JP6481646B2 - Double-sided differential release paper or double-sided differential release film - Google Patents

Description

  The present invention relates to a silicone composition for forming a differential release agent for a silicone pressure-sensitive adhesive, and in particular, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent as a base polymer. Compared to the silicone composition for release agents that expresses light release force, it can express medium to heavy release force, so it expresses the above light release force on each surface of film-like or thin-film silicone adhesive Silicone composition capable of forming so-called differential release force that can form release layers (medium to heavy release layers) having different release forces with respect to the cured product layer (light release layer) of the release agent silicone composition , And cured layers (light release layer and medium-heavy release layer) of silicone compositions having different release forces in combination with each other to form a film or thin film silicone Duplex different differential release paper formed by applying on each surface of Chakuzai or to both surfaces different differential release film.

  Conventionally, for the purpose of preventing adhesion or fixation between a base film such as paper or plastic film (eg, polyethylene film, polypropylene film, polyethylene terephthalate (PET) film) and a pressure-sensitive adhesive substance, A cured film of a silicone composition is formed on the surface to impart releasability, and this is generally referred to as release paper.

  Among the above pressure-sensitive adhesive materials, silicone adhesives based on resin-like (three-dimensional network structure) organopolysiloxane are excellent in heat resistance, cold resistance, chemical resistance, electrical insulation, low toxicity, etc. Therefore, it is used for a wide range of applications. Since the silicone adhesive has a very strong adhesive strength compared to general non-silicone adhesives, in order for the adhesive tape and adhesive label to which it is applied to be easily peeled from the substrate, It is necessary to make the cured silicone film formed on the substrate extremely excellent in releasability.

As a silicone composition that gives a cured silicone film excellent in releasability, an organopolysiloxane composition having a fluorine-containing substituent represented by C _n F _{2n + 1} CH ₂ CH ₂ — (n is an integer of 1 or more) represented by (n is an integer of from 1 to 5) - ones (KOKOKU 5-7434 discloses), formula [CF (CF ₃₎ CF ₂ O] _{n CF (CF 3) CF 2} OCH 2 CH 2 CH 2 An organopolysiloxane composition having a fluorine-containing substituent (Japanese Patent Publication No. 4-76391) has been proposed.

  However, these silicone compositions have a light release force relative to the silicone-based pressure-sensitive adhesive. However, the silicone composition is used as a release layer for process paper or double-sided pressure-sensitive adhesive tape, touch panel OCA (Optical Clear Adhesive) tape. In order to apply different peel strength to each surface of the film-like or thin-film silicone adhesive, a release layer with a light peel strength is provided on one surface, The other surface requires a release layer having a medium to heavy release force. However, when a cured product of a silicone composition for release paper based on an organopolysiloxane having a fluorine-containing substituent as described above is to be applied as the release layer, a general non-fluorine release paper is used. Since there is no peeling force control agent that is often used in silicone compositions for coatings, there is a problem that it cannot be used for such applications. In addition, when applying different peel force in applications such as process paper, double-sided adhesive tape, touch panel OCA tape, etc., the difference in peel force between the light release layer and the medium to heavy release layer is also appropriate depending on the application. Difference in peeling force was required. Furthermore, even when an organopolysiloxane having a perfluoroalkyl group as described above as a fluorine-containing substituent and an organopolysiloxane having a perfluoropolyether group are blended and applied to a composition for a release agent, There was a problem that a stable peeling force according to the blend ratio could not be obtained due to the lack of compatibility.

Japanese Patent Publication No. 5-7434 Japanese Patent Publication No. 4-76391

  The present invention has been made in view of the above circumstances, and a differential release for a silicone pressure-sensitive adhesive that can stably give a cured film capable of controlling the peel strength within a range of medium to heavy peel strength to the silicone pressure-sensitive adhesive. Double-sided difference formed by forming a silicone composition for agent formation, and a cured layer (medium to heavy release layer) and a light release layer of the composition on each surface of a film-like or thin-film silicone adhesive The object is to provide a release paper or a double-sided differential release film.

  As a result of intensive studies to achieve the above object, the present inventor has found that (A) one molecule contains at least two alkenyl groups bonded to a silicon atom and contains two types of bonds bonded to a silicon atom. (B) fluoropolyether group having at least one (a) fluoroalkyl group and (b) fluoropolyether group as the fluorine substituent, and (b) the fluoropolyether group relative to the total of (a) fluoroalkyl group and (b) fluoropolyether group In the addition-curable silicone composition based on an organopolysiloxane having a content of 1 to 99 mol% as a base polymer, by adjusting the ratio (a) / (b), It is possible to obtain a silicone composition that provides a cured film capable of stably controlling the peel force of the cured product within the range of the heavy peel force. In addition, by applying the composition in combination with a silicone release layer having a light release force to the silicone adhesive, the light release layer and the middle to heavy release layer have a suitable release force difference. The inventors have found that a double-sided differential release paper or a double-sided differential release film can be obtained, and have made the present invention.

（式中、ｎは１〜６の整数、ｍは１〜５の整数、ｐは１〜５の整数、ｑは０又は１の整数、ｒは０〜２の整数、Ｘは酸素原子又は単結合である。）
［５］
工程紙、両面粘着テープ、修正テープ又はタッチパネル用ＯＣＡテープのいずれかに用いられるものである［１］〜［４］のいずれかに記載の両面異差剥離紙又は両面異差剥離フィルム。
なお、工程紙、両面粘着テープ、修正テープ又はタッチパネル用ＯＣＡテープ等の用途において、軽剥離層と中〜重剥離層との剥離力の差（異差剥離力）については、通常、基材フィルムとしてポリエチレンテレフタレートの幅２５ｍｍにおける１日後の剥離力の差で、０．１〜１．０［Ｎ／２５ｍｍ］、特には、０．１５〜０．８［Ｎ／２５ｍｍ］程度が好適であり、また、中〜重剥離層の剥離力（絶対値）については、通常、基材フィルムとしてポリエチレンテレフタレートの幅２５ｍｍにおける１日後の剥離力で、０．１〜０．８［Ｎ／２５ｍｍ］、特には０．１２〜０．６［Ｎ／２５ｍｍ］程度であることが、異差剥離紙又は異差剥離シートの作業性等の点から好適である。 Accordingly, the present invention provides the following two aspects different differences release paper or double-sided cross differences release film.
[ 1 ]
Affixing the release layer side of the first base film having a silicone release layer having a light release force to the silicone adhesive on one surface of the silicone adhesive formed into a film or thin film, On the other surface of the silicone pressure-sensitive adhesive , a silicone release layer that is a cured product of the silicone composition for forming a differential release agent for the silicone pressure-sensitive adhesive and has a medium to heavy peeling force with respect to the silicone pressure-sensitive adhesive is formed. In the double-sided difference release paper or the double-sided difference release film formed by pasting the release layer side of the second base film ,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film .
[ 2 ]
On one surface of the base film, a silicone release layer that is a cured product of a silicone composition for forming a differential release agent for a silicone adhesive and has a medium to heavy release force with respect to the silicone adhesive, On the other surface of the base film, a double-sided differential release paper or double-sided differential release film formed by forming a silicone release layer having a light release force against the silicone adhesive ,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film .
[ 3 ]
On one surface of the base film, a silicone release layer that is a cured product of a silicone composition for forming a differential release agent for a silicone adhesive and has a medium to heavy release force with respect to the silicone adhesive, Furthermore, a silicone pressure-sensitive adhesive formed in a film or thin film shape is stuck on the outer surface of the silicone release layer, and on the other hand, a light release force against the silicone pressure-sensitive adhesive on the other surface of the base film. by forming a silicone release layer having, in both different differences release paper or both different differential release film,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film .
[ 4 ]
In the fluorine-containing substituent of the component (A), (a) the fluoroalkyl group is a group represented by the following formula (1), and (b) the fluoropolyether group is a group represented by the following formula (2) [ 1] The double-sided difference release paper or the double-sided difference release film according to any one of [3] .

(In the formula, n is an integer of 1 to 6, m is an integer of 1 to 5, p is an integer of 1 to 5, q is an integer of 0 or 1, r is an integer of 0 to 2, and X is an oxygen atom or single. It is a bond.)
[ 5 ]
The double-sided differential release paper or double-sided differential release film according to any one of [ 1 ] to [ 4 ], which is used for any one of process paper, double-sided adhesive tape, correction tape, or touch panel OCA tape.
In applications such as process paper, double-sided adhesive tape, correction tape or touch panel OCA tape, the difference in peel force between the light release layer and the medium to heavy release layer (differential peel force) is usually a substrate film. As a difference in peel force after 1 day at a width of 25 mm of polyethylene terephthalate, 0.1 to 1.0 [N / 25 mm], particularly 0.15 to 0.8 [N / 25 mm] is preferable, The peel strength (absolute value) of the medium to heavy peel layer is usually 0.1 to 0.8 [N / 25 mm], especially the peel force after 1 day at a width of 25 mm of polyethylene terephthalate as the base film. Is preferably about 0.12 to 0.6 [N / 25 mm] from the viewpoint of workability of the different release paper or the different release sheet.

  The silicone composition of the present invention is capable of stably controlling the peel strength of a cured product in a range of medium to heavy peel strength with respect to the silicone adhesive, and has releasability without pinholes or repellency. Silicone for forming double-sided differential release papers and double-sided differential release films such as process papers, double-sided adhesive tapes, correction tapes, touch panel OCA tapes, etc. Effectively used as a silicone composition for forming differential release agents for adhesives. Also, mold releasability for molding rubber, plastic, etc., fiber treatment agents such as paper and cloth, and food packaging. It can be suitably used for water repellents, oil repellents, and heat-resistant coatings.

It is a schematic sectional drawing of the double-sided difference release paper or double-sided difference release film by the 1st structural example of this invention. It is a schematic sectional drawing of the double-sided difference release paper or double-sided difference release film by the 2nd structural example of this invention. It is a schematic sectional drawing of the double-sided difference release paper or double-sided difference release film by the 3rd structural example of this invention.

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

  The content of fluorine as the organopolysiloxane is adjusted between 1 and 99 mol% as the above-mentioned molar ratio of (b) fluoroether group to the total of (a) fluoroalkyl group and (b) fluoropolyether group. It is possible, and when the ratio is low, the heavy peeling occurs, and when the ratio is high, the light peeling occurs.

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

Here, R ² is an alkenyl group having 2 to 10 carbon atoms, and specific examples 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, specifically an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, cyclohexyl A cycloalkyl group such as a group, an aryl group such as a phenyl group and a tolyl group, an aralkyl group such as a benzyl group and a phenylethyl group, and a hydroxy group, a cyano group or the like in which part or all of the hydrogen atoms of these groups are substituted A propyl group, a cyanoethyl group, etc. are mentioned. 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.

（式中、ｎは１〜６の整数、ｍは１〜５の整数、ｐは１〜５の整数、ｑは０又は１の整数、ｒは０〜２の整数、Ｘは酸素原子又は単結合である。） Rf ¹ is preferably a group represented by the following formula (1) and Rf ² is a group represented by the following formula (2).

(In the formula, n is an integer of 1 to 6, m is an integer of 1 to 5, p is an integer of 1 to 5, q is an integer of 0 or 1, r is an integer of 0 to 2, and X is an oxygen atom or single. It is a bond.)

（式中、ｎは１〜６の整数である。） Specific examples of the formula (1) include the following examples.

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

（式中、ｐは１〜５の整数である。） Specific examples of the formula (2) include the following examples.

(In the formula, p is an integer of 1 to 5.)

As described above, w, x, y, and z are integers of w ≧ 0, x ≧ 1, y ≧ 1, and z ≧ 0, but preferably 0 ≦ w ≦ 5, 1 ≦ x ≦ 500, 1 ≦ y ≦ 500, 0 ≦ z ≦ 1,500, and more preferably 1 ≦ w ≦ 3, 10 ≦ x ≦ 400, 10 ≦ y ≦ 400, and 0 ≦ z ≦ 800. In this case, w + x + y + z is 50 to 1,000, more preferably 100 to 800, still more preferably 200 to 500, and the kinematic viscosity at 25 ° C. is 100 to 10,000 mm ² / s as measured by an Ubbelohde viscometer. More preferably, it is 200-5,000 mm < ² > / s, More preferably, it is preferable that it is 500-3,000 mm < ² > / s.
The organopolysiloxane of component (A) may be either linear or branched. Specifically, what is represented by the following formula is illustrated.

（式中、Ｒｆ¹、Ｒｆ²は上記と同様の意味を示し、Ｖｉはビニル基を表す。ｗ、ｘ、ｙ、ｚはそれぞれｗ≧０、ｘ≧１、ｙ≧１、ｚ≧０の整数である。）

(In the formula, Rf ¹ and Rf ² have the same meaning as described above, and Vi represents a vinyl group. W, x, y, and z are w ≧ 0, x ≧ 1, y ≧ 1, and z ≧ 0, respectively. (It is an integer.)

（式中、Ｒｆ¹、Ｒｆ²は上記と同様の意味を示す。）
で表される含フッ素置換基を有するオルガノシクロトリシロキサン及び式：

（式中、ｖは１以上の整数、Ｖｉはビニル基を示す。）
で表される末端ビニル基停止オルガノシロキサンを必要に応じて加え、式（５）及び又は式（６）

（式中、Ｖｉはビニル基を示す。）
で表されるオルガノシクロトリシロキサンとともに、それぞれ目的に応じた適宜の割合で、酸又はアルカリを触媒として用いる公知の平衡化反応によって重合させることにより製造することができる。 Examples of the organopolysiloxane represented by the above formula include the following formulas (3) and (4):

(In the formula, Rf ¹ and Rf ² have the same meaning as described above.)
An organocyclotrisiloxane having a fluorine-containing substituent represented by the formula:

(In the formula, v represents an integer of 1 or more, and Vi represents a vinyl group.)
A terminal vinyl group-terminated organosiloxane represented by formula (5) and / or formula (6) is added as necessary.

(In the formula, Vi represents a vinyl group.)
In addition to the organocyclotrisiloxane represented by the formula (1), it can be produced by polymerizing by a known equilibration reaction using an acid or alkali as a catalyst at an appropriate ratio depending on the purpose.

  The organohydrogenpolysiloxane of component (B) has at least three hydrogen atoms (SiH groups) bonded to silicon atoms in one molecule, and this SiH group and the alkenyl group in component (A) are added. A cured film is formed by reaction.

  The organohydrogenpolysiloxane preferably has a fluorine content of 40% by mass or less from the viewpoint of compatibility with the organopolysiloxane of component (A). The organopolysiloxane may be linear, branched or cyclic.

  Examples of the component (B) organohydrogenpolysiloxane include those 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 , c is 0 or 1, and r and s are integers of r ≧ 1 and s ≧ 0, respectively. However, r is a number in which the number of hydrogen atoms bonded to the silicon atom is 3 or more. Preferably, 3 ≦ r ≦ 500, 50 ≦ s ≦ 2,000, more preferably 10 ≦ r ≦ 300, and 100 ≦ s ≦ 1,000. Further, 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 as} measured by an Ubbelohde viscometer. / S, more preferably 100 to 3,000 mm ² / s.

  Specific examples of the organohydrogenpolysiloxane of the component (B) include those represented by the following formula.

（式中、ｒ、ｓ、Ｒｆ¹、Ｒｆ²は上記と同様の意味を示し、ｔ≧１の整数である。）

(In the formula, r, s, Rf ¹ and Rf ² have the same meaning as described above, and are integers of t ≧ 1.)

The blending amount of the (B) component organohydrogenpolysiloxane is preferably 0.1 to 20 parts, more preferably 0.2 to 10 parts, relative to 100 parts (parts by mass) of the component (A). When the compounding amount is less than 0.1 part and exceeds 20 parts, the curability of the intended silicone composition may be lowered, or the physical properties of the cured product may be lowered.
In addition, the organohydrogenpolysiloxane of the component (B) has a molar ratio of silicon atom-bonded hydrogen atoms (SiH groups) in the component (B) to alkenyl groups in the component (A) for the same reason as described above. Usually, it can also be added in an amount of about 0.5 to 3.0 (mol / mol), preferably about 0.8 to 2.0 (mol / mol).

  The (C) component platinum group metal catalyst is a catalyst for promoting the addition reaction between the (A) component and the (B) component, and a known catalyst can be used. Examples of such platinum group metal catalysts include platinum-based, palladium-based, and rhodium-based catalysts, and among these, platinum-based catalysts are particularly preferable. Examples of such a platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, and a complex of chloroplatinic acid and various olefins or vinyl siloxane.

  The addition amount of these platinum group metal catalysts may be a catalyst amount, but from the viewpoint of reactivity and economy when obtaining a cured coating, it is 1-1 in terms of mass of platinum group metal with respect to component (A). , Preferably in the range of 1,000 ppm.

  The composition of the present invention can be obtained by blending predetermined amounts of the above components (A) to (C). In addition to the above components, other optional components such as the catalytic activity of platinum group metal catalysts. In order to control the activity, activity control agents such as various organic nitrogen compounds, organophosphorus compounds, organosilicon compounds, acetylene compounds, oxime compounds can be added. Among the activity control agents, 3-methyl-1-butyne- Acetylene compounds such as 3-ol and silylated products thereof, and silicon compounds such as divinyltetramethyldisiloxane and tetravinyltetramethylcyclotetrasiloxane are preferably used.

  When mix | blending an activity control agent, it is preferable that the compounding quantity shall be 0.05-3 parts with respect to 100 parts of (A) component. If it is less than 0.05 part, the target silicone composition may gel, and if it exceeds 3 part, curing of the silicone composition may be inhibited. Moreover, the addition amount of another arbitrary component can be made into a normal amount in the range which does not prevent the effect of this invention.

  In preparing the silicone composition of the present invention, it is preferable to add the components (A) and (B) uniformly in advance, and then add the component (C). You may use the above together.

  When the thus prepared silicone composition is applied to a substrate, the composition may be diluted with a suitable solvent to facilitate the application by uniformly diluting the composition. Examples of such solvents include fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, and perfluoro (2-butyltetrahydrofuran). And fluorine-modified alkylamine solvents such as perfluorotributylamine and perfluorotripentylamine. In particular, fluorine-modified solvents such as m-xylene hexafluoride and ethyl perfluorobutyl ether are preferable in terms of solubility and wettability.

The amount of fluorine-modified solvent used is determined by the Ubbelohde viscometer of the diluted silicone composition from the viewpoints of workability when applying a dissolved silicone composition using the solvent and ease of control of the coating amount. It is preferable to use an amount that gives a viscosity of 100 mm ² / s or less at 25 ° C., and specifically 100 to 20,000 parts with respect to 100 parts of component (A).

  What applied the silicone composition of this invention to the base material, made it harden | cure, and formed the peelable cured film on the base-material surface can be used as a release paper. In this case, the base material is a paper base material such as a plastic film or sheet obtained from a synthetic resin such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, or polyimide, glassine paper, kraft paper, or clay coated paper. And laminated paper base materials such as polyethylene laminated fine paper and polyethylene laminated kraft paper, and metal foils such as aluminum foil.

  As a method for applying the silicone composition to these substrates, known methods such as roll coating, gravure coating, wire doctor coating, air knife coating and dipping coating can be used.

  In order to form a cured film of the silicone composition of the present invention on a substrate, the silicone composition is cured by heating the substrate coated with the silicone composition at a temperature of 80 to 250 ° C. for 2 to 60 seconds, A peelable silicone cured film can be formed on the substrate surface.

The silicone composition of the present invention is effectively used as a release agent, particularly a differential release agent for a silicone adhesive, and is not particularly limited, but the double-sided differential release paper or film shown in FIGS. Can be formed.
The double-sided difference release paper or film of FIG. 1 is formed by laminating and forming a silicone release layer 30 having a light release force on a film-like or thin-film silicone adhesive layer 20 on a first base film 10, The silicone pressure-sensitive adhesive layer 20 is laminated and pasted on the silicone release layer 30, and the silicone release layer 40 having a medium to heavy release force with respect to the silicone pressure-sensitive adhesive layer 20 is laminated on the second base film 10 ′. The silicone release layer 40 side thus adhered is pasted on the silicone pressure-sensitive adhesive layer 20.
To actually produce the double-sided difference release paper or film of FIG. 1, for example, the release layer 30 side of the release paper in which the silicone release layer 30 is integrally formed on the first base film 10, and the second A silicone adhesive layer 20 in the form of a film or thin film is sandwiched between the release layer 40 side of the release paper in which the silicone release layer 40 is integrally formed on the base film 10 ', and the silicone release layer 30 and the silicone adhesive It can be produced by expressing a light release force between the adhesive layer 20 and an intermediate to heavy release force between the silicone release layer 40 and the silicone pressure-sensitive adhesive layer 20.

The double-sided difference release paper or film of FIG. 2 is formed by laminating the medium to heavy release silicone release layer 40 on one surface of the substrate film 10 and the light release silicone release layer 30 on the other surface of the substrate film 10. Are laminated.
To actually produce the double-sided difference release paper or film of FIG. 2, for example, the silicone release layer is further formed on the base film 10 side of the release paper in which the silicone release layer 30 is integrally formed on one side of the base film 10. By forming and integrating 40, the silicone release layer 30 that exhibits a light release force when brought into contact with and bonded to an external silicone adhesive layer (for example, a silicone adhesive sheet having tackiness on both sides) and the medium- It is possible to produce a double-sided difference release paper or film having a silicone release layer 40 expressing a heavy release force on each surface.

The double-sided difference release paper or film of FIG. 3 is formed by laminating and forming the above-mentioned medium to heavy release silicone release layer 40 on one surface of the substrate film 10, and a film- or thin-film silicone adhesive on the silicone release layer 40. The layer 20 is affixed, and the light release silicone release layer 30 is formed on the other surface of the base film.
To actually produce the double-sided difference release paper or film of FIG. 3, for example, a film or thin film is further formed on the side of the silicone release layer 40 of the double-sided difference release paper or film of FIG. The silicone pressure-sensitive adhesive layer 20 can be formed and integrated. In this case, a medium to heavy peeling force can be developed between the silicone release layer 40 and the silicone pressure-sensitive adhesive layer 20. For example, like the double-sided adhesive tape, the double-sided difference release paper or film of FIG. 3 is wound concentrically or spirally so that the silicone release layer 30 faces the outer surface of the silicone adhesive layer 20. By being stored, a light release force can be developed between the silicone release layer 30 and the silicone pressure-sensitive adhesive layer 20.

Here, in the double-sided difference release paper or film, the silicone release layer 30 having a light release force does not contain a fluoroalkyl group (a) as a fluorine-containing substituent in the molecule, and the fluoropolyether group (b). It is preferable to form from the cured | curing material of the addition-curable silicone composition which contains the organopolysiloxane which has only as a base polymer.
The silicone composition will be described in more detail. As the base polymer organopolysiloxane, x = 0 in the above-described formula (A) (that is, a fluoroalkyl group (a) represented by Rf ¹ in the molecule). Organopolysiloxane (not contained) is preferred. In this case, except that x = 0, Rf ² , R ² , R ³ , w, y, and z are the same as those described above, and the same viscosities at w + y + z to 25 ° C. are preferably used. . In addition, the same organohydrogenpolysiloxane and platinum group metal catalyst as those described above may be used.
As the silicone pressure-sensitive adhesive layer 20, for example, an addition-curable silicone pressure-sensitive adhesive or a peroxide-curable silicone pressure-sensitive adhesive containing a resin-like (three-dimensional network structure) organopolysiloxane can be suitably used.
Incidentally, a silicone release layer 30 or 40, bonding of the silicone pressure-sensitive adhesive layer 20, for example 10 to 40 g / cm ^2, preferably under a load of 20 to 30 g / cm ^2, 40 to 100 ° C., preferably 50 to 80 It can be performed under aging for about 0.5 to 30 days, preferably for about 1 to 21 days under heating at ° C.

  Hereinafter, although a reference example, 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 addition, in the following example, a part shows a mass part and% shows the mass%.

(Examples 1-4)
As shown in Table 1, a vinyl group-containing organopolysiloxane (III) having a fluorine substituent represented by the following formulas (I) and (II) and an organohydrogenpolysiloxane represented by the following formula (IV): 4 parts of the composition mixed so that the ratio of SiH group / SiCH = CH ₂ group was 2.5 was diluted with 96 parts of hydrofluoroether Novec7300 (manufactured by 3M Japan), and chloroplatinic acid, vinylsiloxane and A complex solution (platinum concentration 2%) of 0.05 part was added to prepare a treatment solution.

Vinyl group-containing organopolysiloxane

（式中、Ｒｆ²は前記と同じ。）

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

Using the K control coater (model No. 202), a polyethylene terephthalate film (50 μm) was added to the treatment liquid obtained. After coating with one coating bar, it was heated at 150 ° C./60 seconds with a hot air circulating drier to form a cured film (coating amount≈0.3 g / m ² ) to obtain a release film.

  About the peeling film obtained in this way, peeling force and residual adhesive force were measured by the following method. The results are shown in Tables 2 and 3.

(A) Release force A 25 mm wide silicone adhesive tape (Kapton No. 650S # 25, manufactured by Teraoka Seisakusho Co., Ltd.) was bonded to the obtained release film, and a day at 70 ° C. under a load of 25 g / cm ^2. Bonded and aged for 21 days. The bonding tape was peeled off at an angle of 180 ° at a peeling speed of 0.3 m / min using a tensile tester, and the force required for peeling (N / 25 mm) was measured.

(B) Residual adhesive strength Adhesive tape after peeling measurement of (a) was affixed to a SUS plate, pressed by reciprocating 2 kg tape roller, left for 30 minutes, and then this adhesive tape was pulled at an angle of 180 degrees using a tensile tester. Was peeled off at a peeling speed of 0.3 m / min, and the force required for peeling (N / 25 mm) was measured.

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

  According to the silicone composition of the present invention, it is possible to stably control the release force of the cured product within a range of medium to heavy release force with respect to the silicone adhesive, and release without pinholes or repellency. Because it is possible to give a cured film with excellent moldability, especially to form double-sided differential release paper and double-sided differential release film such as process paper, double-sided adhesive tape, correction tape, touch panel OCA tape Suitable as a silicone composition for forming a differential release agent for silicone adhesives, and for mold release for molding rubber, plastic, etc., fiber treatment agents such as paper and cloth, food packaging, etc. Since it can be suitably used for water-repellent agents, oil-repellent agents and heat-resistant coatings, its industrial value is great.

DESCRIPTION OF SYMBOLS 1 1st double-sided difference release paper or double-sided difference release film 2 2nd double-sided difference release paper or double-sided difference release film 3 3rd double-sided difference release paper or double-sided difference release film 10 1st group Material film 10 'Second base film 20 Silicone adhesive layer 30 Silicone release layer (light release layer)
40 Silicone release layer (medium to heavy release layer)

Claims (5)

Affixing the release layer side of the first base film on which a silicone release layer having a light release force to the silicone adhesive is formed on one surface of the silicone adhesive formed into a film or thin film A silicone release layer that is a cured product of a silicone composition for forming a differential release agent for a silicone adhesive and has a medium to heavy release force with respect to the silicone adhesive is formed on the other surface of the silicone adhesive. In the double-sided difference release paper or the double-sided difference release film formed by pasting the release layer side of the second base film ,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film . On one surface of the base film, a silicone release layer that is a cured product of a silicone composition for forming a differential release agent for a silicone adhesive and has a medium to heavy release force with respect to the silicone adhesive, On the other surface of the base film, a double-sided differential release paper or double-sided differential release film formed by forming a silicone release layer having a light release force against the silicone adhesive ,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film . On one surface of the base film, a silicone release layer that is a cured product of a silicone composition for forming a differential release agent for a silicone adhesive and has a medium to heavy release force with respect to the silicone adhesive, Further, the silicone adhesive formed in a film or thin film is stuck on the outer surface of the silicone release layer, and on the other hand, the silicone adhesive is lightly released on the other surface of the base film. In the double-sided difference release paper or double-sided difference release film formed by forming a silicone release layer having strength ,
The silicone composition for forming a differential release agent for the silicone adhesive is,
(A) One molecule contains at least two alkenyl groups bonded to a silicon atom, and (a) a fluoroalkyl group and (b) a fluoropolyether group as two types of fluorine-containing substituents bonded to a silicon atom Each having at least one of (a) a fluoroalkyl group and (b) an organopolysiloxane whose content of the fluoropolyether group is from 1 to 99 mol% based on the total of the fluoropolyether group,
(B) an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule;
(C) Platinum group metal catalyst
And containing
The double-sided silicone release layer having a light release force is composed of a cured product of an addition-curable silicone composition containing, as a base polymer, an organopolysiloxane having only a fluoropolyether group as a fluorine-containing substituent in the molecule. Difference release paper or double-sided difference release film . In the fluorine-containing substituent of component (A), (a) the fluoroalkyl group is a group represented by the following formula (1), and (b) the fluoropolyether group is a group represented by the following formula (2): The double-sided difference release paper or the double-sided difference release film according to any one of Items 1 to 3 .

(In the formula, n is an integer of 1 to 6, m is an integer of 1 to 5, p is an integer of 1 to 5, q is an integer of 0 or 1, r is an integer of 0 to 2, and X is an oxygen atom or single. It is a bond.) The double-sided differential release paper or double-sided differential release film according to any one of claims 1 to 4 , which is used for any one of process paper, double-sided adhesive tape, correction tape, or touch panel OCA tape.

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