対して、３〜５０
重量部の範囲である。これは、本成分の配合量が３重量
部未満であると本発明組成物の硬化が不十分になり、５
０重量部を越えると剥離性硬化皮膜の剥離抵抗値が経時
的に変化するためである。尚、本発明では、（Ａ）成分
と（Ｂ）成分と（Ｃ）成分の配合比率を変えることによ
り、低速度で剥離した場合の剥離抵抗値をコントロール
することができる。(C) The organohydrogenpolysiloxane containing a silicon atom-bonded hydrogen atom is a component that acts as a cross-linking agent, and it is necessary to have at least three silicon atom-bonded hydrogen atoms in one molecule. The position is not particularly limited. Examples of the organic group bonded to a silicon atom other than hydrogen atom include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; benzyl. Groups, monovalent hydrocarbon groups containing no aliphatic unsaturated bond such as aralkyl groups such as phenethyl group and the like. The viscosity of this component at 25 ° C. is 1 to 1000.
It is mPa · s. This component can be produced by a known production method (JP-A-3-170531, JP-A-8-3).
See Japanese Patent No. 11204). The blending amount of this component is 3 to 50 relative to 100 parts by weight of the total of the components (A) and (B).
The range is parts by weight. This is because if the content of this component is less than 3 parts by weight, curing of the composition of the present invention becomes insufficient.
This is because if it exceeds 0 parts by weight, the peel resistance value of the peelable cured film changes with time. In the present invention, the peeling resistance value when peeling at a low speed can be controlled by changing the mixing ratio of the component (A), the component (B) and the component (C).
【００１２】（Ｄ）付加反応促進触媒は本発明組成物の
硬化を促進する成分であり、白金系触媒が好ましい。具
体的には、白金黒，白金担持シリカ，白金担持活性炭等
の白金および塩化白金酸，塩化白金酸のアルコール溶
液，塩化白金酸とオレフィンとの錯体，塩化白金酸とア
ルケニルシロキサンとの錯体が例示される。本成分の配
合量は触媒量であればよく、好ましくは（Ａ）成分と
（Ｂ）成分と（Ｃ）成分の合計量に対して、白金金属量
が１〜１０００ppm となるような量である。The (D) addition reaction accelerating catalyst is a component that accelerates the curing of the composition of the present invention, and is preferably a platinum-based catalyst. Specific examples include platinum and chloroplatinic acid such as platinum black, platinum-supported silica, and platinum-supported activated carbon, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid with olefins, and complexes of chloroplatinic acid with alkenylsiloxanes. To be done. The blending amount of this component may be a catalytic amount, and is preferably an amount such that the amount of platinum metal is 1 to 1000 ppm with respect to the total amount of the components (A), (B) and (C). .
【００１３】本発明組成物は上記（Ａ）成分〜（Ｄ）成
分からなり、実質的に有機溶剤を含有しないものである
が、これらの成分に加えて、硬化遅延剤，微粉末シリカ
等の無機質充填剤，顔料，耐熱性添加剤，有機樹脂粉
末，染料等の剥離性硬化皮膜形成用シリコーン組成物の
添加剤として公知とされる添加剤を添加配合すること
は、本発明の目的を損わない限り差し支えない。本発明
組成物の２５℃における粘度は３０〜５０００ｍＰａ・
ｓの範囲であり、この粘度範囲であれば有機溶剤を使用
せずに塗工することができる。The composition of the present invention comprises the above-mentioned components (A) to (D) and contains substantially no organic solvent. In addition to these components, a curing retarder, fine powder silica, etc. Addition of known additives such as inorganic fillers, pigments, heat-resistant additives, organic resin powders, dyes, etc., which are known as additives for the silicone composition for peelable cured film formation, impairs the object of the present invention. It doesn't matter unless you understand it. The viscosity of the composition of the present invention at 25 ° C. is 30 to 5000 mPa ·
The viscosity is within the range of s, and coating can be performed without using an organic solvent within this viscosity range.
【００１４】本発明組成物は、上記（Ａ）成分〜（Ｄ）
成分を単に均一に混合することにより調製することがで
きる。この場合、（Ａ）成分〜（Ｃ）成分を混合した
後、（Ｄ）成分を加えて混合することが好ましい。The composition of the present invention comprises the above components (A) to (D).
It can be prepared by simply mixing the components homogeneously. In this case, it is preferable that the components (A) to (C) are mixed and then the component (D) is added and mixed.
【００１５】本発明組成物は、これを各種紙，ラミネー
ト紙，合成樹脂フィルム等の各種基材の表面に塗工して
硬化させることにより、これらの基材表面に粘着性物質
に対する剥離性皮膜を形成することができる。粘着性物
質としては、アクリル系粘着剤、ゴム系粘着剤、シリコ
ーン系粘着剤、各種接着剤が例示される。The composition of the present invention is applied to the surface of various base materials such as various papers, laminated papers, synthetic resin films and the like, and cured to give a releasable film for an adhesive substance on the surface of these base materials. Can be formed. Examples of the adhesive substance include acrylic adhesives, rubber adhesives, silicone adhesives, and various adhesives.
【００１６】以上のような本発明組成物は、硬化後の皮
膜が上記した特定の物理強度を有するので、強い摩擦が
かかった場合に皮膜表面が破壊しにくいという特徴を有
する。このため例えば、硬化皮膜表面に加工装置のロー
ルやガイドなどが接触しても硬化皮膜の破損が少なく、
削り取られた硬化皮膜の破片が装置内に堆積して装置が
停止するというトラブルが発生しにくいという利点を有
する。さらに得られた硬化皮膜は、粘着性物質を高速度
で剥離した場合の剥離抵抗値が小さく、また該硬化皮膜
に粘着した粘着性物質の残留接着率を低下させないとい
う特徴を有する。加えて、低速度で剥離した場合の剥離
抵抗値を、大きい値から小さい値までコントロールする
ことができるという利点を有する。また、本発明組成物
は実質的に有機溶剤を含有しないため、環境保全や作業
環境改善等の観点からも有用である。このような本発明
組成物は、剥離ライナ−や剥離性塗料として有用であ
る。The composition of the present invention as described above is characterized in that the film surface after curing has the above-mentioned specific physical strength, so that the surface of the film is unlikely to be broken when strong friction is applied. Therefore, for example, even if the roll or guide of the processing device comes into contact with the surface of the cured film, there is little damage to the cured film,
This has the advantage that the scraped-off pieces of the cured film accumulate in the device and stop the device. Further, the obtained cured film has a feature that the peeling resistance value when the adhesive substance is peeled off at a high speed is small and the residual adhesion rate of the adhesive substance adhered to the cured film is not lowered. In addition, there is an advantage that the peeling resistance value when peeling at a low speed can be controlled from a large value to a small value. Further, since the composition of the present invention contains substantially no organic solvent, it is useful from the viewpoint of environmental protection and work environment improvement. Such a composition of the present invention is useful as a release liner or a release coating material.
【００１７】[0017]
【実施例】以下、本発明を実施例により詳細に説明す
る。なお、実施例中の粘度の値は、２５℃において測定
した値である。また、付加反応硬化性オルガノポリシロ
キサン組成物の硬化皮膜の物理強度、切断試験、剥離抵
抗値、シリコ−ン移行性および粘着性物質の残留接着率
（％）の測定は下記の方法に従って行った。
○物理強度
付加反応硬化性オルガノポリシロキサン組成物を金型に
流し込んだ後、１５０℃のオーブンで１５分間加熱して
硬化させ、厚さ６ｍｍの物理特性測定用シート状試験片
を作成した。このシート状試験片の硬さをＪＩＳ Ｋ６
２５３に基づいて、ＪＩＳタイプＡ硬度計を用いて測定
した。また、切断時伸びは、ＪＩＳ Ｋ６２５１に基づ
いて３号ダンベル試験片を用いて測定した。引裂強さ
は、ＪＩＳＫ６２５２に基づいて切り込み無しアングル
形試験片を用いて測定した。
○切断試験
付加反応硬化性オルガノポリシロキサン組成物を金型に
流し込んだ後、１５０℃のオーブンで１５分間加熱して
硬化させ、厚さ６ｍｍの物理特性測定用シート状試験片
を作成した。このシート状試験片から幅2cm長さ10cmの
試験片を作成し、これを、刃渡り20cmの金ノコ刃を用い
て一定の圧力で、幅方向に5往復させることにより切断
した。切断時に発生した硬化物の切断カスの大きさ及び
量を目視で測定した。切断カスの大きさは大＞中＞小で
表し、また、量は多＞中＞少で表した。
○剥離抵抗値
付加反応硬化性オルガノポリシロキサン組成物の硬化皮
膜表面に、アクリル系粘着剤［東洋インキ（株）製，商
品名：オリバインＢＰＳ５１２７］を塗布し、これを温
度７０℃、２分間の条件で加熱乾燥した。次いでこれに
貼合わせ紙を貼り合わせ、２０g/cm2の荷重をかけて、
温度２５℃、湿度６０％の条件下で２４時間放置した。
次にテンシロンおよび高速剥離試験機を用いて、０.３m
/分，５０m/分，１００m/分の各速度において角度１８
０度で貼合わせ紙を引張り、剥離に要した力(gf)を測定
した。尚、試料幅はすべて２.５ｃｍとした。
○シリコーン移行性
付加反応硬化性オルガノポリシロキサン組成物の硬化皮
膜を形成した剥離紙面上に、清浄なポリエステルフィル
ムを貼合わせ、プレスで１００kg/cm2の荷重をかけて、
２５℃で３０分間放置した。次いで、ポリエステルフィ
ルムをはがし取り、そのポリエステルフィルムの剥離紙
と接触していた面にマジックインキ（登録商標）で線を
書き、インキのはじきの程度を測定した。インキのはじ
きがなければシリコーン移行がないものとし、インキの
はじきがあればシリコーン移行があるものとした。
○残留接着率
付加反応硬化性オルガノポリシロキサン組成物の硬化皮
膜表面に、粘着テープ［日東電工（株）製，商品名：ニ
ットーポリエステル粘着テープ３１Ｂ］を貼合わせ、２
０g/cm2の荷重をかけて７０℃で２０時間エージングし
た。次いで、粘着テープをはがし、このはがした粘着テ
ープをステンレス板に貼付け、２０g/cm2の荷重をかけ
て２５℃で３０分間放置した後、角度１８０度，速度
０.３m/分の条件で粘着テープを引張り、剥離に要した
力(gf1)を測定した。また、ブランク試験として、ポリ
テトラフルオロエチレンシートに上記の粘着テ−プを上
記と同様にエージングした後、ステンレス板に貼付け、
この粘着テープの剥離に要した力(gf2)を上記と同様に
測定した。このブランク試験の粘着テープの剥離に要し
た力(gf2)に対する、オルガノポリシロキサン組成物の
硬化皮膜に貼合わせた粘着テープの剥離に要した力(gf
1)を百分率で表した（gf1／gf2）。EXAMPLES The present invention will be described in detail below with reference to examples. The viscosity value in the examples is a value measured at 25 ° C. Further, the physical strength of the cured film of the addition reaction-curable organopolysiloxane composition, the cutting test, the peel resistance value, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured according to the following methods. . ○ Physical Strength Addition Reaction The curable organopolysiloxane composition was cast into a mold and then heated in an oven at 150 ° C. for 15 minutes to be cured to prepare a sheet-like test piece having a thickness of 6 mm for measuring physical properties. The hardness of this sheet-shaped test piece is JIS K6.
Based on 253, it was measured using a JIS type A hardness tester. The elongation at break was measured using a No. 3 dumbbell test piece based on JIS K6251. The tear strength was measured using an uncut angle type test piece based on JISK6252. Cutting Test After pouring the addition reaction curable organopolysiloxane composition into a mold, the composition was heated in an oven at 150 ° C. for 15 minutes to be cured to prepare a sheet-shaped test piece having a thickness of 6 mm for measuring physical properties. A test piece having a width of 2 cm and a length of 10 cm was prepared from the sheet-shaped test piece, and the test piece was cut by reciprocating 5 times in the width direction at a constant pressure using a metal saw blade having a blade crossing length of 20 cm. The size and amount of the cutting residue of the cured product generated during cutting were visually measured. The size of cut waste was expressed as large>medium> small, and the amount was expressed as large>medium> small. Peeling resistance value addition reaction An acrylic adhesive [TOYO INK CO., LTD., Trade name: Olivine BPS5127] was applied to the surface of the cured film of the curable organopolysiloxane composition, and this was applied at a temperature of 70 ° C. for 2 minutes. It was dried by heating under the conditions. Then attach a piece of laminated paper to it and apply a load of 20 g / cm 2 ,
It was left for 24 hours under the conditions of a temperature of 25 ° C. and a humidity of 60%.
Next, using Tensilon and high-speed peel tester, 0.3m
Angle 18 at speeds of 50 / min, 50m / min, 100m / min
The laminated paper was pulled at 0 degree and the force (gf) required for peeling was measured. The sample widths were all 2.5 cm. ○ A clean polyester film is laminated on the release paper surface on which a cured film of a silicone migration addition reaction curable organopolysiloxane composition is formed, and a load of 100 kg / cm 2 is applied by a press,
It was left at 25 ° C. for 30 minutes. Then, the polyester film was peeled off, a line was drawn with Magic Ink (registered trademark) on the surface of the polyester film that was in contact with the release paper, and the degree of ink repelling was measured. If there was no ink repelling, it was assumed that there was no silicone migration, and if there was ink repelling, there was silicone migration. Residual Adhesion Rate Adhesive tape [Nitto Denko Corporation, trade name: Knit-Polyester adhesive tape 31B] is attached to the surface of the cured film of the addition reaction curable organopolysiloxane composition, and 2
It was aged at 70 ° C. for 20 hours with a load of 0 g / cm 2 . Then, the adhesive tape was peeled off, and the peeled adhesive tape was attached to a stainless steel plate and left at 25 ° C for 30 minutes under a load of 20 g / cm 2 , after which the angle was 180 degrees and the speed was 0.3 m / min. The adhesive tape was pulled and the force required for peeling (gf1) was measured. Also, as a blank test, after aging the above-mentioned adhesive tape to a polytetrafluoroethylene sheet in the same manner as above, it was attached to a stainless steel plate,
The force (gf2) required for peeling the adhesive tape was measured in the same manner as above. For the force (gf2) required for peeling the adhesive tape in this blank test, the force (gf2) required for peeling the adhesive tape attached to the cured film of the organopolysiloxane composition
1) was expressed as a percentage (gf1 / gf2).
【００１８】[0018]
【実施例１】粘度６０ｍＰａ・ｓの分子鎖両末端ジメチ
ルビニルシロキシ基封鎖ジメチルポリシロキサン５重量
部、粘度３７０ｍＰａ・ｓの分子鎖両末端ジメチルビニ
ルシロキシ基封鎖ジメチルポリシロキサン３０重量部、
粘度２００ｍＰａ・ｓの分子鎖両末端ジメチルビニルシ
ロキシ基封鎖ジメチルシロキサン・メチルヘキセニルシ
ロキサン共重合体（ジメチルシロキサン単位９８モル
％，メチルヘキセニルシロキサン単位２モル％）６５重
量部、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチルシ
ロキシ基封鎖メチルハイドロジェンポリシロキサン６．
８重量部および１−エチニル−１−シクロヘキサノール
０．４重量部を均一に混合して溶解させた。次いでこの
混合物に、塩化白金酸とメチルビニルシロキサンとの錯
塩を白金金属量が２００ppmとなるような量添加配合し
て、付加反応硬化性オルガノポリシロキサン組成物を調
製した。得られた付加反応硬化性オルガノポリシロキサ
ン組成物の物理強度および切断試験の結果を表１に示し
た。また、得られた付加反応硬化性オルガノポリシロキ
サン組成物を、ポリエチレンラミネ−ト上質紙の表面に
約１．０g/m2になるような量塗布し、次いでこれを１３
０℃で２０秒加熱処理して硬化皮膜を形成させた。この
硬化皮膜の剥離抵抗値、シリコ−ン移行性および粘着性
物質の残留接着率（％）を測定した。その結果を表２に
示した。Example 1 5 parts by weight of a dimethylvinylsiloxy group-capped dimethylpolysiloxane having both ends of a molecular chain and a viscosity of 60 mPa · s, 30 parts by weight of dimethylpolysiloxane blocked with a dimethylvinylsiloxy group having both ends of a molecular chain having a viscosity of 370 mPa · s,
65 chain parts of a dimethylvinylsiloxy group-capped dimethylsiloxane / methylhexenylsiloxane copolymer (dimethylsiloxane unit 98 mol%, methylhexenylsiloxane unit 2 mol%) with a viscosity of 200 mPa · s and a molecular chain with a viscosity of 20 mPa · s 5. Both ends trimethylsiloxy group blocked methyl hydrogen polysiloxane 6.
8 parts by weight and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed and dissolved. Next, an addition reaction-curable organopolysiloxane composition was prepared by adding to this mixture a complex salt of chloroplatinic acid and methylvinylsiloxane in an amount such that the amount of platinum metal was 200 ppm. The physical strength of the obtained addition reaction-curable organopolysiloxane composition and the result of the cutting test are shown in Table 1. The obtained addition-reaction-curable organopolysiloxane composition was applied to the surface of polyethylene laminated high-quality paper in an amount of about 1.0 g / m 2 , and then 13
A heat treatment was performed at 0 ° C. for 20 seconds to form a cured film. The peel resistance of this cured film, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured. The results are shown in Table 2.
【００１９】[0019]
【実施例２】粘度６０ｍＰａ・ｓの分子鎖両末端ジメチ
ルビニルシロキシ基封鎖ジメチルポリシロキサン１６重
量部、粘度３７０ｍＰａ・ｓの分子鎖両末端ジメチルビ
ニルシロキシ基封鎖ジメチルポリシロキサン５０重量
部、粘度２００ｍＰａ・ｓの分子鎖両末端ジメチルビニ
ルシロキシ基封鎖ジメチルシロキサン・メチルヘキセニ
ルシロキサン共重合体（ジメチルシロキサン単位９８モ
ル％，メチルヘキセニルシロキサン単位２モル％）３４
重量部、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチル
シロキシ基封鎖メチルハイドロジェンポリシロキサン６
重量部および１−エチニル−１−シクロヘキサノール
０．４重量部を均一に溶解させた。次いでこの混合物
に、塩化白金酸とメチルビニルシロキサンとの錯塩を白
金金属量が２００ppmとなるような量添加配合して、付
加反応硬化性オルガノポリシロキサン組成物を調製し
た。得られた付加反応硬化性オルガノポリシロキサン組
成物の物理強度および切断試験の結果を表１に示した。
また、得られた付加反応硬化性オルガノポリシロキサン
組成物を、ポリエチレンラミネ−ト上質紙の表面に約
１．０g/m2になるような量塗布し、次いでこれを１３０
℃で２０秒加熱処理して硬化皮膜を形成させた。この硬
化皮膜の剥離抵抗値、シリコ−ン移行性および粘着性物
質の残留接着率（％）を測定した。その結果を表２に示
した。[Example 2] 16 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 60 mPa · s, 50 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of a molecular chain having a viscosity of 370 mPa · s, viscosity of 200 mPa · s A dimethylvinylsiloxy group-capped dimethylsiloxane / methylhexenylsiloxane copolymer (both ends of dimethylsiloxane unit: 98 mol%, methylhexenylsiloxane unit: 2 mol%) 34
By weight, viscosity of 20 mPa · s molecular chain both ends trimethylsiloxy group blocked methyl hydrogen polysiloxane 6
Parts by weight and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly dissolved. Next, an addition reaction-curable organopolysiloxane composition was prepared by adding to this mixture a complex salt of chloroplatinic acid and methylvinylsiloxane in an amount such that the amount of platinum metal was 200 ppm. The physical strength of the obtained addition reaction-curable organopolysiloxane composition and the result of the cutting test are shown in Table 1.
Further, the obtained addition reaction-curable organopolysiloxane composition was applied on the surface of a polyethylene laminated high-quality paper in an amount of about 1.0 g / m 2, and this was applied to
A heat treatment was performed at 20 ° C. for 20 seconds to form a cured film. The peel resistance of this cured film, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured. The results are shown in Table 2.
【００２０】[0020]
【比較例１】粘度２００ｍＰａ・ｓの分子鎖両末端ジメ
チルビニルシロキシ基封鎖ジメチルシロキサン・メチル
ヘキセニルシロキサン共重合体（ジメチルシロキサン単
位９８モル％，メチルヘキセニルシロキサン単位２モル
％）、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチルシ
ロキシ基封鎖メチルハイドロジェンポリシロキサン６．
８重量部および１−エチニル−１−シクロヘキサノール
０．４重量部を均一に混合して溶解させた。次いでこの
混合物に、塩化白金酸とメチルビニルシロキサンとの錯
塩を白金金属量が２００ppmとなるような量添加配合し
て、付加反応硬化性オルガノポリシロキサン組成物を調
製した。得られた付加反応硬化性オルガノポリシロキサ
ン組成物の物理強度および切断試験の結果を表１に示し
た。また、得られた付加反応硬化性オルガノポリシロキ
サン組成物を、ポリエチレンラミネ−ト上質紙の表面に
約１．０g/m2になるような量塗布し、次いでこれを１３
０℃で２０秒加熱処理して硬化皮膜を形成させた。この
硬化皮膜の剥離抵抗値、シリコ−ン移行性および粘着性
物質の残留接着率（％）を測定した。その結果を表２に
示した。[Comparative Example 1] A dimethylvinylsiloxy group-capped dimethylsiloxane / methylhexenylsiloxane copolymer (viscosity: 200 mPa · s, both ends of a molecular chain) (dimethylsiloxane unit: 98 mol%, methylhexenylsiloxane unit: 2 mol%), viscosity: 20 mPa · s Methyl hydrogen polysiloxane with trimethylsiloxy groups blocked at both ends of the molecular chain 6.
8 parts by weight and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed and dissolved. Next, an addition reaction-curable organopolysiloxane composition was prepared by adding to this mixture a complex salt of chloroplatinic acid and methylvinylsiloxane in an amount such that the amount of platinum metal was 200 ppm. The physical strength of the obtained addition reaction-curable organopolysiloxane composition and the result of the cutting test are shown in Table 1. The obtained addition-reaction-curable organopolysiloxane composition was applied to the surface of polyethylene laminated high-quality paper in an amount of about 1.0 g / m 2 , and then 13
A heat treatment was performed at 0 ° C. for 20 seconds to form a cured film. The peel resistance of this cured film, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured. The results are shown in Table 2.
【００２１】[0021]
【比較例２】粘度６０ｍＰａ・ｓの分子鎖両末端ジメチ
ルビニルシロキシ基封鎖ジメチルポリシロキサン３８重
量部、粘度６００ｍＰａ・ｓの分子鎖両末端ジメチルビ
ニルシロキシ基封鎖ジメチルシロキサン・メチルヘキセ
ニルシロキサン共重合体（ジメチルシロキサン単位９８
モル％，メチルヘキセニルシロキサン単位２モル％）６
２重量部、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチ
ルシロキシ基封鎖メチルハイドロジェンポリシロキサン
６．８重量部および１−エチニル−１−シクロヘキサノ
ール０．４重量部を均一に混合して溶解させた。次いで
この混合物に、塩化白金酸とメチルビニルシロキサンと
の錯塩を白金金属量が２００ppmとなるような量添加配
合して、付加反応硬化性オルガノポリシロキサン組成物
を調製した。得られた付加反応硬化性オルガノポリシロ
キサン組成物の物理強度および切断試験の結果を表１に
示した。また、得られた付加反応硬化性オルガノポリシ
ロキサン組成物を、ポリエチレンラミネ−ト上質紙の表
面に約１．０g/m2になるような量塗布し、次いでこれを
１３０℃で２０秒加熱処理して硬化皮膜を形成させた。
この硬化皮膜の剥離抵抗値、シリコ−ン移行性および粘
着性物質の残留接着率（％）を測定した。その結果を表
２に示した。[Comparative Example 2] 38 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain having a viscosity of 60 mPa · s, dimethylsiloxane / methylhexenylsiloxane copolymer with dimethylvinylsiloxy groups blocked at both ends of the molecular chain having a viscosity of 600 mPa · s ( Dimethyl siloxane unit 98
Mol%, methylhexenyl siloxane unit 2 mol%) 6
2 parts by weight, 6.8 parts by weight of methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain and having a viscosity of 20 mPa · s and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed and dissolved. . Next, an addition reaction-curable organopolysiloxane composition was prepared by adding to this mixture a complex salt of chloroplatinic acid and methylvinylsiloxane in an amount such that the amount of platinum metal was 200 ppm. The physical strength of the obtained addition reaction-curable organopolysiloxane composition and the result of the cutting test are shown in Table 1. The obtained addition reaction-curable organopolysiloxane composition was applied on the surface of polyethylene laminate fine paper in an amount of about 1.0 g / m 2 and then heat-treated at 130 ° C. for 20 seconds. To form a cured film.
The peel resistance of this cured film, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured. The results are shown in Table 2.
【００２２】[0022]
【比較例３】粘度３７０ｍＰａ・ｓの分子鎖両末端ジメ
チルビニルシロキシ基封鎖ジメチルポリシロキサン１０
０重量部、粘度２０ｍＰａ・ｓの分子鎖両末端トリメチ
ルシロキシ基封鎖メチルハイドロジェンポリシロキサン
６．８重量部および１−エチニル−１−シクロヘキサノ
ール０．４重量部を均一に混合して溶解させた。次いで
この混合物に、塩化白金酸とメチルビニルシロキサンと
の錯塩を白金金属量が２００ppmとなるような量添加配
合して、付加反応硬化性オルガノポリシロキサン組成物
を調製した。得られた付加反応硬化性オルガノポリシロ
キサン組成物の物理強度および切断試験の結果を表１に
示した。また、得られた付加反応硬化性オルガノポリシ
ロキサン組成物を、ポリエチレンラミネ−ト上質紙の表
面に約１．０g/m2になるような量塗布し、次いでこれを
１３０℃で２０秒加熱処理して硬化皮膜を形成させた。
この硬化皮膜の剥離抵抗値、シリコ−ン移行性および粘
着性物質の残留接着率（％）を測定した。その結果を表
２に示した。[Comparative Example 3] Dimethylpolysiloxane 10 with a viscosity of 370 mPa · s and both ends of the molecular chain blocked with dimethylvinylsiloxy groups 10
0 parts by weight, 6.8 parts by weight of methyl hydrogen polysiloxane blocked with trimethylsiloxy groups at both ends of the molecular chain and having a viscosity of 20 mPa · s and 0.4 parts by weight of 1-ethynyl-1-cyclohexanol were uniformly mixed and dissolved. . Next, an addition reaction-curable organopolysiloxane composition was prepared by adding to this mixture a complex salt of chloroplatinic acid and methylvinylsiloxane in an amount such that the amount of platinum metal was 200 ppm. The physical strength of the obtained addition reaction-curable organopolysiloxane composition and the result of the cutting test are shown in Table 1. The obtained addition reaction-curable organopolysiloxane composition was applied on the surface of polyethylene laminate fine paper in an amount of about 1.0 g / m 2 and then heat-treated at 130 ° C. for 20 seconds. To form a cured film.
The peel resistance of this cured film, the silicone transferability, and the residual adhesion rate (%) of the adhesive substance were measured. The results are shown in Table 2.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】本発明の無溶剤型付加反応硬化性オルガ
ノポリシロキサン組成物は、硬化後の皮膜が特定の硬度
と引裂強度と伸びを有するので、強い摩擦がかかった場
合にも皮膜表面が破壊しにくく、かつ、粘着性物質を高
速度で剥離した場合の剥離抵抗値が小さいという特徴を
有する。EFFECTS OF THE INVENTION The solventless addition reaction curable organopolysiloxane composition of the present invention has a specific hardness, tear strength and elongation in the cured film, so that the surface of the film is protected even when strong friction is applied. It is characterized in that it is hard to break and has a small peel resistance value when the adhesive substance is peeled at a high speed.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J002 CP04Y CP12W CP12X CP13W CP13X DA076 GH00 GK00 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4J002 CP04Y CP12W CP12X CP13W CP13X DA076 GH00 GK00
Claims (7)
が３５以上であり、 JIS K 6252に規定された切り込み無しアングル形試験
片の引裂強度が１．５Ｎ／ｍｍ以上であり、 JIS K 6251に規定された3号ダンベル試験片の切断時
伸びが１００％以上であることを特徴とする、無溶剤型
付加反応硬化性オルガノポリシロキサン組成物。1. The cured film has a hardness of 35 or more as measured by a JIS type A hardness meter specified in JIS K 6253, and a tear strength of an uncut angle type test piece specified in JIS K 6252 as 1. A solventless addition reaction-curable organopolysiloxane composition characterized by having an elongation at break of a No. 3 dumbbell test piece defined by JIS K 6251 of not less than 5 N / mm and not less than 100%.
ロキサン組成物が、２種類のアルケニル官能性ジオルガ
ノポリシロキサンを主剤とするものであり、その内の一
方が、（ａ）２５℃における粘度が３０〜３００ｍＰａ
・ｓの低粘度物と（ｂ）２５℃における粘度が３００〜
５０００ｍＰａ・ｓの高粘度物の混合物であり、該混合
物中、（ａ）低粘度物と（ｂ）高粘度物の２５℃におけ
る粘度差が３０ｍPa・ｓ以上であり、（ａ）低粘度物の
比率が３０重量％以下であることを特徴とする、請求項
１に記載の無溶剤型付加反応硬化性オルガノポリシロキ
サン組成物。2. A solventless addition reaction-curable organopolysiloxane composition containing two types of alkenyl-functional diorganopolysiloxane as a main component, one of which (a) has a viscosity at 25 ° C. Is 30 to 300 mPa
・ Low viscosity product of s and (b) the viscosity at 25 ° C is 300 ~
A mixture of high-viscosity substances of 5000 mPa · s, in which the viscosity difference between (a) low-viscosity substances and (b) high-viscosity substances at 25 ° C. is 30 mPa · s or more, and (a) low-viscosity substances The solventless addition reaction-curable organopolysiloxane composition according to claim 1, wherein the ratio is 30% by weight or less.
℃における粘度差が５０〜４７００ｍＰａ・ｓである、
請求項２に記載の無溶剤型付加反応硬化性オルガノポリ
シロキサン組成物。3. A low viscosity product (a) and a high viscosity product (b) 25
The viscosity difference at 0 ° C is 50 to 4700 mPa · s,
The solventless addition reaction-curable organopolysiloxane composition according to claim 2.
リシロキサンが、（Ａ）分子鎖末端にのみアルケニル基
を有するジオルガノポリシロキサンと、（Ｂ）分子鎖末
端と側鎖にアルケニル基を有するジオルガノポリシロキ
サンであり、かつ、（Ａ）成分が（ａ）低粘度物と
（ｂ）高粘度物の混合物であることを特徴とする、請求
項２または請求項３に記載の無溶剤型付加反応硬化性オ
ルガノポリシロキサン組成物。4. Two types of alkenyl-functional diorganopolysiloxanes, (A) a diorganopolysiloxane having an alkenyl group only at the molecular chain terminal and (B) a diorganopolysiloxane having an alkenyl group at the molecular chain terminal and side chain. The solventless addition according to claim 2 or 3, which is an organopolysiloxane and in which the component (A) is a mixture of (a) a low viscosity substance and (b) a high viscosity substance. Reaction curable organopolysiloxane composition.
有するジオルガノポリシロキサンの（ａ）低粘度物と
（ｂ）高粘度物の混合物、（Ｂ）分子鎖末端と側鎖にア
ルケニル基を有するジオルガノポリシロキサン、
［（Ａ）成分：（Ｂ）成分＝７０〜２０：３０〜８０重
量％である。］ （Ｃ）ケイ素原子結合水素原子含有オルガノハイドロジ
ェンポリシロキサン（Ａ）成分と（Ｂ）成分の合計１０
０重量部に対して３〜５０重量部、（Ｄ）付加反応促進
触媒 触媒
量からなり、２５℃における粘度が３０〜５０００ｍＰ
ａ・ｓであることを特徴とする、請求項４に記載の無溶
剤型付加反応硬化性オルガノポリシロキサン組成物。5. A mixture of (A) a low-viscosity product (a) of diorganopolysiloxane having an alkenyl group only at the molecular chain end and (b) a high viscosity product, and (B) an alkenyl group at the molecular chain end and side chain. A diorganopolysiloxane having
[Component (A): Component (B) = 70 to 20:30 to 80% by weight. ] (C) Silicon hydrogen atom-containing hydrogen atom-containing organohydrogenpolysiloxane (A) component and (B) component total 10
3 to 50 parts by weight relative to 0 parts by weight, (D) addition reaction accelerating catalyst consisting of a catalytic amount, and a viscosity at 25 ° C. of 30 to 5000 mP
The solventless addition reaction-curable organopolysiloxane composition according to claim 4, wherein the composition is a · s.
するジオルガノポリシロキサンであり、（Ｂ）成分が分
子鎖末端にビニル基を有し、側鎖にヘキセニル基を有す
るジオルガノポリシロキサンである、請求項４または請
求項５に記載の無溶剤型付加反応硬化性オルガノポリシ
ロキサン組成物。6. A diorganopolysiloxane in which the component (A) is a diorganopolysiloxane having a vinyl group at the terminal of the molecular chain, and the component (B) has a vinyl group at the terminal of the molecular chain and a hexenyl group at the side chain. The solventless addition reaction-curable organopolysiloxane composition according to claim 4 or 5, which is a siloxane.
６のいずれか１項に記載の無溶剤型付加反応硬化性オル
ガノポリシロキサン組成物。7. The method according to claim 1, which is for forming a peelable cured film.
7. The solventless addition reaction curable organopolysiloxane composition according to any one of 6 above.
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|---|---|---|---|
| JP2001399739A JP4169976B2 (en) | 2001-12-28 | 2001-12-28 | Solvent-free addition reaction curable organopolysiloxane composition |
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|---|---|---|---|
| JP2001399739A JP4169976B2 (en) | 2001-12-28 | 2001-12-28 | Solvent-free addition reaction curable organopolysiloxane composition |
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| Publication Number | Publication Date |
|---|---|
| JP2003192899A true JP2003192899A (en) | 2003-07-09 |
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ID=27604639
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060554A (en) * | 2003-08-14 | 2005-03-10 | Shin Etsu Chem Co Ltd | Release agent composition for silicone adhesive and release sheet using the same |
| JP2006052302A (en) * | 2004-08-11 | 2006-02-23 | Shin Etsu Chem Co Ltd | Electroconductive silicone rubber composition and method for producing the same |
| JP2006152265A (en) * | 2004-10-29 | 2006-06-15 | Shin Etsu Chem Co Ltd | Hardening silicone release agent composition and release paper using it |
| JP2011026582A (en) * | 2009-07-01 | 2011-02-10 | Dow Corning Toray Co Ltd | Curable organopolysiloxane composition, sheet-like article equipped with cured layer consisting of the composition and method for producing the same |
| WO2019111712A1 (en) * | 2017-12-05 | 2019-06-13 | 信越化学工業株式会社 | Curable silicone release agent composition |
-
2001
- 2001-12-28 JP JP2001399739A patent/JP4169976B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005060554A (en) * | 2003-08-14 | 2005-03-10 | Shin Etsu Chem Co Ltd | Release agent composition for silicone adhesive and release sheet using the same |
| JP4524549B2 (en) * | 2003-08-14 | 2010-08-18 | 信越化学工業株式会社 | Release agent composition for silicone adhesive and release sheet using the same |
| JP2006052302A (en) * | 2004-08-11 | 2006-02-23 | Shin Etsu Chem Co Ltd | Electroconductive silicone rubber composition and method for producing the same |
| JP4636233B2 (en) * | 2004-08-11 | 2011-02-23 | 信越化学工業株式会社 | Conductive silicone rubber composition and method for producing the same |
| JP2006152265A (en) * | 2004-10-29 | 2006-06-15 | Shin Etsu Chem Co Ltd | Hardening silicone release agent composition and release paper using it |
| JP2011026582A (en) * | 2009-07-01 | 2011-02-10 | Dow Corning Toray Co Ltd | Curable organopolysiloxane composition, sheet-like article equipped with cured layer consisting of the composition and method for producing the same |
| WO2019111712A1 (en) * | 2017-12-05 | 2019-06-13 | 信越化学工業株式会社 | Curable silicone release agent composition |
| JP2019099715A (en) * | 2017-12-05 | 2019-06-24 | 信越化学工業株式会社 | Curable silicone release agent composition |
| US11459459B2 (en) | 2017-12-05 | 2022-10-04 | Shin-Etsu Chemical Co., Ltd. | Curable silicone release composition |
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|---|---|
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