TW201809179A - Silicone adhesive silicone composition for forming differentiated releaser and double sided differentiated release paper or film - Google Patents

Abstract

To provide a silicone adhesive silicone composition for forming differentiated releaser that can stably provide a hardened coat in which the release force can be controlled within a range of medium to heavy release force against the silicone adhesive. Provided is a silicone adhesive silicone composition for forming differentiated releaser characterized in containing: (A) an organopolysiloxane containing at least two alkenyl groups bonded to silicon atom in one molecule and having at least one of each 2 kinds fluorine-containing substituents (a) fluoroalkyl group and (b) fluoropolyether group bonded to silicon atom and in which the content of (b) fluoropolyether group with respect to the total of (a) fluoroalkyl group and (b) fluoropolyether group is 1 to 99 mol%; (B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atom in one molecule; and (C) a platinum group metal-based catalyst.

Description

Polysiloxane compound for formation of heterodyne release agent for polysiloxane adhesive and double-sided heterodyne release paper or film

The present invention relates to a polysiloxane composition for the formation of heterodyne release agents for polysiloxane adhesives, and more particularly to a polymerization process using a polysiloxane as a matrix as compared with an organic polysiloxane containing only a fluoropolyether group as a fluorine-containing substituent. The polysiloxane composition for release agents which exhibits light peeling power for polysiloxane adhesives can exhibit moderate to heavy peeling power. Therefore, it can be formed on each surface of film-like or film-like polysiloxane adhesives. Polysilicon exhibiting a different peeling force compared to the hardened layer (light peeling layer) of the silicone composition for a release agent that exhibits light peeling force, and a peeling layer (medium to heavy peeling layer) having a different peeling force. Oxygen composition, and hardened layers (light release layer and medium-heavy release layer) of polysilicone composition with different peeling force are combined with each other to apply to each surface of film-like or thin-film polysiloxane adhesive Double-sided heterodyne release paper or double-sided heterodyne release film.

In the past, substrate or film such as polyethylene film, polypropylene film, polyethylene terephthalate (PET) film, and the like were prevented from adhering or fixing to pressure-sensitive adhesive substances. For the purpose of adhesion, a hardened film of polysiloxane composition is formed on the substrate surface Pre-release, this is generally called release paper.

Among the above pressure-sensitive adhesive substances, a polysiloxane adhesive containing a resinous (three-dimensional network structure) organic polysiloxane as a main component has low heat resistance, cold resistance, chemical resistance, electrical insulation, and low Because of its excellent toxicity, it is used in a wide range of applications. Polysiloxane adhesives have a much stronger adhesive force than ordinary non-polysiloxane adhesives. Therefore, in order to easily peel the adhesive tape or adhesive label coated with the adhesive from the above substrate, it is necessary to form the adhesive. The silicone-cured film on the above-mentioned substrate becomes extremely excellent in releasability.

As a polysiloxane composition system that imparts a polysiloxane hardened film excellent in mold releasability, there are proposed fluorine-containing substituents represented by C _n F _{2n + 1} CH ₂ CH _2- (n is an integer of 1 or more). Organic polysiloxane composition (Japanese Patent Publication No. 5-7434), with the formula [CF (CF ₃ ) CF ₂ O] _n CF (CF ₃ ) CF ₂ OCH ₂ CH ₂ CH _2- (n is 1 An organic polysiloxane composition having a fluorine-containing substituent represented by an integer of ~ 5 (Japanese Patent Publication No. 4-76391) and the like.

However, although these polysiloxane compositions have relatively light peeling power for polysiloxane adhesives, they are suitable for engineering papers or double-sided adhesive tapes and For applications such as OCA (Optical Clear Adhesive) tapes for control panels, in order to impart differential peeling force to each surface of the film-like or film-like polysiloxane adhesive, a light peeling force is required on the surface on one side. The peeling layer on the other side is a peeling layer with medium to heavy peeling force. However, when I want to put the above In the case where a hardened product of a silicone composition for release paper having an organopolysiloxane containing a fluorine-containing substituent as a matrix is used as the release layer, as in a general non-fluorine-based release paper, There is no such thing as a peeling force control agent often used in a silicone composition, so there is a problem that it cannot be used for this purpose. In addition, in the case where a differential peeling force is imparted in applications such as engineering papers, double-sided adhesive tapes, and OCA tapes for touch panels, the difference between the peeling force of the light peeling layer and the medium to heavy peeling layer corresponds to the use. A moderate difference in peel force is also required. Furthermore, even if it is desired to mix an organopolysiloxane having a perfluoroalkyl group as described above as a fluorine-containing substituent with an organopolysiloxane having a perfluoropolyether group, the composition is suitable for a release agent composition. There is also a problem that a stable peeling force corresponding to the blending ratio cannot be obtained due to the lack of compatibility with each other.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 5-7434

[Patent Document 2] Japanese Patent Publication No. 4-76391

The present invention has been made in view of the above circumstances, and an object thereof is to provide a heterogeneous peeling for a silicone adhesive which can stably provide a hardened film which can control the peeling force of the silicone adhesive in a range of medium to heavy peeling force. Polysiloxane composition for agent formation and hardened layer (medium ~) of the composition Heavy peeling layer) and light peeling layer are formed on each surface of a film-like or film-like polysiloxane adhesive, and a double-sided difference release paper or a double-sided difference release film is formed.

As a result of intensive studies in order to achieve the above-mentioned object, the inventors have found that (a) / (b) is adjusted by the addition-hardening type polysiloxane composition using (A) an organopolysiloxane as a matrix polymer. ) Ratio, a polysiloxane composition can be obtained which gives a cured film that can control the peeling force of the cured product stably in a range of medium to heavy peel force for the polysiloxane adhesive. It is suitable for the combination of a polysiloxane release layer with a light release force, and a light release layer and a medium-heavy release layer can have a two-sided difference release paper or a double-sided difference glass film with a suitable release force difference. Therefore, the present invention has been completed. The (A) organopolysiloxane is composed of at least two alkenyl groups bonded to a silicon atom in one molecule, and each is a fluorine-containing substituent bonded to two kinds of silicon atoms. It has at least one (a) fluoroalkyl group and (b) fluoropolyether group, and the content of (b) fluoropolyether group is 1 ~ with respect to the total of (a) fluoroalkyl group and (b) fluoropolyether group. 99 mole%.

Therefore, the present invention provides a polysiloxane composition for forming a heterodyne release agent for a polysiloxane adhesive, and a double-sided heterodyne release paper or a double-sided heterodyne release film.

[1]

Composition of polysiloxane for formation of heterodyne release agent for polysiloxane adhesive It is characterized in that it contains (A) an organopolysiloxane, which contains at least two alkenyl groups bonded to silicon atoms in one molecule, and serves as two kinds of fluorine-containing substituents bonded to silicon atoms. And each has at least one (a) fluoroalkyl group and (b) fluoropolyether group. The content of (b) fluoropolyether group is relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group. 1 ~ 99 mol%, (B) organohydrogen polysiloxane, based on a molecule having at least 3 hydrogen atoms bonded to silicon atoms, (C) platinum group metal catalyst.

[2]

The polysiloxane composition for the formation of heterodyne release agents for the polysiloxane adhesive of [1], wherein (a) the fluoroalkyl group is represented by the following formula (1) among the fluorine-containing substituents of the component (A) ), (B) a fluoropolyether group is a group represented by the following formula (2), (Where n is an integer from 1 to 6, m is an integer from 1 to 5, p is an integer from 1 to 5, q is an integer from 0 or 1, r is an integer from 0 to 2, and X is an oxygen atom or a single key).

[3]

A double-sided heterodyne release paper or a double-sided heterodyne release film, which is the first one to be formed with a polysiloxane release layer having a light peeling force for a polysiloxane adhesive. The release layer side of a base film is attached to the surface of one side of the aforementioned polysiloxane adhesive formed in a film or film form, and attached to the other surface of the polysiloxane adhesive, such as [1] or [2] is a hardened product of the polysiloxane composition and the second base film of the second base film formed with a polysiloxane release layer having a moderate to heavy peeling force to the aforementioned polysiloxane adhesive, and to make.

[4]

A double-sided heterodyne release paper or a double-sided heterodyne release film, which is formed on the surface of one side of a base film, forms a hardened product of a polysiloxane composition such as [1] or [2], and adheres to the polysiloxane The agent has a polysiloxane peeling layer having a medium to heavy peeling force, and a polysiloxane peeling layer having a light peeling force for the aforementioned polysiloxane adhesive is formed on the other surface of the base film.

[5]

A double-sided heterodyne release paper or a double-sided heterodyne release film, which is formed on the surface of one side of a base film, forms a hardened product of a polysiloxane composition such as [1] or [2], and adheres to the polysiloxane The agent has a polysilicone release layer with a medium to heavy peeling force, and further attaches a polysilicone adhesive formed into a film or film on the outer surface of the polysilicone release layer, and is applied to the base film. A polysiloxane peeling layer having a light peeling force to the polysiloxane adhesive is formed on the other surface.

[6]

For example, the double-sided heterodyne release paper or the double-sided heterodyne film according to any one of [3] to [5], wherein the polysiloxane release layer having a light peeling force is composed of a polysiloxane containing organic polysiloxane as a matrix polymer. A hardened product of an addition-curable polysiloxane composition, the organic polysiloxane has only fluoropolyether in the molecule As a fluorine-containing substituent.

[7]

For example, the double-sided uneven release paper or the double-sided uneven release film of any one of [3] to [6], which is used for any of engineering paper, double-sided adhesive tape, correction tape, or OCA tape for touch panels.

In addition, in applications such as engineering papers, double-sided adhesive tapes, correction tapes, or OCA tapes for touch panels, the difference in peeling force (differential difference peeling force) between a light release layer and a medium to heavy release layer is usually used as a base. Based on the difference between the peeling force of polyethylene terephthalate with a width of 25 mm and a day after, the material film is preferably 0.1 to 1.0 [N / 25 mm], especially about 0.15 to 0.8 [N / 25 mm]. Regarding the peeling force (absolute value) of the medium-heavy peeling layer, usually, as the base film, the peeling force after 25 days in width of polyethylene terephthalate is 0.1 to 0.8 [N / 25mm], In particular, about 0.12 to 0.6 [N / 25mm] is preferable in terms of workability of the uneven release paper or the uneven release sheet.

The polysiloxane composition of the present invention can stably control the peeling force of the cured product in the range of medium to heavy peeling force for the polysiloxane adhesive, and can be hardened with excellent releasability without pinholes or cracks. Film, so it can be effectively used as a polysiloxane adhesive for forming double-sided uneven release paper or double-sided uneven release film for engineering paper, double-sided adhesive tape, correction tape, OCA tape for touch panel, etc. Silicone composition for release agent formation, and also suitable for rubber and plastic For mold release properties such as molds, fiber treatment agents for paper and cloth, water repellents for food packaging, oil repellents, and heat-resistant coating applications.

1‧‧‧ The first two-sided heterodyne release paper or the two-sided heterodyne release film

2‧‧‧ The second two-sided difference release paper or the two-sided difference release film

3‧‧‧ the third two-sided heterodyne release paper or the two-sided heterodyne release film

10‧‧‧The first substrate film

10'‧‧‧Second substrate film

20‧‧‧Polysiloxane adhesive layer

30‧‧‧Polysilicone release layer (light release layer)

40‧‧‧Polysilicone release layer (medium to heavy release layer)

[FIG. 1] A schematic cross-sectional view of a double-sided heterodyne release paper or a double-sided heterodyne release film according to the first configuration example of the present invention.

[Fig. 2] A schematic cross-sectional view of a double-sided heterodyne release paper or a double-sided heterodyne release film according to a second configuration example of the present invention.

[Fig. 3] A schematic cross-sectional view of a double-sided heterodyne release paper or a double-sided heterodyne release film according to a third configuration example of the present invention.

Hereinafter, if the present invention is described in more detail, the organopolysiloxane of the component (A) is an alkenyl group having at least two silicon atoms bonded to one molecule and two kinds of silicon atoms bonded to silicon atoms in one molecule. A fluorine-containing substituent having at least one (a) fluoroalkyl group and (b) fluoropolyether group, and the content of (b) fluoropolyether group relative to (a) fluoroalkyl group and (b) fluoropolyether group The total (molar ratio), more specifically, the ratio of y to the total of (x + y) in the following formula (A) is 1 to 99 mol%, preferably 10 to 90 mol% , More preferably 20 ~ 80 mole%.

As an organopolysiloxane, the content of fluorine is a ratio of (b) a fluoropolyether group to a total of (a) a fluoroalkyl group and (b) a fluoropolyether group, which may be 1 to 99 as the above-mentioned molar ratio. Adjust between Moire%, the ratio A case where it is low is a heavy peel, and a case where the ratio is high is a light peel.

As the organopolysiloxane based on the component (A), those represented by the following formula (A) are suitably used.

Here, R ² is an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group, and a hexenyl group.

R ³ is a monovalent hydrocarbon group excluding an unsubstituted or substituted aliphatic unsaturated group having 1 to 10 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, and butyl, and cyclohexyl. Cycloalkyl, phenyl, tolyl and other aryl groups, benzyl, phenylethyl, and other arylalkyl groups and some or all of the hydrogen atoms of these groups are substituted with hydroxy, cyano, etc. And cyanoethyl. b is 1, 2, or 3, and w, x, y, and z are integers of w ≧ 0, x ≧ 1, y ≧ 1, and z ≧ 0, respectively.

Preferably, Rf ¹ is a base represented by the following formula (1) and Rf ² is a base represented by the following formula (2).

(Where n is an integer from 1 to 6, m is an integer from 1 to 5, p is an integer from 1 to 5, q is an integer from 0 or 1, r is an integer from 0 to 2, and X is an oxygen atom or a single key).

Specific examples of the formula (1) include the following examples.

(Where n is an integer from 1 to 6).

Specific examples of the formula (2) include the following examples.

(Where p is an integer from 1 to 5).

Although w, x, y, and z are integers such as w ≧ 0, x ≧ 1, y ≧ 1, and z ≧ 0 as described above, it is preferably 0 ≦ w ≦ 5, 1 ≦ x ≦ 500, 1 ≦ y ≦ 500, 0 ≦ z ≦ 1,500, more preferably 1 ≦ w ≦ 3, 10 ≦ x ≦ 400, 10 ≦ y ≦ 400, 0 ≦ z ≦ 800. In this case, w + x + y + z is 50 to 1,000, more preferably 100 to 800, and even more preferably 200 to 500. The dynamic viscosity at 25 ° C is calculated as a value obtained in Ubbelohde viscosity. ~ 10,000mm ² / s, more preferably 200 ~ 5,000mm ² / s, and still more preferably 500 ~ 3,000mm ² / s.

The (A) component of the organic polysiloxane may be linear or branched. Specifically, those represented by the following formula can be exemplified.

(In the formula, Rf ¹ and Rf ² represent the same meanings as above, and Vi represents vinyl. W, x, y, and z are integers of w ≧ 0, x ≧ 1, y ≧ 1, and z ≧ 0, respectively).

The organopolysiloxane represented by the above formula can be obtained, for example, by having the following formulae (3), (4) (In the formula, Rf ¹ and Rf ^{2 have} the same meanings as described above).

The fluorine-containing organic cyclotrisiloxane represented by the formula is added according to the formula: (In the formula, v is an integer of 1 or more, and Vi represents a vinyl group).

The organosiloxanes terminated by a vinyl group represented by the formula (5) and / or (6) (In the formula, Vi represents a vinyl group).

The organic cyclotrisiloxanes shown are polymerized together by a well-known equilibrium reaction using an acid or a base as a catalyst in an appropriate ratio according to various purposes.

(B) The organohydrogen polysiloxane is one having at least 3 hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and this SiH group reacts with an alkenyl group in the (A) component Those who form a hardened film.

In terms of compatibility with the organopolysiloxane of the component (A), the organic hydrogen polysiloxane is preferably a fluorine content of 40% by mass or less. The organic polysiloxane may be linear, branched, or cyclic.

Examples of the organohydrogenpolysiloxane based on (B) It is represented by the following formula.

In the formula, R ⁴ is at least one kind of base selected from the same bases as R ³ and Rf ² , c is 0 or 1, and r and s are integers of r ≧ 1 and s ≧ 0, respectively. However, the number of hydrogen atoms bonded to the silicon atom in the r system is 3 or more. It is preferably 3 ≦ r ≦ 500, 50 ≦ s ≦ 2,000, and more preferably 10 ≦ r ≦ 300, 100 ≦ s ≦ 1,000. In addition, r + s is 20 to 2,500, more preferably 50 to 2,000, and even more preferably 80 to 1,000. The dynamic viscosity at 25 ° C is 50 to 5,000 mm ² / s based on the value obtained in Ubbelohde viscosity. It is more preferably 100 to 3,000 mm ² / s.

The organohydrogenpolysiloxane as the component (B) can be specifically exemplified by the following formula.

(In the formula, r, s, Rf ¹ , and Rf ² represent the same meanings as above, and t ≧ 1 is an integer).

The blending amount of the organohydrogenpolysiloxane of the component (B) is preferably 0.1 to 20 parts, particularly 0.2 to 10 parts, based on 100 parts (parts by mass, the same below) of the component (A). When the blending amount is less than 0.1 part and more than 20 parts, in either case, the hardenability of the intended silicone composition may be lowered, or the physical properties of the hardened product may be lowered.

In addition, the organohydrogenpolysiloxane of the component (B) can be bonded to the silicon atom-bonded hydrogen atom (SiH) in the component (B) with respect to the alkenyl group in the component (A) for the same reason as described above. The molar ratio is usually 0.5 to 3.0 (mol / mol), and preferably blended in an amount of about 0.8 to 2.0 (mol / mol).

(C) The platinum group metal catalyst is used to promote As a catalyst for the addition reaction of the component (A) and the component (B), a known catalyst can be used. Examples of such platinum group metal-based catalysts include platinum-based, palladium-based, and rhodium-based catalysts. Among these, platinum-based catalysts are particularly preferred. Examples of such a platinum-based catalyst system include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of chloroplatinic acid with various olefins or vinylsiloxanes.

Although the addition amount of these platinum group metal catalysts is only required to be the amount of the catalyst, from the viewpoint of reactivity and economy when a cured film is obtained, it is preferable to use platinum with respect to the component (A). The mass conversion of the group metal is set to a range of 1 to 1,000 ppm.

Although the composition of the present invention is obtained by blending a specific amount of the components (A) to (C), other components can be added in addition to the components described above, for example, for controlling a platinum group metal catalyst A variety of organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds, oxime compounds and other activity control agents for the purpose of catalytic activity. Among the activity control agents, 3-methyl-1-butyne is suitable for use. Acetylene compounds such as 3-alcohols and silicon compounds thereof, divinyltetramethyldisilazane, tetravinyltetramethylcyclotetrasiloxane, etc.

When the activity control agent is blended, the blending amount is preferably 0.05 to 3 parts with respect to 100 parts of the component (A). If it is less than 0.05 parts, the intended polysiloxane composition may gel, and if it exceeds 3 parts, the hardening of the polysiloxane composition may be hindered. Moreover, the addition amount of other arbitrary components can be made into a normal amount in the range which does not inhibit the effect of this invention.

In the preparation of the polysilicone composition of the present invention, it is preferred that the components (A) and (B) are uniformly mixed in advance, and then the component (C) is added. Each component can be used singly, or two or more kinds can be used. And use.

When the polysiloxane composition prepared in this manner is applied to a substrate, the composition may be diluted with an appropriate solvent and used in order to uniformly dilute the composition and facilitate application. Examples of such a solvent system include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and perfluoro Fluorine-denatured ether solvents such as (2-butyltetrahydrofuran); Fluorine-denatured alkylamine solvents such as perfluorotributylamine and perfluorotripentylamine. In particular, in terms of solubility, wettability, and the like, preferred are fluorine-denaturing solvents such as m-xylene hexafluoride and ethyl perfluorobutyl ether.

The amount of the fluorine-denaturing solvent used is preferably a diluted polysilicon composition in terms of workability, ease of control of the amount of coating, and the like when the polysiloxane composition is used after being dissolved. The kinematic viscosity of the silicon oxide composition obtained in Ubbelohde viscosity is 100 mm ² / s or less at 25 ° C. Specifically, it is preferably 100 to 20,000 parts with respect to 100 parts of the component (A).

The polysiloxane composition of the present invention is applied to a substrate and cured to form a cured film with peelability on the surface of the substrate, which can be used as a release paper. In this case, examples of the substrate include plastic films or sheets obtained from synthetic resins such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, and polyimide, cellophane, Paper base materials such as kraft paper, white clay coated paper, polyethylene laminated paper, polyethylene laminated cow Laminated paper substrates such as paper, metal foils such as aluminum foil.

As a method for applying the polysiloxane composition as the base material, known methods such as roll coating, gravure coating, wire doctor coating, air knife coating, and dip coating can be used. method.

In order to form the hardened coating of the polysiloxane composition of the present invention on a substrate, the base material coated with the polysiloxane composition can be heated at a temperature of 80 to 250 ° C. for 2 to 60 seconds, so that The silicone composition is hardened, and a peelable silicone coating is formed on the surface of the substrate.

The polysiloxane composition of the present invention can be effectively used as a release agent, especially a heterogeneous release agent for a polysiloxane adhesive. Although not particularly limited, it can form both sides as shown in Figs. 1 to 3 Variation peeling paper or film.

The two-sided heterodyne release paper or film of FIG. 1 is laminated on the first base film 10 to form a polysiloxane peeling layer 30 having a light peeling force for the film-like or film-like polysiloxane adhesive layer 20. The polysiloxane stripping layer 30 is laminated on top of the polysiloxane adhesive layer 20, and the second base film 10 'is laminated to form a polysilicon having a moderate to heavy peeling force for the polysiloxane stripping layer 20 The polysiloxane stripping layer 40 side of the oxygen stripping layer 40 is adhered to the aforementioned polysiloxane stripping layer 20.

In order to actually make the two-sided heterodyne release paper or film of FIG. 1, for example, the polysiloxane adhesive layer 20 may be sandwiched between the film-like or film-like polysiloxane adhesive layer 20 to form a polysiloxane release layer 30 on the first base. Between the release layer 30 side of the release paper on the base film 10 and the release layer 40 side of the release paper in which the polysiloxane release layer 40 is integrally formed on the second base film 10 ', the polysilicon The oxygen peeling layer 30 and the polysiloxane adhesive layer 20 exhibit a light peeling force, and the polysiloxane peeling layer 40 and the polysiloxane adhesive layer 20 exhibit a medium-heavy peeling force to produce the peeling force.

The two-sided heterodyne release paper or film of FIG. 2 is laminated on one side of the base film 10 to form the above-mentioned medium-to-heavy polysiloxane release layer 40, and is laminated on the other side of the base film 10 to form the light Peeling force polysiloxane stripping layer 30.

In order to actually produce the two-sided heterodyne release paper or film of FIG. 2, for example, the polysiloxane release layer 30 may be integrated on the substrate film 10 side of the release paper on one side of the substrate film 10, and further The polysiloxane stripping layer 40 is integrally formed, and is produced on each surface to exhibit a light peeling force when contacting and bonding with an external polysiloxane adhesive layer (for example, a polysiloxane adhesive sheet having adhesiveness on both sides). The two surfaces of the polysiloxane stripping layer 30 and the polysiloxane stripping layer 40 exhibiting moderate to heavy peeling force are different from each other to release paper or film.

The two-sided heterodyne release paper or film of FIG. 3 is laminated on one side of the base film 10 to form the above-mentioned medium-to-heavy polysiloxane peeling layer 40, and a film-like or A thin-film polysiloxane adhesive layer 20 is formed on the other side of the base film, and the light-peeling polysiloxane removal layer 30 is formed.

In order to actually produce the double-sided heterodyne release paper or film of FIG. 3, for example, the polysiloxane release layer 40 side of the double-sided heterodyne release paper or film of FIG. 2 formed by integration in advance can be further integrated to form The film-like or film-like polysiloxane adhesive layer 20 is produced. In this case, the The polysiloxane peeling layer 40 and the polysiloxane adhesive layer 20 can exhibit a moderate to heavy peeling force. In addition, for example, the double-sided uneven release paper or film of FIG. 3 may be wound up such that the polysiloxane stripping layer 30 faces the outer surface of the polysiloxane adhesive layer 20 like a double-sided adhesive tape. Storage is performed in a concentric circle or a swirl shape, and a light peeling force is exhibited between the polysiloxane peeling layer 30 and the polysiloxane adhesive layer 20.

Here, in the double-sided heterodyne release paper or film, the polysiloxane release layer 30 having a light peeling force is preferably an addition-hardened polysiloxane composition containing an organic polysiloxane as a matrix polymer. The organopolysiloxane is formed as a hardened product and contains only a fluoropolyether group (b) as a fluorine-containing substituent instead of a fluoroalkyl group (a) in the molecule.

If this polysiloxane composition is described in more detail, the organopolysiloxane as the matrix polymer, in the above formula (A), x = 0 (that is, does not contain Rf ¹ in the molecule The organopolysiloxane shown as the fluoroalkyl group (a)) is suitable. In this case, except for x = 0, Rf ² , R ² , R ³ , w, y, and z are preferably the same as those described above, and the value of w + y + z is the same even at 25 ° C. By. In addition, organic hydrogen polysiloxanes and platinum group metal catalysts can be used as described above.

As the polysiloxane adhesive layer 20, for example, an addition-hardening polysiloxane containing a resinous (three-dimensional network structure) organic polysiloxane or a peroxide-hardening polysiloxane can be suitably used. Adhesives, etc.

In addition, the adhesion of the polysiloxane stripping layer 30 or 40 and the polysiloxane adhesive layer 20 can be, for example, under a load of 10 to 40 g / cm ² , preferably 20 to 30 g / cm ² , at 40 to 40 g / cm ² . It is carried out under heating at 100 ° C, preferably 50 to 80 ° C, for about 0.5 to 30 days, and preferably for about 1 to 21 days.

[Example]

Hereinafter, the present invention will be specifically described with reference examples, examples, and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts represent parts by mass and% represents mass%.

(Examples 1 to 4)

As shown in Table 1, a vinyl-containing organic polysiloxane (III) having a fluorine substituent represented by the following formulae (I) and (II) and an organic hydrogen represented by the following formula (IV) Polysiloxane was mixed with 4 parts of the composition so that the ratio of SiH group / SiCH = CH ₂ group was 2.5, diluted with 96 parts of hydrofluoroether Novec7300 (manufactured by 3M Japan), and chloroplatinic acid was added thereto. It is mixed with vinyl siloxane (0.05% platinum concentration) to prepare a treatment solution.

Organopolysiloxanes containing vinyl groups

(In the formula, Rf ² is the same as described above).

The obtained treatment liquid was coated on a polyethylene terephthalate film (50 μm) using a K Control Coater (type No. 202) with a No. 1 coating rod, and then subjected to a hot air circulation dryer at 150 ° C. / Heating was performed for 60 seconds to form a cured film (coating amount ≒ 0.3 g / m ² ), and a release film was obtained.

With respect to the release film obtained in this way, the peeling force and residual adhesive force were measured by the following method. These results are shown in Tables 2 and 3.

(a) Peeling force

A 25 mm wide silicone adhesive tape (kapton No. 650S # 25, manufactured by Teraoka Co., Ltd.) was attached to the obtained release film, and a load of 25 g / cm ² was applied at 70 ° C. for 1 day ~ 21 days of bonding and aging. Using a tensile tester, the adhesive tape was peeled at an angle of 180 degrees at a peeling speed of 0.3 m / min, and the force (N / 25 mm) required for peeling was measured.

(b) Residual adhesion

The adhesive tape after the peel measurement (a) was attached to the SUS board, and it was pressed back and forth with a 2kg tape roller. After standing for 30 minutes, the adhesive tape was peeled at an angle of 180 degrees using a tensile tester. The peeling speed was 0.3 m / min, and the force (N / 25 mm) required for peeling was measured.

(Comparative example 1)

As a vinyl-containing organopolysiloxane having a fluorine substituent, a vinyl-containing compound obtained by blending V-1 (Reference Example 1) and V-6 (blank) at a mass ratio of 1: 1 is used. Except for the organic polysiloxane mixture, the treatment liquid was adjusted in the same manner as in the above example, a release film was made in the same manner, and the peel force was measured in the same manner, but the error of each measurement sample was very large. A release film having a stable peeling force cannot be obtained.

[Industrial availability]

Since the polysiloxane composition according to the present invention can stably control the peeling force of the cured product with respect to the polysiloxane adhesive in the range of medium to heavy peeling force, it can be attached with a pinch or crack-free release property. Hardened film, so it is especially suitable as heterodifference release agent for silicone adhesive for forming double-sided heterogeneous release paper or double-sided heterogeneous release film for engineering paper, double-sided adhesive tape, correction tape, OCA tape for touch panel, etc. Polysiloxane for formation The composition can also be suitably used for mold release properties for molding rubber, plastics, etc., fiber treatment agents for paper and cloth, water repellents for oil packaging, oil repellents, and heat-resistant coating. In use, its industrial value is great.

1‧‧‧ The first two-sided heterodyne release paper or the two-sided heterodyne release film

10‧‧‧The first substrate film

10'‧‧‧Second substrate film

20‧‧‧Polysiloxane adhesive layer

30‧‧‧Polysilicone release layer (light release layer)

40‧‧‧Polysilicone release layer (medium to heavy release layer)

Claims (7)

A polysiloxane composition for the formation of heterodyne release agents for polysiloxane adhesives, which is characterized by containing: (A) an organic polysiloxane, which is composed of at least two silicon atoms bonded to one molecule. An alkenyl group, which has at least one (a) fluoroalkyl group and (b) fluoropolyether group as two kinds of fluorine-containing substituents bonded to a silicon atom, and the content of (b) fluoropolyether group is relative to The total of (a) fluoroalkyl group and (b) fluoropolyether group is 1 to 99 mole%. (B) organohydrogen polysiloxane, which has at least 3 bonds to silicon atoms in one molecule. Hydrogen atom, (C) platinum group metal catalyst. The polysiloxane composition for heterodyne release agents for polysiloxane adhesives according to claim 1, wherein (a) the fluoroalkyl group in the fluorine-containing substituent of the component (A) is represented by the following formula (1) ), (B) a fluoropolyether group is a group represented by the following formula (2), (Where n is an integer from 1 to 6, m is an integer from 1 to 5, p is an integer from 1 to 5, q is an integer from 0 or 1, r is an integer from 0 to 2, and X is an oxygen atom or a single key). A double-sided heterodyne release paper or a double-sided heterodyne release film, which is formed by attaching the release layer side of a first substrate film having a polysiloxane release layer having a light release force to a polysiloxane adhesive to the formation It is a film-shaped or film-shaped one-side surface of the aforementioned polysiloxane adhesive, and the other surface of the polysiloxane adhesive is adhered to form a hardened polysiloxane composition as claimed in claim 1 or 2 It is formed on the release layer side of the second base film of the polysiloxane stripping layer having a moderate to heavy peeling power to the aforementioned polysiloxane adhesive. A double-sided heterodyne release paper or a double-sided heterodyne release film is formed on one surface of a substrate film, and a hardened product of the polysiloxane composition as claimed in claim 1 or 2 is formed and has a polysiloxane adhesive. The polysiloxane peeling layer with a medium to heavy peeling force is formed on the surface of the other side of the base film with a polysiloxane peeling layer having a light peeling force to the aforementioned polysiloxane adhesive. A double-sided heterodyne release paper or a double-sided heterodyne release film is formed on one surface of a substrate film, and a hardened product of the polysiloxane composition as claimed in claim 1 or 2 is formed and has a polysiloxane adhesive. The polysiloxane peeling layer with a medium to heavy peeling force is further attached to the outer surface of the polysiloxane peeling layer, and the aforementioned polysiloxane adhesive formed in a film or film form is attached to another surface of the base film. On one surface, a polysiloxane peeling layer having a light peeling force to the polysiloxane adhesive is formed. For example, the two-sided heterodyne release paper or the two-sided heterodyne film of any of claims 3 to 5, wherein the polysiloxane release layer having light peeling force is an addition of an organic polysiloxane as a matrix polymer. The organopolysiloxane has a fluoropolyether group as a fluorine-containing substituent in the molecule. If the two-sided heterodyne release paper or the double-sided heterodyne release film of any one of claims 3 to 6 is used for any of engineering paper, double-sided adhesive tape, correction tape, or OCA tape for touch panels.