JP5423651B2 - Undercoat silicone emulsion composition for release paper or release film, and treated paper or treated film - Google Patents

Description

  The present invention relates to a release paper or release film undercoat silicone emulsion composition suitable for obtaining a release paper or release film having excellent adhesion, and a treated paper or treated film treated with this composition.

  A method for obtaining a material exhibiting peelability with respect to pressure-sensitive adhesive materials such as pressure-sensitive adhesives by forming a peelable cured film on the surface of various substrates such as paper, laminated paper, and plastic films has long been known. . A silicone composition is used as a material for forming such a peelable cured film. For example, JP-A-62-86061 (Patent Document 1) discloses alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane. A silicone composition comprising a platinum compound has been proposed.

  This type of silicone composition is still used as a main material because it has excellent curing properties and good pot life. However, the adhesion of the cured film to the base material cannot be said to be sufficient, and the base materials that can be applied are limited, and problems such as the need for pretreatment of the base material have been pointed out.

  Recent trends in the base materials used include increasing the use of plastic film base materials that have uniform and stable quality, high smoothness, and can be made into thin films. Now that it can be used as a product, the demand for improved adhesion of silicone compositions has become stronger than before.

Proposals for improving the adhesion have also been made from the viewpoint of silicone compositions. For example, as a method of using a material having better adhesion, attempts have been made to add an organic resin or add a silane coupling agent. However, this method limits the conditions that can be used to reduce the peelability. As a method for improving the base polymer structure of the composition, those having a branched structure containing RSiO _3/2 units are disclosed in JP-A-63-251465, JP-B-3-19267, and JP-A-9. -78032 and JP-A-11-193366 (Patent Documents 2 to 5). These methods are aimed at the effect of light release and improved curability when peeled at a high speed, and as a secondary effect, only improvement in adhesion can be seen. JP 2000-169794 A and JP 2000-177058 A (Patent Documents 6 and 7) improve the base polymer structure by using a solvent-type silicone composition and a solvent-free silicone composition in combination. However, the present invention does not exceed the current solvent-type silicone composition in terms of adhesion.

  As described above, there is no appropriate method for improving the adhesion without affecting the peelability of the silicone composition.

  In recent years, emphasis has been placed on measures such as reducing the amount of solvent used, collecting it, and not discharging it to the outside in terms of environmental pollution, safety, hygiene, and the like. Of these, the use of solvent-free silicone compositions is effective as a method for reducing the amount of solvent used. However, these are uniformly applied to a paper, laminated paper, or plastic film substrate with a film thickness of 1 μm or less. However, expensive coating equipment and technology are required, and changing from a solvent type to a solventless silicone composition is generally not a method that can be easily adopted.

  Another effective method for reducing the amount of solvent used is to use an emulsion type silicone composition. This type of silicone has been conventionally used, and is a mixture of an emulsion composed of an organovinylpolysiloxane, a platinum compound, an emulsifier and water and an emulsion composed of an organohydrogenpolysiloxane, an emulsifier and water (Japanese Patent Publication No. 57-53143). Publication: Patent Document 8), manufactured by emulsion polymerization (Japanese Patent Laid-Open No. Sho 54-52160: Patent Document 9), organovinylsiloxane, organohydrogen emulsified with a specific emulsifier, and platinum compound A mixture of emulsions (Japanese Patent Laid-Open No. 63-314275: Patent Document 10) is known.

  Since these can be arbitrarily diluted with water, there is an advantage that an expensive coating apparatus and technique for thin film coating are not required unlike the solventless type, and the usability is close to that of the solvent type.

  However, emulsion type silicone compositions are not so popular at present because of the disadvantage that the dispersion medium is water. One of the drawbacks is that the latent heat of vaporization of water is large, so high temperature curing is required, and the curing property is poor compared to the solvent type and solventless type. The other is mainly due to the high surface tension of water, resulting in poor wettability to the substrate and poor adhesion. These disadvantages become a serious problem especially for plastic film substrates, and can be said to be a cause of little use.

  Many improvements have been proposed in order to solve these problems, for example, those using organopolysiloxanes having alkenyl groups at the molecular ends (Japanese Patent Laid-Open No. 6-57144: Patent Document 11), non-silicone polymers (Japanese Unexamined Patent Publication No. Hei 11-222557: Patent Document 12) and the like.

  However, there are many improvements for paper base materials, and there are few proposals for silicone emulsions that can provide satisfactory adhesion when applied to plastic film base materials, and there is nothing to be put to practical use. This is a good situation to say.

JP-A-62-86061 JP-A-63-251465 Japanese Patent Publication No. 3-19267 JP-A-9-78032 JP-A-11-193366 JP 2000-169794 A JP 2000-177058 A Japanese Patent Publication No.57-53143 JP-A-54-52160 JP 63-314275 A JP-A-6-57144 JP-A-11-222557 JP 2003-192896 A

  The present invention has been made in view of the above circumstances, and forms a film having excellent adhesion on the surface of various substrates such as paper or plastic film, and the adhesive silicone composition is coated and cured thereon. It is an object of the present invention to provide a release paper or release film undercoat silicone emulsion composition capable of obtaining an excellent release paper or release film, and a treated paper or treated film obtained by treating this composition as an undercoat. .

As a result of intensive studies to achieve the above object, the present inventors have found that an alkenyl group-containing siloxane having a specific structure and / or a functional group that undergoes a radical reaction by heating and / or ultraviolet rays in one molecule. Adhesion with a substrate by using as a primer a silicone emulsion composition comprising a compound having at least one substituent having at least one substituent and at least one substituent having a group capable of reacting with an alkenyl group and / or SiH group It has been found that a release paper and a release film having excellent properties can be obtained.
Further, in the conventional adhesion improving method, the influence on the peeling characteristics is unavoidable, but it has been found that the adhesion can be improved without substantially affecting the peeling characteristics, and the present invention has been made.

  In addition, the present inventors first made good use of organopolysiloxane having a large alkenyl group content mainly having a trifunctional siloxane unit (T unit) as a molecular skeleton for various plastic film substrates. An intimate silicone emulsion was proposed (Japanese Patent Laid-Open No. 2003-192896: Patent Document 13). Although this composition is suitable for production of a relatively heavy release film, the light release film has problems such as an increase in cost, and is not sufficient in terms of covering a wide range of release force. Moreover, since it is a type which hardens | cures by heating, it was not necessarily the optimal curing | hardening prescription for coating hardening to the film base material with low heat resistance. Therefore, we studied a silicone emulsion composition that can achieve good film adhesion without affecting thermal degradation of the base material by heat curing with UV irradiation and without affecting the release properties of the silicone composition. The present invention has been completed.

（式中、Ｒ¹は炭素数２〜１０のアルケニル基を含む置換基を示す。ＡはＲ²又は酸素原子を介して結合した式（１）を満たすように選ばれるシロキサン残基を示し、２個のＡが−Ｏ（ＳｉＲ² ₂Ｏ）_y−として環構造を形成してもよい。Ｒ²は炭素数１〜１０の非置換又は置換の１価炭化水素基、ｘは０〜３の整数、ｙは式（１）のオルガノポリシロキサンの平均重合度２〜５０を満足するように選定される整数である。
Ｍ、Ｍ^A、Ｄ、Ｄ^A、Ｔ、Ｔ^A、Ｑは以下のシロキサン単位であり、Ｏ_1/2は隣接するシロキサン単位と酸素原子を介して結合していることを示す。

ｍ１、ｍ２、ｄ１、ｄ２、ｔ１、ｔ２、ｑ１は以下の式を満足する数である。
ｔ１＋ｔ２＋２×ｑ１≦ｍ１＋ｍ２≦２＋ｔ１＋ｔ２＋２×ｑ１
０≦ｄ１＋ｄ２≦４８、０≦ｔ１＋ｔ２≦３０、０≦ｑ１≦２０
０．２５≦（ｍ２＋ｄ２＋ｔ２）／（ｍ１＋ｍ２＋ｄ１＋ｄ２＋ｔ１＋ｔ２＋ｑ１）≦１）
請求項３：
式（２）のｘが０又は１である請求項２記載の下塗りシリコーンエマルジョン組成物。
請求項４：
（Ａ１）成分が、下記一般式（３）又は（４）で示される直鎖状又は分岐状シロキサン構造を持つ化合物である請求項２又は３記載の下塗りシリコーンエマルジョン組成物。

（式中、Ｒ¹、Ｒ²は上記の通り。Ｙは下記式（３ａ）

で示される基であり、式（３ａ）において、Ｒ¹、Ｒ²、Ｙは上記の通りである。
ａ２、ｂ２、ａｙ、ｂｙは０〜４８の整数であり、ｃ２、ｃｙは０〜３０の整数であり、ｄ２、ｄｙは０〜２０の整数である。
式（３）、（３ａ）はそれぞれランダム構造を示すが、Ｒ¹のアルケニル基を含む置換基がケイ素原子に結合している２個のシロキサン単位が直接又はＲ¹がケイ素原子に結合していないシロキサン単位を３個以下介在した状態で結合している構造を少なくとも１個含む。）

（式中、Ｒ¹、Ｒ²は上記の通り。Ｚは下記式（４ａ）

で示される基であり、式（４ａ）において、Ｒ¹、Ｒ²、Ｚは上記の通りである。
ａ２、ｂ２、ａｙ、ｂｙは０〜４８の整数であり、ｃ２、ｃｙは０〜３０の整数であり、ｄ２、ｄｙは０〜２０の整数である。
式（４）、（４ａ）はそれぞれランダム構造を示すが、Ｒ¹のアルケニル基を含む置換基がケイ素原子に結合している２個のシロキサン単位が直接又はＲ¹がケイ素原子に結合していないシロキサン単位を３個以下介在した状態で結合している構造を少なくとも１個含む。）
請求項５：
（Ａ１）成分が、下記一般式（５）で示される環状シロキサン構造を持つ化合物である請求項２又は３記載の下塗りシリコーンエマルジョン組成物。

（式中、Ｒ¹、Ｒ²は上記の通り。Ｒ³はＯＨ基又はケイ素原子に結合する水素原子を官能基として持つ置換基、又は炭素数１〜１０の脂肪族不飽和結合を持たない非置換又は置換の１価炭化水素基を示し、ａ１は０又は１、ｂ１は１〜６の整数、ｃ１は０〜５の整数であり、ａ１＋ｂ１＋ｃ１は２以上の整数である。）
請求項６：
（Ａ２）成分における、炭素−炭素不飽和結合（二重又は三重結合）を含む置換基が、アルケニル基、アルキニル基、アクリロイルオキシ基又はメタクリロイルオキシ基を含む置換基であり、アルケニル基及び／又はＳｉＨ基と付加反応及び／又は縮合反応可能な基を含む置換基が、ＳｉＨ基又はＯＨ基を官能基として持つ置換基である請求項１記載の下塗りシリコーンエマルジョン組成物。
請求項７：
（Ａ２）成分における、炭素−炭素不飽和結合（二重又は三重結合）を含む置換基が、炭素数２〜１０のアルキニル基、アクリロイルオキシ基又はメタクリロイルオキシ基を含む置換基である請求項１記載の下塗りシリコーンエマルジョン組成物。
請求項８：
（Ａ２）成分が、下記一般式（６−１）で示される２価の構造単位を含む化合物、下記一般式（６−２）と下記一般式（６−３）で示される２価の構造単位を含む化合物、下記一般式（７−１）で示される環状構造からなる化合物、又は下記一般式（７−２）で示される環状構造からなる化合物である請求項１記載の下塗りシリコーンエマルジョン組成物。

（式中、Ｒ²は炭素数１〜１０の非置換又は置換の１価炭化水素基、Ｒ⁴は炭素数２〜１０のアルキニル基、アクリロイルオキシ基又はメタクリロイルオキシ基を含む置換基、Ｒ⁵はＯＨ基又はＳｉＨ基を官能基として持つ置換基、Ｒ⁶は水素原子、炭素数１〜１０の飽和炭化水素基又は芳香族基、Ｒ⁴と同じ基、又はＲ⁵と同じ基、ｄは４〜１０、ｅ＋ｆは３〜９である。）
請求項９：
剥離性シリコーン組成物が、付加反応及び縮合反応で硬化する組成物である請求項１〜８のいずれか１項記載の下塗りシリコーンエマルジョン組成物。
請求項１０：
更に、剥離性シリコーン組成物の成分の一部又は全部を含む請求項１〜９のいずれか１項記載の下塗りシリコーンエマルジョン組成物。
請求項１１：
請求項１〜１０のいずれか１項記載の下塗りシリコーンエマルジョン組成物が塗工され、紫外線照射された処理紙又は処理フィルム基材であって、処理された面に剥離性シリコーン組成物の硬化皮膜が形成される剥離紙又は剥離フィルム用処理紙又は処理フィルム基材。
請求項１２：
請求項１１記載の処理紙又は処理フィルム基材の処理面に、剥離性シリコーン組成物を塗工硬化することにより得られる剥離紙又は剥離フィルム。 Accordingly, the present invention provides the following undercoat silicone emulsion composition for release paper or release film, treated paper or treated film, and release paper or release film.
Claim 1:
An undercoat silicone emulsion composition for release paper or release film that is applied as a primer on paper or a plastic film, and a cured film of the release silicone composition is formed after the coating film is irradiated with ultraviolet rays,
(A) As an adhesion imparting component, the following (A1) and / or (A2) 100 parts by mass,
(A1) The viscosity at 25 ° C. is less than 0.04 Pa · s, the molecule has a substituent containing an alkenyl group bonded to at least two silicon atoms, and the alkenyl group content is 0.3-2. 2 siloxane units within the range of 0 mol / 100 g and having a substituent containing an alkenyl group bonded to a silicon atom are directly or less than 3 siloxane units having no substituent bonded to a silicon atom An organopolysiloxane having a structure bonded in an intervening state,
(A2) Hydrogen bonded to an alkenyl group and / or a silicon atom in at least one substituent containing a carbon-carbon unsaturated bond (double or triple bond) having 2 to 10 carbon atoms as a functional group in one molecule SiH groups or an OH group possess at least one as a substituent containing an atom and an addition reaction and / or condensation reactable groups is a polystyrene-reduced number-average molecular weight by GPC of 1,000 or less, non containing no siloxane structure Silicone compounds,
(B) 0.1-50 mass parts of surfactant,
(C) 100 to 500,000 parts by weight of water
Release paper or a release film for undercoat silicone emulsion composition characterized in that it consists.
Claim 2:
The undercoat silicone emulsion composition according to claim 1, wherein the component (A1) is an organopolysiloxane having an average polymerization degree of 2 to 50 represented by the following composition formula (1) having a structure represented by the following general formula (2). .
^{_{[M] m1 [M A]}} m2 [D] d1 [D A] d2 [T] t1 [T A] t2 [Q] q1 (1)

(In the formula, R ¹ represents a substituent containing an alkenyl group having 2 to 10 carbon atoms. A represents a siloxane residue selected to satisfy Formula (1) bonded via R ² or an oxygen atom, Two A may form a ring structure as —O (SiR ² ₂ O) _y —, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is 0 to 3 And y is an integer selected so as to satisfy an average degree of polymerization of 2 to 50 of the organopolysiloxane of formula (1).
M, M ^A , D, D ^A , T, T ^A , and Q are the following siloxane units, and O _1/2 is bonded to an adjacent siloxane unit through an oxygen atom.

m1, m2, d1, d2, t1, t2, and q1 are numbers satisfying the following expression.
t1 + t2 + 2 × q1 ≦ m1 + m2 ≦ 2 + t1 + t2 + 2 × q1
0 ≦ d1 + d2 ≦ 48, 0 ≦ t1 + t2 ≦ 30, 0 ≦ q1 ≦ 20
0.25 ≦ (m2 + d2 + t2) / (m1 + m2 + d1 + d2 + t1 + t2 + q1) ≦ 1)
Claim 3:
The undercoat silicone emulsion composition according to claim 2, wherein x in the formula (2) is 0 or 1.
Claim 4:
The undercoat silicone emulsion composition according to claim 2 or 3, wherein the component (A1) is a compound having a linear or branched siloxane structure represented by the following general formula (3) or (4).

(Wherein R ¹ and R ² are as described above. Y represents the following formula (3a)

In the formula (3a), R ¹ , R ² and Y are as described above.
a2, b2, ay and by are integers of 0 to 48, c2 and cy are integers of 0 to 30, and d2 and dy are integers of 0 to 20.
Equation (3), bonded to (3a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. )

(In the formula, R ¹ and R ² are as described above. Z represents the following formula (4a)

In the formula (4a), R ¹ , R ² and Z are as described above.
a2, b2, ay and by are integers of 0 to 48, c2 and cy are integers of 0 to 30, and d2 and dy are integers of 0 to 20.
Equation (4), bonded to (4a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. )
Claim 5:
The undercoat silicone emulsion composition according to claim 2 or 3, wherein the component (A1) is a compound having a cyclic siloxane structure represented by the following general formula (5).

(In the formula, R ¹ and R ² are as described above. R ³ does not have an OH group or a substituent having a hydrogen atom bonded to a silicon atom as a functional group or an aliphatic unsaturated bond having 1 to 10 carbon atoms. An unsubstituted or substituted monovalent hydrocarbon group, a1 is 0 or 1, b1 is an integer of 1 to 6, c1 is an integer of 0 to 5, and a1 + b1 + c1 is an integer of 2 or more.)
Claim 6:
In the component (A2), the substituent containing a carbon-carbon unsaturated bond (double or triple bond) is a substituent containing an alkenyl group, alkynyl group, acryloyloxy group or methacryloyloxy group, and the alkenyl group and / or The undercoat silicone emulsion composition according to claim 1, wherein the substituent containing a group capable of addition reaction and / or condensation reaction with a SiH group is a substituent having a SiH group or an OH group as a functional group.
Claim 7:
(A2) in the component, carbon - is a substituent containing a carbon-carbon unsaturated bonds (double or triple bonds), according to claim 1 is a substituent containing an alkynyl group, acryloyloxy group or methacryloyloxy group having 2 to 10 carbon atoms The undercoat silicone emulsion composition described.
Claim 8:
Compound (A2) is a compound containing a divalent structural unit represented by the following general formula (6-1), a divalent structure represented by the following general formula (6-2) and the following general formula (6-3) The undercoat silicone emulsion composition according to claim 1, which is a compound comprising a unit, a compound having a cyclic structure represented by the following general formula (7-1), or a compound having a cyclic structure represented by the following general formula (7-2). object.

Wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is a substituent containing an alkynyl group, acryloyloxy group or methacryloyloxy group having 2 to 10 carbon atoms, R ⁵ Is a substituent having an OH group or SiH group as a functional group, R ⁶ is a hydrogen atom, a saturated hydrocarbon group or aromatic group having 1 to 10 carbon atoms, the same group as R ⁴ , or the same group as R ⁵ , d is 4-10, e + f is 3-9.)
Claim 9:
The undercoat silicone emulsion composition according to any one of claims 1 to 8, wherein the peelable silicone composition is a composition that cures by an addition reaction and a condensation reaction.
Claim 10:
Furthermore, the primer silicone emulsion composition of any one of Claims 1-9 containing a part or all of the component of a peelable silicone composition.
Claim 11:
A treated paper or treated film substrate coated with the undercoat silicone emulsion composition according to any one of claims 1 to 10 and irradiated with ultraviolet rays, wherein the cured surface of the peelable silicone composition is treated on the treated surface. Release paper or release paper treated paper or treatment film substrate on which is formed.
Claim 12:
A release paper or release film obtained by coating and curing a peelable silicone composition on the treated surface of the treated paper or treated film substrate according to claim 11.

  According to the present invention, before applying the conventional release silicone composition for release paper or release film, the base silicone emulsion composition of the present invention containing an adhesion improving component having a specific structure is applied to the substrate. By coating and irradiating with ultraviolet rays, the adhesion between the releasable silicone film formed by the overlying peelable silicone composition and the substrate is improved. Further, according to the present invention, in the conventional adhesion improving method, the influence on the peeling characteristics cannot be avoided, but the adhesion can be improved with little influence on the peeling characteristics.

The present invention will be described in detail below.
The undercoat silicone emulsion composition of the present invention comprises the following components (A1) and / or (A2), (B) a surfactant and (C) water as (A) an adhesion-imparting component, After applying to a plastic film substrate and irradiating with ultraviolet rays, a release paper or release film having excellent adhesion can be obtained by coating and curing the peelable silicone composition thereon.

  The component (A) constituting the undercoat silicone emulsion composition of the present invention is a component that is characteristic for the undercoat silicone emulsion composition of the present invention to exhibit adhesion as an undercoat, and the film substrate and the release silicone It works like a coupling agent that connects the non-adhesive cured film formed by the composition and improves adhesion. Using only one type of reaction to react or interact with a paper or film substrate and a non-adhesive cured film made of a completely different material tends to be biased in either direction, and functions sufficiently as a coupling agent It becomes difficult to express. Therefore, in the present invention, a radical reaction is used for the reaction or interaction with the base material, and an addition reaction or a condensation reaction is used for the non-adhesive cured film.

It is necessary to deal with these two different reactions with one molecule, but one method for this is to have only one kind of substituent containing only functional groups capable of both reactions in one molecule. Although the reaction selectivity by the substituent is low, it is a method of proceeding the two reactions without bias depending on the characteristics of the molecular structure, and the corresponding organosiloxane is the component (A1).
Another method is the substitution of a substituent that causes a radical reaction with a paper or film substrate more easily than an addition reaction or a condensation reaction, and a substituent that causes an addition reaction or condensation reaction with a non-adhesive cured film to occur more easily than a radical reaction. A single molecule has both, and the compound corresponding to this is the component (A2).

  As the component (A), the component (A1) or the component (A2) may be used alone, or the component (A1) and the component (A2) may be used in combination. However, it is preferable to use (A1) :( A2) = 100: 0 to 100: 100 (mass ratio), more preferably 100: 0 to 100: 90. When using both together, it is preferable to set it as 100: 5 or more.

  Since the component (A1) does not need to have a plurality of different functional groups in one molecule unlike the component (A2), it is easy to produce and advantageous in terms of availability and cost. Moreover, being the same silicone compound as the main component of the peelable silicone composition to be overcoated is advantageous for the reaction and interaction with the non-adhesive cured film. This feature is disadvantageous for the reaction and interaction with the substrate surface, which is an organic substance, but it is coated on the substrate in advance as a primer, and the radical reaction is advanced by ultraviolet irradiation, and the alkenyl group. In which the alkenyl group is concentrated in a short siloxane chain to increase the organic property of the functional group portion and promote the radical reaction with the substrate. It is what.

That is, the component (A1) includes two siloxane units in which a substituent containing an alkenyl group is bonded to a silicon atom, or three siloxane units in which a substituent containing the alkenyl group is not bonded to a silicon atom. An organopolysiloxane having a structure bonded in an intervening state below.
In addition, two siloxane units in which a substituent containing an alkenyl group is bonded to a silicon atom as described above intervene with three or less siloxane units in which the substituent containing the alkenyl group is not bonded to a silicon atom. If the structure is bonded in such a state, the two siloxane units in which the substituent containing the alkenyl group is bonded to the silicon atom are bonded to the silicon atom in the substituent not including the alkenyl group. It may have a structure in which four or more siloxane units are interposed. However, all the siloxane units in which the substituent containing the alkenyl group is bonded to the silicon atom do not intervene the siloxane unit in which the substituent not containing the alkenyl group is bonded to the silicon atom, or 3 or less. It is preferable that they are bonded in a state.

（式中、Ｒ¹は炭素数２〜１０のアルケニル基を含む置換基を示す。ＡはＲ²又は酸素原子を介して結合した式（１）を満たすように選ばれるシロキサン残基を示し、２個のＡが−Ｏ（ＳｉＲ² ₂Ｏ）_y−として環構造を形成してもよい。Ｒ²は炭素数１〜１０の非置換又は置換の１価炭化水素基、ｘは０〜３の整数、ｙは式（１）のオルガノポリシロキサンの平均重合度２〜５０を満足するように選定される整数である。
Ｍ、Ｍ^A、Ｄ、Ｄ^A、Ｔ、Ｔ^A、Ｑは以下のシロキサン単位であり、Ｏ_1/2は隣接するシロキサン単位と酸素原子を介して結合していることを示す。

ｍ１、ｍ２、ｄ１、ｄ２、ｔ１、ｔ２、ｑ１は以下の式を満足する数である。
ｔ１＋ｔ２＋２×ｑ１≦ｍ１＋ｍ２≦２＋ｔ１＋ｔ２＋２×ｑ１
０≦ｄ１＋ｄ２≦４８、０≦ｔ１＋ｔ２≦３０、０≦ｑ１≦２０
０．２５≦（ｍ２＋ｄ２＋ｔ２）／（ｍ１＋ｍ２＋ｄ１＋ｄ２＋ｔ１＋ｔ２＋ｑ１）≦１） In this case, the component (A1) can be represented by the following composition formula (1) having a structure represented by the following general formula (2).
^{_{[M] m1 [M A]}} m2 [D] d1 [D A] d2 [T] t1 [T A] t2 [Q] q1 (1)

(In the formula, R ¹ represents a substituent containing an alkenyl group having 2 to 10 carbon atoms. A represents a siloxane residue selected to satisfy Formula (1) bonded via R ² or an oxygen atom, Two A may form a ring structure as —O (SiR ² ₂ O) _y —, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is 0 to 3 And y is an integer selected so as to satisfy an average degree of polymerization of 2 to 50 of the organopolysiloxane of formula (1).
M, M ^A , D, D ^A , T, T ^A , and Q are the following siloxane units, and O _1/2 is bonded to an adjacent siloxane unit through an oxygen atom.

m1, m2, d1, d2, t1, t2, and q1 are numbers satisfying the following expression.
t1 + t2 + 2 × q1 ≦ m1 + m2 ≦ 2 + t1 + t2 + 2 × q1
0 ≦ d1 + d2 ≦ 48, 0 ≦ t1 + t2 ≦ 30, 0 ≦ q1 ≦ 20
0.25 ≦ (m2 + d2 + t2) / (m1 + m2 + d1 + d2 + t1 + t2 + q1) ≦ 1)

Examples of the substituent containing the alkenyl group of R ¹ include alkenyl groups such as vinyl group and allyl group, and (meth) acryloyloxy group-substituted alkyl groups such as acryloyloxypropyl group and methacryloyloxypropyl group.
Examples of the monovalent organic group of R ² include linear, branched or cyclic alkyl groups such as methyl, ethyl, propyl, and hexyl groups, aryl groups such as phenyl and tolyl groups, and benzyl groups. In addition to aralkyl groups, unsubstituted monovalent hydrocarbon groups such as alkenyl groups such as vinyl groups and allyl groups, and some or all of the hydrogen atoms of these unsubstituted monovalent hydrocarbon groups are substituted with halogen atoms. Group, or a hydrogen atom of the above alkyl group is substituted with a (meth) acryloyloxy group, for example, a (meth) acryloyloxypropyl group. Accordingly, R ² may be R ¹ .

In addition, it is preferable that the average degree of polymerization of (A1) component is 2-50, especially 2-40. This average degree of polymerization is a polystyrene conversion value by gel permeation chromatography (GPC) (solvent: toluene).
y is selected so as to satisfy the above average degree of polymerization, and is preferably an integer of 0 to 10, particularly 1 to 8.

As apparent from the above formula (2), the organosiloxane of the component (A1) has two —SiR ¹ A-groups —O— (SiA ₂ O) _x — (x = 0 to 3, particularly 0 or It has a structure connected via 1). That is, two -SiR ¹ A-groups having an alkenyl group bonded to a silicon atom are present in close proximity. In this case, if A is an alkenyl group, it is naturally close. Even if A is an alkyl group such as a methyl group or an aryl group such as a phenyl group, -SiR ¹ A- are close to each other, and x indicating the degree of this proximity is 3 at most, preferably 0 or 1, thereby obtaining the effect of the present invention. On the other hand, when x is 4 or more, the adhesiveness is lowered, and the effect of the present invention of improving the adhesiveness without affecting the peeling performance cannot be achieved.
Although not clearly shown in the formula (2), a structure in which two or more alkenyl groups are bonded on the same silicon atom is also preferable for the same reason. Thus, when the approach is remarkable, the adhesion improving effect tends to be easily influenced by the type of the alkenyl group, and selection of an appropriate structure in accordance with the use situation becomes important.

  As another effect expected by arranging the alkenyl groups adjacent to each other as described above, there is a case where the progress of the addition reaction is delayed to promote the radical reaction, and in order to obtain the effect more effectively, x = It is preferable to set it as 0-1. The reason why the structure in which the alkenyl groups are closer to each other delays the addition reaction is also inferred from the fact that a compound having the same kind of structure can be used as a control agent. If one alkenyl group is changed by a radical reaction, the remaining alkenyl group is easily subjected to an addition reaction, and the reaction with the non-adhesive cured film proceeds, so that it can function effectively as a coupling agent.

  If possible, it is preferable that the number of alkenyl groups in one molecule be 3 or more, or 4 or more so that all alkenyl groups are not consumed by radical reaction alone. Also, the small molecular weight is advantageous because it can act as a coupling agent but can form many bonding points in a large area.

  Specific examples of the organosiloxane having the structure of the above formula (1) include linear or branched organopolysiloxanes of the following general formula (3) or (4).

（式中、Ｒ¹、Ｒ²は上記の通り。Ｙは下記式（３ａ）

で示される基であり、式（３ａ）において、Ｒ¹、Ｒ²、Ｙは上記の通りである。
ａ２、ｂ２、ａｙ、ｂｙは０〜４８、好ましくは０〜４５、更に好ましくは０〜４０の整数であり、ｃ２、ｃｙは０〜３０、好ましくは０〜２５、更に好ましくは０〜２０の整数であり、ｄ２、ｄｙは０〜２０、好ましくは０〜１８、更に好ましくは０〜１５の整数である。
式（３）、（３ａ）はそれぞれランダム構造を示すが、Ｒ¹のアルケニル基を含む置換基がケイ素原子に結合している２個のシロキサン単位が直接又はＲ¹がケイ素原子に結合していないシロキサン単位を３個以下介在した状態で結合している構造を少なくとも１個含む。従って、ｂ２、ｂｙ、ｃｙ、ｄｙが同時に０になることはない。）

(Wherein R ¹ and R ² are as described above. Y represents the following formula (3a)

In the formula (3a), R ¹ , R ² and Y are as described above.
a2, b2, ay and by are integers of 0 to 48, preferably 0 to 45, more preferably 0 to 40, and c2 and cy are 0 to 30, preferably 0 to 25, and more preferably 0 to 20. D2 and dy are integers of 0 to 20, preferably 0 to 18, and more preferably 0 to 15.
Equation (3), bonded to (3a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. Therefore, b2, by, cy, and dy do not become 0 simultaneously. )

（式中、Ｒ¹、Ｒ²は上記の通り。Ｚは下記式（４ａ）

で示される基であり、式（４ａ）において、Ｒ¹、Ｒ²、Ｚは上記の通りである。
ａ２、ｂ２、ａｙ、ｂｙは０〜４８、好ましくは０〜４５、更に好ましくは０〜４０の整数であり、ｃ２、ｃｙは０〜３０、好ましくは０〜２５、更に好ましくは０〜２０の整数であり、ｄ２、ｄｙは０〜２０、好ましくは０〜１８、更に好ましくは０〜１５の整数である。
式（４）、（４ａ）はそれぞれランダム構造を示すが、Ｒ¹のアルケニル基を含む置換基がケイ素原子に結合している２個のシロキサン単位が直接又はＲ¹がケイ素原子に結合していないシロキサン単位を３個以下介在した状態で結合している構造を少なくとも１個含む。）

(In the formula, R ¹ and R ² are as described above. Z represents the following formula (4a)

In the formula (4a), R ¹ , R ² and Z are as described above.
a2, b2, ay and by are integers of 0 to 48, preferably 0 to 45, more preferably 0 to 40, and c2 and cy are 0 to 30, preferably 0 to 25, and more preferably 0 to 20. D2 and dy are integers of 0 to 20, preferably 0 to 18, and more preferably 0 to 15.
Equation (4), bonded to (4a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. )

で示される直鎖状のオルガノポリシロキサン（但し、ｘは上記の通り。）、

で示される三官能又は四官能シロキサン単位で主骨格が形成される分岐状構造のオルガノポリシロキサンも可能である。 A more specific structure as the component (A1) is, for example, the following formula:

A linear organopolysiloxane represented by the formula (where x is as described above),

A branched structure organopolysiloxane in which a main skeleton is formed by a trifunctional or tetrafunctional siloxane unit represented by

（但し、Ｒ²⁰はＲ²又はＲ¹を示す。Ｒ⁰は−Ｏ−（ＳｉＲ²Ｒ²⁰）_y6−ＳｉＲ² ₂Ｒ²⁰を示し、ｙは上記の通り。ｙ１＋ｙ２＋ｙ６＝ｙであり、ｙ１及びｙ６は０以上、ｙ２は１以上の整数である。ｙ３＋ｙ４＝ｙであり、ｙ３、ｙ４は０以上の整数である。ｙ５＝ｙである。） Here, examples of the A siloxane residue, Y, Z, and B are as follows.

(Wherein R ²⁰ represents R ² or R ¹ , R ⁰ represents —O— (SiR ² R ²⁰ ) _y6 —SiR ² ₂ R ²⁰ , y is as described above, y1 + y2 + y6 = y, y1 and (y6 is an integer greater than or equal to 0, y2 is an integer greater than or equal to 1. y3 + y4 = y, and y3 and y4 are integers greater than or equal to 0. y5 = y)

More specifically, the following are mentioned.

（式中、Ｒ¹、Ｒ²は上記の通り。Ｒ³はＯＨ基又はケイ素原子に結合する水素原子を官能基として持つ置換基、又は炭素数１〜１０の脂肪族不飽和結合を持たない非置換又は置換の１価炭化水素基を示し、ａ１は０又は１、ｂ１は１〜６の整数、ｃ１は０〜５の整数であり、ａ１＋ｂ１＋ｃ１は２以上の整数である。） Moreover, as shown by the following general formula (5), by making the organosiloxane of the component (A1) into a cyclic structure, the influence of the siloxane structure can be further reduced, and a more effective structure can be obtained by radical reaction.

(In the formula, R ¹ and R ² are as described above. R ³ does not have an OH group or a substituent having a hydrogen atom bonded to a silicon atom as a functional group or an aliphatic unsaturated bond having 1 to 10 carbon atoms. An unsubstituted or substituted monovalent hydrocarbon group, a1 is 0 or 1, b1 is an integer of 1 to 6, c1 is an integer of 0 to 5, and a1 + b1 + c1 is an integer of 2 or more.)

In the above formula, as a substituent having a hydrogen atom bonded to the OH group or silicon atom of R ³ as a functional group, in addition to a hydroxyl group bonded to a silicon atom and a hydrogen atom, —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ —OH and the like can be mentioned.
Examples of the monovalent hydrocarbon group for R ³ include the same as those exemplified for R ² except that the alkenyl group is not included.

Specific examples of industrially desirable (A1) are as follows. In the above formula (5), R ¹ is a vinyl group, R ² is a methyl group, R ³ is a hydrogen atom, a1 = 0 to 1, b1 = 1 to 4 , C1 = 0-1. More desirably, a1 = 0, b1 = 2 to 4, and c1 = 0.

  The component (A1) is a high alkenyl group-containing siloxane having an alkenyl group content of 0.3 to 2.0 mol / 100 g, more preferably 0.4 to 1.5 mol / 100 g. Low molecular weight with a low degree of siloxane polymerization with an absolute viscosity of less than 0.5 Pa · s measured at 25 ° C, making the reaction and interaction with the substrate easier, preferably only radical reactions It is preferable that the number of alkenyl groups in one molecule is 3 or more, and more preferably 4 or more so that all of them are not consumed. The lower limit of the absolute viscosity is not particularly limited, but is usually 0.1 mPa · s.

  Next, the component (A2) contains at least one substituent containing a carbon-carbon unsaturated bond (double bond or triple bond) having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, as a functional group in one molecule. And a compound having at least one substituent containing an alkenyl group and / or a hydrogen atom bonded to a silicon atom (hereinafter abbreviated as SiH group) and a group capable of addition reaction and / or condensation reaction.

  The substituent having at least one component (A2) having a carbon-carbon unsaturated bond as a functional group means a substituent having a functional group that undergoes a radical reaction by heating and / or ultraviolet rays, but the structure is straightforward. A chain or a branch is not specified, and a cyclic structure such as cyclohexene or norbornadiene may be used, and a substituent containing a functional group generally used in a radical polymerization or radical reaction curing system can be used. When the component (A2) contains a siloxane structure, a carbon-carbon triple bond such as a carbon-carbon double bond such as a methacryloyloxy group, an acetylene group, a propynyl group, or a butynyl group is used to suppress consumption due to an addition reaction. It is preferable to make it a substituent.

  If anything, the (A1) component has a structure that easily reacts and interacts with the peelable silicone composition layer that is an overcoat, whereas the (A2) component is a base material mainly composed of an organic structure. It has a structure that is advantageous for reaction and interaction, and the effect can be obtained by itself, but by using both (A1) and (A2) components, a higher effect can be exerted on a wider range of substrates. Therefore, when the component (A2) contains a siloxane structure, it is desirable that the molecular weight or the degree of polymerization is smaller, and the degree of polymerization is 40 or less, preferably 1 to 10.

  If the component (A2) is an organic substance that does not contain a siloxane structure, access to the base material is facilitated, which is advantageous for reactions and interactions by radical reactions, so the selection of substituents may be further expanded. However, when the molecular weight is increased in a non-silicone system, the compatibility with the silicone becomes too low and it becomes difficult to form a bond or interaction with the non-adhesive cured film, or the solubility in the composition itself is lowered and cannot be used. Therefore, the number average molecular weight in terms of polystyrene by GPC is preferably 1,000 or less. In order to improve the adhesion as a coupling agent more efficiently, there is also a point that a smaller molecular weight is desirable so that many bonding points can be formed in a wide area.

  Substituent having a functional group that undergoes a radical reaction by heating and / or ultraviolet rays of component (A2) is a substrate surface to which the present composition is applied by interaction with radical reaction and / or a group generated by radical reaction. The component (A2) is tied to Radicals may be generated by heating or irradiation with energy rays such as ultraviolet rays. For the purpose of promoting the generation of radicals, radical generators such as peroxides and photosensitizers are added as long as the effects of the present invention are not impaired. May be.

  Many structures that can generate radicals or react with the generated radicals by heat or ultraviolet rays are present in organic base materials, and the base materials are also overwhelming in the absorption rate of infrared and ultraviolet rays that are the energy source for generating radicals. Therefore, radicals can be generated intensively on the base material, which is suitable for promoting the reaction with the base material.

  In the case of a heat-sensitive substrate such as a plastic film, the radical generation method by ultraviolet irradiation is advantageous in that the temperature of the film substrate does not rise so much. If ultraviolet rays that are largely absorbed on the surface of the film base are used, radicals can be generated intensively in the vicinity of the surface of the film base, which is desirable for promoting the reaction with the film base.

  The other substituent which (A2) component has at least one is a substituent having a functional group capable of reacting with an alkenyl group and / or SiH group, wherein the alkenyl group is a top-peelable silicone composition The SiH group is assumed to be a functional group that the crosslinking agent has (that is, it is assumed that the top-peelable silicone composition is an addition reaction curable type). ), An SiH group that can undergo an addition reaction for an alkenyl group, an OH group that can undergo a condensation reaction for an SiH group, or a substituent that has a carbon-carbon double bond that can undergo an addition reaction as a functional group.

  This substituent of component (A2) anchors component (A2) to the non-adhesive cured film by an addition reaction or condensation reaction different from the radical reaction of the first substituent. In combination with the action of the substituent that undergoes a radical reaction, the component (A2) acts as a coupling agent for connecting the non-adhesive cured film and the substrate to improve adhesion.

  When the component (A2) is an organic compound having no siloxane structure, the radical reaction with the base material is likely to proceed, so that a carbon-carbon double bond is formed as a functional group capable of reacting with an alkenyl group and / or SiH group. If the substituents to be included are selected, most of the radical reaction may be consumed. As a result, the amount of addition reaction with the SiH group is reduced, and it may be difficult to act as a coupling agent. In order to prevent this, a SiH group or a hydroxyl group that hardly undergoes radical reaction is selected. For example, a divalent structure represented by the following general formula (6-1), or the following general formulas (6-2) and (6- It can be set as the molecular structure containing two types of bivalent structure shown by 3).

In the above formula, R ² is as described above. R ⁴ is an alkynyl group having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms (for example, acetylene group, propynyl group, butynyl group, etc.), a substituent containing an acryloyloxy group or a methacryloyloxy group, R ⁵ is an OH group, a SiH group Or a substituent having an alkenyl group as a functional group.
In the above formula, an industrially desirable example is HC≡C—C (CH ₃ ) ₂ —OH.

Moreover, the cyclic | annular material shown by the following general formula (7-1), (7-2) etc. are mentioned as a specific structure.

In the above formula, R ⁴ and R ⁵ are as described above. R ⁶ is a hydrogen atom, a saturated hydrocarbon group or aromatic group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, the same group as R ⁴ , or the same group as R ⁵ . d represents 4 to 10, and e + f represents 3 to 9.
In the above formula, ethynylcyclohexanol is an industrially preferable example.

  Although it has been described that both the component (A1) and the component (A2) are advantageously low in molecular weight, when the primer silicone emulsion composition of the present invention is applied to a substrate and heated, the molecular weight is too small. There is a concern that it is removed from the surface of the base material without reacting because the vaporization is too fast. Therefore, it is desirable that the molecular weight be such that the boiling point of the component (A) is 80 ° C. or higher. Using ultraviolet irradiation so as not to raise the temperature is also effective in reducing such effects.

  The surfactant as the component (B) of the present invention is nonionic, for example, an alkyl ether type such as polyoxyethylene lauryl ether or polyoxyethylene tridecyl ether, polyoxyethylene oleate, polyoxyethylene laurate, etc. These non-ionic surfactants (emulsifiers) can be used alone or in combination of two or more. In order to obtain a stable silicone emulsion composition, it is desirable that the HLB of these nonionic surfactants (emulsifiers) alone or after mixing is 10-15.

  Anionic surfactants and cationic surfactants can also be used, but it is desirable to use them together with nonionic surfactants in terms of the stability of the silicone emulsion and the wettability with respect to the substrate.

  The blending amount of the surfactant is desirably a minimum amount that can sufficiently obtain the stability of the silicone emulsion and the wettability to the substrate. Specifically, it is 0.1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-30 mass parts. If it is less than 0.1 part by mass, emulsification becomes difficult, and if it exceeds 50 parts by mass, the adhesion improving effect may be reduced.

  In order to assist emulsification and improve stability, a water-soluble resin can be used in combination with a surfactant. Examples of the water-soluble resin include polyvinyl alcohol and the like, but a resin having a minimal catalytic poisoning effect on the platinum group metal catalyst is selected. As with the surfactant, the blending amount is desirably the minimum amount that can sufficiently obtain the stability of the silicone emulsion and the wettability to the substrate. Specifically, it is 0-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts.

  The amount of water (C) is adjusted so as to satisfy the viscosity suitable for the coating apparatus actually used and the silicone coating amount on the target substrate, but is not particularly limited. The amount is preferably 100 to 500,000 parts by mass with respect to 100 parts by mass of the organopolysiloxane (A). If it is less than 100 parts by mass, it is difficult to obtain an O / W emulsion, and if it exceeds 500,000 parts by mass, the stability is lowered.

  As water that can be used, an impurity concentration that is about the same as tap water is sufficient, but water mixed with strong acid, strong alkali, a large amount of alcohol, salts, and the like is not suitable for use because it lowers the stability of the emulsion.

  A known method can be used for producing the silicone emulsion composition of the present invention. A predetermined amount of the above components (A) and (B) and a part of water (C) are mixed with a planetary mixer, a combination mixer. It is good to mix using the high shearing stirring apparatus, such as a mixer, emulsify by the phase inversion method, and dilute by adding the remainder of water (C). Each component may be used alone or in combination of two or more.

  In the undercoat silicone emulsion composition of the present invention, additives such as a photosensitizer, a radical generator, a leveling agent, a wetting improver, and the like can be blended as needed, as long as the object of the present invention is not impaired. Moreover, you may mix | blend a part or all of the component of the peelable silicone composition mentioned later with the undercoat silicone emulsion composition of this invention in the range which does not inhibit the effect of this invention.

  When applying the undercoat silicone emulsion composition of the present invention, the undercoat silicone emulsion composition of the present invention is directly or appropriately diluted with water, and then a bar coater, a roll coater, a reverse coater, a gravure coater, an air knife coater, and a thin film. The coating is applied to the substrate by a known coating method such as a high-precision offset coater or a multi-stage roll coater.

  Here, examples of the base material include glassine paper, polyethylene laminated paper, kraft paper, clay coated paper, mirror coated paper, and plastic films such as polypropylene, polyethylene, polyethylene terephthalate, and polyvinyl chloride.

The coating amount of the undercoat silicone emulsion composition of the present invention to the substrate varies depending on the type of the material of the substrate to be coated, but the solid content is preferably in the range of 0.0005 to 0.1 g / m ^2. . The substrate on which the undercoat silicone emulsion composition is applied is irradiated with ultraviolet rays, and water is evaporated by air drying or heating to be dried. The ultraviolet irradiation and the drying step may be performed simultaneously or separately, and the order thereof can be changed within a range in which the effect of the present invention can be obtained.

For irradiation with ultraviolet rays, commercially available lamps and bulbs such as mercury lamps, metal halides and fusions can be used. Wavelength distribution lamps and bulbs containing many components with wavelengths shorter than 300 nm, which have a large extinction coefficient of the film substrate, are effective, and the integrated light quantity is 10 to 500 mJ / cm ² , for example, 120 W / cm ¹ or 2 lamps for line speed Irradiation conditions of 10 to 100 m / min. Drying is generally performed at 20 to 120 ° C. for about 5 to 60 seconds.

  The substrate is coated with an undercoat silicone emulsion composition and has excellent substrate adhesion by overcoating the release silicone composition on the coated surface of a treated paper substrate or treated film substrate that has been irradiated with ultraviolet rays. A release paper or release film can be obtained.

As the peelable silicone composition to be overcoated, addition-type and condensation-type compositions can be used, and generally commercially available ones can be used. The form of the product such as a solvent type, a solventless type, and an emulsion type is not particularly limited. Examples of usable addition-type compositions include, but are not limited to, those containing the following components (D) to (F) and, if necessary, component (G).
(D) Organopolysiloxane containing alkenyl group (E) Organohydrogenpolysiloxane (F) Catalyst for addition reaction (G) Organic solvent

  The component (D) of the release silicone composition to be overcoated can be an organopolysiloxane having at least two alkenyl groups in one molecule, and more specifically, represented by the following general formula (8). The thing which has the structure which can be mentioned.

（式中、Ｒ⁷はアルケニル基、Ｒ⁸は脂肪族不飽和結合を含有しない１価の有機基又は水酸基を示し、Ｘ¹は下記式（９）

で示される基である。ａ３、ｂ３、ｃ３、ｄ３、ｅ３はオルガノポリシロキサンの回転粘度計を使用して測定される２５℃の粘度が０．０４Ｐａ・ｓ以上、３０質量％トルエン溶液での回転粘度計を使用して測定される２５℃での絶対粘度が７０Ｐａ・ｓ以下を満たす正数から選ばれ、ｂ３、ｃ３、ｄ３、ｅ３は０であってもよい。α及びβは０又は１〜３の整数である。）

(Wherein R ⁷ represents an alkenyl group, R ⁸ represents a monovalent organic group or a hydroxyl group not containing an aliphatic unsaturated bond, and X ¹ represents the following formula (9):

It is group shown by these. a3, b3, c3, d3, and e3 are measured using a rotational viscometer of organopolysiloxane, and the viscosity at 25 ° C. is 0.04 Pa · s or more, using a rotational viscometer in a 30% by mass toluene solution. The measured absolute viscosity at 25 ° C. is selected from positive numbers satisfying 70 Pa · s or less, and b3, c3, d3, and e3 may be 0. α and β are 0 or an integer of 1 to 3. )

R ⁷ is preferably an alkenyl group having 2 to 6 carbon atoms such as a vinyl group, an allyl group or a butenyl group, and R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, particularly 1 to ⁸ carbon atoms. Group, alkyl group having 1 to 12 carbon atoms such as butyl group, cycloalkyl group having 4 to 20 carbon atoms such as cyclohexyl group, aryl group having 6 to 20 carbon atoms such as phenyl group and tolyl group, or carbons of these groups Substituted monovalent hydrocarbon groups such as chloromethyl, trifluoropropyl, and cyanoethyl groups in which some or all of the hydrogen atoms bonded to the atoms are substituted with halogen atoms, cyano groups, and the like, as well as methoxy groups, ethoxy groups, and propoxy groups. Groups, monovalent hydrocarbon groups including C1-C12 alkoxy groups such as methoxyethoxy groups, hydroxyl groups, C2-C20 epoxy groups such as glycidyl groups, groups Although it is a monovalent organic group selected from a lysidyloxy group, an epoxycyclohexyl group-substituted alkyl group, etc., it does not contain an aliphatic unsaturated bond.
From the viewpoint of production and characteristics, R ⁷ is preferably a vinyl group industrially, and at least 80 mol% of R ⁸ contained in the whole organopolysiloxane of component (D) is a methyl group.

Although (1) molecule of organopolysiloxane of component (D) has 2 or more alkenyl groups, it is preferably 0.001 to 0.3 mol as content per 100 g of organopolysiloxane. As a3, b3, c3, d3, and e3 of the corresponding formula (8) and substituent X ¹ , the number of alkenyl groups c3 + b3 × (e3 + β) + 2α of one molecule is in the range of 2 to 2,500. To be elected.
The (D) component organopolysiloxane may have a silanol group.

  Although the main skeleton structure of the organopolysiloxane of component (D) is a straight chain, those containing a branched chain structure as shown when b3 is not 0 can also be used.

  The component (E) of the peelable silicone composition to be overcoated is an organohydrogenpolysiloxane, and has the following average composition formula (10) having at least three hydrogen atoms (SiH groups) directly bonded to silicon atoms in one molecule. ) Is preferred.

R ⁸ _f H _g SiO _{(4-fg) / 2} (10)
(In the formula, R ⁸ is as described above, f is 0 to 3, g is 0 to 3, and f + g is a positive number of 1 to 3.)

  The molecular structure may be linear, branched or cyclic. The absolute viscosity at 25 ° C. measured using a rotational viscometer may be in the range of several mPa · s to tens of thousands mPa · s. Specific examples of the organohydrogenpolysiloxane include the following organohydrogenpolysiloxanes.

（但し、上記式において、Ｍｅはメチル基、ｈ、ｌ、ｎは３〜５００、ｍ、ｐ、ｓは１〜５００、ｉ、ｊ、ｋ、ｏ、ｑ、ｒ、ｔ、ｕ、ｖ、ｗは０〜５００である。）

(In the above formula, Me is a methyl group, h, l, n are 3 to 500, m, p, and s are 1 to 500, i, j, k, o, q, r, t, u, v, w is 0-500.)

  The compounding amount of the organohydrogenpolysiloxane of the component (E) is such that the number of moles of hydrogen atoms (SiH groups) bonded to the contained silicon atoms is 1 of the total number of moles of alkenyl groups contained in the component (D). It is preferably an amount corresponding to 10 times, particularly 1 to 5 times. Moreover, it can use in 0.1-20 mass parts with respect to 100 mass parts of (D) component organopolysiloxane.

  The component (F) of the peelable silicone composition to be overcoated is an addition reaction catalyst, and any conventionally known one can be used. Examples thereof include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like. The addition reaction catalyst may be blended in an amount of 5 to 1,000 ppm (mass ratio), particularly 10 to 800 ppm (mass ratio) as the amount of platinum or rhodium with respect to the total mass of the component (D) and the component (E). Although it is preferable to form a sufficient cured film, it can be appropriately increased or decreased depending on the reactivity of the components or the desired curing rate.

An organic solvent can be blended as the component (G) in the peelable silicone composition to be overcoated. The organic solvent as the component (G) is intended to improve the stability of the treatment bath and the coating property on various substrates, and adjust the coating amount and viscosity. Specifically, as the organic solvent, for example, an organic solvent that can uniformly dissolve a composition such as toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, and hexane can be used.
As for the compounding quantity in the case of mix | blending an organic solvent, 100-9,900 mass parts is preferable with respect to 100 mass parts of (D) component.
The organic solvent is an optional component, and when not blended, it is adjusted by changing the viscosity of the other components so that appropriate coating properties can be obtained with the coating apparatus used. The treatment bath stability is adjusted using a bath life extender or the like as necessary.

  The releasable silicone composition to be overcoated can be easily produced by uniformly mixing the components (D), (E), (F), and (G), but has a sufficient pot life. In order to ensure, component (F) should be added and mixed immediately before coating. Moreover, when using the organic solvent of (G) component, it is advantageous to mix (F) component, after melt | dissolving (D) component and (E) component uniformly in (G) component.

  When the peelable silicone composition to be overcoated is an emulsion, the water of the component (C) is used instead of the components (D), (E), and (F) and the component (G), and the interface is used as necessary. A composition using the component (B) as an activator can be used.

  If necessary, additives such as pigments, leveling agents, bath life extenders and the like can be blended in the peelable silicone composition to be overcoated as long as the object of the present invention is not impaired.

  When applying a peelable silicone composition to be overcoated, after the peelable silicone composition is diluted directly or with an appropriate organic solvent or water, a bar coater, a roll coater, a reverse coater, a gravure coater, an air knife coater, Further, for the coating of the thin film, the above-mentioned undercoat silicone emulsion composition is applied onto a cured release paper substrate or release film substrate by a known application method such as a high-precision offset coater or a multi-stage roll coater. .

The amount of the releasable silicone composition to be overcoated on the base material is preferably 0.05 to 5 g / m ² as the solid content, although it varies depending on the use on the primer. By heating the base material coated with the peelable silicone composition as described above at 80 to 150 ° C. for 5 to 60 seconds, a cured film is formed on the surface of the base material, and a release paper or a release film can be obtained.

  Note that, as described above, in the present invention, in the undercoat silicone emulsion composition, the wettability to the base, the coatability, and the reason for improving the coatability at the time of overcoating the peelable silicone composition, Part or all of the components of the peelable silicone composition may be blended, and the components (D), (E), and (F) exemplified as the components of the peelable silicone composition can be blended. When mix | blending these components with an undercoat silicone emulsion composition, it is preferable that the compounding quantity of (D) component shall be 1-100 mass parts with respect to 100 mass parts of (A) component.

  (E) The compounding quantity of a component is 1-10 mol with respect to a total of 1 mol of the alkenyl group in (A) component and (D) component, It is preferable to set it as 1-5 mol especially. (E) When there are too many components, pot life may become short and workability | operativity may fall.

  Moreover, the compounding quantity of (F) component is mass ratio 1-1000 ppm as a quantity of platinum or rhodium with respect to the total mass of (A) component, (D) component, and (E) component, especially 5-800 ppm compounding. It is preferable to do. When there are too many compounding quantities, pot life may become short and workability | operativity may fall.

  Thus, when the said (D), (E), (F) component is mix | blended with undercoat silicone emulsion composition, the method and conditions similar to the above are employ | adopted as a coating method, a coating amount, and hardening conditions. can do. In this case, if it is necessary to prevent stickiness, it can be heated after 5 to 30 seconds at 100 to 120 ° C.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. Viscosity is the absolute viscosity at 25 ° C. measured using a rotational viscometer.

[Examples 1 to 19, Comparative Examples 1 to 4 ]
5 liter compound emulsifier (TK combination M type, special machine) having a vertical stirring device that can stir the entire container and a rotatable disc with small tooth-shaped projections alternately arranged on the periphery Chemical Industries, Ltd.), 100 parts by weight of component (A), 100 parts by weight of component (C), and polyoxyethylene alkyl ether surfactant (HLB 13.6, PH 5.4, ion as component (B)) 10 parts by mass of an electrical conductivity of 9.8 μS / cm), 10 parts by mass of polyvinyl alcohol having a saponification degree of 90 mol% as a thickener and a viscosity of 4% by mass of an aqueous solution at 20 ° C. of 30 mPa · s. Then, a homogenizer was used to obtain a homogeneous O / W emulsion having a silicone content of 50% by mass.
The obtained emulsion was diluted with the component (C), and an undercoat silicone composition was prepared so as to have a ratio of (A) to (C) parts by mass shown in Table 1 below. Next, an undercoat silicone composition was applied to a substrate (40 μm PET or OPP) at a thickness of 0.005 g / m ² , and Examples 6, 7, 9, 11, 17, 18, and Comparative Example 4 were 100 ° C. After heat treatment with a hot air circulation dryer for 20 seconds, UV irradiation (accumulated light amount 50 mJ / cm ² ) was performed with a UV lamp 80W2 lamp, a lamp height of 30 cm, and a line speed of 40 m / min to form an undercoat substrate. Other than that, UV irradiation with UV lamp 80W2 lamp, lamp height 30cm, line speed 40m / min (integrated light quantity 50mJ / cm ² ), then heat treatment for 20 seconds with 120 ° C hot air circulation dryer for undercoating Formed.

On the other hand, in the case of solvent type and solventless type, the preparation of the top coat composition (peelable silicone composition) is (D), (E) component and diluent shown in Table 1 below, as necessary. Mix 1 part by mass of acetylene alcohol (3-methyl-1-butyn-3-ol) as a pot life extender so as to form a uniform solution, and add and mix 100 ppm of component (F) as a platinum amount with respect to the silicone component. A top coating composition (peelable silicone composition) was prepared.
When the top coating composition was an emulsion type, a coating solution was prepared by the following method.
5 liter compound emulsifier (TK combination M type, special machine) having a vertical stirring device that can stir the entire container and a rotatable disc with small tooth-shaped projections alternately arranged on the periphery (Made by Kagaku Kogyo Co., Ltd.), (D), (E) component in mass parts shown in Table 1 below, polyoxyethylene alkyl ether surfactant (HLB 13.6, PH 5.4, ionic conductivity 9.8 μS / cm) 2 parts by weight, 2 parts by weight of polyvinyl alcohol having a saponification degree of 90 mol% as a thickener and a 4% by weight aqueous solution having a viscosity at 20 ° C. of 30 mPa · s, and 100 parts of water (C). 1 part by mass of acetylene alcohol (3-methyl-1-butyn-3-ol) as a pot life extender as necessary, and using a homogenizer, 50 parts by mass of silicone content. / I was to give a W type emulsion.
Using the same method, replacing the component (D) with a platinum-based complex-containing polysiloxane, omitting the component (E) to prepare a catalyst emulsion composition having a platinum content of 0.1% by mass, and preparing the emulsion composition previously prepared The composition for coating was prepared by mixing in an amount of 10 parts by mass (100 ppm as the amount of platinum with respect to the siloxane content) per 100 parts by mass of the product.
These topcoat compositions are coated on the above-mentioned undercoat substrate at a thickness of 0.5 g / m ² , and cured by heating at 100 ° C. for 30 seconds, and in the case of emulsion compositions at 120 ° C. for 30 seconds, and then peeled off. A film was prepared and used for evaluation. The solvent type and emulsion type were applied by wire bar coating, and the solventless type was applied by a transfer method using an IR tester.

[Comparative Example 5 ]
The UV irradiation was omitted during the coating and curing of the undercoat composition, and the evaluation was performed only by heat treatment at 120 ° C. for 30 seconds with a hot air circulation dryer.

[Symbols and structure of each component]
In the formula, Me represents a methyl group, and Vi represents a vinyl group.

--- (A) component ---
(A1-1) Siloxane, viscosity 5 mPa · s, Vi content 1.2 mol / 100 g

(A1-2) Siloxane, viscosity 5 mPa · s, Vi content 0.63 mol / 100 g

(A1-3) Siloxane, viscosity 10 mPa · s, Vi content 0.6 mol / 100 g

(A1-4) Siloxane, viscosity 6 mPa · s, Vi content 0.7 mol / 100 g

Ｒ¹は−ＣＨ₂ＣＨ₂ＣＨ₂−Ｏ−ＣＯ−（ＣＨ₃）Ｃ＝ＣＨ₂（１２７）
Ｒ²は−ＣＨ₂ＣＨ₂ＣＨ₂−Ｏ−ＣＨ₂ＣＨ₂−ＯＨ（１０６） (A1-5) Siloxane, viscosity 0.02 Pa · s, alkenyl group content 0.33 mol / 100 g

R ¹ is —CH ₂ CH ₂ CH ₂ —O—CO— (CH ₃ ) C═CH ₂ (127)
R ² represents —CH ₂ CH ₂ CH ₂ —O—CH ₂ CH ₂ —OH (106).

Ｒ¹は−ＣＨ₂ＣＨ₂ＣＨ₂−Ｏ−ＣＯ−（ＣＨ₃）Ｃ＝ＣＨ₂（１２７） (A1-6) Siloxane, viscosity 6 mPa · s, alkenyl group content 0.49 mol / 100 g

R ¹ is —CH ₂ CH ₂ CH ₂ —O—CO— (CH ₃ ) C═CH ₂ (127)

(A1-7) Siloxane, viscosity 5 mPa · s, Vi content 0.32 mol / 100 g

(A1-8) Siloxane, viscosity 6 mPa · s, Vi content 0.32 mol / 100 g

(A1-10) Siloxane, viscosity 0.03 Pa · s, alkenyl group content 0.75 mol / 100 g

(A1-11) Siloxane, viscosity 0.02 Pa · s, alkenyl group content 0.93 mol / 100 g

(A1-12) Siloxane, viscosity 0.04 Pa · s, alkenyl group content 0.88 mol / 100 g

Ｒ¹は−ＣＨ₂ＣＨ₂ＣＨ₂−Ｏ−ＣＯ−ＣＨ＝ＣＨ₂（１１３） (A1-13) Siloxane, viscosity 30 mPa · s, alkenyl group content 0.58 mol / 100 g

R ¹ is —CH ₂ CH ₂ CH ₂ —O—CO—CH═CH ₂ (113)

(A2-1) Acetylene alcohol, 3-methyl-1-butyn-3-ol (A2-2) Acetylene alcohol, 3,5-dimethyl-1-hexyn-3-ol (A2-3) acetylene alcohol, 1- Ethynyl-1-cyclohexanol (A2-4) acetylene compound, 1-octyne

--- Component (B) ---
Polyoxyethylene alkyl ether surfactant (HLB 13.6, PH 5.4, ionic conductivity 9.8 μS / cm)

--- Component (C) ---
Ion exchange water

--- (D) component ---
(D-1) Viscosity of organopolysiloxane, 30% by weight toluene solution at 25 ° C. at 2 Pa · s, Vi content 0.032 mol / 100 g

(D-2) Organopolysiloxane, viscosity 0.2 Pa · s, Vi content 0.026 mol / 100 g

(D-3) Viscosity at 25 ° C. of organopolysiloxane, 30 mass% toluene solution is 1 Pa · s, Vi content 0.035 mol / 100 g

(D-4) Organopolysiloxane, viscosity 0.1 Pa · s, Vi content 0.043 mol / 100 g

--- (E) component ---
(E-1) Methyl hydrogen polysiloxane, viscosity is 25 mPa · s, H content 1.5 mol / 100 g

(E-2) methylhydropolysiloxane, viscosity 60 mPa · s, H content 1.00 mol / 100 g

--- (F) component ---
(F-1) Catalyst, platinum-vinylsiloxane complex

--- (G) component ---
Solvent, toluene / heptane mass ratio = 50/50 mixed solvent

<Evaluation method>
The evaluation of each item and the display of the results were in accordance with the following method.
(1) Peeling force A separator made of a PET film (40 μm) substrate was allowed to stand at 25 ° C. and 50% RH for 1 day, and then treated with an acrylic solvent-type pressure-sensitive adhesive [Olivein BPS-5127 (Toyo Ink Manufacturing Co., Ltd.). And a heat treatment at 100 ° C. for 3 minutes. Next, a PET film (40 μm) was bonded to this treated surface, and the film was pressure-bonded once with a 2 kg roller and aged at 25 ° C. for 20 hours, then the sample was cut to a width of 5 cm, and 180 ° using a tensile tester. The laminated paper was pulled at an angle at a peeling speed of 0.3 m / min, and the force (N) required for peeling was measured. For the measurement, Autograph DCS-500 (manufactured by Shimadzu Corporation) was used.

(2) Adhesiveness The produced separator was allowed to stand under specified conditions, and the cured film surface was rubbed with a finger, and the number of days until the film surface was clouded and dropped was examined.
X, which is clouded or dropped when left at 40 ° C., 80% RH for 1 day, Δ, 40 ° C., 80% RH which is clouded or dropped after 3 days at 40 ° C., 80% RH When the sample was left standing for 1 month, it was shown as ◯, and when it was left at 60 ° C. and 90% RH for 1 month, it was shown as ◎.

Claims (12)

An undercoat silicone emulsion composition for release paper or release film that is applied as a primer on paper or a plastic film, and a cured film of the release silicone composition is formed after the coating film is irradiated with ultraviolet rays,
(A) As an adhesion imparting component, the following (A1) and / or (A2) 100 parts by mass,
(A1) The viscosity at 25 ° C. is less than 0.04 Pa · s, the molecule has a substituent containing an alkenyl group bonded to at least two silicon atoms, and the alkenyl group content is 0.3-2. 2 siloxane units within the range of 0 mol / 100 g and having a substituent containing an alkenyl group bonded to a silicon atom are directly or less than 3 siloxane units having no substituent bonded to a silicon atom An organopolysiloxane having a structure bonded in an intervening state,
(A2) Hydrogen bonded to an alkenyl group and / or a silicon atom in at least one substituent containing a carbon-carbon unsaturated bond (double or triple bond) having 2 to 10 carbon atoms as a functional group in one molecule SiH groups or an OH group possess at least one as a substituent containing an atom and an addition reaction and / or condensation reactable groups is a polystyrene-reduced number-average molecular weight by GPC of 1,000 or less, non containing no siloxane structure Silicone compounds,
(B) 0.1-50 mass parts of surfactant,
(C) 100 to 500,000 parts by weight of water
Release paper or a release film for undercoat silicone emulsion composition characterized in that it consists. The undercoat silicone emulsion composition according to claim 1, wherein the component (A1) is an organopolysiloxane having an average polymerization degree of 2 to 50 represented by the following composition formula (1) having a structure represented by the following general formula (2). .
^{_{[M] m1 [M A]}} m2 [D] d1 [D A] d2 [T] t1 [T A] t2 [Q] q1 (1)

(In the formula, R ¹ represents a substituent containing an alkenyl group having 2 to 10 carbon atoms. A represents a siloxane residue selected to satisfy Formula (1) bonded via R ² or an oxygen atom, Two A may form a ring structure as —O (SiR ² ₂ O) _y —, R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and x is 0 to 3 And y is an integer selected so as to satisfy an average degree of polymerization of 2 to 50 of the organopolysiloxane of formula (1).
M, M ^A , D, D ^A , T, T ^A , and Q are the following siloxane units, and O _1/2 is bonded to an adjacent siloxane unit through an oxygen atom.

m1, m2, d1, d2, t1, t2, and q1 are numbers satisfying the following expression.
t1 + t2 + 2 × q1 ≦ m1 + m2 ≦ 2 + t1 + t2 + 2 × q1
0 ≦ d1 + d2 ≦ 48, 0 ≦ t1 + t2 ≦ 30, 0 ≦ q1 ≦ 20
0.25 ≦ (m2 + d2 + t2) / (m1 + m2 + d1 + d2 + t1 + t2 + q1) ≦ 1)   The undercoat silicone emulsion composition according to claim 2, wherein x in the formula (2) is 0 or 1. The undercoat silicone emulsion composition according to claim 2 or 3, wherein the component (A1) is a compound having a linear or branched siloxane structure represented by the following general formula (3) or (4).

(Wherein R ¹ and R ² are as described above. Y represents the following formula (3a)

In the formula (3a), R ¹ , R ² and Y are as described above.
a2, b2, ay and by are integers of 0 to 48, c2 and cy are integers of 0 to 30, and d2 and dy are integers of 0 to 20.
Equation (3), bonded to (3a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. )

(In the formula, R ¹ and R ² are as described above. Z represents the following formula (4a)

In the formula (4a), R ¹ , R ² and Z are as described above.
a2, b2, ay and by are integers of 0 to 48, c2 and cy are integers of 0 to 30, and d2 and dy are integers of 0 to 20.
Equation (4), bonded to (4a) is shown a random structure, respectively, 2 siloxane units the substituents are bonded to a silicon atom directly or R ¹ is a silicon atom contains an alkenyl group R ¹ It contains at least one structure in which 3 or less siloxane units are bonded together. ) The undercoat silicone emulsion composition according to claim 2 or 3, wherein the component (A1) is a compound having a cyclic siloxane structure represented by the following general formula (5).

(In the formula, R ¹ and R ² are as described above. R ³ does not have an OH group or a substituent having a hydrogen atom bonded to a silicon atom as a functional group or an aliphatic unsaturated bond having 1 to 10 carbon atoms. An unsubstituted or substituted monovalent hydrocarbon group, a1 is 0 or 1, b1 is an integer of 1 to 6, c1 is an integer of 0 to 5, and a1 + b1 + c1 is an integer of 2 or more.) In the component (A2), the substituent containing a carbon-carbon unsaturated bond (double or triple bond) is a substituent containing an alkenyl group, alkynyl group, acryloyloxy group or methacryloyloxy group, and the alkenyl group and / or The undercoat silicone emulsion composition according to claim 1, wherein the substituent containing a group capable of addition reaction and / or condensation reaction with a SiH group is a substituent having a SiH group or an OH group as a functional group. (A2) in the component, carbon - is a substituent containing a carbon-carbon unsaturated bonds (double or triple bonds), according to claim 1 is a substituent containing an alkynyl group, acryloyloxy group or methacryloyloxy group having 2 to 10 carbon atoms The undercoat silicone emulsion composition described. Compound (A2) is a compound containing a divalent structural unit represented by the following general formula (6-1), a divalent structure represented by the following general formula (6-2) and the following general formula (6-3) The undercoat silicone emulsion composition according to claim 1, which is a compound comprising a unit, a compound having a cyclic structure represented by the following general formula (7-1), or a compound having a cyclic structure represented by the following general formula (7-2). object.

Wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is a substituent containing an alkynyl group, acryloyloxy group or methacryloyloxy group having 2 to 10 carbon atoms, R ⁵ Is a substituent having an OH group or SiH group as a functional group, R ⁶ is a hydrogen atom, a saturated hydrocarbon group or aromatic group having 1 to 10 carbon atoms, the same group as R ⁴ , or the same group as R ⁵ , d is 4-10, e + f is 3-9.)   The undercoat silicone emulsion composition according to any one of claims 1 to 8, wherein the peelable silicone composition is a composition that cures by an addition reaction and a condensation reaction.   Furthermore, the primer silicone emulsion composition of any one of Claims 1-9 containing a part or all of the component of a peelable silicone composition.   A treated paper or treated film substrate coated with the undercoat silicone emulsion composition according to any one of claims 1 to 10 and irradiated with ultraviolet rays, wherein the cured surface of the peelable silicone composition is treated on the treated surface. Release paper or release paper treated paper or treatment film substrate on which is formed.   A release paper or release film obtained by coating and curing a peelable silicone composition on the treated surface of the treated paper or treated film substrate according to claim 11.