TWI754630B - Two-sided differential release paper or two-sided differential release film - Google Patents

Abstract

The subject of the present invention is to provide a polysiloxane composition for forming a differential release agent for a polysiloxane adhesive, which can stably impart a peel force control in the range of medium to heavy peel force to the polysiloxane adhesive. of hardened coating.

The solution of the present invention is a polysiloxane composition for forming a differential release agent for a polysiloxane adhesive, which is characterized by containing (A) an organopolysiloxane and containing at least two bonds in one molecule. An alkenyl group bonded to a silicon atom and having at least one fluorine-containing substituent of two types bonded to a silicon atom (a) a fluoroalkyl group and (b) a fluoropolyether group, and (b) one of the fluoropolyether groups The content is 1 to 99 mol % relative to the total of (a) fluoroalkyl groups and (b) fluoropolyether groups, and (B) organohydrogen polysiloxane, which has at least 3 bonds in 1 molecule. Hydrogen atom of silicon atom, (C) platinum group metal catalyst.

Description

Two-sided differential release paper or two-sided differential release film

The present invention relates to a polysiloxane composition for forming a dissimilar release agent for polysiloxane adhesives, and in particular, to a polymer based on an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent as a matrix polymer The polysiloxane composition for a release agent that exhibits light peeling force for polysiloxane adhesives can exhibit medium to heavy peeling force, so it can be formed on each surface of film-like or film-like polysiloxane adhesives. The so-called polysilicon exhibiting different peeling force of the peeling layer (medium-heavy peeling layer) with different peeling force than the cured product layer (light peeling layer) of the polysiloxane composition for release agent exhibiting the aforementioned light peeling force Oxygen composition, and the hardened layer (light peeling layer and medium-heavy peeling layer) of polysiloxane composition with different peeling force are combined with each other to apply to each surface of film or film polysiloxane adhesive. Two-sided differential release paper or two-sided differential release film.

In the past, to prevent adhesion or solidification between substrate films such as paper or plastic films (eg, polyethylene films, polypropylene films, polyethylene terephthalate (PET) films, etc.) and pressure-sensitive adhesive substances For the purpose of sticking, a hardened film of polysiloxane composition is formed on the substrate surface to impart peelability, which is generally called release paper.

Among the above-mentioned pressure-sensitive adhesive substances, polysiloxane-based adhesives containing resin-like (three-dimensional network structure) organopolysiloxane as the main component are due to heat resistance, cold resistance, chemical resistance, electrical insulation, low Since it is excellent in toxicity and the like, it is used in a wide range of applications. Since polysiloxane-based adhesives have very strong adhesive force compared with general non-polysiloxane-based adhesives, in order to make the adhesive tapes or labels coated therewith easily peel off the above-mentioned substrates, it is necessary to form The cured polysiloxane film on the above-mentioned base material is extremely excellent in releasability.

As a polysiloxane composition system for _imparting a cured polysiloxane film excellent in mold _{releasability} , it _is proposed that _:

Organopolysiloxane composition having a fluorine-containing substituent (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 an integer of 1 to 5), an organopolysiloxane composition having a fluorine-containing substituent (JP 4-76391 A) and the like.

However, although these polysiloxane compositions have relatively light peeling force for polysiloxane-based adhesives, when the polysiloxane composition is intended to be used as a peeling layer, it is suitable for engineering paper or double-sided adhesive tape, touch In the case of applications such as OCA (Optical Clear Adhesive) tapes for control panels, in order to impart a different peeling force to each surface of a film-like or film-like polysiloxane-based adhesive, a light peeling force is required on one side of the surface. The peeling layer on the other side is a peeling layer with medium to heavy peeling force. However, when it is desired to use a release paper based on an organopolysiloxane having a fluorine-containing substituent as described above In the case where the cured product of the polysiloxane composition is used as the release layer, there is no release force control agent that is commonly used in general non-fluorine-based polysiloxane compositions for release paper. Problems used for this purpose. In addition, in the case of imparting different peeling force in applications such as engineering paper, double-sided adhesive tape, OCA tape for touch panels, etc., the difference in peeling force between the light peeling layer and the medium-heavy peeling layer corresponds to the application. A moderate difference in peel force is also required. Furthermore, even if it is desired to blend an organopolysiloxane having a perfluoroalkyl group as described above as a fluorine-containing substituent and an organopolysiloxane having a perfluoropolyether group, it is suitable for a release agent composition There is also a problem that stable peeling force corresponding to the blending ratio cannot be obtained due to incompatibility with each other.

[Prior Art 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-mentioned circumstances, and an object of the present invention is to provide differential peeling for polysiloxane adhesives that can stably impart a hardened film with a peel force controllable in the range of medium to heavy peeling force with respect to polysiloxane adhesives A polysiloxane composition for forming an agent, and the cured product layer (medium to heavy peeling layer) and light peeling layer of the composition are formed in a film or thin film-like polysiloxane adhesive Double-sided release paper or double-sided release film formed on each surface of the adhesive.

The inventors of the present invention, as a result of diligent investigations in order to achieve the above-mentioned object, found that (a)/(b are adjusted in an addition-hardening polysiloxane composition having (A) organopolysiloxane as a matrix polymer. ) ratio to obtain a polysiloxane composition that imparts a cured film that 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. Furthermore, it was found that by combining the composition with It is suitable for the combination of polysiloxane adhesive and polysiloxane peeling layer with light peeling force, and can obtain two-sided differential release paper or two-sided differential glass film with suitable peeling force difference between light peeling layer and medium-heavy peeling layer. , thus completing the present invention, the (A) organopolysiloxane system contains at least two alkenyl groups bonded to silicon atoms in one molecule, and as two kinds of fluorine-containing substituents bonded to silicon atoms, respectively It has at least one (a) fluoroalkyl group and (b) fluoropolyether group, and the content of (b) fluoropolyether group is 1~ relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group 99 mole%.

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

[1]

A two-sided differential peeling paper or two-sided differential peeling film, which is the first layer to be formed with a polysiloxane peeling layer having a light peeling force for a polysiloxane adhesive. The peeling layer side of a substrate film is attached to the surface of one side of the polysiloxane adhesive formed in a film or film shape, and the polysiloxane adhesive is attached to the other side surface of the polysiloxane adhesive. A hardened product of a polysiloxane composition for forming a differential release agent for a silicone adhesive and a second base film formed with a polysiloxane release layer having medium-to-heavy peeling force with respect to the aforementioned polysiloxane adhesive The peeling layer side is formed, wherein the polysiloxane composition for forming a differential release agent for the polysiloxane adhesive contains: (A) an organopolysiloxane, which contains at least two bonds in one molecule of silicon alkenyl group of atom, and have at least one content of (a) fluoroalkyl group and (b) fluoropolyether group, (b) fluoropolyether group as two kinds of fluorine-containing substituents bonded to silicon atom, respectively With respect to the total of (a) fluoroalkyl group and (b) fluoropolyether group, it is 1~99 mol%, (B) organohydrogenpolysiloxane, which has at least 3 bonds to silicon in 1 molecule Atomic hydrogen atom, (C) platinum group metal catalyst.

[2]

A two-sided differential peeling paper or two-sided differential peeling film, which is formed on the surface of one side of a base film and has a hardened product of a polysiloxane composition for forming a differential peeling agent for polysiloxane adhesives and A polysiloxane peeling layer with medium to heavy peeling force for the polysiloxane adhesive, and a polysiloxane peeling layer having a light peeling force for the polysiloxane adhesive is formed on the surface of the other side of the base film. The peeling layer is formed, wherein the polysiloxane for forming the differential peeling agent for the aforementioned polysiloxane adhesive is used. The composition contains: (A) an organopolysiloxane containing at least two alkenyl groups bonded to a silicon atom in one molecule, and each having at least two fluorine-containing substituents bonded to the silicon atom. One (a) fluoroalkyl group and (b) fluoropolyether group, the content of (b) fluoropolyether group is 1 to 99 mol relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group Ear%, (B) organohydrogen polysiloxane having at least 3 hydrogen atoms bonded to silicon atoms in 1 molecule, (C) platinum group metal-based catalyst.

[3]

A two-sided differential peeling paper or two-sided differential peeling film, which is formed on the surface of one side of a base film and has a hardened product of a polysiloxane composition for forming a differential peeling agent for polysiloxane adhesives and For the polysiloxane peeling layer with medium to heavy peeling force of the polysiloxane adhesive, a film-like or thin-film-like polysiloxane adhesive is attached to the outer surface of the polysiloxane peeling layer, and placed on the outer surface of the polysiloxane peeling layer. On the surface of the other side of the base film, a polysiloxane peeling layer having light peeling force for the polysiloxane adhesive is formed, wherein the polysiloxane adhesive for forming the differential peeling agent is used for forming the polysiloxane adhesive. The silicon-oxygen composition contains: (A) an organopolysiloxane, which contains at least two alkenyl groups bonded to silicon atoms in one molecule, and is separated as two kinds of fluorine-containing substituents bonded to silicon atoms, respectively. It has at least one (a) fluoroalkyl group and (b) fluoropolyether group, and the content of (b) fluoropolyether group is 1~ relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group 99 mol%, (B) an organohydrogen polysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule, and (C) a platinum group metal-based catalyst.

[4]

(式中，n為1~6之整數，m為1~5之整數，p為1~5之整數，q為0或1之整數，r為0~2之整數，X為氧原子或單鍵)。 As in [1]~[3], the double-sided difference release paper or double-sided difference release film, wherein in the fluorine-containing substituent of (A) component, (a) fluoroalkyl group is represented by the following formula (1) (b) fluoropolyether group is a group represented by the following formula (2),

(In the formula, 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).

[5]

Such as the two-sided differential release paper or two-sided differential film in any one of [1] to [4], wherein, the polysiloxane peeling layer with light peeling force is made of organic polysiloxane as a matrix polymer. It is composed of a cured product of an addition-curable polysiloxane composition, and the organopolysiloxane has only a fluoropolyether group as a fluorine-containing substituent in the molecule.

[6]

For example, the two-sided differential release paper or two-sided differential release film in any one of [1] to [5], which are used for engineering paper, double-sided adhesive tape, correction tape or One of the OCA tapes for touch panels.

In addition, in applications such as engineering paper, double-sided adhesive tape, correction tape, or OCA tape for touch panels, the difference in peel force (differential peel force) between the light peeling layer and the medium to heavy peeling layer is usually used as a base. The difference between the peeling force after 1 day of the width of 25mm of polyethylene terephthalate for the material film is 0.1~1.0[N/25mm], especially about 0.15~0.8[N/25mm]. The peeling force (absolute value) of the medium to heavy peeling layer is usually 0.1 to 0.8 [N/25 mm] in terms of the peeling force after 1 day with a width of 25 mm of polyethylene terephthalate as a base film, In particular, about 0.12 to 0.6 [N/25mm] is suitable from the viewpoint of workability of differential release paper or differential 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 polysiloxane adhesives, and can be attached to hardening with no pinholes or cracks and excellent releasability. Therefore, it can be effectively used as a polysiloxane adhesive for forming double-sided release paper or double-sided release film for engineering paper, double-sided adhesive tape, correction tape, OCA tape for touch panels, etc. Polysiloxane composition for forming release agent, and can also be suitably used for mold release properties for molding rubber, plastic, etc., fiber treatment agent for paper, cloth, etc., water repellent for food packaging, etc., Oil repellent, heat-resistant coating applications.

1: The first two-sided differential release paper or two-sided differential release film

2: The second two-sided differential release paper or two-sided differential release film

3: The third two-sided differential release paper or two-sided differential release film

10: The first base film

10': Second base film

20: polysiloxane adhesive layer

30: Polysiloxane peeling layer (light peeling layer)

40: Polysiloxane peeling layer (medium-heavy peeling layer)

[Fig. 1] is a schematic cross-sectional view of a double-sided release paper or a double-sided release film by the first structural example of the present invention.

[Fig. 2] It is a schematic cross-sectional view of a double-sided release paper or a double-sided release film by the second structural example of the present invention.

[FIG. 3] It is a schematic cross-sectional view of the double-sided release paper or the double-sided release film by the third structural example of the present invention.

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

As the organopolysiloxane, the content of fluorine is the ratio of (b) fluoropolyether group to the sum of (a) fluoroalkyl group and (b) fluoropolyether group, and can be set as the above molar ratio in the range of 1 to 99. The ratio is adjusted between mol%, and when the ratio is low, it is a heavy peeling, and when the ratio is high, it is a light peeling.

As the organopolysiloxane of the component (A), one represented by the following formula (A) is suitably used.

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

R ³ is a monovalent hydrocarbon group excluding unsubstituted or substituted aliphatic unsaturated groups having 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, and butyl, and cyclohexyl groups. Cycloalkyl, phenyl, tolyl and other aryl groups, benzyl, phenylethyl and other aralkyl groups, and hydroxypropyl groups in which part or all of the hydrogen atoms of these groups are substituted with hydroxyl, cyano, etc. base, cyanoethyl, etc. 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 group represented by the following formula (1), and Rf ² is a group represented by the following formula (2).

(式中，n為1~6之整數，m為1~5之整數，p為1~5之整數，q為0或1之整數，r為0~2之整數，X為氧原子或單鍵)。

(In the formula, 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.

[Formula 4] C _n F _2n+1 -CH ₂ CH ₂ - C _n F _2n+1 -CH ₂ CH ₂ CH ₂ -

(In the formula, n is an integer from 1 to 6).

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

(式中，p為1~5之整數)。

(in the formula, p is an integer from 1 to 5).

Although w, x, y, and z are integers of w≧0, x≧1, y≧1, and z≧0 as described above, they are 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 50~1,000, more preferably 100~800, still more preferably 200~500, and the kinematic viscosity at 25°C is 100 based on the value obtained by Ubbelohde viscosity ~10,000mm ² /s, more preferably 200~5,000mm ² /s, still more preferably 500~3,000mm ² /s.

The organopolysiloxane of the component (A) may be linear or branched. Specifically, what is represented by the following formula can be exemplified.

(式中，Rf¹、Rf²係表示與上述相同意思，Vi係表示乙烯基。w、x、y、z分別為w≧0、x≧1、y≧1、z≧0之整數)。

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

(式中，Rf¹、Rf²係表示與上述相同意思)。 The organopolysiloxane represented by the above formula, for example, can be obtained by having the following formulas (3) and (4)

(In the formula, Rf ¹ and Rf ² have the same meanings as described above).

(式中，v為1以上之整數，Vi係表示乙烯基)。 The indicated organocyclotrisiloxanes containing fluorine substituents are added according to the formula:

(in the formula, v is an integer of 1 or more, and Vi represents a vinyl group).

(式中，Vi係表示乙烯基)。 represented by a vinyl-terminated organosiloxane with formula (5) and/or formula (6)

(in the formula, Vi represents a vinyl group).

The indicated organocyclotrisiloxane is produced by polymerizing by a well-known equilibration reaction using an acid or a base as a catalyst in an appropriate ratio according to various purposes.

The organohydrogen polysiloxane of the (B) component has at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and the SiH group undergoes an addition reaction with the alkenyl group in the (A) component And form a hardened coating.

This organohydrogenpolysiloxane preferably has a fluorine content of 40 mass % or less in terms of compatibility with the organopolysiloxane of the component (A). In addition, this organopolysiloxane may be linear, branched, or cyclic.

Examples of organohydrogen polysiloxane-based components (B) include as represented by the following formula.

In the formula, R ⁴ is at least one group selected from the same groups as R ³ and Rf ² above, c is 0 or 1, and r and s are integers of r≧1 and s≧0, respectively. However, r is the number of hydrogen atoms bonded to silicon atoms that is 3 or more. Preferably, 3≦r≦500, 50≦s≦2,000, more preferably 10≦r≦300, 100≦s≦1,000. Furthermore, r+s is 20 to 2,500, more preferably 50 to 2,000, still more preferably 80 to 1,000, and the kinematic viscosity at 25°C is 50 to 5,000 mm ² /s in terms of Ubbelohde viscosity. More preferably, it is 100 to 3,000 mm ² /s.

Specifically, the organohydrogenpolysiloxane as the component (B) is represented by the following formula.

(式中，r、s、Rf¹、Rf²係表示與上述相同意思，t≧1之整數)。

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

The compounding quantity of the organohydrogen polysiloxane of (B) component is 0.1-20 parts with respect to 100 parts (mass parts, the same below) of (A) component, especially 0.2-10 parts is preferable. When the blending amount is less than 0.1 part and more than 20 parts, the curability of the intended polysiloxane composition may decrease or the physical properties of the cured product may decrease in any case.

In addition, the organohydrogen polysiloxane of the (B) component can also bond the hydrogen atom (SiH) to the silicon atom in the (B) component with respect to the alkenyl group in the (A) component for the same reason as described above. The molar ratio is usually 0.5 to 3.0 (mol/mol), preferably about 0.8 to 2.0 (mol/mol), and it is blended.

The platinum group metal catalyst of component (C) is used to promote As a catalyst for the addition reaction of (A) component and (B) component, a well-known one can be used as a reaction catalyst. Examples of such a platinum group metal-based catalyst include platinum-based, palladium-based, and rhodium-based catalysts, and among these, platinum-based catalysts are particularly preferred. Examples of such platinum-based catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid and various olefins or vinylsiloxanes, and the like.

The addition amount of these platinum group metal-based catalysts only needs to be the catalyst amount, but from the viewpoints of reactivity and economical efficiency in obtaining a cured film, it is preferable to use platinum with respect to the component (A) The mass conversion meter of the group metal is set in the range of 1 to 1,000 ppm.

Although the composition of the present invention is obtained by blending the above-mentioned specific amounts of components (A) to (C), in addition to the above-mentioned components, other optional components can also be added, for example, in the control of platinum group metal-based catalysts Various organic nitrogen compounds, organic phosphorus compounds, organic silicon compounds, acetylene compounds, oxime compounds and other activity control agents for the purpose of catalytic activity, 3-methyl-1-butyne- Acetylene compounds such as 3-alcohols and their silyl compounds, silicon compounds such as divinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, etc.

In the case of blending an activity control agent, the blending amount thereof is preferably 0.05 to 3 parts with respect to 100 parts of the (A) component. If it is less than 0.05 part, the intended polysiloxane composition may be gelled, and if it exceeds 3 parts, curing of the polysiloxane composition may be inhibited. In addition, 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.

When preparing the polysiloxane composition of the present invention, it is preferable to add the component (C) after uniformly mixing the components (A) and (B) in advance. use together.

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

The amount of the fluorine-modified solvent to be used is preferably the diluted polysiloxane from the viewpoints of workability when applying the dissolved polysiloxane composition, ease of control of the amount of application, and the like. The kinematic viscosity in terms of Ubbelohde viscosity of the silicon-oxygen composition is an amount of 100 mm ² /s or less at 25° C., and specifically, it is preferably 100 to 20,000 parts with respect to 100 parts of (A) component.

The polysiloxane composition of the present invention is coated on a base material and hardened to form a releasable hardened film on the surface of the base material, which can be used as a release paper. In this case, examples of the base material include plastic films or sheets, cellophane, etc. obtained from synthetic resins such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, and polyimide. Kraft paper, clay coated paper and other paper substrates, polyethylene laminated top quality paper, polyethylene laminated cattle Laminated paper substrates such as vellum, metal foils such as aluminum foil, etc.

As a method of coating the polysiloxane composition on these substrates, 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 cured film of the polysiloxane composition of the present invention on the substrate, the substrate coated with the polysiloxane composition can be heated at a temperature of 80 to 250° C. for 2 to 60 seconds, so that the The polysiloxane composition is cured, and a peelable polysiloxane cured film 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 differential release agent for polysiloxane adhesives. Although there is no particular limitation, it can form two sides as shown in Figs. 1 to 3. Differential release paper or film.

The two-sided differential release paper or film shown in FIG. 1 is laminated on the first base film 10 to form a polysiloxane release layer 30 having a light peeling force for the film-like or film-like polysiloxane adhesive layer 20 . The polysilicon adhesive layer 20 is laminated and attached on the polysilicon release layer 30 , and a polysilicon having medium-to-heavy peeling force for the polysilicon adhesive layer 20 is laminated on the second base film 10 ′. The polysiloxane peeling layer 40 side of the oxygen peeling layer 40 is attached to the aforementioned polysiloxane adhesive layer 20 .

In order to actually produce the two-sided difference release paper or film shown in FIG. 1, for example, the polysiloxane release layer 30 can be integrally formed on the first base by sandwiching the film-like or film-like polysiloxane adhesive layer 20. 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 formed by integrating the polysiloxane release layer 40 on the second base film 10', the polysilicon The oxygen peeling layer 30 and the polysiloxane adhesive layer 20 exhibit light peeling force, and the polysiloxane peeling layer 40 and the polysiloxane adhesive layer 20 exhibit moderate to heavy peeling force.

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

In order to actually produce the two-sided difference release paper or film shown in FIG. 2, for example, the release paper 10 side of the release paper in which the polysiloxane release layer 30 is integrally formed on one side of the base film 10 can be further The polysiloxane peeling layer 40 is integrally formed, and each surface has a light peeling force when contacting and laminating with an external polysiloxane adhesive layer (for example, a polysiloxane adhesive sheet with adhesiveness on both sides, etc.) The two sides of the polysiloxane release layer 30 and the polysiloxane release layer 40 exhibiting medium to heavy release force are different from the two sides of the release paper or film.

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

In order to actually produce the double-sided difference release paper or film of Fig. 3, for example, the polysilicon release layer 40 side of the double-sided difference release paper or film of Fig. 2 can be further integrally formed in advance. A film-like or thin-film-like polysiloxane adhesive layer 20 is produced. In this case, on The polysiloxane peeling layer 40 and the polysiloxane adhesive layer 20 can exhibit moderate to heavy peeling force. In addition, for example, like a double-sided adhesive tape, the double-sided differential release paper or film shown in FIG. It is stored in a concentric or swirling shape, and a light peeling force is exhibited between the polysilicon release layer 30 and the polysiloxane adhesive layer 20 .

Here, in the two-sided differential release paper or film, the polysiloxane release layer 30 with light peeling force is preferably made of an addition-hardening polysiloxane composition containing organopolysiloxane as a matrix polymer. When the cured product is formed, the organopolysiloxane has only a fluoropolyether group (b) as a fluorine-containing substituent without containing 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, the molecule does not contain Rf ¹ in the molecule). The organopolysiloxanes shown as fluoroalkyl groups (a) are preferred. In this case, except for x=0, Rf ² , R ² , R ³ , w, y, and z are preferably the same as the above, and the value of w+y+z and even the viscosity at 25°C are also the same. By. In addition, the organohydrogen polysiloxane and the platinum group metal-based catalyst can also be used the same as those described above.

In addition, as the polysiloxane adhesive layer 20, for example, an addition-curable polysiloxane adhesive containing a resin-like (three-dimensional network structure) organopolysiloxane or a peroxide-curable polysiloxane can be suitably used Adhesives etc.

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

[Example]

Hereinafter, the present invention will be specifically described by showing reference examples, examples and comparative examples, but the present invention is not limited to the following examples. In addition, in the following examples, a part shows a mass part, and % shows a mass %.

(Examples 1 to 4)

As shown in Table 1, the vinyl group-containing organopolysiloxane (III) having fluorine substituents represented by the following formulas (I) and (II) and the organohydrogen represented by the following formula (IV) were combined 4 parts of a composition prepared by mixing polysiloxane so that the ratio of SiH group/SiCH=CH ₂ group may be 2.5, diluted with 96 parts of hydrofluoroether Novec 7300 (manufactured by 3M Japan), and chloroplatinic acid was added thereto. A treatment liquid was prepared with 0.05 part of vinylsiloxane zirconium salt (platinum concentration: 2%).

Organopolysiloxane containing vinyl

(式中，Rf²係與前述相同)。

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

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

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

(a) Peeling force

A polysiloxane-based adhesive tape with a width of 25mm (kapton No.650S # 25, manufactured by (stock) Teraoka Manufacturing Co., Ltd.) was attached to the obtained release film, and under a load of 25g/cm ² , at 70 ° C, after 1 day ~ The 21st fit makes it aged. Using a tensile tester, the adhesive tape was peeled off 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 adhesive force

The adhesive tape after the peeling measurement in (a) was attached to the SUS plate, pressed with a 2 kg tape roller back and forth once, and after standing for 30 minutes, the adhesive tape was peeled off 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 the vinyl group-containing organopolysiloxane having a fluorine substituent, a vinyl group-containing organopolysiloxane obtained by blending V-1 (Reference Example 1) and V-6 (blank) at a mass ratio of 1:1 was used. Organopolysiloxane mixture, except that the treatment liquid was adjusted in the same manner as in the above-mentioned example, a release film was prepared in the same manner, and the peeling force was measured in the same manner, but the error of each measurement sample was very large, A release film having a stable release force could not be obtained.

[Industrial Availability]

According to the polysiloxane composition of the present invention, the peeling force of the cured product can be stably controlled in the range of medium to heavy peeling force for the polysiloxane adhesive, and it can be attached to a mold having no pinholes or cracks and excellent releasability. Since it is a hardened film, it is particularly suitable as a disparity release agent for polysiloxane adhesives to form disparity release paper or disparity release film for construction paper, double-sided adhesive tape, correction tape, OCA tape for touch panels, etc. polysiloxane for forming The composition can also be suitably used for mold release properties for molding rubber, plastic, etc., fiber treatment agents for paper, cloth, etc., water-repellent, oil-repellent, and heat-resistant coating for food packaging, etc. Therefore, its industrial value is great.

1: The first two-sided differential release paper or two-sided differential release film

10: The first base film

10': Second base film

20: polysiloxane adhesive layer

30: Polysiloxane peeling layer (light peeling layer)

40: Polysiloxane peeling layer (medium-heavy peeling layer)

Claims (12)

A two-sided differential release paper, which attaches the release layer side of a first base film film with a polysiloxane release layer having a light release force to a polysiloxane adhesive formed in a film or film shape. On the surface of one side of the aforementioned polysiloxane adhesive, and on the other side surface of the polysiloxane adhesive, a polysiloxane composition for forming a differential release agent for polysiloxane adhesive is attached. The cured product is formed on the peeling layer side of the second substrate film of the polysiloxane peeling layer with medium to heavy peeling force for the polysiloxane adhesive, wherein the differential peeling agent for the polysiloxane adhesive is formed The polysiloxane composition contains: (A) 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, and the content of (b) fluoropolyether group relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group is 1~99 mol%, (B) organohydrogen polysiloxane, which has at least 3 hydrogen atoms bonded to silicon atoms in 1 molecule, (C) platinum group metal-based catalyst. A two-sided differential release paper, which is formed on the surface of one side of a base film and has a hardened product of a polysiloxane composition for forming a differential release agent for polysiloxane adhesives and is suitable for polysiloxane adhesives. A polysiloxane peeling layer with medium to heavy peeling force is formed on the surface of the other side of the base film. It is formed from a polysiloxane peeling layer with a light peeling force for the polysiloxane adhesive, wherein the polysiloxane composition for forming a differential peeling agent for the polysiloxane adhesive contains: (A) organopolysiloxane , which contains at least two alkenyl groups bonded to silicon atoms in one molecule, and has at least one (a) fluoroalkyl group and (b) as two types of fluorine-containing substituents bonded to silicon atoms, respectively Fluoropolyether group, the content of (b) fluoropolyether group is 1~99 mol% relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group, (B) organohydrogenpolysiloxane , which has at least 3 hydrogen atoms bonded to silicon atoms in 1 molecule, (C) platinum group metal catalyst. A two-sided differential release paper, which is formed on the surface of one side of a base film and has a hardened product of a polysiloxane composition for forming a differential release agent for polysiloxane adhesives and is suitable for polysiloxane adhesives. The polysiloxane peeling layer with medium-to-heavy peeling force is further attached to the outer surface of the polysiloxane peeling layer, and the aforementioned polysiloxane adhesive formed in the form of a film or a film is attached, and the substrate film is attached. On the surface of the other side, a polysiloxane peeling layer having a light peeling force for the polysiloxane adhesive is formed, wherein the polysiloxane composition for forming a differential peeling agent for the polysiloxane adhesive contains : (A) Organopolysiloxanes containing at least two alkenyl groups bonded to silicon atoms in one molecule, and as two types of fluorine-containing alkene groups bonded to silicon atoms substituted group and have at least one (a) fluoroalkyl group and (b) fluoropolyether group, respectively, and the content of (b) fluoropolyether group is relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group , is 1~99 mol%, (B) organohydrogen polysiloxane, which has at least 3 hydrogen atoms bonded to silicon atoms in 1 molecule, (C) platinum group metal catalyst. The double-sided difference release paper according to any one of claims 1 to 3, wherein in the fluorine-containing substituent of the component (A), (a) the fluoroalkyl group is a group represented by the following formula (1), ( b) The fluoropolyether group is a group represented by the following formula (2), C _n F _2n+1 -(CH ₂ ) _m - (1)

(In the formula, 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). The two-sided differential release paper according to any one of claims 1 to 3, wherein the polysiloxane release layer with light peeling force is an addition-hardening polysiloxane containing organopolysiloxane as a matrix polymer In the case of the cured product of the composition, the organopolysiloxane has only a fluoropolyether group as a fluorine-containing substituent in the molecule. The two-sided difference release paper according to any one of claims 1 to 3 is used in any one of engineering paper, double-sided adhesive tape, correction tape, or OCA tape for touch panels. A two-sided differential peeling film, which adheres the peeling layer side of a first substrate film with a polysiloxane peeling layer having a light peeling force to a polysiloxane adhesive formed in a film or film shape. On the surface of one side of the aforementioned polysiloxane adhesive, and on the other side surface of the polysiloxane adhesive, a polysiloxane composition for forming a differential release agent for polysiloxane adhesive is attached. The cured product is formed on the peeling layer side of the second substrate film of the polysiloxane peeling layer with medium to heavy peeling force for the polysiloxane adhesive, wherein the differential peeling agent for the polysiloxane adhesive is formed The polysiloxane composition contains: (A) 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, and the content of (b) fluoropolyether group relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group is 1~99 mol%, (B) organohydrogen polysiloxane, which has at least 3 hydrogen atoms bonded to silicon atoms in one molecule, (C) platinum group metal-based catalyst. A two-sided differential peeling film, which is formed on the surface of one side of a base film with polysiloxane for forming a differential peeling agent for polysiloxane adhesives The hardened product of the composition and a polysiloxane peeling layer with moderate to heavy peeling force for the polysiloxane adhesive is formed on the surface of the other side of the base film with light weight for the polysiloxane adhesive. It is formed of a polysiloxane peeling layer with a peeling force, wherein the polysiloxane composition for forming a differential peeling agent for the polysiloxane adhesive contains: (A) an organic polysiloxane, which contains at least 2 in one molecule. one alkenyl group bonded to a silicon atom, and each of the two fluorine-containing substituents bonded to the silicon atom has at least one of (a) a fluoroalkyl group, (b) a fluoropolyether group, and (b) a fluorine group The content of polyether groups is 1 to 99 mol % relative to the sum of (a) fluoroalkyl groups and (b) fluoropolyether groups, and (B) organohydrogen polysiloxanes have at least 3 in 1 molecule. A hydrogen atom bonded to a silicon atom, (C) a platinum group metal-based catalyst. A two-sided differential peeling film, which is formed on the surface of one side of a base film and has a hardened product of a polysiloxane composition for forming a differential peeling agent for polysiloxane adhesives and is suitable for polysiloxane adhesives. The polysiloxane peeling layer with medium-to-heavy peeling force is further attached to the outer surface of the polysiloxane peeling layer, and the aforementioned polysiloxane adhesive formed in the form of a film or a film is attached, and the substrate film is attached. On the surface of the other side, a polysiloxane peeling layer having a light peeling force for the polysiloxane adhesive is formed, wherein the polysiloxane composition for forming a differential peeling agent for the polysiloxane adhesive contains : (A) Organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule, and each having at least one (a) as two types of fluorine-containing substituents bonded to silicon atoms ) fluoroalkyl group and (b) fluoropolyether group, the content of (b) fluoropolyether group is 1 to 99 mol % relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group, ( B) organohydrogen polysiloxane having at least 3 hydrogen atoms bonded to silicon atoms in one molecule, and (C) platinum group metal-based catalyst. The double-sided difference release film according to any one of claims 7 to 9, wherein in the fluorine-containing substituent of the component (A), (a) the fluoroalkyl group is a group represented by the following formula (1), ( b) The fluoropolyether group is a group represented by the following formula (2), C _n F _2n+1 -(CH ₂ ) _m - (1)

(In the formula, 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). The two-sided differential peeling film according to any one of claims 7 to 9, wherein the polysiloxane peeling layer with light peeling force is an addition-hardening polysiloxane containing organopolysiloxane as a matrix polymer It is composed of a hardened product of the composition, and the organopolysiloxane has only a fluoropolyether group in the molecule as a fluorine-containing Substituents. The two-sided differential release film according to any one of claims 7 to 9 is used in any one of engineering paper, double-sided adhesive tape, correction tape, or OCA tape for touch panels.

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