【０００１】[0001]
【産業上の利用分野】本発明は、非ハロゲン系溶剤で希
釈可能で表面エネルギーの小さいシリコーン硬化皮膜を
形成し得る剥離剤用シリコーン組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone composition for a release agent which can be diluted with a non-halogen solvent to form a cured silicone film having a small surface energy.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
紙やプラスチックフィルムなどの基材と感圧性粘着物質
との間の接着又は固着を防止することを目的として、基
材面にシリコーン組成物の硬化皮膜を形成させて剥離性
を付与することが行われており、このものは一般に剥離
紙と称されている。2. Description of the Related Art Conventionally, the problems to be solved by the invention
For the purpose of preventing adhesion or sticking between a base material such as paper or plastic film and a pressure-sensitive adhesive substance, a cured film of a silicone composition may be formed on the surface of the base material to impart releasability. This is commonly referred to as release paper.
【０００３】上記感圧性粘着物質のうち、オルガノポリ
シロキサンを主成分としたシリコーン系粘着剤は、耐熱
性、耐寒性、耐薬品性、電気絶縁性、低毒性などに優れ
ているため、広範囲の用途に用いられている。シリコー
ン系粘着剤は粘着力が非常に強いため、これを塗布した
粘着テープや粘着ラベルが上記基材から容易に剥離する
ようにするためには、上記基材上に形成するシリコーン
硬化皮膜を離型性に優れたものとすることが必要であ
る。Among the above pressure-sensitive adhesive materials, silicone-based adhesives containing organopolysiloxane as a main component are excellent in heat resistance, cold resistance, chemical resistance, electrical insulation, low toxicity, etc. It is used for purposes. Since the silicone-based pressure-sensitive adhesive has a very strong adhesive force, in order to easily peel the pressure-sensitive adhesive tape or pressure-sensitive adhesive label coated with it from the above-mentioned base material, release the silicone cured film formed on the above-mentioned base material. It is necessary to have good moldability.
【０００４】離型性に優れたシリコーン硬化皮膜を与え
るシリコーン組成物としては、式ＣnＦ2n+1ＣＨ2ＣＨ2
−（ｎは１以上の整数）で表される含フッ素置換基を持
つオルガノポリシロキサン組成物（特公平５−７４３４
号公報）、式Ｆ〔ＣＦ（ＣＦ3）ＣＦ2Ｏ〕nＣＦ（Ｃ
Ｆ3）ＣＦ2ＯＣＨ2ＣＨ2ＣＨ2−（ｎは１〜５の整数）
で表される含フッ素置換基を持つオルガノポリシロキサ
ン組成物（特公平４−７６３９１号公報）などが提案さ
れている。A silicone composition which gives a cured silicone coating having excellent releasability is represented by the formula Cn F2n + 1 CH2 CH2
An organopolysiloxane composition having a fluorine-containing substituent represented by-(n is an integer of 1 or more) (Japanese Patent Publication No. 5-7434)
Gazette), the formula F [CF (CF3 ) CF2 O]n CF (C
F3 ) CF2 OCH2 CH2 CH2 — (n is an integer of 1 to 5)
An organopolysiloxane composition having a fluorine-containing substituent represented by (Japanese Patent Publication No. 4-76391) is proposed.
【０００５】これらのオルガノポリシロキサン組成物を
基材に塗布する際にはこれを溶剤で希釈したものを用い
るが、この場合、溶剤としては含フッ素オルガノポリシ
ロキサン組成物の溶解性の点からフッ素系溶剤が好適に
用いられる。When these organopolysiloxane compositions are applied to a substrate, those diluted with a solvent are used. In this case, the solvent is fluorine from the viewpoint of solubility of the fluorine-containing organopolysiloxane composition. A system solvent is preferably used.
【０００６】しかしながら、フッ素系溶剤は、含フッ素
オルガノポリシロキサンを十分に希釈し得るものの、高
価なものであり、また、大気中に拡散した場合、自然環
境に悪影響を及ぼすという問題がある。However, although the fluorine-based solvent can sufficiently dilute the fluorine-containing organopolysiloxane, it is expensive, and if it diffuses into the atmosphere, it has a problem of adversely affecting the natural environment.
【０００７】本発明は上記事情に鑑みなされたもので、
非フッ素系溶剤で希釈することができ、しかも剥離力が
小さく、かつ残留接着率の低下が小さい硬化皮膜を与え
る剥離剤用シリコーン組成物を提供することを目的とす
る。The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a silicone composition for a release agent, which can be diluted with a non-fluorine-based solvent, has a small peeling force, and provides a cured film with a small decrease in residual adhesion rate.
【０００８】[0008]
【課題を解決するための手段及び作用】本発明者は上記
目的を達成するため鋭意検討を行った結果、（Ａ）１分
中にケイ素原子に結合したアルケニル基を少なくとも２
個及びケイ素原子に結合した含フッ素置換基を少なくと
も１個有し、フッ素含有量が２０〜４０重量％であるオ
ルガノポリシロキサン、（Ｂ）１分子中にケイ素原子に
結合した水素原子を少なくとも３個有するオルガノハイ
ドロジェンポリシロキサン、（Ｃ）白金族金属系触媒を
配合することにより、剥離力が小さく、残留接着率の低
下が小さい離型性に優れたシリコーン硬化皮膜を与える
剥離剤用シリコーン組成物を得ることができ、また、こ
の組成物は非フッ素系溶剤に希釈可能であるため、安価
に、かつ大気汚染のおそれもなく剥離性シリコーン硬化
皮膜を作製することができ、更に、この硬化皮膜は撥水
性、撥油性、耐熱性に優れることを知見し、本発明をな
すに至った。Means and Actions for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has found that (A) at least 2 alkenyl groups bonded to a silicon atom in 1 minute.
And at least one fluorine-containing substituent bonded to a silicon atom, and a fluorine content of 20 to 40% by weight, (B) at least 3 hydrogen atoms bonded to a silicon atom in one molecule. A silicone composition for a release agent, which gives a silicone cured coating excellent in releasability with a small peeling force and a small decrease in residual adhesion rate by blending an organohydrogenpolysiloxane having two or more and a platinum group metal catalyst (C) Moreover, since this composition can be diluted with a non-fluorine-based solvent, a peelable silicone cured film can be prepared at low cost and without fear of air pollution. The inventors have found that the film has excellent water repellency, oil repellency, and heat resistance, and completed the present invention.
【０００９】従って、本発明は、（Ａ）１分中にケイ素
原子に結合したアルケニル基を少なくとも２個及びケイ
素原子に結合した含フッ素置換基を少なくとも１個有
し、フッ素含有量が２０〜４０重量％であるオルガノポ
リシロキサン、（Ｂ）１分子中にケイ素原子に結合した
水素原子を少なくとも３個有するオルガノハイドロジェ
ンポリシロキサン、（Ｃ）白金族金属系触媒を含有する
ことを特徴とする剥離剤用シリコーン組成物を提供す
る。Accordingly, the present invention has (A) at least 2 alkenyl groups bonded to a silicon atom and at least one fluorine-containing substituent bonded to a silicon atom per 1 minute, and a fluorine content of 20 to 20. 40% by weight of an organopolysiloxane, (B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule, and (C) a platinum group metal-based catalyst. Provided is a silicone composition for a release agent.
【００１０】以下、本発明を更に詳しく説明すると、
（Ａ）成分のオルガノポリシロキサンは、１分中にケイ
素原子に結合したアルケニル基を少なくとも２個及びケ
イ素原子に結合した含フッ素置換基を少なくとも１個有
し、フッ素含有量が２０〜４０重量％のものである。The present invention will be described in more detail below.
The organopolysiloxane of component (A) has at least two alkenyl groups bonded to silicon atoms and at least one fluorine-containing substituent bonded to silicon atoms per minute, and has a fluorine content of 20 to 40% by weight. %belongs to.
【００１１】オルガノポリシロキサンとしてフッ素の含
有率が４０重量％を越えるものでは非フッ素系溶剤に不
溶のものとなり、２０重量％未満のものでは得られる硬
化皮膜のシリコーン粘着剤に対する離型性が悪くなって
しまう。When the content of fluorine as the organopolysiloxane exceeds 40% by weight, it becomes insoluble in a non-fluorine-containing solvent, and when it is less than 20% by weight, the releasability of the obtained cured film from the silicone adhesive is poor. turn into.
【００１２】（Ａ）成分のオルガノポリシロキサンとし
ては下記式で表されるものが好適に用いられる。As the organopolysiloxane as the component (A), those represented by the following formula are preferably used.
【００１３】[0013]
【化２】[Chemical 2]
【００１４】ここで、Ｒ1は炭素数２〜１０のアルケニ
ル基であり、具体的にはビニル基、アリル基、ヘキセニ
ル基などが挙げられる。Here, R1 is an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group and a hexenyl group.
【００１５】Ｒ2は非置換又は置換の炭素数１〜１０の
脂肪族不飽和基を除く１価炭化水素基であり、具体的に
はメチル基，エチル基，プロピル基，ブチル基等のアル
キル基、シクロヘキシル基等のシクロアルキル基、フェ
ニル基，トリル基等のアリール基及びこれらの基の水素
原子の一部又は全部をヒドロキシ基、シアノ基等で置換
したヒドロキシプロピル基、シアノエチル基などが挙げ
られる。ａは１，２又は３、ｘ、ｙ、ｚはそれぞれｘ≧
０、ｙ≧１、ｚ≧０の整数である。R2Is an unsubstituted or substituted C1-C10
A monovalent hydrocarbon group excluding aliphatic unsaturated groups, specifically
Is an alkyl group such as methyl group, ethyl group, propyl group, butyl group, etc.
A cycloalkyl group such as a kill group or a cyclohexyl group,
Aryl groups such as nyl group and tolyl group, and hydrogen of these groups
Substitution of some or all of the atoms with hydroxy groups, cyano groups, etc.
Examples include hydroxypropyl group and cyanoethyl group
To be a is 1, 2, or 3, x, y, and z are each x ≧
It is an integer of 0, y ≧ 1, and z ≧ 0.
【００１６】Ｒｆは下記式（１）〜（６）で表される含
フッ素置換基から選ばれる少なくとも１個の基である。Rf is at least one group selected from the fluorine-containing substituents represented by the following formulas (1) to (6).
【００１７】[0017]
【化３】（式中、ｎは１〜５の整数、ｍは３〜１０の整数であ
る。）[Chemical 3] (In the formula, n is an integer of 1 to 5 and m is an integer of 3 to 10.)
【００１８】（Ａ）成分のオルガノポリシロキサンは直
鎖状、分岐状のいずれでもよい。具体的には下記式で表
されるものが例示される。The organopolysiloxane as the component (A) may be linear or branched. Specifically, the one represented by the following formula is exemplified.
【００１９】[0019]
【化４】（式中、Ｒｆは上記と同様の意味を示し、Ｍｅはメチル
基、Ｐｈはフェニル基を表す。ｘ、ｙ、ｚ、ｗはそれぞ
れｘ≧０、ｙ≧１、ｚ≧０、ｗ≧１の整数である。）[Chemical 4] (In the formula, Rf has the same meaning as described above, Me represents a methyl group, and Ph represents a phenyl group. X, y, z, and w are x ≧ 0, y ≧ 1, z ≧ 0, and w ≧ 1 respectively. Is an integer.)
【００２０】（Ｂ）成分のオルガノハイドロジェンポリ
シロキサンは１分子中にケイ素原子に結合した水素原子
を少なくとも３個有するものであり、このＳｉＨ基と
（Ａ）成分中のアルケニル基とが付加反応して硬化皮膜
が形成されるものである。The organohydrogenpolysiloxane of component (B) has at least three hydrogen atoms bonded to silicon atoms in one molecule, and this SiH group and the alkenyl group of component (A) undergo an addition reaction. Then, a cured film is formed.
【００２１】このオルガノハイドロジェンポリシロキサ
ンは、（Ａ）成分のオルガノポリシロキサンとの相溶性
の点からフッ素含有率が４０重量％以下であることが好
ましい。また、このオルガノポリシロキサンは直鎖状、
分岐状、環状のいずれであってもよい。The organohydrogenpolysiloxane preferably has a fluorine content of 40% by weight or less from the viewpoint of compatibility with the organopolysiloxane as the component (A). In addition, this organopolysiloxane is linear,
It may be branched or annular.
【００２２】（Ｂ）成分のオルガノハイドロジェンポリ
シロキサンとしては例えば下記式で表されるものが挙げ
られる。Examples of the organohydrogenpolysiloxane as the component (B) include those represented by the following formula.
【００２３】[0023]
【化５】[Chemical 5]
【００２４】式中、Ｒ3は上記Ｒ2、Ｒｆと同様の基及び
Ｒ4−ＣＨ2ＣＨ2−（Ｒ4は炭素数１〜８のパーフルオロ
アルキル基）から選ばれる少なくとも１種の基、ｂは０
又は１、ｐ及びｑはそれぞれｐ≧１，ｑ≧０の整数であ
る。ただし、ｐはケイ素原子に結合した水素原子数が３
以上となる数である。Where R3Is R above2, A group similar to Rf and
RFour-CH2CH2-(RFourIs a perfluoro having 1 to 8 carbon atoms
At least one group selected from alkyl groups) and b is 0
Alternatively, 1, p and q are integers of p ≧ 1 and q ≧ 0, respectively.
It However, p has 3 hydrogen atoms bonded to the silicon atom.
It is the number above.
【００２５】（Ｂ）成分のオルガノハイドロジェンポリ
シロキサンとして具体的には下記式で表されるものが例
示される。Specific examples of the organohydrogenpolysiloxane as the component (B) include those represented by the following formula.
【００２６】[0026]
【化６】（式中、Ｍｅ，ｐ，ｑは上記と同様の意味を示し、ｒ≧
１の整数である。）[Chemical 6] (In the formula, Me, p, and q have the same meanings as described above, and r ≧
It is an integer of 1. )
【００２７】（Ｂ）成分のオルガノポリシロキサンの配
合量は（Ａ）成分１００部（重量部、以下同じ）に対し
て０．１〜２０部、特に０．２〜１０部とすることが好
ましい。配合量が０．１部未満及び２０部を越える場合
はいずれも目的とするシリコーン組成物の硬化性が低下
したり、硬化物の物性が低下したりする場合がある。The blending amount of the organopolysiloxane as the component (B) is preferably 0.1 to 20 parts, particularly 0.2 to 10 parts, relative to 100 parts (part by weight, the same hereinafter) of the component (A). . When the blending amount is less than 0.1 part or more than 20 parts, the curability of the desired silicone composition may be lowered, or the physical properties of the cured product may be lowered.
【００２８】（Ｃ）成分の白金族金属系触媒は、（Ａ）
成分と（Ｂ）成分との付加反応を促進させるための触媒
であり、反応触媒として公知のものが使用できる。この
ような白金族金属系触媒としては、例えば白金系、パラ
ジウム系、ロジウム系などの触媒が挙げられ、これらの
中で特に白金系触媒が好ましい。このような白金系触媒
としては、例えば塩化白金酸、塩化白金酸のアルコール
溶液、塩化白金酸と各種オレフィン又はビニルシロキサ
ンとの錯体などが挙げられる。The platinum group metal-based catalyst of component (C) is (A)
It is a catalyst for promoting the addition reaction between the component and the component (B), and a known reaction catalyst can be used. Examples of such platinum group metal-based catalysts include platinum-based, palladium-based, and rhodium-based catalysts, and of these, platinum-based catalysts are particularly preferable. Examples of such platinum-based catalysts include chloroplatinic acid, alcoholic solutions of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinyl siloxanes.
【００２９】これら白金族金属系触媒の添加量は触媒量
とすればよいが、硬化皮膜を得る際の反応性と経済性の
見地から、（Ａ）成分に対して白金族金属量として１〜
１０００ｐｐｍの範囲とすることが好ましい。The amount of the platinum group metal-based catalyst added may be a catalytic amount, but from the viewpoint of reactivity and economical efficiency in obtaining a cured film, the amount of platinum group metal is 1 to 1 component (A).
It is preferably in the range of 1000 ppm.
【００３０】本発明の組成物は、上記（Ａ）〜（Ｃ）成
分の所定量を配合することによって得られるが、以上の
各成分の外に、他の任意成分、例えば白金族金属系触媒
の触媒活性を制御する目的で、各種有機窒素化合物、有
機リン化合物、有機ケイ素化合物、アセチレン化合物、
オキシム化合物などの活性制御剤を添加することがで
き、活性制御剤の中では３−メチル−１−ブチン−３−
オール等のアセチレン化合物及びそのシリル化物、ジビ
ニルテトラメチルジシロキサン、テトラビニルテトラメ
チルシクロテトラシロキサン等のケイ素化合物が好適に
用いられる。The composition of the present invention can be obtained by mixing predetermined amounts of the above-mentioned components (A) to (C). In addition to the above respective components, other optional components such as a platinum group metal-based catalyst are also included. For the purpose of controlling the catalytic activity of various organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds,
An activity control agent such as an oxime compound can be added. Among the activity control agents, 3-methyl-1-butyne-3-
Acetylene compounds such as oats and silyl compounds thereof, and silicon compounds such as divinyltetramethyldisiloxane and tetravinyltetramethylcyclotetrasiloxane are preferably used.
【００３１】活性制御剤配合量は（Ａ）成分１００部に
対して０．０５〜３部とすることが好ましい。０．０５
部未満では目的とするシリコーン組成物がゲル化する場
合があり、３部を越えるとシリコーン組成物の硬化が阻
害される場合がある。また、他の任意成分の添加量は、
本発明の効果を妨げない範囲で通常量とすることができ
る。The content of the activity control agent is preferably 0.05 to 3 parts with respect to 100 parts of the component (A). 0.05
If it is less than 3 parts, the desired silicone composition may gel, and if it exceeds 3 parts, the curing of the silicone composition may be hindered. In addition, the addition amount of other optional components,
A usual amount can be used within a range that does not impair the effects of the present invention.
【００３２】本発明のシリコーン組成物の調製に際して
は、（Ａ）、（Ｂ）成分及び任意成分を予め均一に混合
した後、（Ｃ）成分を添加することが好ましく、各成分
は単一で使用しても２種以上を併用してもよい。In the preparation of the silicone composition of the present invention, it is preferable that the components (A), (B) and optional components are uniformly mixed in advance and then the component (C) is added. You may use, or may use 2 or more types together.
【００３３】このようにして調製されたシリコーン組成
物を基材に塗布する場合、この組成物を均一に希釈して
塗布を容易にするために溶剤に溶解するが、本発明のシ
リコーン組成物は非ハロゲン系溶剤に溶解可能なもので
ある。非ハロゲン溶剤として、具体的にはヘキサン，ヘ
プタン，オクタン，イソオクタン，石油ベンジン，リグ
ロイン，工業ガソリン，ナフサソルベント等の脂肪族炭
化水素系溶剤、トルエン，キシレン等の芳香族炭化水素
系溶剤、ジエチルエーテル，ジイソプロピルエーテル，
ジブチルエーテル，ジオキサン等のエーテル系溶剤、ア
セトン，メチルエチルケトン，メチルイソブチルケト
ン，シクロヘキサノン等のケトン系溶剤、酢酸メチル，
酢酸エチル，酢酸イソプロピル，酢酸ブチル，プロピオ
ン酸メチル等のエステル系溶剤などが挙げられる。これ
らは単独で又は２種以上を混合して用いることができ
る。When the silicone composition thus prepared is applied to a substrate, the composition is uniformly diluted and dissolved in a solvent for facilitating the application. It is soluble in non-halogen solvents. Specific examples of the non-halogen solvent include hexane, heptane, octane, isooctane, petroleum benzine, ligroine, industrial gasoline, naphtha solvent, and other aliphatic hydrocarbon solvents, toluene, xylene, and other aromatic hydrocarbon solvents, and diethyl ether. , Diisopropyl ether,
Ether-based solvents such as dibutyl ether and dioxane, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methyl acetate,
Examples thereof include ester solvents such as ethyl acetate, isopropyl acetate, butyl acetate, and methyl propionate. These may be used alone or in combination of two or more.
【００３４】本発明のシリコーン組成物を剥離剤として
用いる場合、耐熱性の点からポリエステルフィルムに塗
布することが好ましく、この場合、ポリエステルフィル
ム基材への濡れ性の点から、非ハロゲン系溶剤としては
脂肪族炭化水素系溶剤を使用することが好ましい。When the silicone composition of the present invention is used as a release agent, it is preferably applied to a polyester film from the viewpoint of heat resistance. In this case, from the viewpoint of wettability to a polyester film substrate, it is used as a non-halogen solvent. It is preferable to use an aliphatic hydrocarbon solvent.
【００３５】非ハロゲン系溶剤の使用量は、これを用い
て溶解したシリコーン組成物を塗布する際の作業性、塗
布量の制御しやすさ点で希釈後のシリコーン組成物の粘
度が１００ｃｐ以下となる量を用いることが好ましく、
（Ａ）成分１００部に対して１００〜２０，０００部と
することが好ましい。The amount of the non-halogenated solvent used is such that the viscosity of the diluted silicone composition is 100 cp or less in terms of workability in applying the dissolved silicone composition and ease of control of the applied amount. It is preferable to use
It is preferably 100 to 20,000 parts with respect to 100 parts of the component (A).
【００３６】本発明のシリコーン組成物を基材に塗布
し、硬化させて基材表面に剥離性の硬化皮膜を形成した
ものは、剥離紙として使用することができる。この場
合、基材としては、ポリエステル，ポリプロピレン，ポ
リエチレン，ポリ塩化ビニル，ポリテトラフルオロエチ
レン，ポリイミド等の合成樹脂から得られるプラスチッ
クフィルムやシート、グラシン紙，クラフト紙，クレー
コート紙等の紙基材、ポリエチレンラミネート上質紙，
ポリエチレンラミネートクラフト紙等のラミネート紙基
材、アルミニウム箔などの金属箔などが挙げられる。The silicone composition of the present invention applied to a substrate and cured to form a releasable cured film on the surface of the substrate can be used as release paper. In this case, the base material is a plastic base material such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, or a synthetic resin such as polyimide, or a glass base material such as glassine paper, kraft paper, or clay coated paper. , Polyethylene laminated fine paper,
Examples thereof include laminated paper base materials such as polyethylene laminated kraft paper and metal foils such as aluminum foil.
【００３７】これらの基材にシリコーン組成物を塗布す
る方法としては、ロール塗布、グラビア塗布、ワイヤー
ドクター塗布、エアーナイフ塗布、ディッピング塗布な
どの公知の方法を用いることができる。As a method of applying the silicone composition to these substrates, known methods such as roll coating, gravure coating, wire doctor coating, air knife coating and dipping coating can be used.
【００３８】本発明のシリコーン組成物の硬化皮膜を基
材上に形成するには、シリコーン組成物を塗布した基材
を８０〜２５０℃の温度で２〜６０秒間加熱するか、上
記非ハロゲン系溶剤を揮発させた後、高圧水銀灯などの
紫外線照射装置から紫外線を０．２秒間以上照射するこ
とによってシリコーン組成物を硬化させ、基材表面に剥
離性のシリコーン硬化皮膜を形成することができる。In order to form a cured film of the silicone composition of the present invention on a substrate, the substrate coated with the silicone composition is heated at a temperature of 80 to 250 ° C. for 2 to 60 seconds, or the above-mentioned non-halogenated system is used. After the solvent has been volatilized, the silicone composition can be cured by irradiating it with ultraviolet rays for 0.2 seconds or longer from an ultraviolet irradiation device such as a high pressure mercury lamp to form a peelable silicone cured film on the surface of the substrate.
【００３９】本発明のシリコーン組成物は離型性に優れ
た硬化皮膜を与えるので、粘着テープ、粘着ラベル用は
剥離紙の用途に好適であり、また、ゴム、プラスチック
などを成型するための金型用離型性、紙、布などの繊維
処理剤、食品包装用などの撥水剤、撥油剤、耐熱コーテ
ィング用途に好適に使用できる。Since the silicone composition of the present invention gives a cured film having excellent releasability, it is suitable for use as release paper for adhesive tapes and labels, and it is also suitable for molding rubber and plastics. It can be suitably used for mold releasability, fiber treatment agents such as paper and cloth, water repellent agents for food packaging, oil repellent agents, and heat resistant coating applications.
【００４０】[0040]
【発明の効果】本発明のシリコーン組成物は、離型性に
優れたシリコーン硬化皮膜を与える剥離剤用シリコーン
組成物を得ることができ、また、非ハロゲン系溶剤に希
釈可能であるため、安価に、かつ大気汚染のおそれもな
く剥離性シリコーン硬化皮膜を作製することができ、剥
離剤用として優れた性能を有する。EFFECT OF THE INVENTION The silicone composition of the present invention makes it possible to obtain a silicone composition for a release agent which gives a silicone cured film having excellent releasability, and since it can be diluted with a non-halogen solvent, it is inexpensive. In addition, it is possible to prepare a peelable silicone cured film without fear of air pollution, and it has excellent performance as a release agent.
【００４１】[0041]
【実施例】以下、実験例及び実施例と比較例を示し、本
発明を具体的に説明するが、本発明は下記の実施例に制
限されるものではない。EXAMPLES The present invention will be specifically described below by showing experimental examples, examples and comparative examples, but the present invention is not limited to the following examples.
【００４２】［実験例］表１に示す含フッ素置換基及び
アルケニル基を含有するオルガノポリシロキサンを１５
重量％の濃度で所定の溶剤に希釈し、２５℃での溶解性
を下記基準で評価した。結果を表１に併記する。 ○：均一に溶解した ×：溶解しない[Experimental Example] 15 organopolysiloxanes containing a fluorine-containing substituent and an alkenyl group shown in Table 1 were used.
It was diluted with a predetermined solvent at a concentration of wt% and the solubility at 25 ° C was evaluated according to the following criteria. The results are also shown in Table 1. ◯: Dissolved uniformly ×: Not dissolved
【００４３】[0043]
【表１】[Table 1]
【００４４】[0044]
【化７】[Chemical 7]
【００４５】［実施例１〜１０、比較例］表１に示す含
フッ素置換基及びアルケニル置換基含有オルガノポリシ
ロキサンに対し、表２に示すオルガノハイドロジェンポ
リシロキサンをＳｉＨ基／ＳｉＣＨ＝ＣＨ2基のモル比
が３．５となるように混合したもの１５部を所定の非フ
ッ素系溶剤８５部で希釈し、これに３−メチル−１−ブ
チン−３−オール０．１部を添加し、更に塩化白金酸と
ビニルシロキサンとの錯塩を白金量で３０ｐｐｍとなる
ように添加して表３に示すシリコーン組成物溶液を調製
した。[Examples 1 to 10 and Comparative Example] Organohydrogenpolysiloxanes shown in Table 2 were substituted with SiH groups / SiCH = CH2 groups, in contrast to organopolysiloxanes containing fluorine-containing substituents and alkenyl substituents shown in Table 1. 15 parts mixed to have a molar ratio of 3.5 are diluted with 85 parts of a predetermined non-fluorine-containing solvent, and 0.1 part of 3-methyl-1-butyn-3-ol is added thereto, Further, a complex salt of chloroplatinic acid and vinyl siloxane was added so that the amount of platinum was 30 ppm to prepare a silicone composition solution shown in Table 3.
【００４６】これらのシリコーン組成物溶液の硬化皮膜
の剥離力、残留接着力を下記の方法で測定し、評価し
た。結果を表２に併記する。The peeling force and residual adhesive force of the cured film of these silicone composition solutions were measured and evaluated by the following methods. The results are also shown in Table 2.
【００４７】剥離力 シリコーン組成物溶液を厚さ３８μｍのポリエステルフ
ィルム基材表面に固型分で０．４ｋｇ／ｍ2となるよう
に塗布し、１５０℃の熱風循環式乾燥機中で３０秒間加
熱して硬化皮膜を形成させた。この硬化皮膜表面に幅１
９ｍｍのシリコーン系粘着テープ（ニフトロンＮｏ．９
０３ＵＬ、日東電工（株）社製）を貼り合わせ、２５ｇ
／ｃｍ2の荷重下、２５℃及び７０℃でそれぞれ２０時
間貼り合わせ、エージングさせた。引張り試験機を用い
て試料の貼り合わせテープを１８０度の角度で剥離速度
０．３ｍ／分で剥がし、剥離に要する力（ｇ／１９ｍ
ｍ）を測定した。Peeling power A silicone composition solution was applied on the surface of a polyester film substrate having a thickness of 38 μm so that the solid content was 0.4 kg / m2, and heated for 30 seconds in a hot air circulation dryer at 150 ° C. To form a cured film. Width 1 on the surface of this cured film
9 mm silicone adhesive tape (Niftron No. 9
03UL, Nitto Denko Co., Ltd.) pasted together, 25g
Under a load of / cm2, the laminate was aged at 25 ° C. and 70 ° C. for 20 hours and aged. Using a tensile tester, the sample bonding tape was peeled at an angle of 180 degrees at a peeling speed of 0.3 m / min, and the force required for peeling (g / 19 m
m) was measured.
【００４８】残留接着力 剥離力測定の場合と同様にして硬化皮膜を形成した基材
に同様の粘着テープを貼り合わせ、２０ｇ／ｃｍ2の荷
重下、７０℃で２０時間エージングさせた。エージング
後、粘着テープを剥がし、ポリエステルフィルムに貼り
付けた。引張り試験機を用いて試料の貼り合わせテープ
を１８０度の角度で剥離速度０．３ｍ／分で剥がし、剥
離に要する力（ｇ／１９ｍｍ）を測定した。一方、シリ
コーン硬化皮膜に貼り合わせない未処理テープをポリエ
ステルフィルムから剥離するのに要する力（ｇ／１９ｍ
ｍ）を測定し、これらの比をとって百分率で表した。The same adhesive tape was attached to the base material on which the cured film was formed in the same manner as in the measurement ofresidual adhesive force and peeling force, and aged at 70 ° C. for 20 hours under a load of 20 g / cm2 . After aging, the adhesive tape was peeled off and attached to a polyester film. Using a tensile tester, the laminated tape of the sample was peeled off at an angle of 180 degrees at a peeling speed of 0.3 m / min, and the force required for peeling (g / 19 mm) was measured. On the other hand, the force (g / 19m) required to peel the untreated tape that is not attached to the cured silicone film from the polyester film.
m) was measured and these ratios were taken and expressed as a percentage.
【００４９】[0049]
【表２】[Table 2]
【００５０】[0050]
【化８】[Chemical 8]
フロントページの続き (72)発明者 木下 博文 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内Front page continued (72) Inventor Hirofumi Kinoshita 1 Hitomi, Osamu, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5187474AJP3024445B2 (en) | 1993-06-30 | 1993-06-30 | Silicone composition for release agent and release paper |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5187474AJP3024445B2 (en) | 1993-06-30 | 1993-06-30 | Silicone composition for release agent and release paper |
| Publication Number | Publication Date |
|---|---|
| JPH0718185Atrue JPH0718185A (en) | 1995-01-20 |
| JP3024445B2 JP3024445B2 (en) | 2000-03-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5187474AExpired - LifetimeJP3024445B2 (en) | 1993-06-30 | 1993-06-30 | Silicone composition for release agent and release paper |
| Country | Link |
|---|---|
| JP (1) | JP3024445B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7084229B2 (en) | 2003-03-20 | 2006-08-01 | Shin-Etsu Chemical Co., Ltd. | Silicone composition for release agent |
| JP2007502345A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Silicone with improved surface properties and curable silicone composition for preparing the silicone |
| JP2007502346A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Adhesive having improved chemical resistance and curable silicone composition for preparing adhesive |
| JP2007502344A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Silicone with improved chemical resistance and curable silicone composition with improved migration resistance |
| EP1944341A2 (en) | 2006-12-26 | 2008-07-16 | Shin-Etsu Chemical Company, Ltd. | Diluent for a fluorine-containing silicone coating agent |
| ES2345235A1 (en)* | 2008-07-21 | 2010-09-17 | Bsh Electrodomesticos España, S.A | Thermally insulating housing with conductive penetration |
| EP2395062A2 (en) | 2010-04-09 | 2011-12-14 | Shin-Etsu Chemical Co., Ltd. | Solventless releaser composition for use with silicone pressure-sensitive adhesives and release liner |
| JP2013173944A (en)* | 2013-04-18 | 2013-09-05 | Shin-Etsu Chemical Co Ltd | Laminate including silicone adhesive layer |
| WO2019087759A1 (en)* | 2017-11-02 | 2019-05-09 | 信越化学工業株式会社 | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet |
| WO2020137835A1 (en) | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| JP2020100764A (en)* | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| WO2023228636A1 (en) | 2022-05-24 | 2023-11-30 | 信越化学工業株式会社 | Addition-curable mold-releasing silicone composition for silicone adhesive |
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3536757A1 (en) | 2015-03-26 | 2019-09-11 | Shin-Etsu Chemical Co., Ltd. | Release agent composition for silicone adhesive and release liner |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7084229B2 (en) | 2003-03-20 | 2006-08-01 | Shin-Etsu Chemical Co., Ltd. | Silicone composition for release agent |
| JP2007502345A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Silicone with improved surface properties and curable silicone composition for preparing the silicone |
| JP2007502346A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Adhesive having improved chemical resistance and curable silicone composition for preparing adhesive |
| JP2007502344A (en)* | 2003-08-14 | 2007-02-08 | ダウ・コーニング・コーポレイション | Silicone with improved chemical resistance and curable silicone composition with improved migration resistance |
| US8765870B2 (en) | 2006-12-26 | 2014-07-01 | Shin-Etsu Chemical Co., Ltd. | Diluent for a flourine-containing silicone coating agent |
| EP1944341A2 (en) | 2006-12-26 | 2008-07-16 | Shin-Etsu Chemical Company, Ltd. | Diluent for a fluorine-containing silicone coating agent |
| ES2345235A1 (en)* | 2008-07-21 | 2010-09-17 | Bsh Electrodomesticos España, S.A | Thermally insulating housing with conductive penetration |
| EP2395062A2 (en) | 2010-04-09 | 2011-12-14 | Shin-Etsu Chemical Co., Ltd. | Solventless releaser composition for use with silicone pressure-sensitive adhesives and release liner |
| JP2013173944A (en)* | 2013-04-18 | 2013-09-05 | Shin-Etsu Chemical Co Ltd | Laminate including silicone adhesive layer |
| JPWO2019087759A1 (en)* | 2017-11-02 | 2020-11-26 | 信越化学工業株式会社 | Silicone adhesive composition, adhesive tape, adhesive sheet, and double-sided adhesive sheet |
| WO2019087759A1 (en)* | 2017-11-02 | 2019-05-09 | 信越化学工業株式会社 | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet |
| US11732169B2 (en) | 2017-11-02 | 2023-08-22 | Shin-Etsu Chemical Co., Ltd. | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet |
| KR20200079504A (en)* | 2017-11-02 | 2020-07-03 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone adhesive composition, adhesive tape, adhesive sheet and double-sided adhesive sheet |
| JP2020100764A (en)* | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| KR20210110313A (en) | 2018-12-25 | 2021-09-07 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Silicone Release Agent Compositions, Release Papers and Release Films |
| WO2020137835A1 (en) | 2018-12-25 | 2020-07-02 | 信越化学工業株式会社 | Silicone release agent composition, release sheet and release film |
| WO2023228636A1 (en) | 2022-05-24 | 2023-11-30 | 信越化学工業株式会社 | Addition-curable mold-releasing silicone composition for silicone adhesive |
| KR20250016121A (en) | 2022-05-24 | 2025-02-03 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Additive curing type release silicone composition for silicone adhesive |
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| JP2005146123A (en) | Silicone composition for use in release paper | |
| JPH09169960A (en) | Tacky label or tape and production thereof |
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