JP6471579B2 - LAMINATE, METHOD FOR PRODUCING THE SAME, METHOD FOR USING SUBSTRATE-LESS ADHESIVE SHEET, AND ARTICLE - Google Patents

Description

  The present invention includes a laminate including a silicone pressure-sensitive adhesive layer using a base material treated with a release agent composition for a silicone pressure-sensitive adhesive, a production method thereof, a method of using a base-less pressure-sensitive adhesive sheet, and the base-less pressure-sensitive adhesive sheet. It relates to goods.

  Electronic terminals such as personal computers and mobile phones are widely used all over the world, and their sales volume continues to grow. These electronic terminals have led to miniaturization of the entire terminal as the functions and size of the internal components have increased.

  Conventionally, a personal computer has been composed of a CPU, a main body, and a display composed of a large casing, but the current display is very thin. The same applies to notebook personal computers, where the CPU-containing part and the display are very miniaturized, and recently, tablet terminals without a keypad part have become widespread. The tablet terminal is operated by directly touching the display on the display with a finger or a pen.

  Mobile phones are also becoming smaller and more functional than before, and recently there is no push button, and the share of smartphones that operate on a display like tablet devices is growing rapidly. The touch panel can be operated because the touch panel exists between the glass on the surface and the liquid crystal panel inside.

  There are various types of touch panels, but in recent years, the capacitive type has become the mainstream, and the sensor detects the movement of fingers and pens on the surface with a transparent conductive film made of indium tin oxide (ITO). To do.

  The terminal has a structure in which a cover glass is provided on the surface, a touch panel is provided below the cover glass, and a liquid crystal panel is provided below the touch panel. The cover glass and touch panel, and the touch panel and liquid crystal panel each have a structure in which only the edges are bonded with double-sided tape and an air layer is included in the center. Yes. This is because the interface reflection is suppressed by eliminating the air layer and the visibility is improved, and the structure becomes strong and the impact resistance is improved.

  There are two types of bonding methods. One is a method in which a liquid resin (Optical Clear Resin) is poured between the members and cured and bonded, and the other is a method in which the members are bonded with a double-sided adhesive sheet (OCA: Optical Clear Adhesive) without a base material. It is.

  OCA is a pressure-sensitive adhesive sheet without a substrate having both surfaces sandwiched between peeling substrates. This pressure-sensitive adhesive sheet is prepared by first applying / curing a pressure-sensitive adhesive on the first release substrate to form an adhesive layer, and then bonding the second release substrate to the pressure-sensitive adhesive layer. The material is peeled off and attached to an object, and then the first release substrate is peeled off and attached to another object for use. At this time, a certain peeling force difference is required between the first peeling substrate and the second peeling substrate, and if there is a difference in peeling force, only the second peeling substrate can be peeled off first, This is called differential peeling. When the difference in peel force between the two is small, the phenomenon that the adhesive layer partially remains on each of the second release substrate and the first release substrate even if the second release substrate is peeled off Occurs. In this case, the 2nd peeling base material cannot be peeled off favorably first, and the adhesion layer cannot maintain the shape as a sheet.

  The mainstream of OCA materials is acrylic adhesives, and some urethane adhesives also exist. Acrylic pressure-sensitive adhesives can produce pressure-sensitive adhesives with various characteristics by changing the type and composition ratio of the acrylic monomer that is the raw material, and show excellent adhesion to various adherends. There is also a drawback that the color is not sufficient and easily discolored.

  There is an attempt to produce this OCA with a silicone adhesive because it is believed that the impact resistance is further improved by using a silicone adhesive that is softer than the acrylic adhesive. Further, since the refractive index of silicone is lower than that of acrylic, further improvement in visibility is expected.

  Regarding a double-sided pressure-sensitive adhesive sheet that is a silicone pressure-sensitive adhesive and does not have a base material, JP-A-2005-29712 (Patent Document 1) produces a sheet using a silicone release agent that does not contain fluorine in addition to a fluorine-based release agent. However, a fluorine-free silicone release agent may not be able to release well because of its poor release property for silicone adhesives. In Japanese Patent No. 5553395 (Patent Document 2), a double-sided pressure-sensitive adhesive sheet is produced by applying a difference in peel strength between both sides by modifying the composition of the silicone pressure-sensitive adhesive, but the study on the release agent is still insufficient. The difference in peel force after the two peelable substrates are bonded and placed over time with moisture and heat is reduced, so that crying is likely to occur.

JP 2005-29712 A Japanese Patent No. 5553395

  The present invention has been made in view of the above circumstances, and is a laminate in which a silicone adhesive layer is sandwiched between two release substrates having different peeling forces, a method for producing the same, a method of using a substrate-less pressure-sensitive adhesive sheet, and the substrate-less pressure-sensitive adhesive. An object is to provide an article including a sheet.

As a result of intensive studies to achieve the above object, the present inventor has developed a specific structure as a heavy release component in a silicone adhesive release agent composition using an organopolysiloxane modified with a fluorine-containing organic group. It has been found that the release force of the release agent obtained by coating and curing this can be increased by adding an organopolysiloxane having a viscosity.
The release of the silicone pressure-sensitive adhesive is carried out on two types of the first release substrate treated with the release agent composition not containing the heavy release component and the second release substrate treated with the release agent composition added with the heavy release component. By using as a base material, the peeling force difference between these peeling base materials becomes large, so that both have good peelability and do not cry when the first peeling base material is peeled off. The present inventors have found that a desired laminate can be provided, and have made the present invention.

（式中、Ｒ¹は同一又は異なっていてもよい炭素数１〜１０の脂肪族不飽和結合を有さない非置換もしくは置換の１価炭化水素基又は炭素数２〜１０のアルケニル基含有有機基であり、Ｒ¹のうち少なくとも２個は炭素数２〜１０のアルケニル基含有有機基を含み、Ｒ¹のうち少なくとも１個は炭素数１〜１０のフルオロアルキル基を含む。ａは２以上の整数、ｂは１以上の整数、ｃ及びｄは０以上の整数で、５０≦ａ＋ｂ＋ｃ＋ｄ≦５，０００である。）
で表され、１分子中に少なくとも２個のアルケニル基含有有機基及び少なくとも１個のフルオロアルキル基を有し、アルケニル基が１００ｇ中に０．００１〜０．５モル含まれ、フルオロアルキル基が１００ｇ中に０．１〜０．５モル含まれるオルガノポリシロキサン：１００質量部、
（Ｂ）１分子中に少なくとも３個のＳｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサン：（Ａ）成分と下記（Ｆ）成分のアルケニル基の合計に対し、Ｓｉ−Ｈ基がモル比で１〜１０となる量、
（Ｃ）（Ａ）成分と下記（Ｆ）成分のアルケニル基と（Ｂ）成分のＳｉ−Ｈ基をヒドロシリル化付加して硬化させるための白金族金属系触媒：金属質量が（Ａ）成分に対して１〜５００ｐｐｍとなる量、
（Ｅ）有機溶剤：０〜２，０００質量部、
（Ｆ）アルケニル基を１００ｇ中に０．００１〜０．１モル含み、かつフルオロアルキル基を含まないオルガノポリシロキサン：１〜２５質量部。
〔２〕
シリコーン粘着剤用剥離剤組成物（Ｉ）及び／又はシリコーン粘着剤用剥離剤組成物（ＩＩ）において、更に、（Ｄ）反応制御剤を（Ａ）成分１００質量部に対し、０．０１〜５質量部含有する〔１〕に記載の積層体。
〔３〕
（Ａ）成分が、（Ａ−１）１分子中に少なくとも２個のアルケニル基含有有機基及び少なくとも１個のフルオロアルキル基を有し、アルケニル基が１００ｇ中に０．００１モル以上０．０３モル未満含まれ、フルオロアルキル基が１００ｇ中に０．１〜０．５モル含まれるオルガノポリシロキサン及び／又は（Ａ−２）１分子中に少なくとも２個のアルケニル基含有有機基及び少なくとも１個のフルオロアルキル基を有し、アルケニル基が１００ｇ中に０．０３〜０．５モル含まれ、フルオロアルキル基が１００ｇ中に０．１〜０．５モル含まれるオルガノポリシロキサンであることを特徴とする〔１〕又は〔２〕に記載の積層体。
〔４〕
（Ａ）成分が、前記（Ａ−１）成分と（Ａ−２）成分とを含有し、（Ａ−１）、（Ａ−２）成分の割合が、（Ａ−１）：（Ａ−２）＝２０：８０〜８０：２０（質量比）であることを特徴とする〔３〕に記載の積層体。
〔５〕
（Ａ）成分に含まれるフルオロアルキル基が、３，３，３−トリフルオロプロピル基、３，３，４，４，４−ペンタフルオロブチル基、３，３，４，４，５，５，５−ヘプタフルオロペンチル基、３，３，４，４，５，５，６，６，６−ノナフルオロヘキシル基、３，３，４，４，５，５，６，６，７，７，７−ウンデカフルオロヘプチル基、３，３，４，４，５，５，６，６，７，７，８，８，８−トリデカフルオロオクチル基及び３，３，４，４，５，５，６，６，７，７，８，８，９，９，９−ペンタデカフルオロノニル基からなる群より選ばれるものであることを特徴とする〔１〕〜〔４〕のいずれかに記載の積層体。
〔６〕
（Ｂ）成分がフルオロアルキル基を含むことを特徴とする〔１〕〜〔５〕のいずれかに記載の積層体。
〔７〕
（Ｂ）成分に含まれるフルオロアルキル基が、３，３，３−トリフルオロプロピル基であることを特徴とする〔１〕〜〔６〕のいずれかに記載の積層体。
〔８〕
（Ｆ）成分が、下記構造を表したものから選ばれるオルガノポリシロキサンである請求項１〜７のいずれか１項に記載の積層体。

（式中、ｏは４８〜１，４９８の整数であり、ｐは１〜２０の整数であり、ｑ１は４７〜１，４９７の整数であり、ｑ２は１〜１，４９６の整数であり、ｒは１〜１，４４９の整数であり、ｐ＋ｑ１及びｐ＋ｑ２＋ｒはそれぞれ４８〜１，４９８の整数である。Ｍｅはメチル基、Ｖｉはビニル基、Ｐｈはフェニル基を示す。）

（式中、ｓは５〜１，４９１の整数であり、ｔは５〜１，４９１の整数であり、ｕは０〜１，４７６の整数であり、ｖは１〜７３９の整数である。Ｍｅはメチル基、Ｖｉはビニル基を示す。）
〔９〕
前記粘着層が、
（Ｇ）下記平均組成式（４）
Ｒ⁵ _wＳｉＯ_(4-w)/2 （４）
（式中、Ｒ⁵は独立に炭素数１〜１０の脂肪族不飽和結合を有さない非置換もしくは置換の１価炭化水素基又は炭素数２〜１０のアルケニル基含有有機基であり、ｗは１．８〜２．２の正数である。）
で表される、１分子中に少なくとも２個のアルケニル基含有有機基を有し、アルケニル基が１００ｇ中に０．０００７〜０．０５モル含まれるオルガノポリシロキサン：（Ｇ）及び（Ｈ）成分の合計１００質量部中３０〜７０質量部、
（Ｈ）Ｒ⁶ ₃ＳｉＯ_1/2単位とＳｉＯ_4/2単位とを含み、（Ｒ⁶ ₃ＳｉＯ_1/2単位）／（ＳｉＯ_4/2単位）がモル比で０．５〜１であるオルガノポリシロキサン（Ｒ⁶は独立に脂肪族不飽和結合を有さない炭素数１〜１０の１価炭化水素基又は炭素数２〜６のアルケニル基である。）：（Ｇ）及び（Ｈ）成分の合計１００質量部中７０〜３０質量部、
（Ｉ）下記平均組成式（６）で表され、１分子中に少なくとも３個のＳｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサン：（Ｇ）及び（Ｈ）成分のアルケニル基の合計に対し、Ｓｉ−Ｈ基がモル比で０．２〜２０となる量、
Ｒ⁷ _yＨ_zＳｉＯ_(4-y-z)/2 （６）
（式中、Ｒ⁷は独立に非置換又は置換の炭素数１〜１０の１価炭化水素基であり、ｙ、ｚはｙ＞０、ｚ＞０で、０＜ｙ＋ｚ≦３を満足する正数である。）
（Ｊ）（Ｇ）及び（Ｈ）成分のアルケニル基と（Ｉ）成分のＳｉ−Ｈ基をヒドロシリル化付加して硬化させるための白金族金属系触媒：上記（Ｇ）〜（Ｉ）成分の総量に対し、金属量が１〜５００ｐｐｍとなる量、
（Ｋ）反応制御剤：（Ｇ）及び（Ｈ）成分の総量に対し、０．０１〜５質量部
を含むシリコーン粘着剤組成物の硬化物である〔１〕〜〔８〕のいずれかに記載の積層体。
〔１０〕
前記剥離基材の基材がプラスチックフィルムであることを特徴とする〔１〕〜〔９〕のいずれかに記載の積層体。
〔１１〕
前記シリコーン粘着剤用剥離剤組成物（ＩＩ）で処理された第２の剥離基材を用意し、該剥離基材の処理面上にシリコーン粘着剤組成物を塗工、硬化させて粘着剤層を形成した後、前記シリコーン粘着剤用剥離剤組成物（Ｉ）で処理された第１の剥離基材を貼り合わせる〔１〕〜〔１０〕のいずれかに記載の積層体の作製方法。
〔１２〕
〔１〕〜〔１０〕のいずれかに記載の積層体から第１の剥離基材を剥離後、粘着層面を対象に貼り合わせ、その状態から次に第２の剥離基材を剥離後、先程貼り合わせた粘着層面と反対の粘着層面を別の対象に貼り合わせる、基材レス粘着シートの使用方法。
〔１３〕
〔１２〕に記載の使用方法により得られた基材レス粘着シートを含む物品。 Therefore, this invention provides the following laminated body, its preparation method, the usage method and article | item of a base-material-less adhesive sheet.
[1]
A first release substrate,
Adhesive layer,
It is a laminate comprising a structure in which the second release substrate is laminated in this order, and the release surface (the surface in contact with the adhesive layer) of the first release substrate is the following (A) to (C) and if necessary The release surface (surface in contact with the adhesive layer) of the second release substrate treated with the silicone adhesive release agent composition (I) containing the component (E) and not containing the component (F ) is the following ( A laminate characterized by being treated with a release agent composition for silicone pressure-sensitive adhesive (II) containing components A) to (C), (F) and, if necessary, component (E).
(A) The following average composition formula (1)

(In the formula, R ¹ may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having no C1-C10 aliphatic unsaturated bond or an alkenyl group-containing organic group having 2-10 carbon atoms. a group of at least two of R ¹ include alkenyl group-containing organic group having 2 to 10 carbon atoms, at least one of R ¹ include a fluoroalkyl group having 1 to 10 carbon atoms .a 2 or more And b is an integer of 1 or more, c and d are integers of 0 or more, and 50 ≦ a + b + c + d ≦ 5,000.
And at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule, 0.001 to 0.5 mol of alkenyl group is contained in 100 g, and the fluoroalkyl group is Organopolysiloxane contained in 100 g in an amount of 0.1 to 0.5 mol: 100 parts by mass
(B) Organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule: The Si-H groups are in a molar ratio of 1 with respect to the sum of the alkenyl groups of the (A) component and the following (F) component. An amount of -10,
(C) A platinum group metal catalyst for hydrosilylation addition and curing of the alkenyl group of the component (A), the following component (F), and the Si-H group of the component (B): The metal mass becomes the component (A). In an amount of 1 to 500 ppm,
(E) Organic solvent: 0 to 2,000 parts by mass,
(F) Organopolysiloxane containing 0.001 to 0.1 mol of alkenyl group in 100 g and no fluoroalkyl group: 1 to 25 parts by mass.
[2]
In the release agent composition for silicone pressure-sensitive adhesive (I) and / or the release agent composition for silicone pressure-sensitive adhesive (II), (D) reaction control agent is further added in an amount of 0.01 to 100 parts by mass of component (A). The laminate according to [1], containing 5 parts by mass.
[3]
The component (A) has (A-1) at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule, and the alkenyl group is 0.001 mol or more and 0.03 in 100 g. Organopolysiloxane containing less than 1 mol and containing 0.1 to 0.5 mol of fluoroalkyl group in 100 g and / or (A-2) at least 2 alkenyl group-containing organic groups and at least 1 in 1 molecule It is an organopolysiloxane having a fluoroalkyl group of 0.03-0.5 mol in 100 g and 0.1-0.5 mol of fluoroalkyl group in 100 g. The laminate according to [1] or [2].
[4]
(A) component contains the said (A-1) component and (A-2) component, and the ratio of (A-1) and (A-2) component is (A-1) :( A- 2) = 20: 80 to 80:20 (mass ratio), The laminate according to [3].
[5]
The fluoroalkyl group contained in the component (A) is 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5, 5-heptafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7, 7-undecafluoroheptyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group and 3,3,4,4,5, Any one of [1] to [4], which is selected from the group consisting of 5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl groups The laminated body of description.
[6]
(B) Component contains a fluoroalkyl group, The laminated body in any one of [1]-[5] characterized by the above-mentioned.
[7]
(B) The laminated body in any one of [1]-[6], wherein the fluoroalkyl group contained in the component is a 3,3,3-trifluoropropyl group.
[8]
The laminate according to any one of claims 1 to 7, wherein the component (F) is an organopolysiloxane selected from those representing the following structures.

(In the formula, o is an integer of 48 to 1,498, p is an integer of 1 to 20, q1 is an integer of 47 to 1,497, q2 is an integer of 1 to 1,496, r is an integer of 1 to 1,449, and p + q1 and p + q2 + r are integers of 48 to 1,498, Me is a methyl group, Vi is a vinyl group, and Ph is a phenyl group.)

(In the formula, s is an integer of 5 to 1,491, t is an integer of 5 to 1,491, u is an integer of 0 to 1,476, and v is an integer of 1 to 739. Me represents a methyl group, and Vi represents a vinyl group.)
[ 9 ]
The adhesive layer is
(G) The following average composition formula (4)
R ⁵ _w SiO _{(4-w) / 2} (4)
Wherein R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms or an alkenyl group-containing organic group having 2 to 10 carbon atoms, and w Is a positive number from 1.8 to 2.2.)
An organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and containing 0.0007 to 0.05 mol of alkenyl groups in 100 g: (G) and (H) components 30 to 70 parts by mass in a total of 100 parts by mass of
(H) R ⁶ ₃ SiO _1/2 unit and SiO _4/2 unit are included, and (R ⁶ ₃ SiO _1/2 unit) / (SiO _4/2 unit) is 0.5 to 1 in molar ratio. Organopolysiloxane (R ⁶ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not have an aliphatic unsaturated bond): (G) and (H) 70 to 30 parts by mass of 100 parts by mass of the total components,
(I) Organohydrogenpolysiloxane represented by the following average composition formula (6) and having at least 3 Si—H groups in one molecule: (G) and the total of alkenyl groups of (H) component, An amount of Si—H groups in a molar ratio of 0.2 to 20,
R ⁷ _y H _z SiO _{(4-yz) / 2} (6)
(In the formula, R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, y and z are y> 0, z> 0, and a positive value satisfying 0 <y + z ≦ 3. Number.)
(J) Platinum group metal catalyst for hydrosilylation addition and curing of alkenyl groups of components (G) and (H) and Si-H groups of component (I): of the above components (G) to (I) The amount of metal to be 1 to 500 ppm relative to the total amount,
(K) Reaction control agent: any one of [1] to [ 8 ], which is a cured product of a silicone pressure-sensitive adhesive composition containing 0.01 to 5 parts by mass with respect to the total amount of components (G) and (H). The laminated body of description.
[ 10 ]
The laminate according to any one of [1] to [ 9 ], wherein the substrate of the release substrate is a plastic film.
[11]
A second release substrate treated with the silicone adhesive release agent composition (II) is prepared, and the silicone adhesive composition is applied on the treated surface of the release substrate and cured to obtain an adhesive layer. After forming, the manufacturing method of the laminated body in any one of [1]-[ 10 ] which bonds together the 1st peeling base material processed with the said release agent composition (I) for silicone adhesives.
[1 2 ]
After peeling the first release substrate from the laminate according to any one of [1] to [ 10 ], the adhesive layer surface is bonded to the target, and then the second release substrate is peeled from the state, and then A method of using a substrate-less pressure-sensitive adhesive sheet, wherein a pressure-sensitive adhesive layer surface opposite to the bonded pressure-sensitive adhesive layer surface is bonded to another target.
[1 3 ]
An article comprising a substrate-less pressure-sensitive adhesive sheet obtained by the method according to [1 2 ].

  By using the laminate of the present invention, a double-sided adhesive silicone sheet without a substrate can be produced.

（式中、Ｒ¹は同一又は異なっていてもよい炭素数１〜１０の脂肪族不飽和結合を有さない非置換もしくは置換の１価炭化水素基又は炭素数２〜１０のアルケニル基含有有機基であり、Ｒ¹のうち少なくとも２個は炭素数２〜１０のアルケニル基含有有機基を含み、Ｒ¹のうち少なくとも１個は炭素数１〜１０のフルオロアルキル基を含む。ａは２以上の整数、ｂは１以上の整数、ｃ及びｄは０以上の整数で、５０≦ａ＋ｂ＋ｃ＋ｄ≦５，０００である。）
で表され、１分子中に少なくとも２個のアルケニル基含有有機基及び少なくとも１個のフルオロアルキル基を有し、アルケニル基が１００ｇ中に０．００１〜０．５モル含まれ、フルオロアルキル基が１００ｇ中に０．１〜０．５モル含まれるオルガノポリシロキサン、
（Ｂ）１分子中に少なくとも３個のＳｉ−Ｈ基を有するオルガノハイドロジェンポリシロキサン、
（Ｃ）白金族金属系触媒、
（Ｄ）反応制御剤、
（Ｅ）有機溶剤、
（Ｆ）アルケニル基を１００ｇ中に０．００１〜０．１モル含み、かつフルオロアルキル基を含まないオルガノポリシロキサン。 Details of the present invention will be described below.
The laminate of the present invention is
A first release substrate,
Adhesive layer,
It includes a structure formed by laminating in order of the second release substrate, and the release surface (the surface in contact with the adhesive layer) of the first release substrate is the following (A) to (C) and if necessary (D ), The release agent composition for silicone adhesive (I) containing the component (E), and the release surface (the surface in contact with the adhesive layer) of the second release substrate is the following (A) to (C) , (F) and, if necessary, (D), treated with a release agent composition for silicone pressure-sensitive adhesive (II) containing components (E).
(A) The following average composition formula (1)

(In the formula, R ¹ may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having no C1-C10 aliphatic unsaturated bond or an alkenyl group-containing organic group having 2-10 carbon atoms. a group of at least two of R ¹ include alkenyl group-containing organic group having 2 to 10 carbon atoms, at least one of R ¹ include a fluoroalkyl group having 1 to 10 carbon atoms .a 2 or more And b is an integer of 1 or more, c and d are integers of 0 or more, and 50 ≦ a + b + c + d ≦ 5,000.
And at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule, 0.001 to 0.5 mol of alkenyl group is contained in 100 g, and the fluoroalkyl group is Organopolysiloxane contained in 0.1 to 0.5 mol in 100 g,
(B) an organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule;
(C) platinum group metal catalyst,
(D) a reaction control agent,
(E) an organic solvent,
(F) Organopolysiloxane containing 0.001 to 0.1 mol of alkenyl group in 100 g and no fluoroalkyl group.

[Release compositions for silicone pressure-sensitive adhesives (I), (II)]
Below, each component of release agent composition (I) and (II) for silicone adhesives is explained in full detail.

（式中、Ｒ¹は同一又は異なっていてもよい炭素数１〜１０の脂肪族不飽和結合を有さない非置換もしくは置換の１価炭化水素基又は炭素数２〜１０のアルケニル基含有有機基であり、Ｒ¹のうち少なくとも２個は炭素数２〜１０のアルケニル基含有有機基を含み、Ｒ¹のうち少なくとも１個は炭素数１〜１０のフルオロアルキル基を含む。ａは２以上の整数、ｂは１以上の整数、ｃ及びｄは０以上の整数で、５０≦ａ＋ｂ＋ｃ＋ｄ≦５，０００である。） [(A) component]
The component (A) is represented by the following average composition formula (1) and has at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule. The organopolysiloxane is contained in an amount of 001 to 0.5 mol and 0.1 to 0.5 mol of fluoroalkyl group in 100 g.

(In the formula, R ¹ may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having no C1-C10 aliphatic unsaturated bond or an alkenyl group-containing organic group having 2-10 carbon atoms. a group of at least two of R ¹ include alkenyl group-containing organic group having 2 to 10 carbon atoms, at least one of R ¹ include a fluoroalkyl group having 1 to 10 carbon atoms .a 2 or more And b is an integer of 1 or more, c and d are integers of 0 or more, and 50 ≦ a + b + c + d ≦ 5,000.

In the above formula (1), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, or 2 to 10 carbon atoms, particularly An alkenyl group-containing organic group having 2 to 8 carbon atoms, of which at least two in one molecule are alkenyl group-containing organic groups having 2 to 10 carbon atoms, and at least one in a molecule is fluoro having 1 to 10 carbon atoms It is an alkyl group.

In R ¹ , the alkenyl group-containing organic group having 2 to 10 carbon atoms is preferably one having 2 to 8 carbon atoms, for example, an alkenyl group such as vinyl group, allyl group, hexenyl group, octenyl group, acryloylpropyl group, Examples thereof include acryloylalkyl groups such as acryloylmethyl group and methacryloylpropyl group, cycloalkenylalkyl groups such as methacryloylalkyl group and cyclohexenylethyl group, and alkenyloxyalkyl groups such as vinyloxypropyl group, with vinyl group being particularly preferred.

  Moreover, as a C1-C10 fluoroalkyl group, a C1-C8 thing is preferable, for example, 3,3,3- trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl Group, 3,3,4,4,5,5,5-heptafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4, 4,5,5,6,6,7,7,7-undecafluoroheptyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-trideca Fluorooctyl group, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl group, etc. -A trifluoropropyl group is preferred.

In R ¹ , as monovalent hydrocarbon groups other than the above alkenyl group-containing organic group and fluoroalkyl group, specifically, for example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, cyclohexyl group, etc. Examples thereof include aryl groups such as cycloalkyl groups and phenyl groups, and groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms. Among these, an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group is preferable, and a methyl group and a phenyl group are particularly preferable.

  Regarding a to d in the above formula (1), a is 2 or more, preferably an integer of 2 to 6, b is 1 or more, preferably 1 to 4,998, and c and d are 0 or more, preferably 0 to 0. An integer of 5, 50 ≦ a + b + c + d ≦ 5,000, preferably 80 ≦ a + b + c + d ≦ 3,000. When a + b + c + d is smaller than 50, the reactivity is lowered due to excessive crosslinking points, and when it is larger than 5,000, the viscosity of the composition becomes very high, so that the workability is deteriorated, such as difficulty in stirring and mixing. .

The amount of the alkenyl group contained in the component (A) is 0.001 to 0.5 mol, preferably 0.002 to 0.45 mol, per 100 g of organopolysiloxane, and is preferably 0.003 to 0.4. More preferably, it is a mole. When the amount is less than 0.001 mol, the adhesion to the substrate is deteriorated, and when it is more than 0.5 mol, the curability is deteriorated.
In the present invention, as a method for measuring the amount of alkenyl group, a 10% by mass potassium iodide aqueous solution is added to a sample and stirred to prepare a test solution. It can measure by dripping until it becomes.

  (A) The quantity of the fluoroalkyl group contained in a component is 0.1-0.5 mol per 100 g of organopolysiloxane, it is preferable that it is 0.15-0.45 mol, 0.2-0. More preferably, it is 4 moles. When the amount is less than 0.1 mol, the releasability to the silicone pressure-sensitive adhesive is lowered, and when the amount is more than 0.5 mol, the solubility in an organic solvent is lowered.

（式中、Ｒｆ¹は独立にフルオロアルキル基であり、ｅは５０〜４，９９７、好ましくは６０〜３，０００の整数であり、ｆは１〜１，０００、好ましくは１０〜５００の整数であり、ｇは０〜１００、好ましくは０〜５０の整数であり、ｈは１〜２，０００、好ましくは１０〜１，０００の整数である。） Examples of the specific structure of the component (A) include, but are not limited to, the following. In the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

(In the formula, Rf ¹ is independently a fluoroalkyl group, e is an integer of 50 to 4,997, preferably 60 to 3,000, and f is an integer of 1 to 1,000, preferably 10 to 500. And g is an integer of 0 to 100, preferably 0 to 50, and h is an integer of 1 to 2,000, preferably 10 to 1,000.)

（式中、破線は結合手を示す。） Here, specific examples of Rf ¹ include the following.

(In the formula, a broken line indicates a bond.)

  As the component (A), a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane, a cyclic low molecular siloxane containing an alkenyl group-containing organic group, a cyclic low molecular siloxane containing a fluoroalkyl group, and the like are usually used. Although it is produced by ring-opening polymerization, it contains cyclic low-molecular siloxane as a raw material after polymerization, and thus it is distilled off while heating and reducing the pressure while passing an inert gas through the reaction product. It is preferable to use one.

As the component (A), a single component may be used, but the following component (A-1) and / or the following component (A-2) are preferably used, and the following component (A-1) and / or It is more preferable to use the following component (A-2) in combination.
The component (A-1) is an organopolysiloxane in which an alkenyl group is contained in 100 g in an amount of 0.001 mol or more and less than 0.03 mol in the component (A).
The component (A-2) is an organopolysiloxane in which 0.03 to 0.5 mol of an alkenyl group is contained in 100 g of the component (A).

  The difference between the component (A-1) and the component (A-2) is the content of the alkenyl group, and the component (A-2) has a larger amount of alkenyl group than the component (A-1). When the (A-1) component and the (A-2) component are mixed and used, the release property for the silicone pressure-sensitive adhesive can be improved by using raw materials having different crosslinking densities. Although it is not known, it is presumed that the releasability can be improved by orienting the network having a small crosslink density on the surface.

  The amount of the alkenyl group contained in the component (A-1) is 0.001 mol or more and less than 0.03 mol, preferably 0.002 to 0.025 mol per 100 g of organopolysiloxane, and 0.004 What is -0.02 mol is more preferable. When the amount of the alkenyl group used for the component (A-1) is 0.001 mol or more, adhesion to the substrate can be obtained, and when it is less than 0.03 mol, peelability to the silicone pressure-sensitive adhesive can be obtained. it can.

  The amount of the alkenyl group contained in the component (A-2) is 0.03 to 0.5 mol per 100 g of organopolysiloxane, preferably 0.035 to 0.45 mol, and 0.04 to 0. More preferred is 4 mol. When the amount of the alkenyl group used for the component (A-2) is 0.03 mol or more, peelability for the silicone pressure-sensitive adhesive can be obtained, and when it is 0.5 mol or less, curability can be obtained.

  When the component (A-1) and the component (A-2) are used, the component (A-1) and the component (A-2) are added so that the amount of the alkenyl group contained in the component (A) is within the above range. It is preferable to mix. In this case, the mixing mass ratio of the component (A-1) and the component (A-2) is 20:80 to 80:20, preferably 25:75 to 75:25, more preferably 30:70 to 70. : 30. When the component (A-1) is less than 20% by mass ratio, the peelability to the silicone pressure-sensitive adhesive may be lowered, and when it is more than 80%, the curability may be lowered, and the component (A-2). If the mass ratio is more than 80%, the adhesiveness to the substrate may be lowered, and if it is less than 20%, the peelability to the silicone pressure-sensitive adhesive particularly when bonded and heated may be lowered.

（式中、Ｒ²はそれぞれ独立に非置換もしくは置換の炭素数１〜１０の脂肪族不飽和結合を含まない１価炭化水素基又は水素原子であり、Ｒ³はそれぞれ独立に非置換もしくは置換の炭素数１〜１０の脂肪族不飽和結合を含まない１価炭化水素基であり、ｉは０〜１００の整数であり、ｊは３〜８０の整数である。） [Component (B)]
The component (B) is an organohydrogenpolysiloxane having at least 3 Si—H groups in one molecule, and specifically, one having a structure represented by the following general formula (2) can be used.

(In the formula, each R ² independently represents an unsubstituted or substituted monovalent hydrocarbon group or hydrogen atom that does not contain an aliphatic unsaturated bond having 1 to 10 carbon atoms, and each R ³ independently represents an unsubstituted or substituted group. A monovalent hydrocarbon group containing no aliphatic unsaturated bond having 1 to 10 carbon atoms, i is an integer of 0 to 100, and j is an integer of 3 to 80.)

In the above formula (2), R ² is an unsubstituted or substituted monovalent hydrocarbon group or hydrogen atom that does not contain an aliphatic unsaturated bond having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, which does not contain an aliphatic unsaturated bond. Specific examples of the monovalent hydrocarbon group not containing an aliphatic unsaturated bond of R ² and R ³ include, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, and a cycloalkyl such as a cyclohexyl group. Groups, aryl groups such as phenyl groups, etc., or trifluoromethyl groups in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, etc., 3,3,3-trifluoropropyl Examples are groups. Of these, R ² and R ³ are preferably an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group, particularly preferably a methyl group or a phenyl group.

In the present invention, it is preferable that at least one, preferably 2 to 10 fluoroalkyl groups are contained in R ² and R ³ . This is because it is well compatible when mixed with the component (A). If there is no fluoroalkyl group, it does not mix well with the component (A) and may separate when formed into a composition. . As the fluoroalkyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl Group 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,3,4,4,5,5,6,6 Examples include 7,7,8,8,9,9,9-pentadecafluorononyl group, and 3,3,3-trifluoropropyl group is particularly preferable.

  In the above formula (2), i is an integer of 0 to 100, preferably 0 to 80. J is an integer of 3 to 80, preferably 4 to 70.

（式中、Ｒｆ²は独立にフルオロアルキル基であり、ｉ１は０〜９９、好ましくは０〜８０の整数であり、ｊ１は３〜８０、好ましくは４〜７０の整数であり、ｉ２は１〜４０、好ましくは２〜３０の整数であり、ｉ１＋ｉ２は１〜１００、好ましくは２〜８０の整数である。） Examples of the specific structure of component (B) include, but are not limited to, those shown below. In the following formulae, Me represents a methyl group.

(Wherein Rf ² is independently a fluoroalkyl group, i1 is an integer of 0 to 99, preferably 0 to 80, j1 is an integer of 3 to 80, preferably 4 to 70, and i2 is 1) -40, preferably an integer of 2-30, i1 + i2 is an integer of 1-100, preferably 2-80.)

（式中、破線は結合手を示す。） Here, specific examples of Rf ² include the following.

(In the formula, a broken line indicates a bond.)

  Component (B) is usually a ring-opening polymerization of a cyclic low-molecular siloxane such as octamethylcyclotetrasiloxane and a cyclic low-molecular siloxane containing a Si—H group such as tetramethylcyclotetrasiloxane using an acid catalyst. Since it contains cyclic low-molecular siloxane that is a raw material after polymerization, it is heated and reduced in pressure while distilling off an inert gas in the reaction product. It is preferable.

  The amount of component (B) used is such that the molar ratio of Si—H groups in component (B) to the total alkenyl groups in component (A) and component (F) below is 1 to 10, especially It is preferable that it is the quantity used as the range of 1.2-8. If it is less than 1, a crosslinking density will become low and sclerosis | hardenability will fall. When it exceeds 10, the peelability with respect to the silicone pressure-sensitive adhesive decreases due to an increase in the number of Si-H groups remaining after curing.

[Component (C)]
The component (C) is a platinum group metal catalyst for hydrosilylation addition and curing of an alkenyl group in the component (A) and the component (F) described later and a Si—H group in the component (B). Examples of the central metal of the catalyst include platinum group metals such as platinum, palladium, iridium, rhodium, osmium, and ruthenium, and platinum is particularly preferable. Platinum catalysts include chloroplatinic acid, chloroplatinic acid alcohol solution, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc. Is mentioned.

  As content of (C) component, the quantity from which metal mass becomes 1-500 ppm with respect to the mass of (A) component is preferable, and the quantity from which 2-450 ppm is more preferable. If it is less than 1 ppm, the reaction is slow and the curing becomes insufficient, so that various properties of the peel strength of the cured film are not exhibited. When it exceeds 500 ppm, the flexibility of the cured film becomes poor.

[(D) component]
Component (D) is a reaction control agent. When a silicone adhesive release agent composition is prepared or applied to a substrate, an addition reaction starts before heat-curing and the treatment liquid becomes thickened or gelled. It is a component that is optionally added to prevent the occurrence of The reaction control agent coordinates to the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heated and cured, the coordination is lost and the catalytic activity is exhibited. Any reaction control agent conventionally used in addition reaction curable silicone compositions can be used. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl Examples include -1,3-divinyldisiloxane, maleic acid ester, and adipic acid ester.

  When the reaction control agent is blended, the blending amount is preferably 0.01 to 5 parts by mass, particularly 0.05 to 3 parts by mass with respect to 100 parts by mass of the component (A). If the reaction control agent is too small, the reaction cannot be suppressed and the composition may be cured before the work. If the reaction control agent is too large, the reaction may be delayed and curing may be insufficient.

[(E) component]
Component (E) is an organic solvent, and is an optional component used to improve workability by lowering the viscosity of the composition or to improve wettability when applied to a substrate. Organic solvents include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, isoparaffin, industrial gasoline (rubber volatile oil, etc. ), Hydrocarbon solvents such as petroleum benzine, solvent naphtha, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, cyclohexanone Ketone solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, etc., diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, 1, -Ether solvents such as dimethoxyethane, 1,4-dioxane, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, 2-butoxyethyl acetate, etc. Solvents, hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, siloxane solvents such as tris (trimethylsiloxy) methylsilane, tetrakis (trimethylsiloxy) silane, trifluorotoluene, hexafluoroxylene , Fluorine-based solvents such as methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether, or mixed solvents thereof, and the like. A gasoline (rubber volatile oil, etc.) and isoparaffin.

  (E) The compounding quantity in the case of mix | blending a component is 0-2,000 mass parts with respect to 100 mass parts of (A) component, Especially 20-1,800 mass parts is preferable. When the component (E) exceeds 2,000 parts by mass, the amount of the active ingredient is decreased, so that the coating amount is insufficient and sufficient peelability may not be obtained.

[(F) component]
Component (F) is an organopolysiloxane containing 0.001 to 0.1 mol of alkenyl group in 100 g and no fluoroalkyl group, and is blended only in the release agent composition (II) for silicone pressure-sensitive adhesive. It is a component.
By adding the component (F) to the release agent composition (II) for the silicone pressure-sensitive adhesive, it is possible to increase the peeling force of the second release substrate treated with the composition with respect to the pressure-sensitive adhesive layer. As described above, a release agent based on an organopolysiloxane modified with a fluorine-containing organic group is often used for a release agent composition for a silicone pressure-sensitive adhesive. By adding an organopolysiloxane that contains a certain alkenyl group-containing organic group and does not contain a fluoroalkyl group to such a composition, it is modified with a fluorine-containing organic group when a cured film is formed on the substrate. It is presumed that the peel strength is increased because of the sea-island structure without being completely mixed with the organopolysiloxane.

（式中、Ｒ⁴は同一又は異なっていてもよい炭素数１〜１０の脂肪族不飽和結合を有さない１価炭化水素基又は炭素数２〜１０のアルケニル基含有有機基である。ｋは２以上の整数、ｌは１以上の整数、ｍ及びｎは０以上の整数で、５０≦ｋ＋ｌ＋ｍ＋ｎ≦１，５００である。） The component (F) is preferably an organopolysiloxane represented by the following average composition formula (3), containing 0.001 to 0.1 mol of alkenyl group in 100 g and not containing a fluoroalkyl group.

(Wherein, R ⁴ is a monovalent hydrocarbon group or an alkenyl group-containing organic group having 2 to 10 carbon atoms free of aliphatic unsaturation of the same or different carbon atoms and optionally 1 to 10 .k Is an integer of 2 or more, l is an integer of 1 or more, m and n are integers of 0 or more, and 50 ≦ k + 1 + m + n ≦ 1,500.

In the above formula (3), R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or alkenyl having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms. It is a group-containing organic group, of which 0.001 to 0.1 mol of alkenyl group is contained in 100 g, and no fluoroalkyl group is contained.
Specific examples of the monovalent hydrocarbon group having no aliphatic unsaturated bond for R ⁴ include, for example, alkyl groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, and a cycloalkyl group such as a cyclohexyl group, An aryl group such as a phenyl group is exemplified, and among these, a methyl group and a phenyl group are preferable.
Moreover, as a C2-C10 alkenyl group containing organic group, a C2-C8 thing is preferable, For example, alkenyl groups, such as a vinyl group, an allyl group, a hexenyl group, an octenyl group, acryloylpropyl group, acryloylmethyl And an acryloylalkyl group such as a methacryloylpropyl group, a methacryloylalkyl group, a cycloalkenylalkyl group such as a cyclohexenylethyl group, and an alkenyloxyalkyl group such as a vinyloxypropyl group. Among these, a vinyl group is particularly preferable.

  The amount of the alkenyl group contained in the component (F) is 0.001 to 0.1 mol, preferably 0.0015 to 0.08 mol, more preferably 0.002 to 0, per 100 g of organopolysiloxane. 0.06 mole. When the amount is less than 0.001 mol, the appearance of the cured film is deteriorated. When the amount is more than 0.1 mol, the effect of increasing the peeling force is weakened.

  Regarding k to n in the above formula (3), k is 2 or more, preferably an integer of 2 to 6, l is 1 or more, preferably an integer of 48 to 1,498, m and n are 0 or more, preferably 0 to 0. In an integer of 5, k + 1 + m + n is 50 to 1,500, preferably 80 to 1,400, and more preferably 100 to 1,200. If k + l + m + n is too small, the peel force may not be sufficiently increased. If it is too large, the appearance of the cured film may be deteriorated.

（式中、ｏは４８〜１，４９８、好ましくは７８〜１，３９８の整数であり、ｐは１〜２０、好ましくは２〜１５の整数であり、ｑ１は４７〜１，４９７、好ましくは７８〜１，３９７の整数であり、ｑ２は１〜１，４９６、好ましくは２〜１，３９６の整数であり、ｒは１〜１，４４９、好ましくは７８〜１，３４９の整数であり、ｐ＋ｑ１及びｐ＋ｑ２＋ｒはそれぞれ４８〜１，４９８の整数である。） Examples of the specific structure of component (F) include, but are not limited to, those shown below. In the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

(Wherein o is an integer of 48 to 1,498, preferably 78 to 1,398, p is an integer of 1 to 20, preferably 2 to 15, and q1 is 47 to 1,497, preferably Q is an integer from 78 to 1,397, q2 is an integer from 1 to 1,496, preferably from 2 to 1,396, r is an integer from 1 to 1,449, preferably from 78 to 1,349, p + q1 and p + q2 + r are integers of 48 to 1,498, respectively.)

（式中、ｓは５〜１，４９１、好ましくは１０〜１，３９８の整数であり、ｔは５〜１，４９１、好ましくは１０〜１，３９８の整数であり、ｕは０〜１，４７６、好ましくは０〜１，３７６の整数であり、ｖは１〜７３９、好ましくは１〜６８９の整数である。）

(In the formula, s is an integer of 5 to 1,491, preferably 10 to 1,398, t is an integer of 5 to 1,491, preferably 10 to 1,398, and u is 0 to 1, 476, preferably an integer from 0 to 1,376, and v is an integer from 1 to 739, preferably from 1 to 689.)

  The component (F) is usually produced by ring-opening polymerization of a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane and a cyclic low molecular siloxane containing an alkenyl group-containing organic group using a catalyst. Since it contains cyclic low-molecular siloxane that is a raw material, it is preferable to use a material obtained by distilling the reaction product through an inert gas while heating and reducing pressure.

  The usage-amount of (F) component in release agent composition (II) for silicone adhesives is 1-25 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-20 mass parts. If the amount is less than 1 part by mass, the peel force cannot be sufficiently increased. If the amount exceeds 25 parts by mass, the peelability for the silicone adhesive is deteriorated.

  The release agent compositions (I) and (II) for the silicone pressure-sensitive adhesive of the present invention can be obtained by blending predetermined amounts of each of the above components, respectively, and further include a photopolymerization initiator, an antioxidant, and a reactive dilution. Other components such as an agent, a leveling agent, a filler, an antistatic agent, an antifoaming agent, and a pigment can be added as necessary within a range that does not impair the object and effect of the present invention.

In the release agent composition (I) for the silicone pressure-sensitive adhesive in the present invention, it is desirable that the components (A) and (B) and an optional component are uniformly mixed in advance, and then the component (C) is added immediately before use.
Moreover, the release agent composition for silicone pressure-sensitive adhesives (II) in the present invention is prepared by mixing the above components (A), (B), (F) and optional components uniformly in advance, and then immediately before using the component (C). It is desirable to add.

  A release agent composition for silicone pressure-sensitive adhesive (I) containing the components (A) to (C) and, if necessary, components (D), (E) and other components, and (F) to the composition (I). With the release agent composition for silicone pressure-sensitive adhesives (II) to which components are added, a release substrate obtained by coating / curing the release agent composition for silicone pressure-sensitive adhesives (II) on the substrate by adding the component (F) The silicone adhesive composition is coated / cured on top, and another substrate is bonded together. The peeling force when peeling the bonded substrate and the adhesive from the release substrate is the release for the silicone adhesive. It becomes larger than that of the release substrate obtained by coating / curing the agent composition (I) on the substrate.

[Production method of laminate]
The laminate of the present invention provides a second release substrate treated with the release agent composition (II) for silicone adhesive, and the silicone adhesive composition is coated on the treated surface of the release substrate. It is obtained by bonding the first release substrate treated with the release agent composition for silicone adhesive (I) after curing to form an adhesive layer.

  The silicone pressure-sensitive adhesive composition is applied / cured on the second release substrate obtained by coating / curing the silicone pressure-sensitive adhesive release agent composition (II) on the substrate, and the silicone pressure-sensitive adhesive release agent composition is applied. By sticking the first release substrate obtained by applying / curing the product (I) to the substrate, a difference in peeling force occurs between the two release substrates. This makes it possible to selectively peel off the first release substrate previously treated with the release agent composition (I) for the silicone pressure-sensitive adhesive having a low peel force, thereby preventing crying separation. After peeling off the first release substrate treated with the release agent composition for silicone pressure-sensitive adhesive (I), the pressure-sensitive adhesive layer was bonded to the target, and then treated with the release agent composition for silicone pressure-sensitive adhesive (II). A silicone pressure-sensitive adhesive sheet without a base material can be produced by bonding the pressure-sensitive adhesive layer surface obtained by peeling off the peeling base material to another object.

  Here, paper, a plastic film, glass, and a metal are selected as a base material which applies this release agent composition (I) and (II) for silicone adhesives. Examples of the paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminated paper, and craft paper. As plastic films, polyethylene film, polypropylene film, polyester film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polycarbonate film, polytetrafluoroethylene film, polystyrene film, ethylene-vinyl acetate copolymer Examples thereof include a film, an ethylene-vinyl alcohol copolymer film, a triacetyl cellulose film, a polyether ether ketone film, and a polyphenylene sulfide film. There is no restriction | limiting in particular about thickness, a kind, etc. as glass, What carried out the chemical strengthening process etc. may be used. Glass fiber can also be applied, and the glass fiber may be used alone or in combination with other resins. Examples of the metal include aluminum foil, copper foil, gold foil, silver foil, and nickel foil. When used as a release film, a polyester film is preferred.

  The method for applying the release agent compositions (I) and (II) for the silicone pressure-sensitive adhesive to the base material may be applied using a known coating method, for example, a wire bar, a comma coater, a lip coater, Examples include roll coaters, die coaters, knife coaters, blade coaters, rod coaters, kiss coaters, gravure coaters, screen coating, dip coating, and cast coating.

The coating amount of the release agent compositions (I) and (II) for the silicone pressure-sensitive adhesive on the substrate is in the range of 0.1 to ² g / m ² , particularly 0.2 to ¹ in terms of solid content after curing. The range of 8 g / m ² is preferable, and the curing condition is 80 to 180 ° C., particularly 90 to 160 ° C., and heating may be performed for 10 to 180 seconds, particularly 15 to 150 seconds, but is not limited thereto.

The pressure-sensitive adhesive layer of the present invention is preferably a cured silicone pressure-sensitive adhesive composition containing the following components.
(G) The following average composition formula (4)
R ⁵ _w SiO _{(4-w) / 2} (4)
Wherein R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms or an alkenyl group-containing organic group having 2 to 10 carbon atoms, and w Is a positive number from 1.8 to 2.2.)
An organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and containing 0.0007 to 0.05 mol of alkenyl groups in 100 g,
(H) R ⁶ ₃ SiO _1/2 unit and SiO _4/2 unit are included, and (R ⁶ ₃ SiO _1/2 unit) / (SiO _4/2 unit) is 0.5 to 1 in molar ratio. Organopolysiloxane (R ⁶ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not have an aliphatic unsaturated bond),
(I) an organohydrogenpolysiloxane represented by the following average composition formula (6) and having at least 3 Si-H groups in one molecule;
R ⁷ _y H _z SiO _{(4-yz) / 2} (6)
(In the formula, R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, y and z are y> 0, z> 0, and a positive value satisfying 0 <y + z ≦ 3. Number.)
(J) a platinum group metal catalyst,
(K) Reaction control agent.

[Silicone adhesive composition]
Below, each component of a silicone adhesive composition is explained in full detail.

[(G) component]
The component (G) is represented by the following average composition formula (4), has at least two alkenyl group-containing organic groups in one molecule, and 0.0007 to 0.05 mol of alkenyl groups are contained in 100 g. Organopolysiloxane.
R ⁵ _w SiO _{(4-w) / 2} (4)
Wherein R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms or an alkenyl group-containing organic group having 2 to 10 carbon atoms, and w Is a positive number of 1.8 to 2.2, preferably 1.9 to 2.1.)

In the above formula (4), R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 aliphatic unsaturated bonds, or 2 to 10 carbon atoms, preferably 2 to 8 alkenyl group-containing organic groups, two or more of which are alkenyl group-containing organic groups.
Specific examples of the unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms of R ⁵ include, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. An alkyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, and the like, a trifluoromethyl group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, Examples include 3,3,3-trifluoropropyl group. Among these, an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group is preferable, and a methyl group and a phenyl group are particularly preferable.

  Moreover, as a C2-C10 alkenyl group containing organic group, a C2-C8 thing is preferable, For example, alkenyl groups, such as a vinyl group, an allyl group, a hexenyl group, an octenyl group, acryloylpropyl group, acryloylmethyl Groups, acryloylalkyl groups such as methacryloylpropyl group, cycloalkenylalkyl groups such as methacryloylalkyl group, cyclohexenylethyl group, alkenyloxyalkyl groups such as vinyloxypropyl group, etc., and vinyl group is particularly preferable.

  The amount of the alkenyl group contained in the component (G) is 0.0007 to 0.05 mol, preferably 0.001 to 0.04 mol, and 0.001 to 0.03, per 100 g of organopolysiloxane. More preferably, it is a mole. If the amount is less than 0.0007 mol, the crosslink density may be reduced and cohesive failure of the silicone pressure-sensitive adhesive layer may occur. If the amount is more than 0.05 mol, the silicone pressure-sensitive adhesive layer will become hard, and appropriate adhesive strength and tack can be obtained. It may not be possible.

（式中、Ｒ⁵は上記と同じであり、そのうち２個以上がアルケニル基含有有機基である。ｘは５０〜１５，０００の整数である。） (G) As a component, although what is represented by following General formula (5) can be illustrated, it is not limited to this.

(In the formula, R ⁵ is the same as above, and two or more of them are alkenyl group-containing organic groups. X is an integer of 50 to 15,000.)

  X in the above formula (5) is a positive number of 50 to 15,000, preferably 200 to 12,000. If it is less than 50, the reactivity may decrease due to too many crosslinking points, and if it is more than 15,000, the viscosity of the composition becomes very high, so that the workability becomes worse, such as difficulty in stirring and mixing. There is a case.

（式中、ｘ１は５０以上、好ましくは１００〜１４，９９７の整数であり、ｘ２は１以上、好ましくは１〜１００の整数であり、ｘ３は１以上、好ましくは２〜１５０の整数である。） Examples of the specific structure of the component (G) include, but are not limited to, the following. In the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively.

(In the formula, x1 is an integer of 50 or more, preferably 100 to 14,997, x2 is an integer of 1 or more, preferably 1 to 100, and x3 is an integer of 1 or more, preferably 2 to 150. .)

  The component (G) is usually produced by ring-opening polymerization of a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane and a cyclic low molecular siloxane containing an alkenyl group-containing organic group using a catalyst. Since it contains cyclic low-molecular siloxane that is a raw material, it is preferable to use a material obtained by distilling the reaction product through an inert gas while heating and reducing pressure.

[(H) component]
The component (H) is an R ⁶ ₃ SiO _1/2 unit (wherein R ⁶ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an aliphatic unsaturated bond having 2 to 6 carbon atoms). Is an alkenyl group) and SiO _4/2 units, and (R ⁶ ₃ SiO _1/2 units) / (SiO _4/2 units) is 0.5 to 1, preferably 0.6 to An organopolysiloxane that is 0.9. When this molar ratio is less than 0.5, the adhesive strength and tack of the resulting cured product may be reduced, and when it exceeds 1, the adhesive strength and holding power of the obtained cured product may be reduced.

R ⁶ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms that does not have an aliphatic unsaturated bond. As a C1-C10 monovalent hydrocarbon group which does not have an aliphatic unsaturated bond, Preferably it is a C1-C6 alkyl group, a phenyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, An aryl group having preferably 6 to 10 carbon atoms, such as a tolyl group, can be mentioned. Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, and a butenyl group. R ⁶ is preferably a methyl group.

The component (H) may contain a silanol group or a hydrolyzable alkoxy group in addition to R ⁶ , and the content thereof is 0.01 to 4% by mass of the total mass of the component (H). An amount of 0.05 to 3.5% by mass is more preferable. If it is less than 0.01% by mass, the cohesive force of the pressure-sensitive adhesive may be lowered, and if it is more than 4% by mass, the tack of the pressure-sensitive adhesive may be lowered. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a phenoxy group, and the like. When used, a methoxy group is preferable.

The component (H) can also contain R ⁶ SiO _3/2 units and R ⁶ ₂ SiO _2/2 units (R ⁶ is the same as described above) within a range not impairing the characteristics of the present invention. When the R ⁶ SiO _3/2 unit and the R ⁶ ₂ SiO _2/2 unit are contained, the ratio is preferably 1 to 20% by mass of the total mass of the component (H), and 3 to 15% by mass. More preferably.
(H) A component may be used individually by 1 type, or may use 2 or more types together.

  As the component (H), a component subjected to a condensation reaction in the presence of a catalyst may be used. This is an arbitrary pretreatment operation in which hydrolyzable groups present in the component (H) are reacted with each other, and an effect such as improvement of the adhesive strength of the obtained cured product can be expected. Specifically, an alkaline catalyst may be used, and the reaction may be performed at room temperature to reflux, and neutralized as necessary.

  Here, examples of the alkaline catalyst include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. Metal salts alkoxides such as sodium methoxide and potassium butoxide; Organic metals such as butyl lithium; potassium silanolates; nitrogen compounds such as ammonia gas, aqueous ammonia, methylamine, trimethylamine, and triethylamine. Ammonia water is preferred. The temperature of the condensation reaction may be from room temperature to the reflux temperature of the organic solvent. The reaction time is not particularly limited, but may be 0.5 to 20 hours, preferably 1 to 16 hours.

  Furthermore, a neutralizing agent that neutralizes the alkaline catalyst may be added as necessary after completion of the reaction. Examples of the neutralizing agent include acidic gases such as hydrogen chloride and carbon dioxide; organic acids such as acetic acid, octylic acid and citric acid; and mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid. When ammonia gas or ammonia water or a low boiling point amine compound is used as the alkaline catalyst, an inert gas such as nitrogen may be vented and distilled off.

  The mass ratio of the component (G) to the component (H) is (G) / (H) = 30/70 to 70/30, preferably (G) / (H) = 32/68 to 65/35. More preferably, (G) / (H) = 33/67 to 60/40. If the component (G) is less than 30, the peelability of the resulting pressure-sensitive adhesive may be reduced. If it is more than 70, the silicone pressure-sensitive adhesive release agent composition (I) and the silicone pressure-sensitive adhesive release agent composition (II) ) May have a small difference in peel strength with respect to the cured film formed.

[(I) component]
The component (I) is an organohydrogenpolysiloxane having at least 3 Si—H groups in one molecule, and is represented by the following average composition formula (6).
R ⁷ _y H _z SiO _{(4-yz) / 2} (6)
(In the formula, R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, y and z are y> 0, z> 0, and a positive value satisfying 0 <y + z ≦ 3. Number.)

In the above formula (6), R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and specifically includes, for example, a methyl group, an ethyl group, and a propyl group. , An alkyl group such as a butyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, a hexenyl group, an octenyl group, an aryl group such as a phenyl group, or the like, or a carbon atom of these groups Examples thereof include a trifluoromethyl group and a 3,3,3-trifluoropropyl group in which part or all of the hydrogen atoms are substituted with halogen atoms. Among these, those not containing an aliphatic unsaturated bond are preferable, and an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group is particularly preferable, and a methyl group or a phenyl group is particularly preferable.

  In the above formula (6), y is a positive number of y> 0, preferably 1 ≦ y <3, z is a positive number of z> 0, preferably 1 ≦ z <3, and y + z is 0 <y + z ≦ 3, preferably a number satisfying 1-2.

（式中、Ｒ⁷はそれぞれ独立に非置換もしくは置換の炭素数１〜１０の１価炭化水素基であり、Ｒ⁸はそれぞれ独立に非置換もしくは置換の炭素数１〜１０の１価炭化水素基又は水素原子であり、Ａは０〜１００の整数であり、Ｂは３〜８０の整数である。） Examples of the component (I) include those represented by the following general formula (7), but are not limited thereto.

(Wherein R ⁷ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁸ is each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. A group or a hydrogen atom, A is an integer of 0 to 100, and B is an integer of 3 to 80.)

In the above formula (7), R ⁷ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. R ⁸ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Specific examples of monovalent hydrocarbon groups for R ⁷ and R ⁸ include alkyl groups such as methyl, ethyl, propyl, and butyl groups, cycloalkyl groups such as cyclohexyl groups, vinyl groups, allyl groups, A trifluoromethyl group in which a hexenyl group, an alkenyl group such as an octenyl group, an aryl group such as a phenyl group, etc., or a hydrogen atom bonded to a carbon atom of these groups is partially or entirely substituted with a halogen atom or the like; , 3,3-trifluoropropyl group and the like. R ⁷ and R ⁸ are preferably those that do not contain an aliphatic unsaturated bond, particularly an aliphatic saturated hydrocarbon group or an aromatic hydrocarbon group, and particularly preferably a methyl group or a phenyl group.

  In said formula (7), A is 0-100, Preferably it is an integer of 0-80. B is an integer of 3 to 80, preferably 4 to 70.

（式中、Ａ１は０〜１００、好ましくは０〜８０の整数であり、Ｂ１は３〜８０、好ましくは４〜７０の整数である。） Examples of the specific structure of component (I) include, but are not limited to, those shown below. In the following formulae, Me represents a methyl group.

(In the formula, A1 is an integer of 0 to 100, preferably 0 to 80, and B1 is an integer of 3 to 80, preferably 4 to 70.)

  The component (I) is usually a ring-opening polymerization of a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane and a cyclic low molecular siloxane containing a Si—H group such as tetramethylcyclotetrasiloxane using an acid catalyst. However, after polymerization, it contains cyclic low-molecular siloxane, which is a raw material, so use it by distilling it while heating and reducing the pressure while passing an inert gas through the reaction product. Is preferred.

  The amount of component (I) used is preferably such that the molar ratio of Si—H groups in component (I) to alkenyl groups in components (G) and (H) is 0.2-20. An amount of 5 to 18 is more preferred. When the molar ratio is less than 0.2, the crosslinking density is lowered, and the cohesive force and holding force of the cured product obtained thereby may be lowered. If it exceeds 20, the crosslink density increases, and the resulting cured product may not have adequate adhesive strength and tackiness.

[(J) component]
The component (J) is a platinum group metal catalyst for hydrosilylation addition and curing of the alkenyl group in the component (G) and the component (H) and the Si—H group in the component (I). Examples of the central metal of the catalyst include platinum group metals such as platinum, palladium, iridium, rhodium, osmium, and ruthenium, and platinum is particularly preferable. Platinum catalysts include chloroplatinic acid, chloroplatinic acid alcohol solution, reaction product of chloroplatinic acid and alcohol, reaction product of chloroplatinic acid and olefin compound, reaction product of chloroplatinic acid and vinyl group-containing siloxane, etc. Is mentioned.

  (J) As content of a component, the quantity from which metal mass becomes 1-500 ppm is preferable with respect to the total mass of (G)-(I) component, and the quantity from which 2-450 ppm is more preferable. If it is less than 1 ppm, the reaction is slow and the curing becomes insufficient, so that various properties such as the adhesive strength and holding power of the obtained cured product may not be exhibited. If it exceeds 500 ppm, the flexibility of the resulting cured product may be poor.

[(K) component]
Component (K) is a reaction control agent, and when a silicone pressure-sensitive adhesive composition is prepared or applied to a base material, an addition reaction starts before heat curing and the treatment liquid does not cause thickening or gelation. It is a component added in order to make it. The reaction control agent coordinates to the platinum group metal which is an addition reaction catalyst to suppress the addition reaction, and when heated and cured, the coordination is lost and the catalytic activity is exhibited. Any reaction control agent conventionally used in addition reaction curable silicone compositions can be used. Specific examples include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, 3 -Methyl-3-trimethylsiloxy-1-butyne, 3-methyl-3-trimethylsiloxy-1-pentyne, 3,5-dimethyl-3-trimethylsiloxy-1-hexyne, 1-ethynyl-1-trimethylsiloxycyclohexane, Bis (2,2-dimethyl-3-butynoxy) dimethylsilane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,1,3,3-tetramethyl Examples include -1,3-divinyldisiloxane, maleic acid ester, and adipic acid ester.

  When the reaction control agent is blended, the blending amount is preferably 0.01 to 5 parts by mass, particularly 0.05 to 3 parts by mass with respect to 100 parts by mass in total of the components (G) to (I). If the reaction control agent is too small, the reaction cannot be suppressed and the composition may be cured before the work. If the reaction control agent is too large, the reaction may be delayed and curing may be insufficient.

  In the silicone pressure-sensitive adhesive composition, it is desirable to add the component (J) immediately before use after the components (G) to (I) and the component (K) are uniformly mixed in advance.

[Adhesive layer]
The pressure-sensitive adhesive layer of the present invention is obtained by curing the silicone pressure-sensitive adhesive composition. In the present invention, the silicone adhesive composition is applied to the release agent-treated surface on the second release substrate obtained by applying / curing the release agent composition (II) for silicone adhesive to the substrate. It is preferable to cure.

  In this case, the silicone pressure-sensitive adhesive composition may be applied using a known coating method, such as a comma coater, lip coater, roll coater, die coater, knife coater, blade coater, rod coater. Kiss coater, gravure coater, screen coating, dip coating, cast coating and the like.

  Although there is no restriction | limiting in particular about the coating amount of a silicone adhesive composition, It can be set as the quantity from which the thickness after hardening will be 0.1-300 micrometers, Preferably it is the quantity used as 0.5-200 micrometers. The curing conditions for the silicone pressure-sensitive adhesive composition may be 10 seconds to 10 minutes at 80 to 150 ° C., but are not limited thereto.

The release agent-treated surface on the first release substrate obtained by applying / curing the above-described release agent composition for silicone adhesive (I) to the substrate on the obtained adhesive layer surface on the second release substrate A laminated body is obtained by bonding together.
Here, the bonding of the pressure-sensitive adhesive layer and the first release substrate is not particularly limited, and a load may or may not be applied after bonding, and is -20 to 100 ° C, preferably room temperature (25 ° C). Bonding can be performed at ˜70 ° C. for an arbitrary time.

  The laminate obtained by the above production method is prepared by peeling the first release substrate from the laminate, then bonding the adhesive layer surface to the target, and then peeling the second release substrate from that state. By sticking the pressure-sensitive adhesive layer surface opposite to the bonded pressure-sensitive adhesive layer surface to another object, it can be used as a substrate-less pressure-sensitive adhesive sheet.

  The base material-less adhesive sheet obtained by this method of use is, for example, a cover glass and a touch panel of an electronic terminal such as a personal computer or a mobile phone, a bonding of a touch panel and a liquid crystal panel, a smartphone, a tablet terminal, a car navigation display, a ticket machine, It can be used for a housing game machine, ATM, a photo terminal, a karaoke remote controller, a cash register terminal, and the like.

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. In the following examples, Me represents a methyl group, Vi represents a vinyl group, and Ph represents a phenyl group.
The peeling strength of the release agent compositions for silicone pressure-sensitive adhesives of Examples and Comparative Examples, the presence / absence of the tearing phenomenon, and the method for evaluating the adhesive strength are shown below.

<Peeling force 1 of release agent composition (I) for silicone pressure-sensitive adhesive>
A polyethylene terephthalate (PET) film having a thickness of 50 μm is coated with a release agent composition (I) for silicone pressure-sensitive adhesive using a wire bar so that the solid content after curing is 0.5 g / m ^2. A release substrate was produced by air drying at a temperature of 30 ° C./30 seconds. In addition, after the silicone adhesive composition is applied to a PET film having a thickness of 25 μm using an applicator so that the thickness after curing is 30 μm, the adhesive layer is heated and cured at 130 ° C./1 minute. The formed film was produced, and the adhesive layer and the cured film surface of the aforementioned release substrate were bonded together to produce a tape cut to a width of 25 mm. This tape is reciprocated once with a 2 kg roller and pressure-aged and aged. Using a tensile tester, a 25 μm-thick PET film and an adhesive layer are peeled from a 50 μm-thick release substrate at a speed of 0.3 m / min in the 180 ° direction. The peel force when peeled with was measured. Aging was performed under the following two conditions.
・ Stand for 1 day at a pressure of 70 g / m ² at 25 ° C./Stand for 7 days at a pressure of 20 g / m ² at 70 ° C.

<Peeling force 2 of release agent composition (II) for silicone pressure-sensitive adhesive>
It is applied to a PET film having a thickness of 50 μm using a wire bar so that the solid content after curing of the silicone adhesive release agent composition (II) is 0.5 g / m ² at 140 ° C./30 seconds. A release substrate was produced by air drying. The release substrate was cut into a width of 25 mm, and the silicone adhesive composition was applied to the cured film surface of the cut release substrate using an applicator so that the thickness after curing was 30 μm, and then 130 ° C./1. A film having an adhesive layer formed by heating and curing under the conditions of minutes was prepared. A 25 μm thick PET film was bonded to the adhesive layer of the film, and a tape cut to a width of 25 mm was prepared in accordance with the width of the adhesive layer. This tape is reciprocated once with a 2 kg roller and pressure-aged and aged. Using a tensile tester, a 25 μm-thick PET film and an adhesive layer are peeled from a 50 μm-thick release substrate at a speed of 0.3 m / min in the 180 ° direction. The peel force when peeled with was measured. Aging was performed under the following two conditions.
・ Stand for 1 day at a pressure of 70 g / m ² at 25 ° C./Stand for 7 days at a pressure of 20 g / m ² at 70 ° C.

<Presence or absence of crying phenomenon>
It is applied to a PET film having a thickness of 50 μm using a wire bar so that the solid content after curing of the silicone adhesive release agent composition (II) is 0.5 g / m ² at 140 ° C./30 seconds. The 2nd peeling base material was produced by making it air dry. The second release substrate was cut to a width of 25 mm, and the silicone adhesive composition was applied to the cured film surface of the cut substrate using an applicator so that the thickness after curing was 30 μm, and then 130 ° C. A film having an adhesive layer formed by heating and curing for 1 minute was prepared. Moreover, it apply | coats to a PET film with a thickness of 50 micrometers using a wire bar so that solid content after hardening may be set to 0.5 g / m < ² >, and 140 degreeC / 30 may be applied. A first release substrate was produced by air drying in seconds. The cured film surface of the 1st peeling base material and the adhesion layer of the film in which the said adhesion layer was formed were bonded together, and it cut | disconnected to 25 mm width, and produced the laminated body containing an adhesion layer. When the first release substrate treated with the release agent composition (I) for silicone pressure-sensitive adhesive of the laminate was peeled off, it was visually confirmed whether or not tearing occurred.
○: Crying does not occur ×: Crying occurs

<Adhesive strength>
A film having an adhesive layer peeled off in the measurement of the peeling force 2 is attached to a stainless steel plate, reciprocated once with a 2 kg roller, and allowed to stand at room temperature for 2 hours, and then 180 ° direction using a tensile tester. The force required to peel the film having the adhesive layer from the stainless steel plate at a speed of 0.3 m / min was defined as the adhesive strength (N / 25 mm).

（Ａ−２）成分として下記平均組成式（ａ−２）で表されるジメチルポリシロキサン４５．５質量部（１００ｇあたりフルオロアルキル基０．２８モル、ビニル基０．０３８モル含有）、

（Ｂ）成分として下記平均組成式（ｂ−１）で表されるジメチルポリシロキサン１２．６質量部、

（Ｄ）成分としてエチニルシクロヘキサノール３質量部、
（Ｅ）成分としてゴム揮発油２５質量部
を混合し、組成物（Ｉ）を作製した（（Ｂ）成分中のＳｉ−Ｈ基は、（Ａ）成分中のビニル基に対しモル比で２．０倍）。 [Example 1]
(A-1) 55.5 parts by mass of dimethylpolysiloxane represented by the following average composition formula (a-1) as a component (containing 0.28 mol of fluoroalkyl group and 0.0035 mol of vinyl group per 100 g),

(A-2) 45.5 parts by mass of dimethylpolysiloxane represented by the following average composition formula (a-2) as a component (containing 0.28 mol of fluoroalkyl group and 0.038 mol of vinyl group per 100 g),

(B) 12.6 parts by mass of dimethylpolysiloxane represented by the following average composition formula (b-1) as a component:

(D) 3 parts by mass of ethynylcyclohexanol as component,
(E) 25 parts by mass of volatile rubber oil was mixed as a component to prepare a composition (I) (the Si—H group in the component (B) was 2 in molar ratio to the vinyl group in the component (A). .0 times).

を添加して組成物（ＩＩ）を作製した（（Ｂ）成分中のＳｉ−Ｈ基は、（Ａ）成分と（Ｆ）成分に含まれる合計のビニル基に対しモル比で１．９倍）。 In addition, the composition (I)
(F) 10 parts by mass of dimethylpolysiloxane represented by the following average composition formula (f-1) as a component (containing 0.0025 mol of vinyl groups per 100 g)

To prepare a composition (II) (Si-H group in component (B) is 1.9 times in molar ratio to the total vinyl groups contained in component (A) and component (F)) ).

In each composition
As a component (C), 5 parts by mass of a toluene solution containing 0.5% by mass of platinum content of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex is added, and hexane and methyl ethyl ketone are added. The silicone pressure-sensitive adhesive release agent compositions (I) and (II) were prepared by diluting with a solution in which the mass ratio was 1: 1 so that the solid content was 12% by mass.

  The peel strength 1 was measured using the release agent composition (I) for silicone pressure-sensitive adhesive, and the peel strength 2 was measured using the release agent composition (II) for silicone pressure-sensitive adhesive. Moreover, the presence or absence of the above-mentioned tearing-off phenomenon was confirmed using the release agent compositions (I) and (II) for the silicone pressure-sensitive adhesive.

（Ｈ）成分としてＭｅ₃ＳｉＯ_1/2単位及びＳｉＯ₂単位を含有し、（Ｍｅ₃ＳｉＯ_1/2単位）／（ＳｉＯ₂単位）のモル比が０．８５であるメチルポリシロキサン（ｈ）の６０質量％トルエン溶液を不揮発分として６５質量部、
（Ｉ）成分として下記平均組成式（Ｉ−１）で表されるメチルハイドロジェンポリシロキサン０．２３質量部、

（Ｋ）成分としてエチニルシクロヘキサノール０．２５質量部
を混合し、トルエンで希釈して有効成分６０質量％の組成物を得た。
得られた組成物１００質量部に、トルエン５０質量部を加え、
（Ｊ）成分として１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン白金（０）錯体の白金分を０．５質量％含むトルエン溶液０．５質量部
を添加し、シリコーン粘着剤組成物を作製した（（Ｉ）成分中のＳｉ−Ｈ基は、（Ｇ）成分中のビニル基に対しモル比で１１．４倍）。 In addition, the silicone adhesive composition was produced as follows.
(G) 35 parts by mass of dimethylpolysiloxane represented by the following average composition formula (g-1) as a component (containing 0.0009 mol of vinyl groups per 100 g),

(H) Methyl polysiloxane (h) containing Me ₃ SiO _1/2 units and SiO ₂ units as component and having a (Me ₃ SiO _1/2 unit) / (SiO ₂ unit) molar ratio of 0.85 65 parts by mass of a 60 mass% toluene solution of
(I) 0.23 parts by mass of methyl hydrogen polysiloxane represented by the following average composition formula (I-1) as a component:

As a component (K), 0.25 part by mass of ethynylcyclohexanol was mixed and diluted with toluene to obtain a composition having an active ingredient of 60% by mass.
To 100 parts by mass of the obtained composition, 50 parts by mass of toluene is added,
(J) 0.5 parts by mass of a toluene solution containing 0.5% by mass of platinum of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) complex is added as a component, and silicone A pressure-sensitive adhesive composition was prepared (the Si—H group in the component (I) was 11.4 times in molar ratio to the vinyl group in the component (G)).

[Example 2]
(F) The same procedure as in Example 1 was used except that dimethylpolysiloxane represented by the following average composition formula (f-2) (containing 0.0036 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.9 times in molar ratio to the total vinyl groups contained in the component (A) and the component (F).

[Example 3]
(F) The same procedure as in Example 1 was used except that dimethylpolysiloxane represented by the following average composition formula (f-3) (containing 0.0053 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.9 times in molar ratio to the total vinyl groups contained in the component (A) and the component (F).

[Example 4]
(F) Same as Example 1 except that dimethylpolysiloxane represented by the following average composition formula (f-4) (containing 0.006 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.9 times in molar ratio to the total vinyl groups contained in the component (A) and the component (F).

[Example 5]
(F) The same procedure as in Example 1 was performed except that dimethylpolysiloxane represented by the following average composition formula (f-5) (containing 0.012 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.8 times in molar ratio to the total vinyl groups contained in the components (A) and (F).

[Example 6]
(F) The same procedure as in Example 1 was performed except that dimethylpolysiloxane represented by the following average composition formula (f-6) (containing 0.028 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.7 times in molar ratio to the total vinyl groups contained in the components (A) and (F).

[Example 7]
(F) The same procedure as in Example 1 was used except that dimethylpolysiloxane represented by the following average composition formula (f-7) (containing 0.0038 mol of vinyl group per 100 g) was used as the component (for silicone adhesive) The Si—H group in the component (B) in the release agent composition (II) is 1.9 times in molar ratio to the total vinyl groups contained in the component (A) and the component (F).

[Example 8]
(F) It was carried out similarly to Example 2 except having added 5 mass parts of dimethylpolysiloxane represented by (f-2) as a component (in silicone adhesive release agent composition (II) ( B) Si—H groups in component are 1.9 times in molar ratio to the total vinyl groups contained in components (A) and (F).

[Example 9]
(F) The same procedure as in Example 2 was carried out except that the amount of dimethylpolysiloxane represented by (f-2) as component (f-2) was 7.5 parts by mass (release agent composition for silicone pressure-sensitive adhesive (II)) In the component (B), the Si—H group is 1.9 times in molar ratio to the total vinyl groups contained in the component (A) and the component (F).

[Example 10]
(F) It was carried out similarly to Example 2 except having added 15 mass parts of dimethylpolysiloxane represented by (f-2) as a component (in silicone adhesive release agent composition (II) ( B) Si—H groups in component are 1.9 times in molar ratio to the total vinyl groups contained in components (A) and (F).

[Example 11]
(F) The same procedure as in Example 2 was carried out except that the amount of the dimethylpolysiloxane represented by (f-2) was 20 parts by mass (in the silicone adhesive release agent composition (II) ( B) Si—H groups in component are 1.9 times in molar ratio to the total vinyl groups contained in components (A) and (F).

[Comparative Example 1]
In Example 1, the component (F) was not used, and only the silicone adhesive release agent composition (I) was used (that is, the silicone adhesive release agent composition (II) was used instead of the silicone adhesive release agent composition (II)). After measuring peel force 1 and peel force 2 (using agent composition (I)), the adhesive force was measured to confirm the presence or absence of the tearing phenomenon.

[Comparative Example 2]
Example 1 except that dimethylpolysiloxane represented by the following average composition formula (f-8) (containing 0.12 mol of fluoroalkyl group and 0.0081 mol of vinyl group per 100 g) was used as the component (F). (Similarly, the Si-H group in the component (B) in the release agent composition (II) for silicone pressure-sensitive adhesive was 1 in molar ratio to the total vinyl groups contained in the components (A) and (F)). .9)).

[Comparative Example 3]
(F) The same procedure as in Example 1 except that dimethylpolysiloxane represented by the following average composition formula (f-9) (0 mole of vinyl group per 100 g) was used as a component (release agent composition for silicone adhesive) In the product (II), the Si—H group in the component (B) is 2.0 times in molar ratio to the vinyl group in the component (A).

[Comparative Example 4]
(F) Except having used the dimethylpolysiloxane represented by said (b-1) as a component, it carried out similarly to Example 1 ((B) component in silicone adhesive release agent composition (II) and ( F) The total Si—H groups contained in the component is 3.5 times the molar ratio with respect to the vinyl groups in the component (A).

[Comparative Example 5]
(F) The same procedure as in Example 1 was used except that the methylpolysiloxane represented by (h) was used as the component (Si— in the component (B) in the release agent composition for silicone pressure-sensitive adhesive (II)). H group is 2.0 times in molar ratio to vinyl group in component (A)).

下記式（ｂ−２）で表されるジメチルポリシロキサン０．２７質量部（（ｂ−２）成分中のＳｉ−Ｈ基は、（ａ−３）成分中のビニル基に対しモル比で２．０倍）、

３−メチル−１−ブチン−３−オール０．０２質量部、メタキシレンヘキサフロライド１９０質量部、塩化白金酸／ビニルシロキサン錯塩を（ａ−３）に対して白金金属質量が３０ｐｐｍとなるように混合し、シリコーン粘着剤用剥離剤組成物を作製した。この組成物を、厚み５０μｍのＰＥＴフィルムに、硬化後の固形分が０．２ｇ／ｍ²となるようにワイヤーバーを用いて塗工して１５０℃／１分で風乾させることで剥離基材を作製した。 [Comparative Example 6]
After measuring peeling force 1 and peeling force 2 using the peeling base material prepared with the release agent composition Ia described in Japanese Patent No. 5553395, the adhesive force was measured to confirm the presence or absence of the tearing-off phenomenon. That is,
9.73 parts by mass of dimethylpolysiloxane represented by the following formula (a-3),

0.27 parts by mass of dimethylpolysiloxane represented by the following formula (b-2) (Si—H group in component (b-2) is 2 in molar ratio to vinyl group in component (a-3). .0 times),

0.02 part by mass of 3-methyl-1-butyn-3-ol, 190 parts by mass of metaxylene hexafluoride, and chloroplatinic acid / vinylsiloxane complex salt so that the platinum metal mass becomes 30 ppm with respect to (a-3) To prepare a release agent composition for silicone pressure-sensitive adhesive. This composition is applied to a PET film having a thickness of 50 μm using a wire bar so that the solid content after curing is 0.2 g / m ² and then air-dried at 150 ° C./1 minute to release the substrate. Was made.

下記式（ｂ−２）で表されるジメチルポリシロキサン０．９４質量部（（ｂ−２）成分中のＳｉ−Ｈ基は、（ａ−４）成分中のビニル基に対しモル比で２．５倍）、

３−メチル−１−ブチン−３−オール０．０２質量部、ジイソプロピルエーテル１９０質量部、塩化白金酸／ビニルシロキサン錯塩を（ａ−３）に対して白金金属質量が３０ｐｐｍとなるように混合し、シリコーン粘着剤用剥離剤組成物を作製した。この組成物を、厚み５０μｍのＰＥＴフィルムに、硬化後の固形分が０．２ｇ／ｍ²となるようにワイヤーバーを用いて塗工して１５０℃／１分で風乾させることで剥離基材を作製した。 [Comparative Example 7]
After measuring peeling force 1 and peeling force 2 using the peeling base material produced with the release agent composition Ib described in Japanese Patent No. 5553395, the adhesive strength was measured to confirm the presence or absence of the tearing-off phenomenon. That is,
9.06 parts by mass of dimethylpolysiloxane represented by the following formula (a-4),

0.94 parts by mass of dimethylpolysiloxane represented by the following formula (b-2) (Si—H group in component (b-2) is 2 in molar ratio to vinyl group in component (a-4). .5 times)

0.02 part by mass of 3-methyl-1-butyn-3-ol, 190 parts by mass of diisopropyl ether, and a chloroplatinic acid / vinylsiloxane complex salt were mixed so that the platinum metal mass was 30 ppm with respect to (a-3). A release agent composition for a silicone pressure-sensitive adhesive was prepared. This composition is applied to a PET film having a thickness of 50 μm using a wire bar so that the solid content after curing is 0.2 g / m ² and then air-dried at 150 ° C./1 minute to release the substrate. Was made.

  From the result of Table 1, in Examples 1-11, by processing a base material with the composition which added the (F) component of this invention as release agent composition (II) for silicone adhesives, it is for silicone adhesives. It was possible to increase the difference in peeling force between the substrate treated with the release agent composition (I) and to suppress the occurrence of the crying phenomenon when peeling off one (first) release substrate. . Thus, the other (second) release substrate could be peeled off after the adhesive layer was bonded to the adherend, and a substrate-less silicone adhesive sheet could be produced. It was also confirmed that good adhesiveness was maintained in the adhesive layer after the release substrate treated with the release agent composition (II) for silicone adhesive was peeled off.

In Comparative Example 1, since the same release agent composition for a silicone pressure-sensitive adhesive was used, a tearing phenomenon occurred because the difference in the release force between the two release substrates was small.
In Comparative Examples 2 to 5, studies were made to increase the peel force difference using various additives. Even when the dimethylpolysiloxane represented by (f-8) containing a fluoroalkyl group was added, the difference in peeling force between the two peeling substrates could not be increased, resulting in a tearing phenomenon (Comparative Example 2). Addition of dimethylpolysiloxane represented by (f-9) containing no alkenyl group also caused a tearing phenomenon (Comparative Example 3).
The addition of the dimethylpolysiloxane represented by (b-1) tried to increase the peel force difference by increasing the remaining Si—H groups, but the effect was limited (Comparative Example 4). .
The methylpolysiloxane represented by (h) is a tackifier for the silicone pressure-sensitive adhesive composition, and is sometimes used as a heavy release component, but it was unsuitable because it caused zipping when added (Comparative Example). 5).
In Comparative Examples 6 and 7, there was a difference in peeling force when bonding at room temperature and no crying phenomenon occurred, but in the case of bonding with heat, a phenomenon of crying separation occurred because the difference in peeling force was small.

Claims (13)

A first release substrate,
Adhesive layer,
It is a laminate comprising a structure in which the second release substrate is laminated in this order, and the release surface (the surface in contact with the adhesive layer) of the first release substrate is the following (A) to (C) and if necessary The release surface (surface in contact with the adhesive layer) of the second release substrate treated with the silicone adhesive release agent composition (I) containing the component (E) and not containing the component (F ) is the following ( A laminate characterized by being treated with a release agent composition for silicone pressure-sensitive adhesive (II) containing components A) to (C), (F) and, if necessary, component (E).
(A) The following average composition formula (1)

(In the formula, R ¹ may be the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having no C1-C10 aliphatic unsaturated bond or an alkenyl group-containing organic group having 2-10 carbon atoms. a group of at least two of R ¹ include alkenyl group-containing organic group having 2 to 10 carbon atoms, at least one of R ¹ include a fluoroalkyl group having 1 to 10 carbon atoms .a 2 or more And b is an integer of 1 or more, c and d are integers of 0 or more, and 50 ≦ a + b + c + d ≦ 5,000.
And at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule, 0.001 to 0.5 mol of alkenyl group is contained in 100 g, and the fluoroalkyl group is Organopolysiloxane contained in 100 g in an amount of 0.1 to 0.5 mol: 100 parts by mass
(B) Organohydrogenpolysiloxane having at least 3 Si-H groups in one molecule: The Si-H groups are in a molar ratio of 1 with respect to the sum of the alkenyl groups of the (A) component and the following (F) component. An amount of -10,
(C) A platinum group metal catalyst for hydrosilylation addition and curing of the alkenyl group of the component (A), the following component (F), and the Si-H group of the component (B): The metal mass becomes the component (A). In an amount of 1 to 500 ppm,
(E) Organic solvent: 0 to 2,000 parts by mass,
(F) Organopolysiloxane containing 0.001 to 0.1 mol of alkenyl group in 100 g and no fluoroalkyl group: 1 to 25 parts by mass.   In the release agent composition for silicone pressure-sensitive adhesive (I) and / or the release agent composition for silicone pressure-sensitive adhesive (II), (D) reaction control agent is further added in an amount of 0.01 to 100 parts by mass of component (A). The laminate according to claim 1, containing 5 parts by mass.   The component (A) has (A-1) at least two alkenyl group-containing organic groups and at least one fluoroalkyl group in one molecule, and the alkenyl group is 0.001 mol or more and 0.03 in 100 g. Organopolysiloxane containing less than 1 mol and containing 0.1 to 0.5 mol of fluoroalkyl group in 100 g and / or (A-2) at least 2 alkenyl group-containing organic groups and at least 1 in 1 molecule It is an organopolysiloxane having a fluoroalkyl group of 0.03-0.5 mol in 100 g and 0.1-0.5 mol of fluoroalkyl group in 100 g. The laminate according to claim 1 or 2.   (A) component contains the said (A-1) component and (A-2) component, and the ratio of (A-1) and (A-2) component is (A-1) :( A- 2) = 20: 80 to 80:20 (mass ratio), The laminate according to claim 3. The fluoroalkyl group contained in the component (A) is 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5, 5-heptafluoropentyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7, 7-undecafluoroheptyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group and 3,3,4,4,5, 5. The method according to any one of claims 1 to 4, which is selected from the group consisting of 5,6,6,7,7,8,8,9,9,9-pentadecafluorononyl groups. The laminated body of description.   (B) A component contains a fluoroalkyl group, The laminated body of any one of Claims 1-5 characterized by the above-mentioned.   The laminate according to any one of claims 1 to 6, wherein the fluoroalkyl group contained in the component (B) is a 3,3,3-trifluoropropyl group. The laminate according to any one of claims 1 to 7, wherein the component (F) is an organopolysiloxane selected from those representing the following structures.

(In the formula, o is an integer of 48 to 1,498, p is an integer of 1 to 20, q1 is an integer of 47 to 1,497, q2 is an integer of 1 to 1,496, r is an integer of 1 to 1,449, and p + q1 and p + q2 + r are integers of 48 to 1,498, Me is a methyl group, Vi is a vinyl group, and Ph is a phenyl group.)

(In the formula, s is an integer of 5 to 1,491, t is an integer of 5 to 1,491, u is an integer of 0 to 1,476, and v is an integer of 1 to 739. Me represents a methyl group, and Vi represents a vinyl group.) The adhesive layer is
(G) The following average composition formula (4)
R ⁵ _w SiO _{(4-w) / 2} (4)
Wherein R ⁵ is independently an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond having 1 to 10 carbon atoms or an alkenyl group-containing organic group having 2 to 10 carbon atoms, and w Is a positive number from 1.8 to 2.2.)
An organopolysiloxane having at least two alkenyl group-containing organic groups in one molecule and containing 0.0007 to 0.05 mol of alkenyl groups in 100 g: (G) and (H) components 30 to 70 parts by mass in a total of 100 parts by mass of
(H) R ⁶ ₃ SiO _1/2 unit and SiO _4/2 unit are included, and (R ⁶ ₃ SiO _1/2 unit) / (SiO _4/2 unit) is 0.5 to 1 in molar ratio. Organopolysiloxane (R ⁶ is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkenyl group having 2 to 6 carbon atoms which does not have an aliphatic unsaturated bond): (G) and (H) 70 to 30 parts by mass of 100 parts by mass of the total components,
(I) Organohydrogenpolysiloxane represented by the following average composition formula (6) and having at least 3 Si—H groups in one molecule: (G) and the total of alkenyl groups of (H) component, An amount of Si—H groups in a molar ratio of 0.2 to 20,
R ⁷ _y H _z SiO _{(4-yz) / 2} (6)
(In the formula, R ⁷ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, y and z are y> 0, z> 0, and a positive value satisfying 0 <y + z ≦ 3. Number.)
(J) Platinum group metal catalyst for hydrosilylation addition and curing of alkenyl groups of components (G) and (H) and Si-H groups of component (I): of the above components (G) to (I) The amount of metal to be 1 to 500 ppm relative to the total amount,
(K) The reaction control agent: relative to the total amount of (G) and (H) component, any one of claim 1 to 8 which is a cured product of the silicone pressure sensitive adhesive composition comprising 0.01 to 5 parts by weight The laminated body of description. The laminate according to any one of claims 1 to 9 , wherein the substrate of the release substrate is a plastic film. A second release substrate treated with the silicone adhesive release agent composition (II) is prepared, and the silicone adhesive composition is applied on the treated surface of the release substrate and cured to obtain an adhesive layer. The method for producing a laminate according to any one of claims 1 to 10 , wherein the first release substrate treated with the release agent composition for silicone pressure-sensitive adhesive (I) is bonded to the laminate. After peeling off the first release substrate from the laminate according to any one of claims 1 to 10 laminated to subject the adhesive layer surface, after then peeling the second release substrate from that state, just A method of using a substrate-less pressure-sensitive adhesive sheet, wherein a pressure-sensitive adhesive layer surface opposite to the bonded pressure-sensitive adhesive layer surface is bonded to another target. Article comprising a substrate-less pressure-sensitive adhesive sheet obtained by use of claim 1 2.