JP4994292B2 - Solvent-free silicone release agent composition for film and release film using the same - Google Patents

Description

  The present invention relates to a solvent-free curable silicone release agent composition having excellent adhesion to a plastic film, and a release film in which the cured film of the composition is formed on a base film is an adhesive label or an adhesive tape. Are preferably used.

  Conventionally, for the purpose of preventing adhesion or fixation between a base material such as paper or plastic film and an adhesive substance, a cured film of a silicone composition can be formed on the base material surface to impart releasability. Has been done.

  In this case, as a method of forming a silicone film on the surface of the substrate, a method of forming a peelable film by addition reaction of an organopolysiloxane containing an alkenyl group and an organohydrogenpolysiloxane using a platinum compound as a catalyst. (See, for example, Patent Document 1) is widely used.

  In recent years, silicone release agents have been switched from a solvent type containing an organic solvent such as toluene and xylene to a solventless type containing no organic solvent from the viewpoint of safety and hygiene.

  Various types of solventless silicone compositions are known. (For example, see Patent Document 2 and Patent Document 3) However, although these compositions have good adhesion to a paper substrate, there is a problem that adhesion to a plastic film substrate is poor.

In order to solve the above problems, Patent Documents 4 and 5 have been proposed. In Patent Document 4, satisfactory adhesion to a polyester film cannot be obtained, and in Patent Document 5, although the adhesion is improved, the peeling resistance with the pressure-sensitive adhesive layer is extremely large, that is, heavy peeling occurs. It was difficult to obtain good peelability. In addition, Patent Document 6 proposes a method of forming a two-layer coating in order to achieve both adhesion and peelability, but this is not preferable because the number of steps increases.
Japanese Patent Laid-Open No. 47-32072 Japanese Patent Laid-Open No. 50-141591 Japanese Patent Laid-Open No. 52-39791 Japanese Patent Laid-Open No. 06-238881 Japanese Patent Laid-Open No. 2003-026925 JP 2005-231355 A

  The present invention has been made in view of the above circumstances. A solvent-free curable silicone release agent composition having good adhesion to a plastic film substrate and excellent in releasability, and a cured film of the composition are plastic film substrates It aims at providing the peeling film formed on top.

  As a result of various studies on the alkenyl group-containing organopolysiloxane which is the main component of the addition-curable silicone composition in order to achieve the above object, the present inventor has found that two specific alkenyl group-containing organopolysiloxanes are used in combination. It has been found that the above problem can be solved.

That is, the present invention has (A) an average of 1.4 or more and less than 2.0 alkenyl groups bonded to silicon atoms in one molecule, and a viscosity at 25 ° C. of 50 to 5,000 mPa.s. A linear diorganopolysiloxane in the range of s, or an average of 1.6 or more alkenyl groups having one trifunctional siloxane unit in one molecule and bonded to a silicon atom The viscosity at 25 ° C. is 50 to 5,000 mPa.s. a branched diorganopolysiloxane in the range of s, or a mixture thereof: 100 parts by weight,

(B) It has an alkenyl group bonded to a silicon atom represented by the average composition formula (1) and has a viscosity at 25 ° C. of 5 to 100 mPa.s. organopolysiloxane in the range of s: 1 to 50 parts by weight,

（１）
（式中、Ｒ¹はアルケニル基、Ｒ²は一価の炭化水素基、Ｒ³は水素原子または炭素原子数１〜８のアルキル基、ｍ，ｎは正数、ｐは０または正数で、０．６≦（ｎ＋ｐ）／ｍ≦１．５、０≦ｐ／（ｎ＋ｐ）≦０．０５であり、かつ、ｍ、ｎ、ｐはこのオルガノポリシロキサンの２５℃における粘度を５〜１００ｍＰａ．ｓとする数である。）
（Ｃ）１分子中にけい素原子に結合した水素原子を少なくとも３個有し２５℃における粘度が５〜１，０００ｍPa.sであるオルガノハイドロジェンポリシロキサン：２〜５０質量部、
（Ｄ）有効量の付加反応抑制剤、並びに、
（Ｅ）有効量の白金族金属系触媒
を含有し、２５℃における粘度が１００〜１，５００ｍＰａ.ｓの範囲内であることを特徴とする無溶剤型硬化性シリコーン剥離剤組成物を提供する。

(1)
(In the formula, R ¹ is an alkenyl group, R ² is a monovalent hydrocarbon group, R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m and n are positive numbers, and p is 0 or a positive number. 0.6 ≦ (n + p) /m≦1.5, 0 ≦ p / (n + p) ≦ 0.05, and m, n and p represent the viscosity of this organopolysiloxane at 25 ° C. of 5 to 100 mPa .S is a number)
(C) Organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule and having a viscosity at 25 ° C. of 5 to 1,000 mPa.s: 2 to 50 parts by mass
(D) an effective amount of addition reaction inhibitor, and
(E) A solventless curable silicone release agent composition comprising an effective amount of a platinum group metal catalyst and having a viscosity at 25 ° C. in the range of 100 to 1,500 mPa.s is provided. .

  Moreover, this invention provides the peelable plastic film which has a plastic base film and the cured film of said silicone release agent composition formed in the at least single side | surface of this base film.

  According to the solvent-free curable silicone release agent composition of the present invention, it is possible to form a cured film having both adhesiveness to a plastic film substrate and excellent release property to an adhesive layer.

  Hereinafter, the present invention will be described in more detail.

-(A) component-
The organopolysiloxane used as the component (A), which is the main component in the present invention,
(A-1) An average of 1.4 to less than 2.0 alkenyl groups bonded to silicon atoms in one molecule, and a viscosity at 25 ° C. of 50 to 5,000 mPa.s. a linear diorganopolysiloxane (abbreviated as a linear type) within the range of s, or (A-2) having one trifunctional siloxane unit in one molecule and having a silicon atom The average number of bonded alkenyl groups is 1.6 or more and less than 3.0, and the viscosity at 25 ° C. is 50 to 5,000 mPa.s. Branched diorganopolysiloxane in the range of s (abbreviated as branched type)
These can also be used as a mixture.

  In the straight chain type, the average number of alkenyl groups bonded to silicon atoms per molecule is 1.4 or more and less than 2.0, usually 1.4 to 1.98, preferably 1.45. In the branched type, it is preferable to have one branch point. In that case, the average number of alkenyl groups bonded to silicon atoms per molecule is 1.6 or more and 3.0. The number is less than 1, usually 1.6 to 2.98, preferably 1.7 to 2.9. By suppressing the number of cross-linking points, the followability to the deformation of the cured film is improved, so that the adhesion to the plastic film is considered to be improved.

  Preferred examples of the linear diorganopolysiloxane include those represented by the following formula (2), and preferred examples of the branched diorganopolysiloxane include those represented by the following formula (3).

(R ¹ R ₂ SiO _1/2 ) _a (R ₃ SiO _1/2 ) _b (R ₂ SiO) _x (2)
Here, R ¹ is an alkenyl group, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and a and b are 1.4 ≦ a <2, 0 <b ≦ 0.6. , A + b = 2 and x is a number satisfying 35 ≦ x ≦ 400.
(R ¹ R ₂ SiO _1/2 ) _c (R ₃ SiO _1/2 ) _d (R ₂ SiO) _Y (RSiO _3/2 ) (3)
Here, R ¹ is an alkenyl group, R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, and c and d are 1.6 ≦ c <3, 0 <d ≦ 1.4. , C + d = 3 and Y is a number satisfying 40 ≦ Y ≦ 450.

Examples of the alkenyl group R ¹ include a vinyl group, an allyl group, a propenyl group, a hexenyl group, an octenyl group, and a decenyl group. A vinyl group is preferable from the viewpoint of cost and performance.

  Examples of the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond represented by R include alkyl groups such as methyl, ethyl and propyl groups, and aryl groups such as phenyl and tolyl groups. However, it is preferable that 80 mol% or more is a methyl group from the viewpoint of improving curability and peelability.

  A and c are in the range of 1.4 ≦ a <2 and 1.6 ≦ c <3, respectively, more preferably 1.45 ≦ a <1.95, from the viewpoints of curability and adhesion. The range is 1.7 ≦ c <2.9.

  Furthermore, from the viewpoint of the coating property of the composition, the viscosity at 25 ° C., which is an appropriate viscosity range as the composition, is 100 to 1,500 mPa.s. In order to make s, x is 35 ≦ x ≦ 400, preferably 40 ≦ x ≦ 350, and Y is 40 ≦ Y ≦ 450, preferably 45 ≦ Y ≦ 400. The component (A) may be a single type or a combination of two or more types.

-(B) component-
Component (B) is an organopolysiloxane having an alkenyl group bonded to a silicon atom, represented by the following average composition formula (1). By partially introducing the (B) component having such a rigid structure into the cured film of the main component (A), the synergistic effect greatly improves the adhesion to the plastic substrate. A cured film can be obtained.

…（１）
〔ここで、Ｒ¹はアルケニル基、Ｒ²は一価の炭化水素基、Ｒ³は水素原子または炭素原子数１〜８のアルキル基である。〕

... (1)
[Wherein R ¹ is an alkenyl group, R ² is a monovalent hydrocarbon group, and R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Examples of the alkenyl group R ¹ include a vinyl group, an allyl group, a propenyl group, a hexenyl group, an octenyl group, and a decenyl group. A vinyl group is preferable from the viewpoint of cost and performance. Examples of the monovalent hydrocarbon group R ² include an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a phenyl group and a tolyl group, and the alkenyl group described above. Examples of the alkyl group for R ³ include a methyl group, an ethyl group, and a propyl group.

  m, n and p have a viscosity of this organopolysiloxane at 25 ° C. of 5 to 100 mPa.s. s, preferably 10 to 70 mPa.s. s is a number selected so that m and n are positive numbers, p is 0 or a positive number, and the value of (n + p) / m is 0.6 to 1.5, preferably 0. It is a number that satisfies the range of 8 to 1.3. This is because if the value of (n + p) / m is less than 0.6, the adhesion to the plastic substrate is lowered, and if it exceeds 1.5, synthesis is difficult and stability is also lowered.

  Moreover, p / (n + p) is 0-0.05, Preferably it is the range of 0-0.03. This is because when this value exceeds 0.05, that is, when the number of hydroxyl groups or alkoxy groups bonded to silicon atoms increases, the curability and adhesion deteriorate.

  Furthermore, the viscosity at 25 ° C. of this organopolysiloxane is 5 to 100 mPa · s as described above. s, preferably 10 to 80 mPa.s. It is the range of s. 5 mPa.s. If it is less than s, curability decreases, and 100 mPa.s. This is because if s exceeds s, the adhesiveness decreases.

  (B) The compounding quantity of the organopolysiloxane of a component shall be 1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it shall be the range of 2-45 mass parts. When the amount is less than 1 part by mass, good adhesion cannot be obtained, and when the amount exceeds 50 parts by mass, the peeling resistance with the pressure-sensitive adhesive layer increases, that is, heavy peeling occurs.

-(C) component-
The organohydrogenpolysiloxane of component (C) has 3 or more hydrogen atoms bonded to silicon atoms in 1 minute, and the SiH group and the alkenyl group in component (A) and component (B) are A cured film is formed by addition reaction, which may be linear, branched or cyclic, and has a viscosity at 25 ° C. of 5 to 1,000 mPa · s. As the component (C), such organohydrogenpolysiloxanes can be used singly or in combination of two or more.

Examples of such organohydrogenpolysiloxane include those of the following formula (4), but are not limited thereto.
(R ⁷ R ₂ SiO _1/2 ) _{2 + t} (HRSiO) _r (R ₂ SiO) _s (RSiO _3/2 ) _t (4)
Wherein H is a hydrogen atom, R is a monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ⁷ is H or a monovalent hydrocarbon group containing no aliphatic unsaturated bond, and t is 0 or 1.

When R ⁷ is H, r and s are numbers satisfying 1 ≦ r ≦ 250, 0 ≦ s ≦ 250, and 8 ≦ r + s ≦ 250, and R ⁷ does not contain an aliphatic unsaturated bond. In the case of a monovalent hydrocarbon group, r and s are numbers satisfying 3 ≦ r ≦ 250, 0 ≦ s ≦ 250, and 8 ≦ r + s ≦ 250. ]

Examples of the monovalent hydrocarbon group containing no aliphatic unsaturated bond represented by R and R ⁷ include alkyl groups such as methyl, ethyl and propyl groups, and aryl groups such as phenyl and tolyl groups. From the viewpoint of improving the addition reaction rate, a methyl group is preferable.

Moreover, the compounding quantity of (C) component is 2-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 3-45 mass parts. Furthermore, at this time, in the case where there are other optional components having an alkenyl group bonded to a silicon atom as in the component (A) and the component (B) (the component (F) described later), The ratio of the SiH group in the component (C) to the amount of the total (including the alkenyl group) is in the range of 1.0 to 5.0 by mole ratio, and further in the range of 1.3 to 4.0. Preferably there is. If this molar ratio is too small, a good cured film cannot be formed, and if the molar ratio is too large, the peeling resistance increases, which is not preferable.
In addition, as described above, when there is an optional component having an alkenyl group bonded to a silicon atom in addition to the component (A) and the component (B), the component (A) occupying such all alkenyl groups And the ratio of the alkenyl group contained in the component (B) is preferably 50 mol% or more, and more preferably 80 mol% or more.

-(D) component-
The component (D) addition reaction control agent is a so-called pot life extender that suppresses the catalytic activity of the platinum group metal catalyst, which is the component (E) at room temperature, and extends the pot life of the composition. For example, various known organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, organic chloro compounds, and the like can be used alone or in combination of two or more. Particularly preferred are acetylene alcohols and silylated products of acetylene alcohol.

  In addition, the blending amount of the component (D) may be an effective amount as appropriate in consideration of the required curability and required pot life balance. Specifically, the amount is usually based on 100 parts by mass of the component (A). The range may be 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass.

-(E) component-
The platinum group metal catalyst of component (E) has an alkenyl group bonded to a silicon atom in components (A) and (B) (as component (F) described later, an alkenyl group bonded to a silicon atom). When used, the alkenyl group is also a catalyst for promoting the addition reaction between the hydrogen atom bonded to the silicon atom in component (C). Any known catalyst for this type of addition reaction can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts, and among these, platinum-based catalysts are particularly preferable. Examples of such platinum-based catalysts include chloroplatinic acid, alcohol solutions and aldehyde solutions of chloroplatinic acid, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.

  The addition amount of these platinum group metal-based catalysts is an effective amount (so-called catalyst amount). From the economical viewpoint, while obtaining a good cured film, the platinum group metal amount (mass) is 1 with respect to the entire composition. It is preferable to set it as the range of -1,000 ppm.

-Other ingredients-
The composition of the present invention can be obtained by blending predetermined amounts of the above components (A) to (E). In addition to the above components, the object and effects of the present invention are impaired as necessary. Other components exemplified below can be blended to the limit.

  -(F) component: The viscosity in 25 degreeC shown by following formula (5) in order to provide slipperiness to a cured film is 10,000-5,000,000 mPa.s. Diorganopolysiloxane in the range of s: 0.5 to 50 parts by mass can be contained.

(R ⁴ R ₂ SiO _1/2 ) ₂ (R ₂ SiO) _z (5)
Wherein R is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, R ⁴ is independently a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, a hydroxyl group or an alkenyl group, and z is 500 ≦ (The number is such that z ≦ 3,000.)
In the formula (5), if z is less than 500, slipperiness is not sufficiently imparted, and if it exceeds 3,000, the viscosity of the composition is increased, which is not preferable in terms of coating properties. R is as illustrated with respect to formula (4), but is preferably a methyl group from the viewpoint of the transparency of the resulting cured film.

R ⁴ is independently a monovalent hydrocarbon group, alkenyl group or hydroxyl group that does not contain an aliphatic unsaturated bond, and the monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond is as described for formula (4). . R ⁴ is preferably an alkenyl group, particularly a vinyl group, in order to prevent the silicone component from transferring from the cured film to the pressure-sensitive adhesive layer.

  Although the component (F) is used for the purpose of imparting slipperiness, it also acts to improve adhesion.

  Other additives include antistatic agents exemplified by polyethers, quaternary ammonia salts, and the like; vinyltrimethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxy Adhesion improvers exemplified by known silane coupling agents such as silane and partial hydrolysis condensates thereof, isocyanurate compounds and the like can be mentioned. The following isocyanurate compounds are particularly preferred.

Component (G): isocyanurate compound having at least one substituent bonded to a nitrogen atom containing an alkenyl group, an epoxy group or a trialkoxysilyl group: This component may optionally be blended as necessary And when mix | blending, it is 0.05-10 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.1-8 mass parts. Thereby, the adhesiveness with the plastic film base material of the composition of this invention may improve further.

  As the isocyanurate compound of the component (G), a compound represented by the following formula (6) is particularly preferable.

（６）

(6)

[Wherein at least one T is represented by the following formula (i):
_{^{(R 5 O) 3 Si-}} R 6 - (i)
(In formula (i), R ⁵ is an alkyl group having 1 to 8 carbon atoms, and R ⁶ is an alkylene group having 2 to 5 carbon atoms.)
In the case where other T is present, the T is independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an aralkyl having 7 to 8 carbon atoms. Group, an epoxy group-containing group having 3 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. ]
Here, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Examples of the aryl group and aralkyl group include a phenyl group, a tolyl group, and a benzyl group. Examples of the epoxy group-containing group include epoxy alkyl groups such as 2,3-epoxypropyl group, 3,4-epoxybutyl group, and 4,5-epoxypropyl group. Examples of the alkenyl group include a vinyl group, an allyl group, an isopropenyl group, and a butenyl group. Among these, an allyl group and a 2,3-epoxypropyl group are particularly preferable.

R ⁵ in formula (i) is the alkyl group having 1 to 8 carbon atoms described above. Examples of R ⁶ include an ethylene group, a propylene group, and a butylene group. The group represented by formula (i) is preferably a trimethoxysilylpropyl group or a triethoxysilylpropyl group.

  Examples of the isocyanurate compound as component (G) include compounds represented by the following structural formula.

  (G) When mix | blending a component, the compounding quantity shall be 0.05-10 mass parts normally with respect to 100 mass parts of (A) component, Preferably it shall be in the range of 0.1-8 mass parts.

-Preparation and use of the composition-
In preparing the silicone composition of the present invention, it is preferable to add components other than (E) uniformly, and then add component (E) at the end. Each component may be used alone or in combination of two or more. May be. However, the viscosity of the composition as a whole at 25 ° C. is in the range of 100 to 1,500 mPa.s, preferably 110 to 1,300 mPa.s. When the viscosity of the composition exceeds 1,500 mPa.s, it is difficult to use practically because it decreases during coating.

-Release film-
The release film of the present invention comprises a cured film of the silicone release agent composition formed on at least one side of a plastic substrate film.

  Next, although an example of the manufacturing method of this peeling film is described, the peeling film of this invention is not manufactured only by the following method, The other manufacturing method performed normally can be used.

  Examples of the plastic substrate film on which the composition of the present invention is applied to form a cured film include films obtained from synthetic resins such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, and polyimide. The thickness of the film is usually 10 to 150 μm, preferably 15 to 100 μm.

The method for applying the composition of the present invention to the substrate film is not particularly limited. For example, a known method such as a gravure offset three roll method or a multi-stage roll method such as five or six can be used. . The coating amount is preferably 0.01 to 5.0 g / m ² , particularly preferably within the range of 0.1 to 2.0 g / m ² , and partially on the entire surface of the base material or a portion where releasability is required. Apply. After apply | coating to a base material, it is made to harden | cure by heating for 1 second-5 minutes at 60-200 degreeC, and the peeling film of this invention is obtained. At this time, the thickness of the cured coating is usually 0.01 to 5.0 μm, preferably 0.1 to 2.0 μm.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples. In addition, all the parts in each example are mass parts, and a viscosity is a value in 25 degreeC.

  Moreover, the sclerosis | hardenability of a silicone composition, adhesiveness (initial stage and aging), and peeling force were measured with the following method.

(Curable)
The silicone composition was applied to the surface of the base film made of polyethylene terephthalate resin by applying 0.4 to 0.5 g / m ² using a RI-2 type printing proper machine (manufactured by Ishikawajima Industrial Machinery Co., Ltd.), and hot air at 120 ° C. The cured silicone film immediately after forming the cured film is rubbed 10 times with a finger after heating for 20 seconds in an oven, and the curability is evaluated by observing the presence or absence of cloudiness on the cured film.
Cloudy was not recognized: ○
Cloudy was recognized: ×

(Initial and aging adhesion)
Under the same conditions as in the above curable test, the silicone composition is applied to the surface of the base film, heated to form a cured coating, and then stored in an atmosphere of 25 ° C. and 60% humidity for the following period.

・ Initial: 1 hour / Aging: 60 days After storage under the respective conditions, the silicone cured film is rubbed 10 times with a finger, and the adhesion is evaluated by the presence or absence of dropping.
・ No dropout: ○
-With omission: ×
In addition, in the adhesiveness over time, for those dropped out without waiting for 60 days, the number of days at that time is evaluated as the adhesiveness over time.

(Peeling force)
Under the same conditions as in the above-described curability test, the silicone composition was applied to the surface of the base film, heated to form a cured film, and after aging at 25 ° C. for 24 hours, acrylic resin was applied to the surface of the cured film. Solvent-based pressure-sensitive adhesive, orivine BPS-5127 (trade name, manufactured by Toyo Ink Manufacturing Co., Ltd.) is applied wet to a thickness of 110 μm (thickness with pressure-sensitive adhesive containing solvent), and heat-treated at 100 ° C. for 3 minutes To do. Next, the film which consists of the same polyethylene terephthalate resin as the base material which apply | coated the silicone composition above on the surface of the adhesive layer processed in this way was bonded together as a surface base material. The obtained laminate is aged at 25 ° C. for 20 hours, and then the laminate is cut into a strip having a width of 50 mm to prepare a test piece. A part of the base film having a cured film formed on one end of the test piece is peeled off from the surface base film with an adhesive layer, and both ends are pulled by a tensile tester (DSC-500 type tester manufactured by Shimadzu Corporation). And both ends are pulled at an angle of 180 degrees in the opposite direction at a peeling speed of 0.3 m / min. At this time, the minimum force (N) required for peeling (referred to as “peeling force”) is measured.

[Example 1]
As the component (A), 2.4 dimethylvinylsiloxy groups represented by the following structural formula A-1 are averaged in one molecule, and the viscosity is 260 mPa.s. 100 parts of branched dimethylpolysiloxane which is s,

…Ａ-１

... A-1

  (B) As a component, it is shown by the following average structural formula B-1, a vinyl value is 0.52 mol / g, and a viscosity is 30 mPa.s. 9.5 parts of polysiloxane which is s,

…Ｂ-１

... B-1

As the component (C), the viscosity represented by the following structural formula C-1 is 25 mPa.s. 8 parts [SiH / (SiCH═CH ₂ ) = 1.8] of methylhydrogenpolysiloxane which is s

…Ｃ-１

... C-1

After adding 0.3 part of 1-ethynyl-1-cyclohexanol as the component (D) and stirring until uniform, as the component (E), the formula: Pt / [H ₂ C═C (CH ₃ ) ₂ A silicone composition having a viscosity of 180 mPa.s was prepared by adding a complex of platinum and vinylsiloxane represented by [Si] ₂ O to 98 ppm in terms of platinum with respect to the entire composition.

Next, the obtained silicone composition was applied to a polyester film (made by Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 38 μm in an amount of 0.4 to 0.5 g / m ² and the curability was heated at 120 ° C. for 20 seconds. A cured film was used, and adhesion (initial and aging) and peel strength were measured using a cured film formed by heating at 120 ° C. for 30 seconds. These measurement results are shown in Table 2.

[Examples 2-6, Comparative Examples 1-5]
Examples 2 to 7 and Comparative Examples 1 to 6 were made by combining the components of Examples and the components shown in Table 1 below.

  Table 2 shows the composition and physical properties of the composition.

（実施例の評価）
本発明の無溶剤型のシリコーン組成物はプラスチックフィルムに対する経時での密着性が良好であることに加え、優れた剥離性能を提供する硬化性被膜を形成することが可能であることが示された。

(Evaluation of Examples)
It was shown that the solvent-free silicone composition of the present invention can form a curable film that provides excellent peeling performance in addition to good adhesion to plastic films over time. .

Claims (7)

(A) An average of 1.4 or more and less than 2.0 alkenyl groups bonded to silicon atoms in one molecule, and a viscosity at 25 ° C. of 50 to 5,000 mPa.s. A linear diorganopolysiloxane in the range of s, or an average of 1.6 or more alkenyl groups having one trifunctional siloxane unit in one molecule and bonded to a silicon atom The viscosity at 25 ° C. is 50 to 5,000 mPa.s. a branched diorganopolysiloxane in the range of s, or a mixture thereof: 100 parts by weight,

(B) It has an alkenyl group bonded to a silicon atom represented by the average composition formula (1) and has a viscosity at 25 ° C. of 5 to 100 mPa.s. organopolysiloxane in the range of s: 1 to 50 parts by weight,

(1)
(In the formula, R ¹ is an alkenyl group, R ² is a monovalent hydrocarbon group, R ³ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, m and n are positive numbers, and p is 0 or a positive number. 0.6 ≦ (n + p) /m≦1.5, 0 ≦ p / (n + p) ≦ 0.05, and m, n and p represent the viscosity of this organopolysiloxane at 25 ° C. of 5 to 100 mPa .S is a number)
(C) Organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule and having a viscosity at 25 ° C. of 5 to 1,000 mPa.s: 2 to 50 parts by mass
(D) an effective amount of addition reaction inhibitor, and
(E) A solvent-free curable silicone release agent composition containing an effective amount of a platinum group metal catalyst and having a viscosity at 25 ° C. in the range of 100 to 1,500 mPa.s. An average of 1.4 to less than 2.0 alkenyl groups bonded to silicon atoms in one molecule, and a viscosity at 25 ° C. of 50 to 5,000 mPa.s. A linear diorganopolysiloxane in the range of s is represented by the following formula (2):
(R ¹ R ₂ SiO _1/2 ) _a (R ₃ SiO _1/2 ) _b (R ₂ SiO ₂ ) _x (2)
Wherein R ¹ is an alkenyl group, R is the same or different hydrocarbon group not containing an aliphatic unsaturated bond, and a and b are 1.4 ≦ a <2, 0 <b ≦ 0.6, (a number satisfying a + b = 2, x is a number satisfying 35 ≦ x ≦ 400)
Is represented by an equation, and
One molecule has 1.6 to less than 3.0 alkenyl groups bonded to silicon atoms, and a viscosity at 25 ° C. of 50 to 5,000 mPa.s. A branched diorganopolysiloxane in the range of s is represented by the following formula (3):
(R ¹ R ₂ SiO _1/2 ) _c (R ₃ SiO _1/2 ) _d (R ₂ SiO) _Y (RSiO _3/2 ) (3)
Wherein R ¹ is an alkenyl group, R is the same or different hydrocarbon group not containing an aliphatic unsaturated bond, c and d are 1.6 ≦ c <3, 0 <d ≦ 1.4, (The number satisfying c + d = 3, Y is a number satisfying 40 ≦ Y ≦ 450.)
The silicone release agent composition according to claim 1, which is represented by the formula: Furthermore, (F) the viscosity in 25 degreeC shown by following formula (5) is 10,000-5,000,000 mPa.s. Diorganopolysiloxane in the range of s: The silicone release agent composition according to claim 1 or 2, comprising 0.5 to 50 parts by mass.
(R ⁴ R ₂ SiO _1/2 ) ₂ (R ₂ SiO) _z (5)
(Wherein R is a hydrocarbon group not containing an aliphatic unsaturated bond, R ⁴ is a hydrocarbon group not containing an aliphatic unsaturated bond, a hydroxyl group or an alkenyl group, and z is 500 ≦ z ≦ 3, 000.)   Furthermore, (G) isocyanurate compound which has at least 1 substituent couple | bonded with the nitrogen atom containing an alkenyl group, an epoxy group, or a trialkoxy silyl group: 0.05-10 mass parts in any one of Claims 1-3 2. The silicone release agent composition according to item 1. The silicone release agent composition according to claim 4, wherein the isocyanurate compound of the component (G) is represented by the following formula (6).

(6)
[Wherein at least one T is represented by the following formula (i):
_{^{(R 5 O) 3 Si-}} R 6 - (i)
(In formula (i), R ⁵ is an alkyl group having 1 to 8 carbon atoms, and R ⁶ is an alkylene group having 2 to 5 carbon atoms.)
In the case where other T is present, the T is independently an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an aralkyl having 7 to 8 carbon atoms. Group, an epoxy group-containing group having 3 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. ] The silicone release agent composition according to any one of claims 1 to 5, which is used for a plastic film.   A peelable plastic film comprising a plastic base film and a cured film of the silicone release agent composition according to any one of claims 1 to 5 formed on at least one side of the base film.