JP4718146B2 - Emulsion-type silicone pressure-sensitive adhesive composition for porous sheet and releasable pressure-sensitive adhesive sheet - Google Patents
Emulsion-type silicone pressure-sensitive adhesive composition for porous sheet and releasable pressure-sensitive adhesive sheet Download PDFInfo
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本発明は、多孔質シート用エマルション型シリコーン粘着剤組成物および多孔質シートの片面に再剥離性を有するシリコーン粘着剤層が形成された粘着シートに関する。 The present invention relates to an emulsion-type silicone pressure-sensitive adhesive composition for porous sheets and a pressure-sensitive adhesive sheet in which a silicone pressure-sensitive adhesive layer having removability is formed on one side of a porous sheet.
シリコーン粘着剤は耐熱性、耐寒性、耐候性、耐薬品性に優れることから、アクリル系粘着剤やゴム系粘着剤では粘着特性が劣化してしまうような環境下で使用されている。従来のシリコーン粘着剤は、その主原料が超高粘度のシリコーン生ゴムと固形状のシリコーンレジンであるので、布、紙、プラスチックフィルム等の支持体への塗工、塗布が困難であり、そのためそれらを有機溶剤に溶解し希釈してなる溶液型シリコーン粘着剤組成物が知られている（特公平６−３７６１４号公報参照）。有機溶剤に溶解すると塗工作業性が向上する反面、有機溶剤は可燃性であり人体に有害であるので、安全対策、環境対策が必要となる。そのため、その主原料が液状シリコーン（低級アルケニル基含有ジオルガノポリシロキサン）と固形状のシリコーンレジンである無溶剤型のシリコーン粘着剤組成物（特公平６−８４４９４号公報参照）や、液状シリコーン（低級アルケニル基含有ジオルガノポリシロキサン）と固形状のシリコーンレジンを乳化剤により水中に乳化してなるエマルション型のシリコーン粘着剤組成物が提案されている（特開平７−３３１２２０号公報参照）。 Silicone adhesives are excellent in heat resistance, cold resistance, weather resistance, and chemical resistance, so acrylic adhesives and rubber adhesives are used in an environment where the adhesive properties deteriorate. Since the main raw materials of conventional silicone adhesives are ultra-high-viscosity silicone raw rubber and solid silicone resin, it is difficult to apply and apply to substrates such as cloth, paper, and plastic films. A solution-type silicone pressure-sensitive adhesive composition obtained by dissolving and diluting in an organic solvent is known (see Japanese Patent Publication No. 6-37614). When dissolved in an organic solvent, the coating workability is improved. However, since the organic solvent is flammable and harmful to the human body, safety measures and environmental measures are required. Therefore, a solvent-free silicone pressure-sensitive adhesive composition (see Japanese Patent Publication No. 6-84494), which is mainly composed of liquid silicone (lower alkenyl group-containing diorganopolysiloxane) and a solid silicone resin, and liquid silicone ( An emulsion-type silicone pressure-sensitive adhesive composition obtained by emulsifying a lower alkenyl group-containing diorganopolysiloxane) and a solid silicone resin in water with an emulsifier has been proposed (see JP-A-7-33220).
ところが、シリコーン粘着剤組成物を付着させる支持体が織物、編物、不織布、紙のような多孔質シート（テープを含む。以下同様）であると、支持体の片面に適用した上記無溶剤型のシリコーン粘着剤組成物や上記エマルション型のシリコーン粘着剤組成物は、該支持体の裏側にまで浸透することが多いという問題がある。シリコーン粘着剤組成物が裏側に浸透すると、裏側は往々にして斑模様となり見苦しいだけでなく、手指や意図していない他の物に粘着しやすく、取扱性や作業性が低下し、用途が制約される。また、上記エマルション型のシリコーン粘着剤組成物は、界面活性剤系の乳化剤を必須成分としているが、界面活性剤は一般に皮膚刺激性があるので、人体に接触する粘着シート用の粘着剤としては好ましくない。
ところで、粘着シートは、一度貼着に供されると剥がすことのない永久粘着型と、粘着に供した後引き剥がしてしまう再剥離可能型に大別される。再剥離可能型は、被着体によく粘着し、かつ、被着体に粘着したものを剥離するとき、被着体上に糊残りや汚染がないことが要求される。再剥離可能な粘着シートは、粘着剤層の粘着力が強すぎると、その再剥離が困難であるという問題があり、粘着剤層の粘着力が弱すぎると、粘着シートが被着体から容易に脱落するという問題がある。
However, when the support to which the silicone pressure-sensitive adhesive composition is attached is a porous sheet (including a tape; the same applies hereinafter) such as a woven fabric, a knitted fabric, a nonwoven fabric, or paper, the above-mentioned solventless type applied to one side of the support. The silicone pressure-sensitive adhesive composition and the emulsion-type silicone pressure-sensitive adhesive composition have a problem that they often penetrate to the back side of the support. When the silicone adhesive composition penetrates into the back side, the back side often becomes spotted and unsightly, and it tends to stick to fingers and other unintended objects, reducing handling and workability, and restricting applications Is done. The emulsion-type silicone pressure-sensitive adhesive composition contains a surfactant-based emulsifier as an essential component, but since surfactants generally have skin irritation, the pressure-sensitive adhesive for pressure-sensitive adhesive sheets that come into contact with the human body It is not preferable.
By the way, the pressure-sensitive adhesive sheet is roughly classified into a permanent pressure-sensitive adhesive mold that is not peeled once it is subjected to sticking, and a re-peelable mold that is peeled off after being subjected to pressure-sensitive adhesive. The re-peelable mold is required to adhere well to the adherend and to have no adhesive residue or contamination on the adherend when the adherend adheres to the adherend. If the pressure-sensitive adhesive sheet has a too strong pressure-sensitive adhesive strength, it is difficult to remove the pressure-sensitive adhesive layer. If the pressure-sensitive adhesive strength of the pressure-sensitive adhesive layer is too weak, the pressure-sensitive adhesive sheet is easily removed from the adherend. There is a problem of dropping out.
そこで、本発明者らは、織物、編物、不織布、紙のような多孔質シートの片面に適用しても、適用面の裏側に浸透しにくく、粘着剤層は被着体に粘着しやすく、必要時には被着体から剥離しやすく、界面活性剤含有量が皆無であるか、含有しても少量であるエマルション型のシリコーン粘着剤組成物、および、多孔質シートの片面に界面活性剤含有量が皆無であるか、含有しても少量であるシリコーン粘着剤層を有し、反対面にはシリコーン粘着剤が浸出しておらず、被着体に粘着しやすく、必要時には被着体から剥離しやすい粘着シートを開発すべく鋭意研究した結果、本発明に到達した。本発明の目的は、織物、編物、不織布、紙のような多孔質シートの片面に適用しても、適用面の裏側に浸透しにくく、粘着剤層は被着物に粘着しやすく、必要時には剥離しやすく、界面活性剤含有量が皆無であるか、含有しても少量であるエマルション型のシリコーン粘着剤組成物、および、多孔質シートの片面に界面活性剤含有量が皆無であるか、含有しても少量であるシリコーン粘着剤層を有し、反対面にはシリコーン粘着剤が浸出しておらず、被着体に粘着しやすく、必要時には被着体から剥離しやすい粘着シートを提供することにある。 Therefore, the present inventors, even when applied to one side of a porous sheet such as woven fabric, knitted fabric, nonwoven fabric, paper, hardly penetrate the back side of the application surface, the adhesive layer is easy to adhere to the adherend, Emulsion-type silicone pressure-sensitive adhesive composition that is easily peeled off from the adherend when necessary and has little or no surfactant content, and a surfactant content on one side of the porous sheet There is no or even a small amount of silicone adhesive layer, and the silicone adhesive is not leached on the opposite side, it is easy to stick to the adherend, and peels off from the adherend when necessary As a result of diligent research to develop a pressure-sensitive adhesive sheet, the present invention has been achieved. The object of the present invention is that even when applied to one side of a porous sheet such as woven fabric, knitted fabric, non-woven fabric, and paper, it does not easily penetrate the back side of the applied surface, and the adhesive layer easily adheres to the adherend, and peels off when necessary. Emulsion-type silicone pressure-sensitive adhesive composition that has no surfactant content or a small amount even if contained, and has no surfactant content on one side of the porous sheet Even if there is a small amount of silicone adhesive layer, the silicone adhesive is not leached on the opposite surface, and it is easy to stick to the adherend, and when necessary, an adhesive sheet that is easy to peel off from the adherend is provided. There is.
これらの目的は、「（Ａ）１分子中に少なくとも２個のケイ素原子結合アルケニル基を有するジオルガノポリシロキサン １００重量部、
（Ｂ）補強性シリカ微粉末 ５〜３０重量部
（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノハイドロジェンポリシロキサン、
本成分中のケイ素原子結合水素原子のモル数（Ｈ）と成分（Ａ）中のジオルガノポリシロキサン中のアルケニル基のモル数（Ｖ）のモル比（Ｈ／Ｖ）が０．５〜１５の範囲にある量、
（Ｄ）Ｒ３ＳｉＯ０．５単位（但し、式中のＲは１価炭化水素基）及びＳｉＯ２単位からなり、Ｒ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．３の範囲にあるオルガノポリシロキサンレジン ５〜５０重量部、
（Ｅ）触媒量の白金系触媒、
（Ｆ）スメクタイトクレー含有水 ５〜１００重量部、および
成分（Ａ）、成分（Ｃ）および成分（Ｄ）を乳化するのに必要な量の（Ｇ）乳化剤から成ることを特徴とする多孔質シート用エマルション型シリコーン粘着剤組成物。
[2] （Ａ）１分子中に少なくとも２個のケイ素原子結合アルケニル基を有するジオルガノポリシロキサン１００重量部と（Ｂ）補強性シリカ微粉末５〜３０重量部との混合物、
（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノハイドロジェンポリシロキサン、
本成分中のケイ素原子結合水素原子のモル数（Ｈ）と成分（Ａ）中のジオルガノポリシロキサン中のアルケニル基のモル数（Ｖ）のモル比（Ｈ／Ｖ）が０．５〜１５の範囲にある量、
（Ｄ）Ｒ３ＳｉＯ０．５単位（但し、式中のＲは１価炭化水素基）及びＳｉＯ２単位からなり、Ｒ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．３の範囲にあるオルガノポリシロキサンレジン ５〜５０重量部、
（Ｅ）触媒量の白金系触媒、
（Ｆ）スメクタイトクレー含有水 ５〜１００重量部、および
成分（Ａ）と成分（Ｂ）の混合物、成分（Ｃ）および成分（Ｄ）を乳化するのに必要な量の（Ｇ）乳化剤から成ることを特徴とする多孔質シート用エマルション型シリコーン粘着剤組成物。
[3] 成分（Ｆ）が水１００重量部当たりスメクタイトクレーを０．５〜９.１重量部含有するものであることを特徴とする[1]または[2]記載の多孔質シート用エマルション型シリコーン粘着剤組成物。
[4] 多孔質シートの片面に請求項１または請求項２記載のエマルション型シリコーン粘着剤組成物の硬化乾燥物からなる粘着剤層を有し、反対面に前記粘着剤が浸出していないことを特徴とする再剥離性粘着シート。
[5] 多孔質シートが、織物、編物または不織布である[4]記載の再剥離性粘着シート。」により達成される。
These purposes are as follows: (A) 100 parts by weight of diorganopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule;
(B) Reinforcing silica fine powder 5 to 30 parts by weight (C) Organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule,
The molar ratio (H / V) of the number of moles (H) of silicon-bonded hydrogen atoms in this component to the number of moles (V) of alkenyl groups in the diorganopolysiloxane in component (A) is 0.5-15. An amount in the range of,
(D) R 3 SiO 0.5 units (wherein R is a monovalent hydrocarbon group) and SiO 2 units, and the molar ratio of R 3 SiO 0.5 units / SiO 2 units is 0.6 to 5-50 parts by weight of an organopolysiloxane resin in the range of 1.3,
(E) a catalytic amount of a platinum-based catalyst;
(F) A porous material comprising 5 to 100 parts by weight of smectite clay-containing water and an amount of (G) emulsifier necessary for emulsifying component (A), component (C) and component (D) Emulsion type silicone pressure-sensitive adhesive composition for sheet.
[2] (A) a mixture of 100 parts by weight of a diorganopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule and (B) 5 to 30 parts by weight of reinforcing silica fine powder;
(C) an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule;
The molar ratio (H / V) of the number of moles (H) of silicon-bonded hydrogen atoms in this component to the number of moles (V) of alkenyl groups in the diorganopolysiloxane in component (A) is 0.5-15. An amount in the range of,
(D) R 3 SiO 0.5 units (wherein R is a monovalent hydrocarbon group) and SiO 2 units, and the molar ratio of R 3 SiO 0.5 units / SiO 2 units is 0.6 to 5-50 parts by weight of an organopolysiloxane resin in the range of 1.3,
(E) a catalytic amount of a platinum-based catalyst;
(F) 5 to 100 parts by weight of smectite clay-containing water and a mixture of component (A) and component (B), and an amount of (G) emulsifier necessary to emulsify component (C) and component (D) An emulsion-type silicone pressure-sensitive adhesive composition for porous sheets.
[3] The emulsion type for porous sheets according to [1] or [2], wherein the component (F) contains 0.5 to 9.1 parts by weight of smectite clay per 100 parts by weight of water. Silicone adhesive composition.
[4] It has an adhesive layer made of a cured and dried product of the emulsion-type silicone adhesive composition according to claim 1 or 2 on one side of the porous sheet, and the adhesive is not leached on the opposite side. Re-peelable pressure-sensitive adhesive sheet characterized by
[5] The releasable pressure-sensitive adhesive sheet according to [4], wherein the porous sheet is a woven fabric, a knitted fabric or a nonwoven fabric. Is achieved.
本発明のエマルション型シリコーン粘着剤組成物は、織物、編物、不織布、紙のような多孔質シートの片面に適用しても、適用面の裏側に浸透しにくく、界面活性剤を含有しないか含有しても少量であるので、人や動物の皮膚に安全である。本発明のエマルション型シリコーン粘着剤組成物は、硬化乾燥後に被着体への粘着性が優れるが、被着体から再剥離可能なシリコーン粘着剤層を形成することができる。
本発明の粘着シートは、織物、編物、不織布、紙のような多孔質シートの片面にのみシリコーン粘着剤層があるので、裏面が手指や意図していない他の物に粘着することがなく、粘着作業性が優れている。本発明の粘着シートは、シリコーン粘着剤層中のシリコーン粘着剤が、界面活性剤を含有しないか含有しても少量であるので、人や動物の皮膚に安全である。本発明の粘着シートは、被着体への粘着性が優れるが、被着体から再剥離可能である。
Even if the emulsion type silicone pressure-sensitive adhesive composition of the present invention is applied to one side of a porous sheet such as a woven fabric, a knitted fabric, a nonwoven fabric, or paper, it does not easily permeate the back side of the applied surface and does not contain or contain a surfactant. Even a small amount is safe for human and animal skin. The emulsion-type silicone pressure-sensitive adhesive composition of the present invention is excellent in adhesiveness to an adherend after curing and drying, but can form a silicone pressure-sensitive adhesive layer that can be removed from the adherend.
Since the pressure-sensitive adhesive sheet of the present invention has a silicone pressure-sensitive adhesive layer only on one side of a porous sheet such as woven fabric, knitted fabric, nonwoven fabric, and paper, the back side does not stick to fingers or other unintended items, Adhesive workability is excellent. The pressure-sensitive adhesive sheet of the present invention is safe for human and animal skin because the silicone pressure-sensitive adhesive in the silicone pressure-sensitive adhesive layer does not contain a surfactant or is contained in a small amount. The pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness to an adherend, but can be peeled off again from the adherend.
本発明のエマルション型シリコーン粘着剤組成物では、（Ａ）１分子中に少なくとも２個のアルケニル基を有するジオルガノポリシロキサン中のアルケニル基と、（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を有するオルガノポリシロキサン中のケイ素原子結合水素原子とが、白金系触媒の作用により、付加反応し架橋してエラストマー状になる。 In the emulsion type silicone pressure-sensitive adhesive composition of the present invention, (A) an alkenyl group in a diorganopolysiloxane having at least two alkenyl groups in one molecule, and (C) at least two silicon atoms in one molecule. Silicon atom-bonded hydrogen atoms in the organopolysiloxane having bonded hydrogen atoms undergo an addition reaction and cross-link to become elastomeric due to the action of the platinum-based catalyst.
（A）１分子中に少なくとも２個のアルケニル基を有するジオルガノポリシロキサンは、シリコーン粘着剤組成物の主剤であり、架橋反応により硬化させるために１分子中に少なくとも２個のケイ素原子結合アルケニル基を有することが必要である。このようなアルケニル基としてはビニル基、アリル基、プロペニル基が例示される。アルケニル基以外の有機基としては、メチル基、エチル基、プロピル基で例示されるアルキル基；フェニル基、トリル基で例示されるアリール基；３，３，３−トリフロロプロピル基、３−クロロプロピル基で例示される置換アルキル基が例示される。
本成分の分子構造は直鎖状が好ましいが、やや分枝した直鎖状でもよい。本成分は乳化性の点で常温で液状であることが好ましく、乳化性の点で２５℃における粘度が１００，０００ｍPa・ｓ以下であることが好ましく、硬化物の物性の点で２５℃における粘度が１００ｍＰａ・ｓ以上であることが好ましい。本成分は上記ジオルガノポリシロキサンを２種以上組み合わせてもよい。
(A) A diorganopolysiloxane having at least two alkenyl groups in one molecule is the main component of the silicone pressure-sensitive adhesive composition, and has at least two silicon atom-bonded alkenyls in one molecule for curing by a crosslinking reaction. It is necessary to have a group. Examples of such an alkenyl group include a vinyl group, an allyl group, and a propenyl group. Examples of organic groups other than alkenyl groups include alkyl groups exemplified by methyl, ethyl and propyl groups; aryl groups exemplified by phenyl and tolyl groups; 3,3,3-trifluoropropyl groups and 3-chloro Examples thereof include substituted alkyl groups exemplified by propyl group.
The molecular structure of this component is preferably a straight chain, but may be a slightly branched straight chain. This component is preferably liquid at room temperature in terms of emulsification, preferably has a viscosity at 25 ° C. of not more than 100,000 mPa · s in terms of emulsification, and has a viscosity at 25 ° C. in terms of physical properties of the cured product. Is preferably 100 mPa · s or more. This component may combine 2 or more types of the said diorganopolysiloxane.
（Ｂ）補強性シリカ微粉末は、エマルションの粘性を向上し、シリコーン粘着剤組成物が硬化乾燥したときに粘着剤層の強度を向上して再剥離性を向上する作用がある。補強性シリカ微粉末は成分（Ａ）と混練してペースト状またはスラリー状にしてから他成分を混合することが好ましい。補強性シリカの代表例としてフュームドシリカと沈降法シリカ、および、それらをトリメチルクロロシラン、ジメチルジクロロシラン、メチルトリメトキシシラン、ヘキサメチルジシラザンのような有機珪素化合物で処理した疎水性フュームドシリカと疎水性沈降法シリカがある。補強性シリカ微粉末は成分（Ａ）１００重量部当たり５〜３０重量部であるが、１０〜２０重量部がより好ましい。 (B) Reinforcing silica fine powder has the effect of improving the viscosity of the emulsion and improving the strength of the pressure-sensitive adhesive layer and improving the removability when the silicone pressure-sensitive adhesive composition is cured and dried. The reinforcing silica fine powder is preferably kneaded with the component (A) to form a paste or slurry and then mixed with other components. As typical examples of reinforcing silica, fumed silica and precipitated silica, and hydrophobic fumed silica treated with organosilicon compounds such as trimethylchlorosilane, dimethyldichlorosilane, methyltrimethoxysilane, and hexamethyldisilazane There is hydrophobic precipitated silica. The reinforcing silica fine powder is 5 to 30 parts by weight per 100 parts by weight of the component (A), and more preferably 10 to 20 parts by weight.
（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノポリシロキサンは、（Ｄ）白金系触媒の存在下で、本成分中のケイ素原子結合水素原子が、成分（Ａ）中のケイ素原子結合アルケニル基に付加反応して架橋し、硬化させるものである。したがって、成分（Ａ）中のケイ素原子結合アルケニル基が３個以上のときは、ケイ素原子結合水素原子は１分子中に２個あれば十分であり、成分（Ａ）中のケイ素原子結合アルケニル基が２個のときは、ケイ素原子結合水素原子は１分子中に３個以上であることが必要である。成分（Ｂ）中のケイ素原子結合有機基としては、メチル基、エチル基、プロピル基などのアルキル基；フェニル基、トリル基などのアリール基；３，３，３−トリフロロプロピル基、３−クロロプロピル基などのハロゲン化アルキル基；アルコキシ基が例示される。本成分の分子構造は、直鎖状、分枝状、環状、網目状のいずれでもよい。本成分は２量体以上であればよいが、常温で液状であることが好ましく、２５℃における粘度は、３ｍＰａ・ｓ以上、１０，０００ｍＰａ・ｓ以下であることが好ましい。
成分（Ｃ）は、本成分のケイ素原子結合水素原子のモル数（Ｈ）と成分（Ａ）のケイ素原子結合アルケニル基のモル数（Ｖ）のモル比（Ｈ／Ｖ）が０．５〜１５、好ましくは０．６〜５となるような量配合される。これは、このモル比が０．５未満になると架橋密度が小さくなって粘着剤層の強度が低くなり、１５を超えると硬化時に発泡したり、経時変化で粘着剤が硬くなり粘着性が低下するためである。
(C) An organopolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule is (D) in the presence of a platinum-based catalyst, and the silicon-bonded hydrogen atoms in this component are It is subjected to an addition reaction with a silicon atom-bonded alkenyl group to be crosslinked and cured. Accordingly, when the number of silicon atom-bonded alkenyl groups in the component (A) is 3 or more, two silicon atom-bonded hydrogen atoms per molecule are sufficient, and the silicon atom-bonded alkenyl group in the component (A) is sufficient. When there are two, it is necessary that the number of silicon-bonded hydrogen atoms be 3 or more per molecule. Examples of the silicon-bonded organic group in the component (B) include alkyl groups such as methyl group, ethyl group and propyl group; aryl groups such as phenyl group and tolyl group; 3,3,3-trifluoropropyl group, 3- Examples include halogenated alkyl groups such as chloropropyl group; alkoxy groups. The molecular structure of this component may be linear, branched, cyclic, or network. Although this component should just be a dimer or more, it is preferable that it is a liquid at normal temperature, and it is preferable that the viscosity in 25 degreeC is 3 mPa * s or more and 10,000 mPa * s or less.
Component (C) has a molar ratio (H / V) of the number of moles (H) of silicon-bonded hydrogen atoms of this component to the number of moles (V) of silicon-bonded alkenyl groups of component (A) of 0.5- 15, preferably in an amount of 0.6 to 5. This is because when the molar ratio is less than 0.5, the crosslink density is reduced and the strength of the pressure-sensitive adhesive layer is reduced. It is to do.
（Ｄ）Ｒ３ＳｉＯ０．５単位（但し、式中のＲは１価炭化水素基）及びＳｉＯ２単位からなり、Ｒ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．３の範囲にあるオルガノポリシロキサンレジンは、成分（Ａ）と成分（Ｃ）の架橋物に粘着性を付与する作用がある。式中のＲは１価炭化水素基であり、メチル基、エチル基、プロピル基、ブチル基等のアルキル基；ビニル基、アリル基、ヘキセニル基等のアルケニル基；フエニル基、トリル基等のアリール基；３，３，３−トリフロロプロピル基、３−クロロプロピル基などのハロゲン化アルキル基；アルコキシ基が例示されるが、粘着性付与効果の点でアルキル基、特にはメチル基が好ましい。成分（Ｄ）は、ケイ素原子結合水酸基を有することが好ましい。Ｒ３ＳｉＯ０．５単位／ＳｉＯ２単位のモル比が０．６〜１．３であるのは、０．６未満では粘着力が低く、１．３を超えると粘着皮膜強度が低下する場合があるからである。成分（Ｄ）は、上記シロキサン単位の他に、少量であればＲ２ＳｉＯ単位および／またはＲＳｉＯ１．５単位を含有していてもよい。成分（Ｄ）は成分（Ａ）１００重量部当たり５〜５０重量部配合される。 (D) R 3 SiO 0.5 units (wherein R is a monovalent hydrocarbon group) and SiO 2 units, and the molar ratio of R 3 SiO 0.5 units / SiO 2 units is 0.6 to The organopolysiloxane resin in the range of 1.3 has an action of imparting tackiness to the crosslinked product of the component (A) and the component (C). R in the formula is a monovalent hydrocarbon group, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; an alkenyl group such as a vinyl group, an allyl group or a hexenyl group; an aryl such as a phenyl group or a tolyl group Groups: halogenated alkyl groups such as 3,3,3-trifluoropropyl group and 3-chloropropyl group; alkoxy groups are exemplified, but an alkyl group, particularly a methyl group is preferred in terms of tackiness-imparting effect. Component (D) preferably has a silicon atom-bonded hydroxyl group. The reason why the molar ratio of R 3 SiO 0.5 unit / SiO 2 unit is 0.6 to 1.3 is that the adhesive strength is low when it is less than 0.6, and the adhesive film strength decreases when it exceeds 1.3. Because there is. The component (D) may contain R 2 SiO units and / or RSiO 1.5 units in addition to the siloxane units as long as the amount is small. Component (D) is blended in an amount of 5 to 50 parts by weight per 100 parts by weight of component (A).
（Ｅ）白金系触媒は、成分（Ａ）中のアルケニル基と成分（Ｃ）中のケイ素原子結合水素原子との付加反応を促進する。これには、白金微粉末、白金黒、塩化白金酸、塩化白金酸のオレフィン錯体、白金のβ-ジケトン錯体、塩化白金酸と１，３-ジビニルテトラメチルジシロキサンとの錯体、ロジウム化合物、パラジウム化合物が例示される。成分（Ｅ）は触媒量、すなわち、成分（Ａ）と成分（Ｃ）が架橋してエラストマー状になるのに十分な量を配合すればよい。 (E) The platinum-based catalyst promotes the addition reaction between the alkenyl group in component (A) and the silicon-bonded hydrogen atom in component (C). This includes platinum fine powder, platinum black, chloroplatinic acid, chloroplatinic acid olefin complexes, platinum β-diketone complexes, chloroplatinic acid and 1,3-divinyltetramethyldisiloxane complexes, rhodium compounds, palladium Examples are compounds. Component (E) may be added in a catalytic amount, that is, an amount sufficient to crosslink component (A) and component (C) into an elastomer.
（Ｆ）スメクタイトクレー含有水は、成分（Ａ）と成分（Ｃ）と成分（Ｄ）、あるいは成分（Ａ）と成分（Ｂ）の混合物、成分（Ｃ）および成分（Ｄ）とを乳化する作用をする。成分（Ｆ）中のスメクタイトクレーは、水中で膨潤して水の粘度を高める。そして、エマルション型シリコーン粘着剤組成物の粘性を高め、多孔質シートへの浸出性を低下させる作用をする。成分（Ｆ）中の水は、エマルションの媒質である。水は清浄であればよく、その種類は制限されない。例えば、水道水、井戸水、イオン交換水、蒸留水があげられる。
スメクタイトクレーは、成分（Ｆ）中に好ましくは０.５〜９.１重量％、より好ましくは１〜８重量％存在する。その量が０．５重量％より少ないと成分（Ｆ）の粘性が低くなり安定なエマルションを得にくくなりがちであり、９.１重量％を超えると粘性が大きくなりすぎて乳化作用が低下することがある。
スメクタイトクレーは、ベントナイト、モンモリロナイト、ヘクトライト、サボナイト、ソーコナイト、バイデライト、ノントロナイト等の天然もしくは合成のスメクタイト族クレーを総称するものであるが、合成サポナイトが好適である。いずれも、粉末状のものが好ましい。スメクタイトクレーは、例えばメチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、ヘキシルトリメトキシシランなどのアルキルトリアルコキシシラン；３−グリシドキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシランなどのシランカップリング剤で処理して変性したものであってもよい。
スメクタイトクレーを他成分と直接混合するのではなく、あらかじめ水と混合して膨潤させたものを他成分と混合するところに意味がある。
成分（Ｆ）の配合量は、成分（Ａ）１００重量部当り５〜１００重量部であり、好ましくは１０〜７０重量部である。５重量部より少ないときには水性エマルションの形態をとり難く、１００重量部を超えると乳化が困難となるからである。
(F) Smectite clay-containing water emulsifies component (A) and component (C) and component (D), or a mixture of component (A) and component (B), component (C) and component (D). Works. The smectite clay in component (F) swells in water and increases the viscosity of water. And it acts to increase the viscosity of the emulsion-type silicone pressure-sensitive adhesive composition and to reduce the leaching property to the porous sheet. Water in component (F) is the medium of the emulsion. The water is not limited as long as it is clean. For example, tap water, well water, ion exchange water, and distilled water can be mentioned.
The smectite clay is preferably present in component (F) in an amount of 0.5 to 9.1% by weight, more preferably 1 to 8% by weight. If the amount is less than 0.5% by weight, the viscosity of the component (F) tends to be low and it is difficult to obtain a stable emulsion. If the amount exceeds 9.1% by weight, the viscosity becomes too large and the emulsifying action decreases. Sometimes.
The smectite clay is a generic term for natural or synthetic smectite clays such as bentonite, montmorillonite, hectorite, saponite, saconite, beidellite, nontronite, etc., but synthetic saponite is preferred. In any case, a powder form is preferable. Examples of smectite clays include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and hexyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. It may be modified by treatment with a silane coupling agent.
It does not mean that smectite clay is directly mixed with other components, but it is meaningful to mix with water swollen with water in advance.
The amount of component (F) is 5 to 100 parts by weight, preferably 10 to 70 parts by weight, per 100 parts by weight of component (A). When the amount is less than 5 parts by weight, it is difficult to take the form of an aqueous emulsion, and when it exceeds 100 parts by weight, emulsification becomes difficult.
（Ｇ）乳化剤は、（Ｆ）スメクタイトクレー含有水だけでは成分（Ａ）、成分（Ｃ）および成分（Ｄ）、あるいは成分（Ａ）と成分（Ｂ）の混合物、成分（Ｃ）および成分（Ｄ）を乳化できないときに最小必要量配合されるものであり、その配合量はこれら成分を乳化するのに十分な量でよく、目安として成分（Ａ）１００重量部当たり０（０を含まない）〜１０重量部であり、好ましくは、０（０を含まない）〜２重量部である。成分（Ａ）と成分（Ｃ）の付加反応を阻害するものでなければその種類は特には限定されない。こうした観点から非イオン性界面活性剤が好ましい。非イオン性界面活性剤は、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレン高級脂肪酸エステル、エチレングリコールモノ脂肪酸エステル、プロピレングリコールモノ脂肪酸エステル、ソルビタンモノ脂肪酸エステル、ソルビタントリ脂肪酸エステル、ポリオキシエチレンモノ脂肪酸エステル、ポリオキシエチレンジ脂肪酸エステル、ポリオキシエチレンプロピレングリコール脂肪酸エステル、POE多価アルコール類が例示される。本成分は２種以上を併用してもよい。 (G) The emulsifier is (F) component (A), component (C) and component (D), or a mixture of component (A) and component (B), component (C) and component ( When D) cannot be emulsified, the minimum necessary amount is blended. The blending amount may be sufficient to emulsify these components, and as a guideline, 0 (not including 0) per 100 parts by weight of component (A) ) To 10 parts by weight, preferably 0 (not including 0) to 2 parts by weight. The type is not particularly limited as long as it does not inhibit the addition reaction between component (A) and component (C). From such a viewpoint, a nonionic surfactant is preferable. Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene higher fatty acid ester, ethylene glycol mono fatty acid ester, propylene glycol mono fatty acid ester, sorbitan mono fatty acid ester, sorbitan tri fatty acid ester, Examples include polyoxyethylene mono fatty acid esters, polyoxyethylene di fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, and POE polyhydric alcohols. Two or more of these components may be used in combination.
本発明のエマルション型シリコーン粘着剤組成物は、上記成分（Ａ）〜成分（Ｆ）、あるいは成分（Ａ）〜成分（Ｇ）からなるが、さらに付加反応抑制剤を配合することが好ましい。付加反応抑制剤を配合することにより、常温での保存時間を延長することができる。 The emulsion type silicone pressure-sensitive adhesive composition of the present invention comprises the above components (A) to (F), or components (A) to (G), but it is preferable to further add an addition reaction inhibitor. By adding an addition reaction inhibitor, the storage time at room temperature can be extended.
本発明のエマルション型シリコーン粘着剤組成物には、増粘剤として、アルギン酸、アルギン酸ナトリウム、カルボキシメチルセルロースのナトリウム塩、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、変性デンプン、ポリビニールアルコール、ポリアクリレートのナトリウム塩、ポリメタアクリレートのナトリウム塩などの水溶性ポリマー；ポリアクリル酸系、ポリアクリロニトリル系、アクリル酸塩―ビニルアルコール共重合体系、アクリル酸塩―アクリルアミド共重合体系、カルボキシルメチルセルロース系、デンプン−ポリアクリルニトリル系、デンプン−ポリアクリル酸塩グラフト共重合体架橋物などの吸水性ポリマーなどを乳化や粘着特性を損なわない範囲で配合してもよい。水溶性ポリマーは水溶液にしてから、吸水性ポリマーは水で膨潤させてゲル状にしてから配合することが好ましい。 In the emulsion type silicone pressure-sensitive adhesive composition of the present invention, as a thickener, alginic acid, sodium alginate, sodium salt of carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, modified starch, polyvinyl alcohol, sodium salt of polyacrylate, polyacrylate Water-soluble polymers such as sodium salt of methacrylate; polyacrylic acid system, polyacrylonitrile system, acrylate-vinyl alcohol copolymer system, acrylate-acrylamide copolymer system, carboxymethyl cellulose system, starch-polyacrylonitrile system, You may mix | blend water-absorbing polymers, such as a starch-polyacrylate graft copolymer crosslinked material, in the range which does not impair emulsification and adhesive properties. It is preferable that the water-soluble polymer is made into an aqueous solution and the water-absorbing polymer is swollen with water to form a gel and then blended.
本発明のエマルション型シリコーン粘着剤組成物には、本発明の目的を損なわない限り、カーボンブラック、焼成シリカ、コロイド状炭酸カルシウム、ヒュームド二酸化チタンなどの補強性充填剤；金、銀、ニッケル、銅、アルミニウム、鉄、コバルト、ニッケル、チタン、ゲルマニウム、ネオジューム等の金属粉末；酸化アルミニウム、酸化マグネシウム、酸化カルシウム、酸化ホウ素、酸化バリウム、酸化ジルコニウム、酸化鉄、酸化セリウム、酸化ランタン、沈降法酸化チタン、酸化ビスマス、酸化スズ等の金属酸化物粉末；鉄酸コバルトビスマス、ジルコン酸バリウム；石英、珪藻土、セリサイト、カオリン、ゼオライト、トルマリン等の鉱物粉末；炭化チタン、炭化アルミニウム、炭化タングステン、炭化ジルコニウム、窒化ケイ素、窒化アルミニウム、窒化クロム、窒化ジルコン等の金属炭化物粉末および金属窒化物粉末；炭酸亜鉛、炭酸マンガン、炭酸カルシウム、炭酸マグネシウム等の金属炭酸塩粉末；水酸化アルミニウム、水酸化カルシウム、水酸化ビスマス、アパタイト等の金属水酸化物粉末；ガラスバルーン、ホウ珪酸マイクロバルーン、シラスバルーン、樹脂バルーン等の微小中空粒子；上記充填剤や粉末を疎水化処理や表面処理したもの、アルコール類、耐熱剤、難燃剤、可塑剤、有機過酸化物、接着性付与剤、防黴剤、抗菌剤、整汗剤、保湿剤、美白剤、精油、薬剤、各種ビタミン剤などを配合してもよい。 The emulsion-type silicone pressure-sensitive adhesive composition of the present invention includes reinforcing fillers such as carbon black, calcined silica, colloidal calcium carbonate, and fumed titanium dioxide, as long as the object of the present invention is not impaired; gold, silver, nickel, copper Metal powder such as aluminum, iron, cobalt, nickel, titanium, germanium, neodymium; aluminum oxide, magnesium oxide, calcium oxide, boron oxide, barium oxide, zirconium oxide, iron oxide, cerium oxide, lanthanum oxide, precipitated titanium oxide , Metal oxide powders such as bismuth oxide and tin oxide; cobalt bismuth ferrate, barium zirconate; mineral powders such as quartz, diatomaceous earth, sericite, kaolin, zeolite, tourmaline; titanium carbide, aluminum carbide, tungsten carbide, zirconium carbide , Nitride Metal carbide powders and metal nitride powders such as aluminum nitride, chromium nitride and zircon nitride; metal carbonate powders such as zinc carbonate, manganese carbonate, calcium carbonate and magnesium carbonate; aluminum hydroxide, calcium hydroxide, bismuth hydroxide, Metal hydroxide powders such as apatite; fine hollow particles such as glass balloons, borosilicate microballoons, shirasu balloons, resin balloons; hydrophobized or surface-treated fillers and powders, alcohols, heat-resistant agents, difficult You may mix | blend a flame retardant, a plasticizer, an organic peroxide, an adhesive imparting agent, an antifungal agent, an antibacterial agent, an antiperspirant, a moisturizer, a whitening agent, an essential oil, a drug, various vitamins, etc.
本発明の上記成分（Ａ）〜成分（Ｆ）からなるエマルション型シリコーン粘着剤組成物、あるいは成分（Ａ）〜成分（Ｇ）からなるエマルション型シリコーン粘着剤組成物は、下記の方法で製造することができる。
（１）所定量の成分（Ａ）と成分（Ｂ）の混合物および所定量の成分（Ｄ）を３本ロールで混合した後に、その混合物所定量と所定量の成分（Ｆ）と必要に応じて所定量の成分（Ｇ）を高速攪拌ミキサーに投入し、所定時間攪拌混合した後に、所定量の成分（Ｃ）と所定量の成分（Ｅ）を投入し、攪拌混合する。
（２）成分（Ａ）と成分（Ｂ）の混合物、所定量の成分（Ｄ）および所定量の成分（Ｃ）を３本ロールで混合した後に、その混合物所定量と所定量の成分（Ｆ）と、必要に応じて所定量の成分（Ｇ）を高速攪拌ミキサーに投入し、所定時間攪拌混合した後に所定量の成分（Ｅ）を投入し、攪拌混合する。
（３）成分（Ａ）と成分（Ｂ）の混合物、成分（Ｄ）、成分（Ｅ）の各所定量を３本ロールで混合した後に、その混合物所定量、所定量の成分（Ｆ）、必要に応じて所定量の成分（Ｇ）を高速攪拌ミキサーに投入し、所定時間攪拌混合した後に、所定量の成分（Ｃ）を攪拌混合する。
The emulsion type silicone pressure-sensitive adhesive composition comprising the above components (A) to (F) or the emulsion type silicone pressure-sensitive adhesive composition comprising components (A) to (G) is produced by the following method. be able to.
(1) A mixture of a predetermined amount of component (A) and component (B) and a predetermined amount of component (D) are mixed with three rolls, and then the predetermined amount of mixture, a predetermined amount of component (F), and if necessary Then, a predetermined amount of the component (G) is charged into a high-speed stirring mixer and stirred and mixed for a predetermined time, and then a predetermined amount of the component (C) and a predetermined amount of the component (E) are charged and mixed.
(2) A mixture of the component (A) and the component (B), a predetermined amount of the component (D), and a predetermined amount of the component (C) are mixed with three rolls, and then the predetermined amount of the mixture and the predetermined amount of the component (F And a predetermined amount of the component (G) in a high-speed stirring mixer as required, and after stirring and mixing for a predetermined time, the predetermined amount of the component (E) is added and stirred and mixed.
(3) After mixing predetermined amounts of the mixture of component (A) and component (B), component (D), and component (E) with three rolls, the mixture predetermined amount, predetermined amount of component (F), necessary In accordance with the above, a predetermined amount of the component (G) is put into a high-speed stirring mixer, and after stirring for a predetermined time, the predetermined amount of component (C) is stirred and mixed.
ここで使用するミキサーとしてはホモミキサー、パドルミキサー、ヘンシェルミキサー、ホモディスパー、コロイドミル、真空混合攪拌ミキサー、遊星式攪拌ミキサーが例示されるが、安定なエマルションが得られるものであれば、特に限定されない。 Examples of the mixer used here include a homomixer, a paddle mixer, a Henschel mixer, a homodisper, a colloid mill, a vacuum mixing and stirring mixer, and a planetary stirring mixer, but are particularly limited as long as a stable emulsion can be obtained. Not.
かかるエマルション型シリコーン粘着剤組成物が、混合時に気泡を巻き込んでいるときは、減圧下において脱気後、織物、編物、不織布、紙などの多孔質シートの片面にスクリーンメッシュやコーター、ディスペンサーなどを使用して塗工し、常温から１５０℃、好ましくは５０℃から１２０℃の温度で硬化させつつ乾燥、あるいは、硬化させた後乾燥すると、多孔質シートの片面にシリコーン粘着剤層が形成され、反対面に該シリコーン粘着剤が浸出しておらず、被着体に粘着しやすく、必要時に再剥離しやすい粘着シートが得られる。もちろん、同一のエマルション型シリコーン粘着剤組成物であっても、織物、編物、不織布、紙などの多孔質シートの材質や空隙度合いによって浸透性が変わるので、適合したエマルション型シリコーン粘着剤組成物を選択することが好ましい。 When such an emulsion-type silicone pressure-sensitive adhesive composition entrains bubbles during mixing, after degassing under reduced pressure, a screen mesh, coater, dispenser, etc. is applied to one side of a porous sheet such as woven fabric, knitted fabric, non-woven fabric, and paper. When used, coated and dried at room temperature to 150 ° C., preferably 50 ° C. to 120 ° C. while being cured, or dried after being cured, a silicone adhesive layer is formed on one side of the porous sheet, The silicone pressure-sensitive adhesive is not leached on the opposite surface, and a pressure-sensitive adhesive sheet that easily adheres to the adherend and easily peels off when necessary can be obtained. Of course, even with the same emulsion type silicone adhesive composition, the permeability changes depending on the material and the degree of voids of the porous sheet such as woven fabric, knitted fabric, nonwoven fabric and paper. It is preferable to select.
以下、本発明の実施例と比較例を掲げる。実施例と比較例中、部は重量部のことであり、％とあるのは重量％のことで、粘度は２５℃での測定値を示す。なお、本発明は、これら実施例によって限定されるものではない。 Examples of the present invention and comparative examples are listed below. In Examples and Comparative Examples, “part” means “part by weight”, “%” means “% by weight”, and the viscosity indicates a measured value at 25 ° C. In addition, this invention is not limited by these Examples.
乳化状態：エマルションの外観を目視により観察して判定した。
エマルションの粘度：回転粘度計（リオン社のビスコテスターVT−０４型２号ローター）により回転数６２．５ｒｐｍで測定した。
裏面への浸出性：脱気したエマション型シリコーン粘着剤組成物またはペースト状粘着剤組成物を、ポリエステルスパン（番手６０／２糸使用、織密度縦１０４本／インチ、横６０コース／インチ）平織りテープの片面に６０メッシュ、膜厚３５０μｍのスクリーンを用いてスクリーン印刷した後、１１０℃の熱風循環式オーブンに１５分間入れて硬化乾燥または硬化した。該テープ裏面へのシリコーン粘着剤の浸出状況を目視で観察し、判定した。
粘着力：片面にシリコーン粘着剤層を有する前記平織りテープのシリコーン粘着剤面（長さ４５ｍｍ／幅３０ｍｍ）を、２８０番耐水研磨紙で表面を磨いたステンレス板（ＳＵＳ３０４）に貼り付け、鉄ローラーにより４００ｇｆの力で圧着させ、室温下で１０分間静置後、引張り試験機を用いて、ステンレス板（ＳＵＳ３０４）からシリコーン粘着剤層を有する前記平織りテープを０．３４ｍ／ｍｉｎの速さで剥離する時の応力を粘着力とした。
再剥離性：前記粘着力の測定時に、ステンレス板（ＳＵＳ３０４）にシリコーン粘着剤が残留したか否かを目視により観察して判定した。
Emulsified state: Judgment was made by visually observing the appearance of the emulsion.
Viscosity of emulsion: Measured at a rotational speed of 62.5 rpm with a rotational viscometer (Viscotester VT-04 No. 2 rotor manufactured by Rion).
Leachability on the back side: Degassed emulsification type silicone pressure-sensitive adhesive composition or paste-type pressure-sensitive adhesive composition is polyester weave (using yarn count of 60/2, weaving density of 104 yarns / inch, width of 60 courses / inch) plain weave The screen was printed on one side of the tape using a screen of 60 mesh and a film thickness of 350 μm, and then placed in a hot air circulation oven at 110 ° C. for 15 minutes for curing and drying or curing. The leaching situation of the silicone adhesive on the back surface of the tape was visually observed and judged.
Adhesive strength: A silicone adhesive surface (length 45 mm / width 30 mm) of the plain weave tape having a silicone adhesive layer on one side is affixed to a stainless steel plate (SUS304) whose surface is polished with No. 280 water resistant abrasive paper, and an iron roller After crimping with a force of 400 gf and leaving at room temperature for 10 minutes, the plain weave tape having a silicone adhesive layer is peeled off at a rate of 0.34 m / min from a stainless steel plate (SUS304) using a tensile tester. The stress at the time of doing was made into adhesive force.
Removability: At the time of measuring the adhesive strength, whether or not the silicone adhesive remained on the stainless steel plate (SUS304) was determined by visual observation.
実施例と比較例で使用した成分は下記の通りである。
Ａ−１：粘度１０，０００ｍＰａ・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（ビニル基含有量０．１４％）。
Ｂ−１：ヘキサメチルジシラザンで表面処理した比表面積２００ｍ２／ｇの疎水性ヒュームドシリカ。
Ａ−１とＢ−１の加熱混合物：ミキサーに１００部のＡ−１と１７部のＢ−１を投入して均一に混合し、１８０℃で２時間熱処理を行って調製した流動性のあるペースト状物。
Ｃ−１：粘度５ｍＰａ・ｓの両末端トリメチルシロキシキ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサンコポリマー（ケイ素原子結合水素含有量０．８％）。
Ｄ−１：（ＣＨ３）３ＳｉＯ１/２単位とＳｉＯ４/２単位（モル比０.７：１）とからなるメチルポリシロキサンレジン。
Ｅ−１：塩化白金酸とジビニルテトラメチルジシロキサンとの錯体。
Ｆ−１：合成サポナイトであるスメクトンＳＡ（クニミネ工業株式会社製）含有水（スメクトンＳＡ含有量３％）。
Ｆ−２：合成サポナイトであるスメクトンＳＡ（クニミネ工業株式会社製）含有水（スメクトンＳＡ含有量８％）。
Ｇ−１：ソルビタンモノオレエート（ＨＬＢ値４.９）。
Ｗ：イオン交換水。
The components used in Examples and Comparative Examples are as follows.
A-1: dimethylpolysiloxane blocked with dimethylvinylsiloxy group-blocked dimethylpolysiloxane having a viscosity of 10,000 mPa · s (vinyl group content 0.14%).
B-1: Hydrophobic fumed silica having a specific surface area of 200 m 2 / g surface-treated with hexamethyldisilazane.
A-1 and B-1 heated mixture: 100 parts of A-1 and 17 parts of B-1 were added to a mixer, mixed uniformly, and heat-treated at 180 ° C. for 2 hours. Pasty material.
C-1: A trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer having a viscosity of 5 mPa · s (silicon-bonded hydrogen content 0.8%).
D-1: A methylpolysiloxane resin consisting of (CH 3 ) 3 SiO 1/2 units and SiO 4/2 units (molar ratio 0.7: 1).
E-1: Complex of chloroplatinic acid and divinyltetramethyldisiloxane.
F-1: Water containing smecton SA (manufactured by Kunimine Kogyo Co., Ltd.) which is a synthetic saponite (3% smecton SA content).
F-2: Sumecton SA (manufactured by Kunimine Industries Co., Ltd.) containing synthetic saponite containing water (Smecton SA content 8%).
G-1: Sorbitan monooleate (HLB value 4.9).
W: Ion exchange water.
〔実施例１〕
１００部のＡ−１とＢ−１の加熱混合物と１０部のＤ−１を直径６インチの３本ロールで混合し、該混合物と１５部のＦ−１を、マゼルスターＫＫ−１００型乳化機（クラボウ株式会社製）に投入し、公転回転数１３００ｒｐｍ、自転回転数９００ｒｐｍで１２０秒間かけて攪拌混合して、水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて、公転回転数１３００ｒｐｍ、自転回転数９００ｒｐｍで４０秒間かけて攪拌混合したのち、公転回転数１３００ｒｐｍで９０秒間かけて脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。これらの結果から、本実施例のエマルション型シリコーン粘着剤組成物は裏面への浸出、移行がなく、裏面の汚染がなく、再剥離性を有することが判った。
[Example 1]
100 parts of a heated mixture of A-1 and B-1 and 10 parts of D-1 are mixed with a three-inch roll of 6 inches, and the mixture and 15 parts of F-1 are mixed with a Mazerustar KK-100 type emulsifier. (A product of Kurabo Industries, Inc.) was stirred and mixed at a revolution speed of 1300 rpm and a rotation speed of 900 rpm for 120 seconds to prepare an aqueous emulsion. Next, C-1 and E-1 were added to the aqueous emulsion at the mixing ratios shown in Table 1, respectively, and stirred and mixed for 40 seconds at a revolution speed of 1300 rpm and a rotation speed of 900 rpm, and then at a revolution speed of 1300 rpm. Degassed for 90 seconds. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1. From these results, it was found that the emulsion type silicone pressure-sensitive adhesive composition of the present example did not ooze and migrate to the back surface, had no back surface contamination, and had removability.
〔実施例２〕
１００部のＡ−１とＢ−１の加熱混合物と３０部のＤ−１を直径６インチの３本ロールで混合し、該混合物と１５部のＦ−１をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて実施例１と同一の条件で攪拌混合し脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。これらの結果から、本実施例のエマルション型シリコーン粘着剤組成物は裏面への浸出、移行がなく、裏面の汚染がなく、再剥離性を有することが判った。
[Example 2]
100 parts of the heated mixture of A-1 and B-1 and 30 parts of D-1 are mixed with a 6-inch diameter three roll, and the mixture and 15 parts of F-1 are mixed into a Mazerustar KK-100 type emulsifier. The aqueous emulsion was prepared under the same conditions as in Example 1. Next, C-1 and E-1 were added to the aqueous emulsion in the mixing ratios shown in Table 1, respectively, and the mixture was stirred and mixed under the same conditions as in Example 1 for deaeration. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1. From these results, it was found that the emulsion type silicone pressure-sensitive adhesive composition of the present example did not ooze and migrate to the back surface, had no back surface contamination, and had removability.
〔実施例３〕
１００部のＡ−１とＢ−１の加熱混合物と、１０部のＤ−１を直径６インチの３本ロールで混合し、９０部のＦ−１と１.０部のＧ−１をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて実施例１と同一の条件で攪拌混合し脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。これらの結果から、本実施例のエマルション型シリコーン粘着剤組成物は裏面への浸出、移行がなく、裏面の汚染がなく、再剥離性を有することが判った。
Example 3
100 parts of the heated mixture of A-1 and B-1 and 10 parts of D-1 are mixed with 3 rolls of 6 inches in diameter, 90 parts of F-1 and 1.0 part of G-1 are mixed with Mazerustar. An aqueous emulsion was prepared under the same conditions as in Example 1 by charging into a KK-100 type emulsifier. Next, C-1 and E-1 were added to the aqueous emulsion in the mixing ratios shown in Table 1, respectively, and the mixture was stirred and mixed under the same conditions as in Example 1 for deaeration. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1. From these results, it was found that the emulsion type silicone pressure-sensitive adhesive composition of the present example did not ooze and migrate to the back surface, had no back surface contamination, and had removability.
〔実施例４〕
８０部のＡ−１とＢ−１の加熱混合物と、２０部のＡ−１と１０部のＤ−１を直径６インチの３本ロールで混合し、１５部のＦ−１をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて実施例１と同一の条件で攪拌混合し脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。これらの結果から、本実施例のエマルション型シリコーン粘着剤組成物は裏面への浸出、移行がなく、裏面の汚染がなく、再剥離性を有することが判った。
Example 4
80 parts of the heated mixture of A-1 and B-1, 20 parts of A-1 and 10 parts of D-1 are mixed with 3 rolls having a diameter of 6 inches, and 15 parts of F-1 is mixed with Mazerustar KK- An aqueous emulsion was prepared under the same conditions as in Example 1 by charging into a 100 type emulsifier. Next, C-1 and E-1 were added to the aqueous emulsion in the mixing ratios shown in Table 1, respectively, and the mixture was stirred and mixed under the same conditions as in Example 1 for deaeration. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1. From these results, it was found that the emulsion type silicone pressure-sensitive adhesive composition of the present example did not ooze and migrate to the back surface, had no back surface contamination, and had removability.
〔比較例１〕
１００部のＡ−１とＢ−１の加熱混合物と３０部のＤ−１を直径６インチの３本ロールで混合した。撹拌羽付きミキサーにこの混合物を投入し、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて混合してペースト状粘着剤組成物を調製し、脱気した。このペースト状粘着剤組成物の粘度を測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。
[Comparative Example 1]
100 parts of the heated mixture of A-1 and B-1 and 30 parts of D-1 were mixed in a 6-inch diameter three roll. This mixture was put into a mixer equipped with stirring blades, C-1 and E-1 were added and mixed at the blending ratios shown in Table 1 to prepare a paste-like pressure-sensitive adhesive composition, and deaerated. The viscosity of this paste-like pressure-sensitive adhesive composition was measured, the leaching property to the back surface was observed, the adhesive force was measured, the removability was observed, and the results are shown in Table 1.
〔比較例２〕
１００部のＡ−１とＢ−１の加熱混合物と１５部のＤ−１を直径６インチの３本ロールで混合し、１２０部のＦ−１と３.０部のＧ−１をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製し、脱気した。水性エマルションの乳化状況を観察して、その結果を表１に示した。
[Comparative Example 2]
100 parts of the heated mixture of A-1 and B-1 and 15 parts of D-1 are mixed with 3 rolls of 6 inches in diameter, and 120 parts of F-1 and 3.0 parts of G-1 are mixed with Mazerustar KK. An aqueous emulsion was prepared and degassed under the same conditions as in Example 1 by charging into a −100 type emulsifier. The state of emulsification of the aqueous emulsion was observed, and the results are shown in Table 1.
〔比較例３〕
１００部のＡ−１と１０部のＤ−１を直径６インチの３本ロールで混合し、該混合物と１５部のＦ−２をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて実施例１と同一の条件で攪拌混合し脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。
[Comparative Example 3]
100 parts of A-1 and 10 parts of D-1 were mixed with a three-inch 6-inch diameter roll, and the mixture and 15 parts of F-2 were introduced into a Mazerustar KK-100 type emulsifier. An aqueous emulsion was prepared under the same conditions. Next, C-1 and E-1 were added to the aqueous emulsion in the mixing ratios shown in Table 1, respectively, and the mixture was stirred and mixed under the same conditions as in Example 1 for deaeration. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1.
〔比較例４〕
１００部のＡ−１と１０部のＤ−１を直径６インチの３本ロールで混合し、該混合物と１５部のＷと１．０部のＧ−１をマゼルスターＫＫ−１００型乳化機に投入して、実施例１と同一の条件で水性エマルションを調製した。次に、この水性エマルションに、表１の配合比でそれぞれＣ−１、Ｅ−１を加えて実施例１と同一の条件で攪拌混合し脱気した。この水性エマルションの乳化状況と粘度を観察・測定し、裏面への浸出性を観察し、粘着力を測定し、再剥離性を観察して、その結果を表１に示した。
[Comparative Example 4]
100 parts of A-1 and 10 parts of D-1 are mixed with 3 rolls of 6 inches in diameter, and the mixture, 15 parts of W and 1.0 part of G-1 are mixed into a Mazerustar KK-100 type emulsifier. The aqueous emulsion was prepared under the same conditions as in Example 1. Next, C-1 and E-1 were added to the aqueous emulsion in the mixing ratios shown in Table 1, respectively, and the mixture was stirred and mixed under the same conditions as in Example 1 for deaeration. The emulsification status and viscosity of this aqueous emulsion were observed and measured, the leaching property to the back surface was observed, the adhesive force was measured, and the removability was observed. The results are shown in Table 1.
〔実施例５〕
実施例１で調製したエマルション型シリコーン粘着剤組成物を、ナイロンとポリウレタンからなる花柄のストレッチラッセルレースに実施例１と同一の条件でスクリーン印刷し、硬化乾燥を行ったところ、レース裏面へのシリコーン粘着剤の浸透がなく、レース裏面の汚染がなく、再剥離性を有することがわかった。
Example 5
The emulsion-type silicone pressure-sensitive adhesive composition prepared in Example 1 was screen-printed under the same conditions as in Example 1 on a stretch lace lace with a floral pattern made of nylon and polyurethane, and cured and dried. It was found that there was no penetration of the silicone adhesive, there was no contamination of the back of the race, and it had removability.
本発明の多孔質シート用エマルション型シリコーン粘着剤組成物は、織物、編物、不織布、紙のような多孔質シートの片面に適用して片面にのみ粘着剤層を有する再剥離性粘着シートを製造するのに有用である。本発明の再剥離性粘着シートは、皮膚や、種々の基材（例、金属、ガラス、セラミック、石、プラスチック、ゴム、木、織物、編物、不織布、紙、皮革）表面に粘着させ、必要に応じて再剥離するのに有用である。
The emulsion type silicone pressure-sensitive adhesive composition for porous sheets of the present invention is applied to one side of a porous sheet such as woven fabric, knitted fabric, non-woven fabric and paper to produce a releasable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer only on one side. Useful to do. The re-peelable pressure-sensitive adhesive sheet of the present invention is required to adhere to the surface of skin and various base materials (eg, metal, glass, ceramic, stone, plastic, rubber, wood, woven fabric, knitted fabric, non-woven fabric, paper, leather). It is useful for re-peeling depending on the condition.
Claims (4)
（Ｂ）補強性シリカ微粉末 ５〜３０重量部、
（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノハイドロジェンポリシロキサン、
本成分中のケイ素原子結合水素原子のモル数（Ｈ）と成分（Ａ）中のジオルガノポリシロキサン中のアルケニル基のモル数（Ｖ）のモル比（Ｈ／Ｖ）が０．５〜１５の範囲にある量、
（Ｄ）Ｒ 3 ＳｉＯ 0.5 単位（但し、式中のＲは１価炭化水素基）及びＳｉＯ 2 単位からなり、Ｒ 3 ＳｉＯ 0.5 単位／ＳｉＯ 2 単位のモル比が０．６〜１．３の範囲にあるオルガノポリシロキサンレジン ５〜５０重量部、
（Ｅ）触媒量の白金系触媒、
（Ｆ）水１００重量部当たりスメクタイトクレーを０．５〜１０重量部含有するスメクタイトクレー含有水 ５〜１００重量部、および
成分（Ａ）、成分（Ｃ）および成分（Ｄ）を乳化するのに必要な量の（Ｇ）乳化剤から成ることを特徴とする多孔質シート用エマルション型シリコーン粘着剤組成物。 (A) 100 parts by weight of a diorganopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule;
(B) 5-30 parts by weight of reinforcing silica fine powder,
(C) an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule;
The molar ratio (H / V) of the number of moles (H) of silicon-bonded hydrogen atoms in this component to the number of moles (V) of alkenyl groups in the diorganopolysiloxane in component (A) is 0.5-15. An amount in the range of,
(D) R 3 Si O 0.5 units (Here, R in the formula is a monovalent hydrocarbon group) consists and Si O 2 units, the molar ratio of R 3 Si O 0.5 units / Si O 2 unit 0.6 5-50 parts by weight of an organopolysiloxane resin in the range of 1.3,
(E) a catalytic amount of a platinum-based catalyst;
(F) 5 to 100 parts by weight of smectite clay-containing water containing 0.5 to 10 parts by weight of smectite clay per 100 parts by weight of water, and emulsifying component (A), component (C) and component (D) An emulsion-type silicone pressure-sensitive adhesive composition for porous sheets, comprising a necessary amount of (G) an emulsifier.
（Ｃ）１分子中に少なくとも２個のケイ素原子結合水素原子を含有するオルガノハイドロジェンポリシロキサン、
本成分中のケイ素原子結合水素原子のモル数（Ｈ）と成分（Ａ）中のジオルガノポリシロキサン中のアルケニル基のモル数（Ｖ）のモル比（Ｈ／Ｖ）が０．５〜１５の範囲にある量、
（Ｄ）Ｒ 3 ＳｉＯ 0.5 単位（但し、式中のＲは１価炭化水素基）及びＳｉＯ 2 単位からなり、Ｒ 3 ＳｉＯ 0.5 単位／ＳｉＯ 2 単位のモル比が０．６〜１．３の範囲にあるオルガノポリシロキサンレジン ５〜５０重量部、
（Ｅ）触媒量の白金系触媒、
（Ｆ）水１００重量部当たりスメクタイトクレーを０．５〜１０重量部含有するスメクタイトクレー含有水 ５〜１００重量部、および
成分（Ａ）と成分（Ｂ）の混合物、成分（Ｃ）および成分（Ｄ）を乳化するのに必要な量の（Ｇ）乳化剤から成ることを特徴とする多孔質シート用エマルション型シリコーン粘着剤組成物。 (A) a mixture of 100 parts by weight of a diorganopolysiloxane having at least two silicon-bonded alkenyl groups in one molecule and (B) 5 to 30 parts by weight of reinforcing silica fine powder,
(C) an organohydrogenpolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule;
The molar ratio (H / V) of the number of moles (H) of silicon-bonded hydrogen atoms in this component to the number of moles (V) of alkenyl groups in the diorganopolysiloxane in component (A) is 0.5-15. An amount in the range of,
(D) R 3 Si O 0.5 units (Here, R in the formula is a monovalent hydrocarbon group) consists and Si O 2 units, the molar ratio of R 3 Si O 0.5 units / Si O 2 unit 0.6 5-50 parts by weight of an organopolysiloxane resin in the range of 1.3,
(E) a catalytic amount of a platinum-based catalyst;
(F) 5 to 100 parts by weight of smectite clay-containing water containing 0.5 to 10 parts by weight of smectite clay per 100 parts by weight of water, and a mixture of component (A) and component (B), component (C) and component ( An emulsion type silicone pressure-sensitive adhesive composition for porous sheets, comprising an amount of (G) an emulsifier necessary for emulsifying D).
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| JP2008189858A (en) * | 2007-02-07 | 2008-08-21 | Nitto Denko Corp | Pressure-sensitive self-adhesive tape |
| JP2008214518A (en) * | 2007-03-06 | 2008-09-18 | Nitto Denko Corp | Self-adhesive tape |
| JP5001955B2 (en) * | 2007-12-12 | 2012-08-15 | 積水化学工業株式会社 | Double-sided adhesive tape for semiconductor processing |
| JP5465429B2 (en) * | 2008-12-24 | 2014-04-09 | 株式会社Ｓｈｉｎｄｏ | Silicone rubber sponge-forming emulsion composition and method for producing silicone rubber sponge |
| CA2814374A1 (en) * | 2010-10-21 | 2012-06-14 | University Of Massachusetts | High capacity easy release extended use adhesive devices |
| US10370571B2 (en) | 2012-12-07 | 2019-08-06 | 3M Innovative Properties Company | Silicone gel adhesive with hydrophillic and antimicrobial properties |
| TWI663236B (en) * | 2014-10-16 | 2019-06-21 | Dow Silicones Corporation | Silicone composition and a pressure sensitive adhesive film having a pressure sensitive adhesive layer made from the composition |
| JP2020015865A (en) * | 2018-07-27 | 2020-01-30 | 信越化学工業株式会社 | Addition reaction curable silicone adhesive composition for applying to skin and adhesive tape for applying to skin |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331220A (en) * | 1994-06-07 | 1995-12-19 | Shin Etsu Chem Co Ltd | Silicone emulsion adhesive composition |
| JPH0812954A (en) * | 1994-06-29 | 1996-01-16 | Sekisui Chem Co Ltd | Adhesive tape |
| JPH08283426A (en) * | 1995-04-19 | 1996-10-29 | Bando Chem Ind Ltd | Bonding between canvas and thermoplastic elastomer |
| JPH10259329A (en) * | 1997-03-18 | 1998-09-29 | Morimura Badische Kk | Easily dispersible organic-bentonite-containing powder composition |
| JP2000044921A (en) * | 1998-08-04 | 2000-02-15 | Dow Corning Toray Silicone Co Ltd | Suspension-type silicone adhesive, preparation thereof and preparation of adhesive substrate |
| JP2001066993A (en) * | 1999-08-25 | 2001-03-16 | Toppan Forms Co Ltd | Linerless thermosensitive recording label sheet and its production |
| JP2001081436A (en) * | 1999-09-07 | 2001-03-27 | Dow Corning Corp | Silicone composition and silicone perssure-sensitive adheive formed therefrom |
| JP2002167557A (en) * | 2000-12-01 | 2002-06-11 | Sekisui Chem Co Ltd | Composition for pressure-sensitive adhesive, pressure- sensitive adhesive and pressure-sensitive adhesive sheet |
| JP2002180025A (en) * | 2000-12-08 | 2002-06-26 | Sliontec Corp | Silicone-based adhesive composition, silicone-based adhesive tape by using the same and method for producing the same |
| JP2002274839A (en) * | 2001-03-19 | 2002-09-25 | Shionogi & Co Ltd | Inorgtanic viscosity control agent for water based coating material |
| JP2002363528A (en) * | 2001-06-11 | 2002-12-18 | Ge Toshiba Silicones Co Ltd | Emulsion composition for adhesion and method for bonding fiber substrate to silicone rubber substrate |
| JP2003514086A (en) * | 1999-11-06 | 2003-04-15 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Self-crosslinkable polyurethanes and polyurethane-based graft copolymers and their use for producing coating materials, adhesives and packing materials |
| JP2004091262A (en) * | 2002-08-30 | 2004-03-25 | Topy Ind Ltd | Organized layered silicate and its manufacturing method |
| JP2004346248A (en) * | 2003-05-23 | 2004-12-09 | Shindo Seni Kogyo Kk | Emulsion composition for use in silicone rubber |
-
2004
- 2004-09-01 JP JP2004253809A patent/JP4718146B2/en not_active Expired - Fee Related
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07331220A (en) * | 1994-06-07 | 1995-12-19 | Shin Etsu Chem Co Ltd | Silicone emulsion adhesive composition |
| JPH0812954A (en) * | 1994-06-29 | 1996-01-16 | Sekisui Chem Co Ltd | Adhesive tape |
| JPH08283426A (en) * | 1995-04-19 | 1996-10-29 | Bando Chem Ind Ltd | Bonding between canvas and thermoplastic elastomer |
| JPH10259329A (en) * | 1997-03-18 | 1998-09-29 | Morimura Badische Kk | Easily dispersible organic-bentonite-containing powder composition |
| JP2000044921A (en) * | 1998-08-04 | 2000-02-15 | Dow Corning Toray Silicone Co Ltd | Suspension-type silicone adhesive, preparation thereof and preparation of adhesive substrate |
| JP2001066993A (en) * | 1999-08-25 | 2001-03-16 | Toppan Forms Co Ltd | Linerless thermosensitive recording label sheet and its production |
| JP2001081436A (en) * | 1999-09-07 | 2001-03-27 | Dow Corning Corp | Silicone composition and silicone perssure-sensitive adheive formed therefrom |
| JP2003514086A (en) * | 1999-11-06 | 2003-04-15 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Self-crosslinkable polyurethanes and polyurethane-based graft copolymers and their use for producing coating materials, adhesives and packing materials |
| JP2002167557A (en) * | 2000-12-01 | 2002-06-11 | Sekisui Chem Co Ltd | Composition for pressure-sensitive adhesive, pressure- sensitive adhesive and pressure-sensitive adhesive sheet |
| JP2002180025A (en) * | 2000-12-08 | 2002-06-26 | Sliontec Corp | Silicone-based adhesive composition, silicone-based adhesive tape by using the same and method for producing the same |
| JP2002274839A (en) * | 2001-03-19 | 2002-09-25 | Shionogi & Co Ltd | Inorgtanic viscosity control agent for water based coating material |
| JP2002363528A (en) * | 2001-06-11 | 2002-12-18 | Ge Toshiba Silicones Co Ltd | Emulsion composition for adhesion and method for bonding fiber substrate to silicone rubber substrate |
| JP2004091262A (en) * | 2002-08-30 | 2004-03-25 | Topy Ind Ltd | Organized layered silicate and its manufacturing method |
| JP2004346248A (en) * | 2003-05-23 | 2004-12-09 | Shindo Seni Kogyo Kk | Emulsion composition for use in silicone rubber |
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