JPWO2006070947A1 - Solvent-free peelable cured film-forming organopolysiloxane composition - Google Patents

Solvent-free peelable cured film-forming organopolysiloxane composition Download PDF

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JPWO2006070947A1
JPWO2006070947A1 JP2006550882A JP2006550882A JPWO2006070947A1 JP WO2006070947 A1 JPWO2006070947 A1 JP WO2006070947A1 JP 2006550882 A JP2006550882 A JP 2006550882A JP 2006550882 A JP2006550882 A JP 2006550882A JP WO2006070947 A1 JPWO2006070947 A1 JP WO2006070947A1
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organopolysiloxane composition
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JP5101888B2 (en
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堀 誠司
誠司 堀
山田 修司
修司 山田
高照 山田
高照 山田
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DuPont Toray Specialty Materials KK
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00Presence of polysiloxane
    • C09J2483/006Presence of polysiloxane in the substrate

Abstract

[課題] 取り扱いが容易であり、硬化皮膜のすべり性と粘着性物質に対する剥離性に優れる硬化皮膜を形成可能な無溶剤型オルガノポリシロキサン組成物、該硬化皮膜を有するシート状基材およびその製法を提供する。[解決手段] (A)粘度が20〜300mPa・sであり、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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサン、(B)粘度が100,000mPa・s以上であるオルガノポリシロキサン、(C)粘度が1〜1,000mPa・sであり、かつ、1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オルガノハイドロジェンポリシロキサン、および(D)ヒドロシリル化反応触媒からなることを特徴とする無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。[PROBLEMS] Solvent-free organopolysiloxane composition capable of forming a cured film that is easy to handle and has excellent slipperiness of the cured film and excellent releasability from adhesive substances, a sheet-like substrate having the cured film, and a method for producing the same I will provide a. [Solution] (A) Organopolysiloxane having a viscosity of 20 to 300 mPa · s and having at least two silicon-bonded alkenyl groups and at least two silicon-bonded phenyl groups in one molecule, (B) viscosity Having a viscosity of 1 to 1,000 mPa · s, and having at least three silicon-bonded hydrogen atoms in one molecule And (D) a solvent-free peelable cured film-forming organopolysiloxane composition comprising a hydrosilylation reaction catalyst.

Description

本発明は、取り扱いが容易であり、基材表面に硬化皮膜を形成し、粘着性物質に対する良好な剥離性と被処理面の円滑なすべり性を付与することができる無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物に関し、該組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材およびその製造方法に関するものである。  The present invention is easy to handle, forms a cured film on the surface of a substrate, and can provide a good peelability to an adhesive substance and a smooth slipperiness of the surface to be treated. The present invention relates to a formable organopolysiloxane composition, and relates to a sheet-like substrate having a peelable cured film obtained by curing the composition and a method for producing the same.

各種紙,ラミネート紙,合成フィルム,金属箔等の基材表面にオルガノポリシロキサン組成物の硬化皮膜を形成させることにより、粘着性物質に対する剥離性を付与する方法はよく知られている。この場合、剥離性硬化皮膜を形成する方法として、ヒドロシリル化反応触媒の存在下、不飽和炭化水素基を有するオルガノポリシロキサンとオルガノハイドロジェンポリシロキサンとを付加反応させる、付加反応型のオルガノポリシロキサン組成物(例えば、特開昭47−32072号公報参照)が広く用いられており、これらの剥離性硬化皮膜形成性オルガノポリシロキサン組成物の性状として、これらをトルエン等の有機溶剤に溶解された溶剤型、これらをエマルジョン化したエマルジョン型、オルガノポリシロキサンのみからなる無溶剤型が知られている。近年、安全・環境に対する配慮から、溶剤型に代わり、無溶剤型の剥離性硬化皮膜形成性オルガノポリシロキサン組成物が広範な用途で求められている。例えば、特開2004−307691号公報には無溶剤型の剥離性硬化皮膜形成性オルガノポリシロキサン組成物が開示されている。  A method of imparting releasability to an adhesive substance by forming a cured film of an organopolysiloxane composition on the surface of a substrate such as various papers, laminated papers, synthetic films, and metal foils is well known. In this case, as a method for forming a peelable cured film, an addition reaction type organopolysiloxane in which an organopolysiloxane having an unsaturated hydrocarbon group and an organohydrogenpolysiloxane are subjected to an addition reaction in the presence of a hydrosilylation reaction catalyst. Compositions (see, for example, JP-A-47-32072) have been widely used, and as properties of these peelable cured film-forming organopolysiloxane compositions, these were dissolved in an organic solvent such as toluene. A solvent type, an emulsion type obtained by emulsifying these, and a solventless type consisting only of organopolysiloxane are known. In recent years, from the viewpoint of safety and the environment, a solvent-free peelable cured film-forming organopolysiloxane composition has been demanded for a wide range of applications in place of the solvent type. For example, JP-A-2004-307691 discloses a solvent-free peelable cured film-forming organopolysiloxane composition.

しかしながら、従来の無溶剤型の剥離性硬化皮膜形成性オルガノポリシロキサン組成物は、主剤とするオルガノポリシロキサンの粘度が粘度が50〜1000cs程度と低粘度であり、高粘度のオルガノポリシロキサンを含まないため、途工性に優れる反面、形成された硬化皮膜のすべり性が悪く、用途が限定されるという不利があった。すなわち、これらの低粘度のオルガノポリシロキサンを主剤として用いた無溶剤型の組成物は、クラフトテープの離型剤として使用されると、形成された硬化皮膜のすべり性が悪く、テープをダンボールなどに貼る作業がスムーズに行われず、また粘着剤が完全に接着せず剥げ落ちることがあった。また紙、ラミネート紙またはプラスチックフィルムに硬化皮膜を形成させた場合でも、硬化皮膜のすべり性が悪く、テープを傷つけたり、テープがスムーズに回転せず工程上で二次的なトラブルの原因になるという問題があった。さらに、この種の低粘度のオルガノポリシロキサンを主剤として用いた無溶剤型のオルガノポリシロキサン組成物を紙またはプラスティックフィルムに塗工し、硬化皮膜を形成させて剥離紙を製造すると、硬化皮膜のすべり性が悪いために、剥離紙を巻き取る前に硬化皮膜と金属あるいはプラスチックのロールとが接触するとにより、硬化皮膜が傷ついたものとなったり、後で粘着塗工されたときに離型性のバラツキが生じたりして、紙またはプラスチックフィルムの巻き取りがスムーズには行えないという問題があった。  However, the conventional solvent-free peelable cured film-forming organopolysiloxane composition has a low viscosity of about 50 to 1000 cs, and contains a high-viscosity organopolysiloxane. However, there is a disadvantage that the formed film is poorly slidable and its application is limited. That is, the solventless composition using these low-viscosity organopolysiloxanes as the main agent, when used as a release agent for kraft tape, the formed cured film has poor sliding properties, and the tape is made of cardboard, etc. The sticking work was not performed smoothly, and the pressure-sensitive adhesive was not completely adhered and sometimes peeled off. In addition, even when a cured film is formed on paper, laminated paper, or plastic film, the cured film is not slippery and may damage the tape or cause the tape to rotate smoothly and cause secondary troubles in the process. There was a problem. Furthermore, when a solvent-free organopolysiloxane composition using this type of low-viscosity organopolysiloxane as a main ingredient is applied to paper or a plastic film to form a cured film, a release paper is produced. Due to poor slipping property, the cured film comes into contact with the metal or plastic roll before winding the release paper, resulting in damage to the cured film or releasability when adhesive coating is applied later. There was a problem that the paper or plastic film could not be smoothly wound.

特開昭61−159480号公報には、硬化皮膜のすべり性を改善する目的で、ビニル基の含有量が0.5〜10.0モル%以下であり、25℃における粘度が50〜100,000cpsであるオルガノポリシロキサンを添加する方法を提案されている。また、特開昭61−264052号公報には、ビニル基の含有量が全有機基の0.5〜10.0%であり、25℃における粘度が50〜10,000cpsであるオルガノポリシロキサンと分子鎖末端に水酸基を有し25℃における粘度が100,000cps以上の実質的に直鎖状のオルガノポリシロキサンを含有する、25℃における粘度が50〜10,000csの無溶剤型の離型紙用シリコーン組成物が提案されている。しかし、これらの組成物はビニル基の含有量の少ないオルガノポリシロキサンを多量に添加する必要があるため、剥離性硬化皮膜形成性オルガノポリシロキサン組成物の粘度が上昇し、その取り扱いが困難になるという問題があった。さらに、そのすべり性も十分満足できるものではなかった。  In JP-A-61-159480, the content of vinyl groups is 0.5 to 10.0 mol% or less and the viscosity at 25 ° C. is 50 to 100, for the purpose of improving the slipperiness of the cured film. A method of adding organopolysiloxane at 000 cps has been proposed. JP-A-61-264052 discloses an organopolysiloxane having a vinyl group content of 0.5 to 10.0% of all organic groups and a viscosity at 25 ° C. of 50 to 10,000 cps; For solvent-free release paper having a viscosity of 50 to 10,000 cs at 25 ° C., which contains a substantially linear organopolysiloxane having a hydroxyl group at the molecular chain end and a viscosity at 25 ° C. of 100,000 cps or more. Silicone compositions have been proposed. However, these compositions require the addition of a large amount of organopolysiloxane having a low vinyl group content, which increases the viscosity of the peelable cured film-forming organopolysiloxane composition and makes it difficult to handle. There was a problem. Furthermore, the slipperiness was not satisfactory.

特開昭47−32072号公報Japanese Patent Laid-Open No. 47-32072 特開2004−307691号公報JP 2004-307691 A 特開昭61−159480号公報Japanese Patent Laid-Open No. 61-159480 特開昭61−264052号公報JP-A-61-264052

本発明は上記問題を解決すべくなされたものであり、取り扱いが容易であり、形成される硬化皮膜のすべり性と粘着性物質に対する剥離性に優れた無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を提供する。また、該組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材およびその製造方法を提供する。  The present invention has been made to solve the above-mentioned problems, is easy to handle, and has a non-solvent releasable cured film-forming organopolyester that is easy to handle and excellent in the slipperiness of the formed cured film and releasable from adhesive substances. A siloxane composition is provided. Moreover, the sheet-like base material which has a peelable cured film formed by hardening this composition, and its manufacturing method are provided.

本発明者らは、上記目的を達成するために鋭意検討した結果、
(A)25℃における粘度が20〜300mPa・sであり、下記一般式で表される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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサン: 100重量部

Figure 2006070947
(式中、Rはそれぞれ独立に炭素原子数1〜8の1価のアルキル基であり、RはR、炭素原子数2〜8の1価のアルケニル基またはフェニル基からなる群から選択される同一または異種の基、Rはフェニル基、Rは炭素原子数2〜8のアルケニル基であり、R〜Rのうち少なくとも2つ以上はアルケニル基である。xは2≦x≦10であり、yは1≦y≦10であり、zは20≦z≦97であり、x+y+zは前記粘度範囲を満足する数である)、
(B)25℃における粘度が100,000mPa・s以上であり、ケイ素原子に結合した全ての有機基のうち90モル%以上が非反応性のアルキル基またはアリール基であるオルガノポリシロキサン: 0.5〜15重量部
(C)25℃における粘度が1〜1,000mPa・sであり、かつ、1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し、脂肪族不飽和結合を有しないオルガノハイドロジェンポリシロキサン: 0.5〜30重量部、および
(D)ヒドロシリル化反応触媒: 触媒量
からなることを特徴とする無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物および該組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材により前記課題を解決できることを見出し、本発明に到達した。As a result of intensive studies to achieve the above object, the present inventors
(A) Organopoly having a viscosity of 20 to 300 mPa · s at 25 ° C. and having at least two silicon atom-bonded alkenyl groups and at least two silicon atom-bonded phenyl groups in one molecule represented by the following general formula: Siloxane: 100 parts by weight
Figure 2006070947
Wherein R 1 is independently a monovalent alkyl group having 1 to 8 carbon atoms, and R 2 is a group consisting of R 1 , a monovalent alkenyl group having 2 to 8 carbon atoms or a phenyl group. The same or different groups selected, R 3 is a phenyl group, R 4 is an alkenyl group having 2 to 8 carbon atoms, and at least two of R 1 to R 4 are alkenyl groups, x is 2 ≦ x ≦ 10, y is 1 ≦ y ≦ 10, z is 20 ≦ z ≦ 97, and x + y + z is a number satisfying the viscosity range).
(B) Organopolysiloxane having a viscosity at 25 ° C. of 100,000 mPa · s or more and 90 mol% or more of all organic groups bonded to silicon atoms being a non-reactive alkyl group or aryl group: 5 to 15 parts by weight (C) The viscosity at 25 ° C. is 1 to 1,000 mPa · s, has at least 3 silicon-bonded hydrogen atoms in one molecule, and does not have an aliphatic unsaturated bond Organohydrogenpolysiloxane: 0.5 to 30 parts by weight, and (D) hydrosilylation reaction catalyst: a solvent-free peelable cured film-forming organopolysiloxane composition characterized by comprising a catalytic amount and the composition The present inventors have found that the above-mentioned problems can be solved by a sheet-like substrate having a peelable cured film obtained by curing the resin.

すなわち、本発明は、
「 [1](A)25℃における粘度が20〜300mPa・sであり、下記一般式で表れる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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサン: 100重量部、

Figure 2006070947
(式中、Rはそれぞれ独立に炭素原子数1〜8の1価のアルキル基であり、RはR、炭素原子数2〜8の1価のアルケニル基またはフェニル基からなる群から選択される同一または異種の基、Rはフェニル基、Rは炭素原子数2〜8のアルケニル基であり、R〜Rのうち少なくとも2つ以上はアルケニル基である。xは2≦x≦10であり、yは1≦y≦10であり、zは20≦z≦97であり、x+y+zは前記粘度範囲を満足する数である)、
(B)25℃における粘度が100,000mPa・s以上であり、ケイ素原子に結合した全ての有機基のうち90モル%以上が非反応性のアルキル基またはアリール基であるオルガノポリシロキサン: 0.5〜15重量部
(C)25℃における粘度が1〜1,000mPa・sであり、かつ、1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し、脂肪族不飽和結合を有しないオルガノハイドロジェンポリシロキサン: 0.5〜30重量部、および
(D)ヒドロシリル化反応触媒: 触媒量
からなることを特徴とする無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。
[2](B)成分が、25℃における粘度が100,000mPa・s以上である分子鎖末端がトリメチルシロキシ基,シラノール基またはビニル基からなる群から選択される同一または異種の基で封鎖された直鎖状もしくは分岐状のジメチルポリシロキサンであることを特徴とする、[1]に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。
[3]25℃における組成物全体の粘度が50〜2,000mPa・sであることを特徴とする、[1]に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。
[4]さらに(E)ヒドロシリル化反応抑制剤:0.001〜5重量部からなり、常温で非硬化性であり、加熱硬化性である[1]〜[3]のいずれか1項に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。
[5][1]〜[4]のいずれか1項に記載の剥離性硬化皮膜形成性オルガノポリシロキサン組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材。
[6]基材が、ポリエチレンラミネート紙またはプラスチックフィルムである[5]に記載のシート状基材。
[7]シート状基材上に[1]〜[6]のいずれか1項に記載の剥離性硬化皮膜形成性オルガノポリシロキサン組成物をコーテイングし、加熱して硬化させることを特徴とする剥離性硬化皮膜を有するシート状基材の製造方法。
[8]シート状基材が、ポリエチレンラミネート紙またはプラスチックフィルムである[7]に記載のシート状基材の製造方法。」である。That is, the present invention
“[1] (A) The viscosity at 25 ° C. is 20 to 300 mPa · s, and it has at least two silicon atom-bonded alkenyl groups and at least two silicon atom-bonded phenyl groups in one molecule represented by the following general formula. Organopolysiloxane: 100 parts by weight
Figure 2006070947
Wherein R 1 is independently a monovalent alkyl group having 1 to 8 carbon atoms, and R 2 is a group consisting of R 1 , a monovalent alkenyl group having 2 to 8 carbon atoms or a phenyl group. The same or different groups selected, R 3 is a phenyl group, R 4 is an alkenyl group having 2 to 8 carbon atoms, and at least two of R 1 to R 4 are alkenyl groups, x is 2 ≦ x ≦ 10, y is 1 ≦ y ≦ 10, z is 20 ≦ z ≦ 97, and x + y + z is a number satisfying the viscosity range).
(B) Organopolysiloxane having a viscosity at 25 ° C. of 100,000 mPa · s or more and 90 mol% or more of all organic groups bonded to silicon atoms being a non-reactive alkyl group or aryl group: 5 to 15 parts by weight (C) The viscosity at 25 ° C. is 1 to 1,000 mPa · s, has at least 3 silicon-bonded hydrogen atoms in one molecule, and does not have an aliphatic unsaturated bond Organohydrogenpolysiloxane: 0.5-30 parts by weight, and (D) hydrosilylation reaction catalyst: A solvent-free peelable cured film-forming organopolysiloxane composition characterized by comprising a catalytic amount.
[2] The component (B) is blocked with the same or different group selected from the group consisting of trimethylsiloxy group, silanol group or vinyl group at the molecular chain terminal having a viscosity at 25 ° C. of 100,000 mPa · s or more. The solvent-free peelable cured film-forming organopolysiloxane composition according to [1], which is a linear or branched dimethylpolysiloxane.
[3] The solvent-free peelable cured film-forming organopolysiloxane composition according to [1], wherein the viscosity of the entire composition at 25 ° C. is 50 to 2,000 mPa · s.
[4] Furthermore, (E) hydrosilylation reaction inhibitor: 0.001 to 5 parts by weight, non-curable at normal temperature, and heat-curable [1] to [3] Solvent-free peelable cured film-forming organopolysiloxane composition.
[5] A sheet-like substrate having a peelable cured film obtained by curing the peelable cured film-forming organopolysiloxane composition according to any one of [1] to [4].
[6] The sheet-like substrate according to [5], wherein the substrate is polyethylene laminated paper or a plastic film.
[7] Peeling characterized in that the peelable cured film-forming organopolysiloxane composition according to any one of [1] to [6] is coated on a sheet-like substrate, and cured by heating. For producing a sheet-like substrate having a heat-resistant cured film.
[8] The method for producing a sheet-like substrate according to [7], wherein the sheet-like substrate is polyethylene laminated paper or a plastic film. It is.

本発明によれば、取り扱いが容易であり、形成される硬化皮膜のすべり性と粘着性物質に対する剥離性に優れた無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を提供できる。また、該組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材およびその製造方法を提供できる。  According to the present invention, it is possible to provide a solventless releasable cured film-forming organopolysiloxane composition that is easy to handle and excellent in the slipperiness of the formed cured film and the releasability from adhesive substances. Moreover, the sheet-like base material which has a peelable cured film formed by hardening this composition, and its manufacturing method can be provided.

(A)成分は本発明の主要成分であり、硬化皮膜にすべり性を付与する(B)成分との相溶性が低いため、付加反応により形成された硬化皮膜の表面に(B)成分を効果的に浮き出させることができる。このため、少量の(B)成分を添加するだけで、優れたすべり性を硬化皮膜に付与することができるものである。かかる(A)成分は粘度が25℃における粘度が20〜300mPa・sであり、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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサンであるものである。以下、(A)成分について具体的に説明する。  The component (A) is a main component of the present invention, and since the compatibility with the component (B) that imparts slipperiness to the cured film is low, the component (B) is effective on the surface of the cured film formed by the addition reaction. Can be raised. For this reason, only by adding a small amount of (B) component, the outstanding slip property can be provided to a cured film. The component (A) is an organopolysiloxane having a viscosity of 20 to 300 mPa · s at 25 ° C. and having at least two silicon atom-bonded alkenyl groups and at least two silicon atom-bonded phenyl groups in one molecule. There is something. Hereinafter, the component (A) will be specifically described.

(A)成分は25℃における粘度が20〜300mPa・sであり、下記一般式で表される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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサンである。

Figure 2006070947
上式中、Rはそれぞれ独立に炭素原子数1〜8の1価のアルキル基であり、具体的にはメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、ヘプチル基、オクチル基が例示され、好ましくはメチル基である。RはR、炭素原子数2〜8の1価のアルケニル基またはフェニル基からなる群から選択される同一または異種の基であり、具体的には前記のRやビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基などのアルケニル基、またはフェニル基が例示される。Rはフェニル基、Rは炭素原子数2〜8のアルケニル基であり、R〜Rのうち少なくとも2つ以上はアルケニル基である。xは2≦x≦10であり、一分子中に少なくとも2個のケイ素原子結合フェニル基を有する。また、yは1≦y≦10であり、側鎖部分に少なくとも1個のケイ素原子結合アルケニル基を有する。zは20≦z≦97であり、x+y+zは前記粘度範囲を満足する数である。xが前記上限を超えると(B)成分との相溶性が著しく悪くなり、組成物全体が白濁しやすくなる。またyが前記上限を超えると本発明組成物からなる硬化皮膜の被着体との密着性が低下する可能性がある。また、(A)成分の25℃における粘度は20〜300mPa・sであり、より好ましくは、50〜250mPa・sである。(A)成分の粘度が前記上限を超えると、組成物の粘度が高くなりすぎるため塗工性に劣る結果となる。Component (A) has a viscosity at 25 ° C. of 20 to 300 mPa · s, and has at least two silicon atom-bonded alkenyl groups and at least two silicon atom-bonded phenyl groups in one molecule represented by the following general formula. Organopolysiloxane.
Figure 2006070947
In the above formula, each R 1 is independently a monovalent alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, or an octyl group. Illustratively, a methyl group is preferable. R 2 is R 1 , the same or different group selected from the group consisting of a monovalent alkenyl group having 2 to 8 carbon atoms or a phenyl group, and specifically R 1 , a vinyl group, or an allyl group. , An alkenyl group such as a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, or a phenyl group. R 3 is a phenyl group, R 4 is an alkenyl group having 2 to 8 carbon atoms, and at least two of R 1 to R 4 are alkenyl groups. x is 2 ≦ x ≦ 10, and has at least two silicon-bonded phenyl groups in one molecule. Y is 1 ≦ y ≦ 10 and has at least one silicon-bonded alkenyl group in the side chain portion. z is 20 ≦ z ≦ 97, and x + y + z is a number satisfying the viscosity range. When x exceeds the above upper limit, the compatibility with the component (B) is remarkably deteriorated, and the whole composition tends to become cloudy. Moreover, when y exceeds the said upper limit, the adhesiveness with the adherend of the cured film which consists of this invention composition may fall. Moreover, the viscosity in 25 degreeC of (A) component is 20-300 mPa * s, More preferably, it is 50-250 mPa * s. When the viscosity of the component (A) exceeds the above upper limit, the viscosity of the composition becomes too high, resulting in poor coatability.

(B)成分は本発明組成中で、すべり性を出すための添加剤として作用している。かかる(B)成分は25℃における粘度が100,000mPa・s以上であるジオルガノポリシロキサンであり、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,プロピル基などのアルキル基;ビニル基,アリル基,5−ヘキセニル基などのアルケニル基;フェニル基などのアリール基;3,3,3−トリフルオロプロピル基,ノナフルオロヘキシル基などのハロアルキル基;シラノール基が例示される。本発明の目的を達成するためには、ケイ素原子に結合した有機基の90%以上が非反応性のアルキル基またはアリール基であることが必要である。(B)成分の性状は100,000mPa・s以上の液体でも生ゴム状であっても良く、液体の場合には粘度が1000,000mPa・s以上であることが好ましい。また、(B)成分が生ゴム状である場合、その可塑度(JIS K 6249に規定される方法に準じて可塑度計で測定された可塑度:25℃で4.2gの球状試料に1kgfの荷量を3分間かけたときの値)が0.5〜10.0mmの範囲内であることが好ましく、特には0.9〜3.0mmの範囲内であることが好ましい。  The component (B) acts as an additive for providing slipperiness in the composition of the present invention. The component (B) is a diorganopolysiloxane having a viscosity at 25 ° C. of 100,000 mPa · s or more. Examples of the organic group bonded to the silicon atom include alkyl groups such as a methyl group, an ethyl group, and a propyl group; vinyl Examples include alkenyl groups such as a group, allyl group and 5-hexenyl group; aryl groups such as phenyl group; haloalkyl groups such as 3,3,3-trifluoropropyl group and nonafluorohexyl group; and silanol groups. In order to achieve the object of the present invention, it is necessary that 90% or more of the organic group bonded to the silicon atom is a non-reactive alkyl group or aryl group. Component (B) may be in the form of a liquid having a viscosity of 100,000 mPa · s or more or a raw rubber. In the case of a liquid, the viscosity is preferably 1,000,000 mPa · s or more. Further, when the component (B) is in the form of raw rubber, its plasticity (plasticity measured by a plasticity meter according to the method specified in JIS K 6249: 1 kgf on a spherical sample of 4.2 g at 25 ° C. The value when the load is applied for 3 minutes is preferably in the range of 0.5 to 10.0 mm, particularly preferably in the range of 0.9 to 3.0 mm.

(B)成分として、具体的には、分子鎖末端がケイ素原子に結合したアルキル基,アルケニル基,アリール基,ハロアルキル基またはシラノール基からなる群から選択される同一または異種の基で封鎖されたポリジメチルシロキサン,ジメチルシロキサン・フェニルメチルシロキサン共重合体,ジメチルシロキサン・ジフェニルシロキサン共重合体が例示される。このような(B)成分として、分子鎖末端がトリメチルシロキシ基,シラノール基またはビニル基からなる群から選択される同一または異種の基で封鎖された直鎖状もしくは分岐状のジメチルポリシロキサンが特に好ましい。また、重合度の異なるポリジメチルシロキサンの混合物を使用してもよい。  As the component (B), specifically, the molecular chain terminal is blocked with the same or different group selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, a haloalkyl group, or a silanol group bonded to a silicon atom. Examples thereof include polydimethylsiloxane, dimethylsiloxane / phenylmethylsiloxane copolymer, and dimethylsiloxane / diphenylsiloxane copolymer. As such component (B), a linear or branched dimethylpolysiloxane whose molecular chain end is blocked with the same or different group selected from the group consisting of trimethylsiloxy group, silanol group or vinyl group is particularly preferred. preferable. A mixture of polydimethylsiloxanes having different degrees of polymerization may be used.

本発明の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物は、前記の(A)成分 100重量部に対して、(B)成分を0.5〜15重量部含む。(B)成分の含有量が前記下限より少ないと硬化皮膜表面のすべり性が不十分であり、前記上限を超えるとオルガノポリシロキサン組成物の粘度が高くなりすぎて、実作業に支障をきたす。  The solvent-free peelable cured film-forming organopolysiloxane composition of the present invention contains 0.5 to 15 parts by weight of component (B) with respect to 100 parts by weight of component (A). When the content of the component (B) is less than the lower limit, the surface of the cured film is insufficiently slipped. When the content exceeds the upper limit, the viscosity of the organopolysiloxane composition becomes too high, which hinders actual work.

(C)成分は、25℃における粘度が1〜1,000mPa・sであり、かつ、1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し、アルケニル基を有しないオルガノハイドロジェンポリシロキサンであり、前記の(A)成の架橋剤として機能し、硬化皮膜を形成する。(C)成分は、1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が、ケイ素原子結合水素原子の含有量はオルガノポリシロキサン組成物全体の0.1〜2.0重量%であることが好ましく、0.5〜1.8重量%であることがより好ましい。また、前記の(A)成分に含まれるアルケニル基の量に対する、ケイ素原子に直接結合している水素原子の量はモル比で1.0〜5.0の範囲であることが好ましい。同モル比が前記下限より小さいと硬化性が低下し、前記上限を超えると剥離抵抗が大きくなり、実用的な剥離性が得られなくなる。
また、水素原子以外で、(C)成分が含有する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,オクチル基のアルキル基が例示され、メチル基であることが好ましい。また、その分子構造としては、直鎖状,分岐鎖状,分岐状環状が例示される。直鎖状または分岐鎖状の場合、分子鎖末端基としてはトリメチルシロキシ基,ジメチルハイドロジェンシロキシ基が例示される。
Component (C) is an organohydrogenpolysiloxane having a viscosity at 25 ° C. of 1 to 1,000 mPa · s, having at least three silicon-bonded hydrogen atoms in one molecule, and having no alkenyl group. And functions as the above-mentioned (A) crosslinking agent to form a cured film. Component (C) needs to have at least three silicon-bonded hydrogen atoms in one molecule, and the bonding position is not particularly limited, but the content of silicon-bonded hydrogen atoms is an organopolysiloxane composition. The total amount is preferably 0.1 to 2.0% by weight, and more preferably 0.5 to 1.8% by weight. The amount of hydrogen atoms directly bonded to silicon atoms relative to the amount of alkenyl groups contained in component (A) is preferably in the range of 1.0 to 5.0 in terms of molar ratio. When the molar ratio is less than the lower limit, curability is lowered, and when the upper limit is exceeded, the peel resistance increases and practical peelability cannot be obtained.
Moreover, as an organic group couple | bonded with the silicon atom which (C) component contains other than a hydrogen atom, the alkyl group of a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group is illustrated, and is a methyl group Is preferred. In addition, examples of the molecular structure include straight chain, branched chain, and branched ring. In the case of a straight chain or branched chain, examples of the molecular chain terminal group include a trimethylsiloxy group and a dimethylhydrogensiloxy group.

(C)成分の25℃における粘度は1〜1,000mPa・sであり、好ましくは5〜500mPa・sである。これは、25℃における粘度が1mPa・s未満であると、(C)成分がオルガノポリシロキサン組成物中から揮発し易く、1,000mPa・sを超えると、オルガノポリシロキサン組成物の硬化時間が長くなるためである。このような(C)成分として、具体的には、両末端トリメチルシロキシ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共重合体,両末端ジメチルハイドロジェンシロキシ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共重合体,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,環状メチルハイドロジェンポリシロキサン,環状メチルハイドロジェンシロキサン・ジメチルシロキサン共重合体が例示される。  (C) The viscosity in 25 degreeC of a component is 1-1000 mPa * s, Preferably it is 5-500 mPa * s. When the viscosity at 25 ° C. is less than 1 mPa · s, the component (C) is easily volatilized from the organopolysiloxane composition, and when it exceeds 1,000 mPa · s, the curing time of the organopolysiloxane composition is This is because it becomes longer. Specific examples of such a component (C) include a trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, a dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, Examples thereof include trimethylsiloxy group-blocked methyl hydrogen polysiloxane, cyclic methyl hydrogen polysiloxane, and cyclic methyl hydrogen siloxane / dimethyl siloxane copolymer.

本発明の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物は、前記の(A)成分 100重量部に対して、(C)成分を0.5〜30重量部含むものであり、1〜20重量部含むことが好ましい。(C)成分の含有量が前記下限未満であるとオルガノポリシロキサン組成物の硬化が不十分となり、前記上限を超えると本発明組成物の剥離性硬化皮膜の剥離抵抗が大きくなり、さらに経時的に剥離抵抗が増大するためである。  The solvent-free peelable cured film-forming organopolysiloxane composition of the present invention contains 0.5 to 30 parts by weight of component (C) with respect to 100 parts by weight of component (A). It is preferable to contain -20 weight part. When the content of the component (C) is less than the lower limit, the curing of the organopolysiloxane composition becomes insufficient, and when the content exceeds the upper limit, the peel resistance of the peelable cured film of the composition of the present invention increases, and further with time. This is because the peeling resistance increases.

(D)成分はヒドロシリル化反応触媒であり、(A)成分と(C)成分とを付加反応により架橋させる成分である。このような(D)成分は、ヒドロシリル化反応に用いられる触媒であれば特に限定されるものではないが、具体的には、塩化白金酸、アルコール変性塩化白金酸,塩化白金酸のオレフィン錯体,塩化白金酸とケトン類との錯体,白金とアルケニルシロキサンとの錯体、四塩化白金、白金微粉末、アルミナまたはシリカの担体に固体状白金を担持させたもの、白金黒、白金のオレフィン錯体、白金のカルボニル錯体、これらの白金系触媒を含むメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリスチレン樹脂、シリコーン樹脂等の熱可塑性有機樹脂粉末の白金系触媒;式:[Rh(OCCH、Rh(OCCH、Rh(C15、Rh(C、Rh(C)(CO)、Rh(CO)[PhP](C)、RhX[(RS]、(R P)Rh(CO)X、(R P)Rh(CO)H、Rh、HRh(E)Cl、またはRh[O(CO)R]−n(OH)で表されるロジウム系触媒(式中、Xは水素原子、塩素原子、臭素原子、またはヨウ素原子であり、Yはアルキル基、CO、C14であり、Rはアルキル基、シクロアルキル基、またはアリール基であり、Rはアルキル基、アリール基、アルキルオキシ基、またはアリールオキシ基であり、Eはオレフィンであり、aは0または1であり、bは1または2であり、cは1〜4の整数であり、dは2、3、または4であり、nは0または1である。);式:Ir(OOCCH、Ir(C、[Ir(Z)(E)、または[Ir(Z)(Dien)]で表されるイリジウム系触媒(式中、Zは塩素原子、臭素原子、ヨウ素原子、またはアルコキシ基であり、Eはオレフィンであり、Dienはシクロオクタジエンである。)が例示される。塩化白金酸,白金のオレフィン錯体,白金とビニルシロキサンとの錯体を用いることが好ましく、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,塩化白金酸とテトラメチルテトラビニルシクロテトラシロキサンとの錯体,白金ジビニルテトラメチルジシロキサン錯体,白金テトラメチルテトラビニルシクロテトラシロキサン錯体等の白金アルケニルシロキサン錯体が特に好ましい。(D)成分の添加量は触媒量であればよく、通常、本発明の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物の全体質量に対し、(D)成分が含有する金属量で1〜1,000ppmであり、好ましくは5〜500ppmの範囲とすることが好ましい。Component (D) is a hydrosilylation reaction catalyst, and is a component that crosslinks (A) component and (C) component by addition reaction. Such component (D) is not particularly limited as long as it is a catalyst used in the hydrosilylation reaction. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complexes of chloroplatinic acid, Complex of chloroplatinic acid and ketones, complex of platinum and alkenylsiloxane, platinum tetrachloride, platinum fine powder, alumina or silica supported on solid platinum, platinum black, platinum olefin complex, platinum A platinum-based catalyst of a thermoplastic organic resin powder such as methyl methacrylate resin, polycarbonate resin, polystyrene resin, and silicone resin containing these platinum-based catalysts; Formula: [Rh (O 2 CCH 3 ) 2 ] 2 , Rh (O 2 CCH 3 ) 3 , Rh 2 (C 8 H 15 O 2 ) 4 , Rh (C 5 H 7 O 2 ) 3 , Rh (C 5 H 7 O 2 ) (CO) 2 , Rh (CO) [Ph 3 P] (C 5 H 7 O 2 ), RhX 3 [(R 6 ) 2 S] 3 , (R 7 3 P) 2 Rh (CO) X, ( R 7 3 P) 2 Rh (CO) H, Rh 2 X 2 Y 4 , H a Rh b (E) c Cl d , or Rh [O (CO) R] 3 -n (OH) n Rhodium catalyst (wherein X is a hydrogen atom, chlorine atom, bromine atom, or iodine atom, Y is an alkyl group, CO, C 8 H 14 , R 6 is an alkyl group, a cycloalkyl group, or an aryl group) R 7 is an alkyl group, aryl group, alkyloxy group, or aryloxy group, E is an olefin, a is 0 or 1, b is 1 or 2, and c is 1 to 2. An integer of 4, d is 2, 3, or 4 and n is 0 or 1 .); The formula: Ir (OOCCH 3) 3, Ir (C 5 H 7 O 2) 3, represented by 2 [Ir (Z) (E ) 2] 2 , or, [Ir (Z) (Dien )] Examples include iridium-based catalysts (wherein Z is a chlorine atom, bromine atom, iodine atom, or alkoxy group, E is an olefin, and Dien is cyclooctadiene). It is preferable to use a chloroplatinic acid, an olefin complex of platinum, a complex of platinum and vinylsiloxane, a complex of chloroplatinic acid and divinyltetramethyldisiloxane, a complex of chloroplatinic acid and tetramethyltetravinylcyclotetrasiloxane, Platinum alkenylsiloxane complexes such as platinum divinyltetramethyldisiloxane complex and platinum tetramethyltetravinylcyclotetrasiloxane complex are particularly preferred. The amount of component (D) added may be a catalytic amount, and is usually the amount of metal contained in component (D) with respect to the total mass of the solvent-free peelable cured film-forming organopolysiloxane composition of the present invention. It is preferably 1 to 1,000 ppm, and more preferably in the range of 5 to 500 ppm.

本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物は、上記成分以外に、常温下でのゲル化、硬化を抑制して保存安定性を向上させ、加熱硬化性とするために、(E)ヒドロシリル化反応抑制剤を含有することが好ましい。ヒドロシリル化反応抑制剤として、アセチレン系化合物、エンイン化合物、有機窒素化合物、有機燐化合物、オキシム化合物が例示され、具体的には、3−メチル−1−ブチン−3−オール、3,5−ジメチル−1−ヘキシン−3−オール、3−メチル−1−ペンテン−3−オール、フェニルブチノール等のアルキニルアルコール;3−メチル−3−ペンテン−1−イン、3,5−ジメチル−1−ヘキシン−3−イン、ベンゾトリアゾール、1−エチニル−1−シクロヘキサノール、メチルビニルシクロシロキサンが例示される。この付加反応抑制剤の配合量は、通常、成分(A)100重量部当り0.001〜5重量部の範囲内であるが、本成分の種類、ヒドロシリル化反応触媒の性能と含有量、成分(A)中のアルケニル基量、成分(C)中のケイ素原子結合水素原子量に応じて適宜選定するとよい。  In addition to the above components, the peelable cured film-forming organopolysiloxane composition of the present invention suppresses gelation and curing at room temperature, improves storage stability, and is heat curable (E ) It preferably contains a hydrosilylation reaction inhibitor. Examples of the hydrosilylation reaction inhibitor include acetylene compounds, enyne compounds, organic nitrogen compounds, organic phosphorus compounds, and oxime compounds. Specific examples include 3-methyl-1-butyn-3-ol and 3,5-dimethyl. Alkynyl alcohols such as -1-hexyn-3-ol, 3-methyl-1-penten-3-ol, phenylbutynol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-1-hexyne Examples include -3-in, benzotriazole, 1-ethynyl-1-cyclohexanol, and methylvinylcyclosiloxane. The amount of addition reaction inhibitor is usually in the range of 0.001 to 5 parts by weight per 100 parts by weight of component (A), but the type of this component, the performance and content of the hydrosilylation reaction catalyst, and the component It may be selected appropriately according to the amount of alkenyl groups in (A) and the amount of silicon atom-bonded hydrogen atoms in component (C).

本発明組成物は(A)成分、(B)成分、(C)成分、(D)成分および任意で(E)成分からなるものであるが、硬化被膜の粘着性物質に対する剥離力を低下させるためにアルケニル基含有オルガノポリシロキサンレジンをさらに配合してもよい。また、塗工液の粘度を大きくするためにシリカ微粉末等の増粘剤をさらに配合してもよい。さらには、本発明の目的、効果を損なわないかぎり耐熱剤,染料,顔料等の公知の添加剤をさらに配合してもよい。また、本発明組成物はシート状基材へのコーテイング性の点で、25℃における組成物全体の粘度が50〜2,000mPa・sの範囲にあることが好ましい。  The composition of the present invention comprises the component (A), the component (B), the component (C), the component (D), and optionally the component (E), but reduces the peel strength of the cured film to the adhesive substance. Therefore, an alkenyl group-containing organopolysiloxane resin may be further blended. Further, a thickener such as silica fine powder may be further blended in order to increase the viscosity of the coating solution. Furthermore, known additives such as heat-resistant agents, dyes, and pigments may be further blended so long as the object and effect of the present invention are not impaired. The composition of the present invention preferably has a viscosity of the entire composition at 25 ° C. in the range of 50 to 2,000 mPa · s from the viewpoint of coating properties to the sheet-like substrate.

本発明組成物は、前記(A)成分〜(D)成分さらに(E)成分およびその他の任意成分を単に均一に混合することにより製造することができる。各成分の添加順序は特に制限されるものではないが、混合後、直ちに使用しないときは、(A)成分、(B)成分および(C)成分を混合したものと、(D)成分を別々に保存しておき、使用直前に両者を混合することが好ましい。また、(A)成分〜(D)成分さらに(E)成分からなる組成物において、成分(E)の配合量を調整することにより常温では架橋せず、加熱すると架橋して硬化するようにした組成物も好ましい。  The composition of the present invention can be produced by simply uniformly mixing the components (A) to (D), the component (E) and other optional components. The order of addition of each component is not particularly limited, but when not immediately used after mixing, the component (A), the component (B) and the component (C) are mixed with the component (D) separately. It is preferable to store them in a mixture and mix them immediately before use. Moreover, in the composition consisting of the component (A) to the component (D) and the component (E), the amount of the component (E) is adjusted so that it is not crosslinked at room temperature, and is crosslinked and cured when heated. Compositions are also preferred.

以上のような本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物を、紙,ダンボール紙,クレーコート紙,ポリオレフィンラミネート紙,特にはポリエチレンラミネート紙,合成樹脂フィルム,布,合成繊維,金属箔等の各種シート状基材表面に均一に塗工し、成分(A)と成分(C)がヒドロシリル化反応して架橋するのに十分な条件下で加熱すると、これらのシート状基材表面に、すべり性に優れ、粘着性物質に対して適度な剥離抵抗を有する硬化皮膜を形成する。しかも、当該硬化皮膜はシート状基材への密着性に優れるという特徴を有する。  The peelable cured film-forming organopolysiloxane composition of the present invention as described above is applied to paper, corrugated paper, clay coated paper, polyolefin laminated paper, especially polyethylene laminated paper, synthetic resin film, cloth, synthetic fiber, and metal foil. When uniformly coated on the surface of various sheet-like substrates such as component (A) and component (C) under conditions sufficient for hydrosilylation reaction and crosslinking, these sheet-like substrate surfaces It forms a cured film that is excellent in slipperiness and has an appropriate peeling resistance against adhesive substances. In addition, the cured film is characterized by excellent adhesion to the sheet-like substrate.

シート状基材上での本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物の硬化温度は、一般に50〜200℃が適切であるが、シート状基材の耐熱性が良好であれば200℃以上でもよい。加熱方法は特に限定されるものではなく、熱風循環式オーブン中での加熱、長尺の加熱炉への通過、赤外線ランプやハロゲンランプによる熱線輻射が例示される。また、加熱と紫外線照射を併用して硬化させてもよい。(D)成分が白金アルケニルシロキサン錯体触媒であると、その配合量が組成物の合計量部当り白金金属量で80〜200ppmであっても、100〜150℃で1〜40秒間という短時間で、シート状基材への密着性に優れ、粘着性物質に対する剥離性の優れた硬化皮膜を容易に得ることができる。  The curing temperature of the peelable cured film-forming organopolysiloxane composition of the present invention on a sheet-like substrate is generally appropriately 50 to 200 ° C., but 200 ° if the heat resistance of the sheet-like substrate is good. It may be higher than ℃. The heating method is not particularly limited, and examples include heating in a hot air circulation oven, passing through a long heating furnace, and heat ray radiation using an infrared lamp or a halogen lamp. Moreover, you may make it harden | cure using heating and ultraviolet irradiation together. When the component (D) is a platinum alkenylsiloxane complex catalyst, even if the blending amount is 80 to 200 ppm in terms of platinum metal amount per total amount of the composition, in a short time of 1 to 40 seconds at 100 to 150 ° C. Moreover, it is possible to easily obtain a cured film having excellent adhesion to a sheet-like substrate and excellent releasability from an adhesive substance.

本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物を適用するシート状基材は、ポリオレフィンラミネート紙が好ましく、ポリエチレンラミネート紙がより好ましい。ポリエチレンラミネート紙は、ポリエチレン面をコロナ放電で処理していてもよい。  The sheet-like substrate to which the peelable cured film-forming organopolysiloxane composition of the present invention is applied is preferably polyolefin laminated paper, more preferably polyethylene laminated paper. The polyethylene laminated paper may have a polyethylene surface treated with corona discharge.

本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物をシート状基材表面に塗工するためのコーターは、特に限定されず、ロールコーター,グラビヤコーター,エアーコーター,カーテンフローコーター,オフセット転写ロールコーターが例示される。シート状基材表面に本発明の剥離性硬化皮膜形成性オルガノポリシロキサン組成物を塗工し硬化させてなる剥離性シートに適用する粘着性物質は、各種粘着剤、各種接着剤等であり、アクリル樹脂系粘着剤、ゴム系粘着剤、シリコーン系粘着剤;アクリル樹脂系接着剤、合成ゴム系接着剤、シリコーン系接着剤、エポキシ樹脂系接着剤、ポリウレタン系接着剤が例示される。また、アスファルト、餅のような粘着性食品、糊、鳥もちが例示される。  The coater for applying the peelable cured film-forming organopolysiloxane composition of the present invention to the surface of the sheet-like substrate is not particularly limited, and is a roll coater, gravure coater, air coater, curtain flow coater, offset transfer roll. A coater is exemplified. The adhesive substance applied to the peelable sheet formed by applying and curing the peelable cured film-forming organopolysiloxane composition of the present invention on the surface of the sheet-like substrate is various adhesives, various adhesives, etc. Examples include acrylic resin adhesives, rubber adhesives, silicone adhesives; acrylic resin adhesives, synthetic rubber adhesives, silicone adhesives, epoxy resin adhesives, and polyurethane adhesives. Moreover, sticky foods such as asphalt and straw, glue, and bird rice cake are exemplified.

本発明組成物は、表面のすべり性と粘着性物質に対する剥離性に優れた硬化皮膜を形成させるのに有用であり、特に工程紙、アスファルト包装紙、各種プラスティックフィルムの剥離性硬化皮膜形成剤として好適である。また、本発明組成物を硬化させてなる剥離性皮膜を有するシート状基材は、特に工程紙、粘着物質包装紙、粘着テープ、粘着ラベル等に好適に使用することができる。  The composition of the present invention is useful for forming a cured film having excellent surface slipperiness and releasability to adhesive substances, and particularly as a peelable cured film forming agent for process paper, asphalt wrapping paper, and various plastic films. Is preferred. Moreover, the sheet-like substrate having a peelable film obtained by curing the composition of the present invention can be suitably used particularly for process paper, adhesive material wrapping paper, adhesive tape, adhesive label, and the like.

以下、実施例および比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、下記の例において、部はいずれも重量部であり、粘度および可塑度は25℃において測定した値である。また、無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物の硬化皮膜のすべり性、粘着性物質に対する剥離性は以下に示す方法により動摩擦係数,剥離抵抗値をそれぞれ測定することにより評価した。
[剥離抵抗値]
無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を、印刷適正試験機[(株)明製作所製;RI−2]を用いてポリエチレンラミネート紙の表面にシロキサン換算で0.8g/mとなる量塗工した後、熱風循環式オーブン中で130℃で30秒間加熱処理することにより、硬化皮膜を形成させた。この硬化皮膜面にアクリル系溶剤型粘着剤[東洋インキ製造株式会社製、商品名オリバインBPS−5127]をウエット厚が70μmとなるようにアプリケーターを用いて均一に塗布し、温度70℃で2分間加熱乾燥した。次いで、これに貼合わせ紙を貼合わせ、20g/cm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。この後、引っ張り試験機を用いて、角度180度、剥離速度0.3m/minまたは剥離速度100m/minの条件で貼合わせ紙を反対方向に引張り、剥離に要した力(gf)を測定した。試料幅は剥離速度0.3m/minの場合では5cm、剥離速度100m/minの場合では2.5cmとした。
[動摩擦係数]
上記の剥離抵抗値の測定と同じ条件で、2枚の硬化皮膜を形成させた。これらの硬化皮膜を、硬化皮膜面同士が接触するように重ね合わせ、荷重200g、引張速度5m/minの条件で高速剥離試験機で引っ張り、引っ張りに要した力(g)を測定した。さらに、引っ張りに要した力(g)/200(g)を、硬化皮膜の動摩擦係数として算出した。
[実施例1]
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example. In the following examples, all parts are parts by weight, and the viscosity and plasticity are values measured at 25 ° C. Further, the sliding property of the cured film of the solvent-free peelable cured film-forming organopolysiloxane composition and the peelability of the adhesive substance were evaluated by measuring the dynamic friction coefficient and the peel resistance value by the following methods.
[Peeling resistance value]
Solvent-free peelable cured film-forming organopolysiloxane composition is 0.8 g / m 2 in terms of siloxane on the surface of polyethylene laminated paper using a printing tester [manufactured by Akira Seisakusho; RI-2]. After coating, the cured film was formed by heat treatment at 130 ° C. for 30 seconds in a hot air circulating oven. An acrylic solvent-type adhesive [trade name: Orbine BPS-5127, manufactured by Toyo Ink Manufacturing Co., Ltd., product name] was uniformly applied to the cured film surface using an applicator so that the wet thickness became 70 μm, and the temperature was 70 ° C. for 2 minutes. Heat-dried. Next, a pasting paper was pasted on this, a load of 20 g / cm 2 was applied, and it was left for 24 hours under conditions of a temperature of 25 ° C. and a humidity of 60%. Thereafter, using a tensile tester, the laminated paper was pulled in the opposite direction under the conditions of an angle of 180 degrees, a peeling speed of 0.3 m / min, or a peeling speed of 100 m / min, and the force (gf) required for peeling was measured. . The sample width was 5 cm when the peeling speed was 0.3 m / min, and 2.5 cm when the peeling speed was 100 m / min.
[Dynamic friction coefficient]
Two cured films were formed under the same conditions as the measurement of the above-described peeling resistance value. These cured films were overlapped so that the cured film surfaces were in contact with each other, and pulled with a high-speed peel tester under the conditions of a load of 200 g and a tensile speed of 5 m / min, and the force (g) required for the tension was measured. Furthermore, the force (g) / 200 (g) required for pulling was calculated as the dynamic friction coefficient of the cured film.
[Example 1]

(A)下記平均構造式で示されるオルガノポリシロキサンA(粘度70mPa・s) 100部、

Figure 2006070947
(B)可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム3.0部、(C)粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%)7.0部、(E)1−エチル−1−シクロヘキサノール0.3部を均一に混合した。この混合物に、(D)塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度90mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られたオルガノポリシロキサン組成物を前記の方法で硬化させて得た硬化皮膜の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[実施例2](A) 100 parts of an organopolysiloxane A (viscosity 70 mPa · s) represented by the following average structural formula,
Figure 2006070947
(B) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end has a plasticity of 1.4 mm and is blocked with a vinyl group, (C) molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s ( 7.0 parts of silicon-bonded hydrogen atom content (1.6% by weight) and (E) 0.3 part of 1-ethyl-1-cyclohexanol were uniformly mixed. In this mixture, (D) chloroplatinic acid • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending was performed to obtain a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 90 mPa · s. The dynamic friction coefficient and peel resistance value of the cured film obtained by curing the obtained organopolysiloxane composition by the above-mentioned method were measured, and the results are shown in Table 1.
[Example 2]

(A)下記平均構造式で示されるオルガノポリシロキサンB(粘度70mPa・s) 100部、

Figure 2006070947
(B)可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム3.0部、(C)粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%)11.0部、(E)1−エチル−1−シクロヘキサノール0.3部を均一に混合した。この混合物に、(D)塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度90mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[実施例3](A) 100 parts of an organopolysiloxane B (viscosity 70 mPa · s) represented by the following average structural formula,
Figure 2006070947
(B) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end has a plasticity of 1.4 mm and is blocked with a vinyl group, (C) molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s ( 11.0 parts of silicon atom-bonded hydrogen atom content (1.6% by weight) and (E) 0.3 part of 1-ethyl-1-cyclohexanol were uniformly mixed. In this mixture, (D) chloroplatinic acid • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending was performed to obtain a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 90 mPa · s. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Example 3]

(A)下記平均構造式で示されるオルガノポリシロキサンC(粘度190mPa・s) 100部、

Figure 2006070947
(B)可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム3.0部、(C)粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%)12.0部、(E)1−エチル−1−シクロヘキサノール0.3部を均一に混合した。この混合物に、(D)塩化白金酸とジビニルテトラメチルジシロキサンの錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度200mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[実施例4](A) 100 parts of an organopolysiloxane C (viscosity 190 mPa · s) represented by the following average structural formula,
Figure 2006070947
(B) 3.0 parts of dimethylsiloxane raw rubber whose molecular chain end has a plasticity of 1.4 mm and is blocked with a vinyl group, (C) molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s ( 12.0 parts of silicon atom-bonded hydrogen atom content (1.6% by weight) and (E) 0.3 part of 1-ethyl-1-cyclohexanol were uniformly mixed. To this mixture, (D) a complex of chloroplatinic acid and divinyltetramethyldisiloxane (platinum metal content 0.6% by weight) was added and blended so that the amount of platinum metal was 100 ppm, and a solvent-free solvent having a viscosity of 200 mPa · s. A mold-peelable cured film-forming organopolysiloxane composition was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Example 4]

(A)前記のオルガノポリシロキサンA(粘度70mPa・s)100部、(B)可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム6.0部、(C)粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%)7.0部、(E)1−エチル−1−シクロヘキサノール0.3部を均一に混合した。この混合物に、(D)塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度90mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られたオルガノポリシロキサン組成物を前記の方法で硬化させて得た硬化皮膜の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[実施例5]
(A) 100 parts of the above-mentioned organopolysiloxane A (viscosity 70 mPa · s), (B) 6.0 parts of dimethylsiloxane raw rubber whose molecular chain end having a plasticity of 1.4 mm is blocked with a vinyl group, and (C) viscosity 25 mPa · s molecular chain both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane (silicon atom-bonded hydrogen atom content 1.6 wt%) 7.0 parts, (E) 1-ethyl-1-cyclohexanol 0.3 The parts were mixed uniformly. In this mixture, (D) chloroplatinic acid • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) is added in an amount such that the platinum metal amount becomes 100 ppm. Addition and blending was performed to obtain a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 90 mPa · s. The dynamic friction coefficient and peel resistance value of the cured film obtained by curing the obtained organopolysiloxane composition by the above-mentioned method were measured, and the results are shown in Table 1.
[Example 5]

(A)前記のオルガノポリシロキサンA(粘度70mPa・s)100部、(B)粘度が1,000,000mPa・sで分子鎖末端がトリメチルシロキシ基で封鎖されたジメチルシロキサン6.0部、(C)粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%)7.0部、(E)1−エチル−1−シクロヘキサノール0.3部を均一に混合した。この混合物に、(D)塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度120mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[比較例1]
(A) 100 parts of the above-mentioned organopolysiloxane A (viscosity 70 mPa · s), (B) 6.0 parts of dimethylsiloxane having a viscosity of 1,000,000 mPa · s and a molecular chain end blocked with a trimethylsiloxy group, C) Molecular hydrogen both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane having a viscosity of 25 mPa · s (silicon atom-bonded hydrogen atom content 1.6 wt%) 7.0 parts, (E) 1-ethyl-1-cyclohexanol 0.3 part was mixed uniformly. In this mixture, (D) chloroplatinic acid • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) is added in an amount such that the platinum metal amount becomes 100 ppm. An additive-blended organopolysiloxane composition having a viscosity of 120 mPa · s and having a viscosity of 120 mPa · s was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Comparative Example 1]

下記平均構造式で示されるオルガノポリシロキサン(粘度100mPa・s) 100部、

Figure 2006070947
可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム 3.0部、粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%) 4.7部、1−エチル−1−シクロヘキサノール 0.3部を均一に混合した。この混合物に、塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度130mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[比較例2]100 parts of an organopolysiloxane represented by the following average structural formula (viscosity: 100 mPa · s),
Figure 2006070947
3.0 parts of dimethylsiloxane raw rubber whose molecular chain end is blocked with a vinyl group having a plasticity of 1.4 mm, and trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s (containing silicon-bonded hydrogen atoms) (Amount 1.6 wt%) 4.7 parts and 0.3 part of 1-ethyl-1-cyclohexanol were mixed uniformly. To this mixture, chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) was added and added so that the amount of platinum metal was 100 ppm. Thus, a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 130 mPa · s was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Comparative Example 2]

下記平均構造式で示されるオルガノポリシロキサン(粘度70mPa・s) 100部、

Figure 2006070947
可塑度が1.4mmの分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム 3.0部、粘度25mPa・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(ケイ素原子結合水素原子含有量1.6重量%) 7.0部、1−エチル−1−シクロヘキサノール 0.3部を均一に混合した。この混合物に、塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、粘度90mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[比較例3]100 parts of an organopolysiloxane represented by the following average structural formula (viscosity: 70 mPa · s),
Figure 2006070947
3.0 parts of dimethylsiloxane raw rubber whose molecular chain end is blocked with a vinyl group having a plasticity of 1.4 mm, and trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 25 mPa · s (containing silicon-bonded hydrogen atoms) (Amount 1.6 wt%) 7.0 parts and 0.3 part of 1-ethyl-1-cyclohexanol were mixed uniformly. To this mixture, chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) was added and added so that the amount of platinum metal was 100 ppm. Thus, a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 90 mPa · s was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Comparative Example 3]

実施例1において、分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム3.0部を配合しなかった以外は実施例1と同様にして、粘度65mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[比較例4]
In Example 1, a solvent-free peelable cured film having a viscosity of 65 mPa · s was formed in the same manner as in Example 1 except that 3.0 parts of dimethylsiloxane raw rubber whose molecular chain ends were blocked with vinyl groups was not blended. An organopolysiloxane composition was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Comparative Example 4]

実施例1において、分子鎖末端がビニル基で封鎖されたジメチルシロキサン生ゴム3.0部の代わりに粘度1,000mPa・sのジメチルポリシロキサン 3.0部を配合する以外は、実施例1と同様にして、粘度70mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。
[比較例5]
Example 1 is the same as Example 1 except that 3.0 parts of dimethylpolysiloxane having a viscosity of 1,000 mPa · s is blended in place of 3.0 parts of dimethylsiloxane raw rubber whose molecular chain ends are blocked with vinyl groups. Thus, a solvent-free peelable cured film-forming organopolysiloxane composition having a viscosity of 70 mPa · s was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.
[Comparative Example 5]

下記平均構造式で示される分子鎖両末端ジメチルビニルシロキシ基で封鎖されたジメチルポリシロキサン(粘度400mPa・s) 100部、

Figure 2006070947
分子鎖末端がジメチルビニルシロキシ基およびトリメチルシロキシ基で封鎖され、ジフェニルシロキサン単位を5モル%含有するメチルフェニルポリシロキサン(粘度3,000mPa・s) 1.8部、(C)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(ケイ素原子結合水素原子含有量1.6重量%) 2.0部、(E)1−エチル−1−シクロヘキサノール 0.3部を均一に混合した。この混合物に、(D)塩化白金酸・1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体(白金金属含有率0.6重量%)を白金金属量が100ppmとなる量添加配合して、25℃における粘度400mPa・sの無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物を得た。得られた組成物の動摩擦係数、剥離抵抗値を測定し、それらの結果を表1に示した。100 parts of dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain represented by the following average structural formula (viscosity 400 mPa · s),
Figure 2006070947
The molecular chain end is blocked with a dimethylvinylsiloxy group and a trimethylsiloxy group, and 1.8 parts of methylphenylpolysiloxane (viscosity 3,000 mPa · s) containing 5 mol% of diphenylsiloxane units, and (C) a viscosity of 20 mPa · s. Molecular chain both ends trimethylsiloxy group-blocked methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom content 1.6 wt%) 2.0 parts, (E) 1-ethyl-1-cyclohexanol 0.3 parts uniformly Mixed. In this mixture, (D) chloroplatinic acid • 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content 0.6% by weight) is added in an amount such that the platinum metal amount becomes 100 ppm. An additive-blended organopolysiloxane composition having a viscosity of 400 mPa · s at 25 ° C. and having a viscosity of 400 mPa · s was obtained. The dynamic friction coefficient and peel resistance value of the obtained composition were measured, and the results are shown in Table 1.

Figure 2006070947
Figure 2006070947

Claims (8)

(A)25℃における粘度が20〜300mPa・sであり、下記一般式で表される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と少なくとも2個のケイ素原子結合フェニル基を有するオルガノポリシロキサン: 100重量部、
Figure 2006070947
(式中、Rはそれぞれ独立に炭素原子数1〜8の1価のアルキル基であり、RはR、炭素原子数2〜8の1価のアルケニル基またはフェニル基からなる群から選択される同一または異種の基、Rはフェニル基、Rは炭素原子数2〜8のアルケニル基であり、R〜Rのうち少なくとも2つ以上はアルケニル基である。xは2≦x≦10であり、yは1≦y≦10であり、zは20≦z≦97であり、x+y+zは前記粘度範囲を満足する数である)、
(B)25℃における粘度が100,000mPa・s以上であり、ケイ素原子に結合した全ての有機基のうち90モル%以上が非反応性のアルキル基またはアリール基であるオルガノポリシロキサン: 0.5〜15重量部
(C)25℃における粘度が1〜1,000mPa・sであり、かつ、1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し、脂肪族不飽和結合を有しないオルガノハイドロジェンポリシロキサン: 0.5〜30重量部、および
(D)ヒドロシリル化反応触媒: 触媒量
からなることを特徴とする無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。
(A) Organopoly having a viscosity of 20 to 300 mPa · s at 25 ° C. and having at least two silicon atom-bonded alkenyl groups and at least two silicon atom-bonded phenyl groups in one molecule represented by the following general formula: Siloxane: 100 parts by weight
Figure 2006070947
Wherein R 1 is independently a monovalent alkyl group having 1 to 8 carbon atoms, and R 2 is a group consisting of R 1 , a monovalent alkenyl group having 2 to 8 carbon atoms or a phenyl group. The same or different groups selected, R 3 is a phenyl group, R 4 is an alkenyl group having 2 to 8 carbon atoms, and at least two of R 1 to R 4 are alkenyl groups, x is 2 ≦ x ≦ 10, y is 1 ≦ y ≦ 10, z is 20 ≦ z ≦ 97, and x + y + z is a number satisfying the viscosity range).
(B) Organopolysiloxane having a viscosity at 25 ° C. of 100,000 mPa · s or more and 90 mol% or more of all organic groups bonded to silicon atoms being a non-reactive alkyl group or aryl group: 5 to 15 parts by weight (C) The viscosity at 25 ° C. is 1 to 1,000 mPa · s, has at least 3 silicon-bonded hydrogen atoms in one molecule, and does not have an aliphatic unsaturated bond Organohydrogenpolysiloxane: 0.5-30 parts by weight, and (D) hydrosilylation reaction catalyst: A solvent-free peelable cured film-forming organopolysiloxane composition characterized by comprising a catalytic amount.
(B)成分が、25℃における粘度が100,000mPa・s以上である分子鎖末端がトリメチルシロキシ基,シラノール基またはビニル基からなる群から選択される同一または異種の基で封鎖された直鎖状もしくは分岐状のジメチルポリシロキサンであることを特徴とする、請求項1に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。  (B) A linear chain in which the end of the molecular chain having a viscosity at 25 ° C. of 100,000 mPa · s or more is blocked with the same or different group selected from the group consisting of a trimethylsiloxy group, a silanol group or a vinyl group The solvent-free peelable cured film-forming organopolysiloxane composition according to claim 1, wherein the composition is a dimethylpolysiloxane in the form of a branch or a branch. 25℃における組成物全体の粘度が50〜2,000mPa・sであることを特徴とする、請求項1に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。  The solvent-free peelable cured film-forming organopolysiloxane composition according to claim 1, wherein the viscosity of the entire composition at 25 ° C is 50 to 2,000 mPa · s. さらに(E)ヒドロシリル化反応抑制剤:0.001〜5重量部からなり、常温で非硬化性であり、加熱硬化性である請求項1〜請求項3のいずれか1項に記載の無溶剤型剥離性硬化皮膜形成性オルガノポリシロキサン組成物。  Furthermore, (E) Hydrosilylation reaction inhibitor: It consists of 0.001-5 weight part, is non-hardening at normal temperature, and is heat-hardening, The solvent-free of any one of Claims 1-3 Mold-peelable cured film-forming organopolysiloxane composition. 請求項1〜請求項4のいずれか1項に記載の剥離性硬化皮膜形成性オルガノポリシロキサン組成物を硬化させてなる剥離性硬化皮膜を有するシート状基材。  The sheet-like base material which has a peelable cured film formed by hardening | curing the peelable cured film forming organopolysiloxane composition of any one of Claims 1-4. 基材が、ポリエチレンラミネート紙またはプラスチックフィルムである請求項5に記載のシート状基材。  The sheet-like substrate according to claim 5, wherein the substrate is polyethylene laminated paper or a plastic film. シート状基材上に請求項1〜請求項6のいずれか1項に記載の剥離性硬化皮膜形成性オルガノポリシロキサン組成物をコーテイングし、加熱して硬化させることを特徴とする剥離性硬化皮膜を有するシート状基材の製造方法。  A peelable cured film characterized by coating the peelable cured film-forming organopolysiloxane composition according to any one of claims 1 to 6 on a sheet-like substrate, and curing it by heating. The manufacturing method of the sheet-like base material which has this. シート状基材が、ポリエチレンラミネート紙またはプラスチックフィルムである請求項7に記載のシート状基材の製造方法。  The method for producing a sheet-like substrate according to claim 7, wherein the sheet-like substrate is polyethylene laminated paper or a plastic film.
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