JP2009154457A - Release film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a release film that implements excellent mold release, excellent adhesion between a substrate film and a release layer, especially in an environment attacked by an organic solvent, and less foreign matter in the release layer. <P>SOLUTION: The release film has the release layer comprising a release agent composition which includes (A) a base agent consisting of a polysiloxane having an unsaturated group, (B) a crosslinking agent consisting of a hydrogen polysiloxane having a hydrogen atom directly bonded to a silicon atom, (C) an organosilicon compound containing an alkenyl group, (D) an organosilicon compound containing a glycidyl group, and (E) a platinum catalyst, and which has a content ratio of the alkenyl group containing organosilicon compound (C) to the glycidyl group containing organosilicon compound (D) within a particular numerical range. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a release film.

  Conventionally, as a release film, a film having a release layer formed on the surface of the film has been proposed. Among them, many release films using a polyester film as the film and a layer made of a silicone composition as the layer having the release property have been proposed. In such a release film, since the adhesiveness between the polyester film and the silicone composition is generally low, improvement has been demanded. Therefore, for example, Patent Documents 1 to 5 have been studied for the purpose of improving the adhesion.

Japanese Patent Laid-Open No. 6-16941 JP 2003-292894 A JP-A-64-5838 Japanese Patent Laid-Open No. 3-120042 JP-A-10-29288

  However, although the release films disclosed in Patent Documents 1 and 2 have an effect of improving the adhesion to some extent, the adhesion required in recent years has not been achieved, and further improvement is necessary. In particular, in recent years, there has been an increasing demand for adhesion in an environment affected by an organic solvent, and further improvement is required. In addition, the release films disclosed in Patent Documents 3 to 5 have a problem that a complicated process is required to coat the anchor coat layer and the cost is increased. Furthermore, in the step of forming the release layer, there is a problem that the anchor coat layer is scraped off by a coating roll such as a gravure roll and becomes a foreign matter in the release layer. Such a foreign substance becomes a big problem, for example, when used as a release film for manufacturing a thin film ceramic capacitor in recent years.

  The present invention solves such problems, has excellent releasability, excellent adhesion between the base film and the release layer, particularly excellent adhesion in an environment affected by an organic solvent, and foreign matter in the release layer An object of the present invention is to provide a release film with a low content.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a specific main agent, a specific cross-linking agent, an alkenyl group-containing organosilicon compound, a glycidyl group-containing organosilicon compound, and a platinum catalyst. It has been found that the above object can be achieved by a release film having a release layer composed of a release agent composition containing as a constituent component. That is, according to the present invention, at least one side of the base film has at least two main atoms (A) composed of polysiloxane having at least two unsaturated groups in one molecule and hydrogen atoms directly bonded to silicon atoms in one molecule. A cross-linking agent (B) comprising hydrogenpolysiloxane, an alkenyl group-containing organosilicon compound (C) represented by the following formula [Chemical Formula 1], and a glycidyl group-containing organosilicon compound (D) represented by the following Formula [Chemical Formula 2] ) And a platinum-based catalyst (E) as a constituent component, a release film having a release layer obtained by applying a release agent composition, the alkenyl group-containing organic in the release agent composition A release film in which the content ratio of the silicon compound (C) and the glycidyl group-containing organosilicon compound (D) satisfies the following formula [Equation 1].

（式中、Ｘ^１はアルケニル基、Ｘ^２はグリシジル基またはグリシジル基を有する炭化水素基、あるいはグリシドキシ基またはグリシドキシ基を有する炭化水素基をそれぞれ表し、Ｒ^１、Ｒ^２はそれぞれアルコキシ基、アシルオキシ基、ハロゲンから選ばれた加水分解可能な基、またはアルキル基を表す。ａおよびｂはそれぞれ１以上３以下の整数を表す。）

(Wherein, X ¹ represents an alkenyl group, X ² represents a glycidyl group or a hydrocarbon group having a glycidyl group, or a glycidoxy group or a hydrocarbon group having a glycidoxy group, and R ¹ and R ² represent an alkoxy group and an acyloxy group, respectively. A hydrolyzable group selected from a group, halogen, or an alkyl group, and a and b each represent an integer of 1 to 3.

（式中、Ｙ^１は、離型剤組成物中におけるアルケニル基含有有機珪素化合物（Ｃ）由来のＸ^１基の総モル数を表し、またＹ^２は、離型剤組成物中におけるグリシジル基含有有機珪素化合物（Ｄ）由来のＸ^２基の総モル数を表す。）

(In the formula, Y ¹ represents the total number of moles of X ¹ groups derived from the alkenyl group-containing organosilicon compound (C) in the release agent composition, and Y ² represents a glycidyl group in the release agent composition. This represents the total number of moles of X ² groups derived from the contained organosilicon compound (D).)

  Furthermore, in the present invention, the total of the content of the alkenyl group-containing organosilicon compound (C) and the content of the glycidyl group-containing organosilicon compound (D) is 0.00 on the basis of the solid content weight of the release agent composition. By adopting an embodiment in which the content is 5% by mass or more and 4.0% by mass or less, a further excellent release film can be obtained.

  According to the present invention, the release property is excellent, the adhesion between the base film and the release layer is excellent, particularly the adhesion in an environment affected by an organic solvent is excellent, and the release in the release layer is less foreign matter. A film can be provided. In particular, it is possible to provide a release film suitably used as a carrier film for producing a temporary protective film for an adhesive product or an adhesive sheet.

  The release film of the present invention comprises a main component (A), a crosslinking agent (B), an alkenyl group-containing organosilicon compound (C), a glycidyl group-containing organosilicon compound (D), and a platinum-based catalyst (E) as constituent components. The mold release layer which consists of a mold release agent composition to contain is a mold release film coated on the at least single side | surface of the base film. Hereinafter, each component in the present invention will be described.

<Main agent (A)>
The main agent (A) in the present invention comprises a polysiloxane having at least two unsaturated groups in one molecule. Such an unsaturated group is an alkenyl group having 2 to 10 carbon atoms. By having such an unsaturated group, the strength of the release layer is excellent. The unsaturated group is preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group. Examples of such polysiloxanes include polysiloxanes represented by the following formulas [Chemical Formula 3] and [Chemical Formula 4].

  In the above formulas [Chemical Formula 3] and [Chemical Formula 4], m and n are integers of 1 or more, and m is 1 to 100, n is 20 to 5000, and m + n is in the range of 30 to 5000. Preferably proceeds and the strength of the release layer is improved. The above formulas [Chemical Formula 3] and [Chemical Formula 4] do not mean an embodiment that is a block copolymer, but these simply indicate that the total number of each unit is m and n. It should be understood that it is only there. Therefore, the polysiloxane in the above formulas [Chemical Formula 3] and [Chemical Formula 4] may be a random copolymer or a block copolymer.

  In the present invention, as the main agent (A), one kind of the above polysiloxane may be used alone, or a polysiloxane having two or more different alkenyl groups in one molecule may be used. In addition, two or more kinds of polysiloxanes having different structures such as having different alkenyl groups may be used in combination.

<Crosslinking agent (B)>
The crosslinking agent (B) in the present invention comprises hydrogen polysiloxane having at least two hydrogen atoms bonded directly to silicon atoms in one molecule. Examples of the hydrogen polysiloxane include polysiloxanes represented by the following formulas [Chemical Formula 5] and [Chemical Formula 6].

  In the above formulas [Chemical Formula 5] and [Chemical Formula 6], p and q are integers of 1 or more, and when p is in the range of 1 to 20, q is in the range of 3 to 200, and p + q is in the range of 5 to 200, the crosslinking reaction Preferably proceeds and the strength of the release layer is improved. In addition, the above formulas [Chemical Formula 5] and [Chemical Formula 6] do not mean an embodiment that is a block copolymer, but these simply indicate that the total number of each unit is p and q. It should be understood that it is only there. Therefore, the hydrogenpolysiloxane in the above formulas [Chemical Formula 5] and [Chemical Formula 6] may be a random copolymer or a block copolymer.

  In the present invention, as the crosslinking agent (B), one kind of hydrogen polysiloxane as described above may be used alone, or the number of hydrogen atoms directly bonded to silicon atoms in one molecule is different. Two or more types of hydrogen polysiloxanes having different structures may be used in combination.

In the present invention, the main component of the release layer is a product obtained by addition polymerization of the main agent (A) and the cross-linking agent (B) in the presence of a platinum-based catalyst (E) described later. The term addition polymerization and has a functional group at the molecular ends or in the molecular side chains in the base resin (A) represented by ~Si-CH = CH ₂ or _{~Si-R-CH = CH 2} , H-Si~ in the functional group at the molecular ends or in the molecular side chains in the cross-linking agent (B) which is _shown, that the reaction to be _~Si-CH 2 _CH 2 -Si~ or _{~Si-R-CH 2 CH 2} -Si~ It is. However, “˜” in the functional group indicates that the molecule is further connected. When the reaction at this time is expressed as a reaction formula, it is represented by the following formula [Chemical Formula 7] or [Chemical Formula 8]. Here, R represents an alkylene group having 1 to 8 carbon atoms.

  The ratio of the main agent (A) and the crosslinking agent (B) in the addition polymerization is such that the SiH group in the crosslinking agent (B) is 1.0 mol or more and 2.0 mol with respect to 1.0 mol of the alkenyl group in the main agent (A). It is preferable to make it less than mol. By setting it as such an aspect, the improvement effect of mold release property can be made high and the intensity | strength of a mold release layer improves.

  In the present invention, a commercially available product in which the main agent (A) and the crosslinking agent (B) are mixed in advance can be used. Specific examples of such commercially available products include KS-718, KS-774, KS-775, KS-778, KS-779H, KS-830, KS-835, KS-837, and KS- manufactured by Shin-Etsu Chemical Co., Ltd. 838, KS-839, KS-841, KS-843, KS-847, KS-847H, KS-847T, KS-3600, KS-3601, X-62-2418, X-2422, X-2125, X- 2492, X-2494, X-470, X-2366, X-630, X-92-140, X-128, KS-723A, B, KS-705F, KS-708A, KS-883, KS-709, KS-719, TPR-6701, TPR-6702, TPR-6703, TPR-3704, TPR-6705, TPR manufactured by GE Toshiba Silicone Co., Ltd. 6722, TPR-6721, TPR-6700, TPR-6710, TPR-6712, DK-Q3-202, DK-Q3-203, DK-Q3-204, DK-Q3-210, DK-Q3 manufactured by Dow Corning -240, DK-Q3-3003, DK-Q3-205, DK-Q3-3057, SFXF-2560, LTC-750A, LTC-760A, LTC-300B, LTC-306, LTC manufactured by Toray Dow Corning Co., Ltd. -350G, LTC-370G, LTC-371G, LTC-851, SD-7226, SD-7320, SD-7328, SD-7234, SD-7229, BY24-900, BY24-171, BY24-312, BY24-374 , SRX-375, SYL-OFF23, SRX-244, S X-290, can be mentioned ICI Japan SILCOLEASE425 etc. Co., Ltd..

<Alkenyl group-containing organosilicon compound (C)>
The release agent composition in the present invention contains an alkenyl group-containing organosilicon compound (C) represented by the following formula [Chemical Formula 9] as a constituent component.

  A in Formula [Chemical Formula 9] represents an integer of 1 or more and 3 or less. In particular, a is preferably 1. With such an embodiment, the adhesiveness between the base film and the release layer is excellent. In addition, the adhesiveness in an environment affected by an organic solvent is excellent.

X ¹ in the above formula [Chemical 9] represents an alkenyl group. As such an alkenyl group, an alkenyl group having 2 to 8 carbon atoms is preferable, an alkenyl group having 2 to 4 carbon atoms is more preferable, and a vinyl group is particularly preferable. By X ¹ is the manner described above, and has excellent adhesion between the base film and the release layer. In addition, the adhesiveness in an environment affected by an organic solvent is excellent. In the above formula [Chemical Formula 9], it represents that a number of X ¹ is bonded to Si, and these X ¹ may be of the same type or of different types. Also good.

In the above formula [Chemical Formula 9], R ¹ represents a hydrolyzable group selected from an alkoxy group, an acyloxy group, and a halogen, or an alkyl group. Of these, an alkoxy group and an acyloxy group are preferable. As an alkoxy group, a C1-C10 alkoxy group is preferable, a C1-C6 alkoxy group is more preferable, and a methoxy group and an ethoxy group are especially preferable. As the acyloxy group, an acyloxy group having 2 to 11 carbon atoms is preferable, an acyloxy group having 2 to 7 carbon atoms is more preferable, and an acetoxy group is particularly preferable. As the halogen, a chloro group is preferable. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable. When R ¹ is in the above-described manner, the adhesiveness between the base film and the release layer is excellent. In addition, the adhesiveness in an environment affected by an organic solvent is excellent. In the above formula [Chemical Formula 9], (4-a) R ¹ is bonded to Si, and these R ¹ may be of the same type or of different types. It may be a thing. In the present invention, an embodiment in which at least one of (4-a) R ¹ is an alkoxy group or an acyloxy group is preferred, and an embodiment in which all R ¹ are an alkoxy group or an acyloxy group is more preferred.

  Examples of such alkenyl group-containing organosilicon compounds (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyldimethoxymonoacetoxysilane, vinylmonomethoxydiacetoxysilane, and vinyldiethoxymonoacetoxy. Preferable examples include silane, vinyl monoethoxydiacetoxysilane, vinyltriacetoxysilane, allyltrimethoxysilane, allyltriethoxysilane and the like.

In the present invention, a mixture of two or more different alkenyl group-containing organosilicon compounds (C) can be used as the alkenyl group-containing organosilicon compound (C). When used as a mixture, an embodiment containing a monoacetoxy compound in which one of R ¹ in the above formula [Chemical Formula 9] is an acetoxy group is preferable, and 50 mol% or more based on the total amount of the alkenyl group-containing organosilicon compound (C) An embodiment containing a monoacetoxy compound is more preferable. Moreover, the aspect containing the trimethoxy body whose three R < ¹ > in the said Formula [Chemical Formula 9] is a methoxy group is preferable, and the aspect containing 20 mol% or more of a trimethoxy body on the basis of the whole quantity of an alkenyl group containing organosilicon compound (C) Is more preferable. By using the mixture of such an aspect, it becomes more excellent in the adhesiveness of a base film and a release layer. In addition, the adhesiveness in an environment affected by an organic solvent is superior.

<Glycidyl group-containing organosilicon compound (D)>
The release agent composition in the present invention contains a glycidyl group-containing organosilicon compound (D) represented by the following formula [Chemical Formula 10] as a constituent component.

  B in the above formula [Chemical Formula 10] represents an integer of 1 or more and 3 or less. In particular, b is preferably 1. With such an embodiment, the adhesiveness between the base film and the release layer is excellent. In addition, the adhesiveness in an environment affected by an organic solvent is excellent.

X ² in the above formula [Chemical Formula 10] represents a glycidyl group or a hydrocarbon group having a glycidyl group, or a hydrocarbon group having a glycidoxy group or a glycidoxy group. As such a hydrocarbon group, a hydrocarbon group having 1 to 10 carbon atoms is preferable, a hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a hydrocarbon group having 3 to 6 carbon atoms is particularly preferable. By X ² is the manner described above, and has excellent adhesion between the base film and the release layer. In addition, the adhesiveness in an environment affected by an organic solvent is excellent. In the above formula [Chemical Formula 10], it represents that b pieces of X ² are bonded to Si, and these X ² may be of the same type or of different types. Also good.

In the above formula [Chemical Formula 10], R ² represents a hydrolyzable group selected from an alkoxy group, an acyloxy group, and a halogen, or an alkyl group. Of these, an alkoxy group and an acyloxy group are preferable. As an alkoxy group, a C1-C10 alkoxy group is preferable, a C1-C6 alkoxy group is more preferable, and a methoxy group and an ethoxy group are especially preferable. As the acyloxy group, an acyloxy group having 2 to 11 carbon atoms is preferable, an acyloxy group having 2 to 7 carbon atoms is more preferable, and an acetoxy group is particularly preferable. As the halogen, a chloro group is preferable. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable. When R ² is in the above-described manner, the adhesiveness between the base film and the release layer is excellent. In addition, the adhesiveness in an environment affected by an organic solvent is excellent. In the above formula [Chemical Formula 10], (4-b) pieces of R ² are bonded to Si, and these R ^{2 s} may be of the same type or of different types. It may be a thing. In the present invention, an embodiment in which at least one of (4-b) R ² is an alkoxy group or an acyloxy group is preferred, and an embodiment in which all R ² are an alkoxy group or an acyloxy group is more preferred.

  Examples of such glycidyl group-containing organosilicon compounds (D) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid. Xylpropylmethyldiethoxysilane, γ-glycidoxypropyldimethoxymonoacetoxysilane, γ-glycidoxypropylmonomethoxydiacetoxysilane, γ-glycidoxypropyldiethoxymonoacetoxysilane, γ-glycidoxypropylmonoethoxy Preferred examples include diacetoxysilane and γ-glycidoxypropyltriacetoxysilane.

In the present invention, as the glycidyl group-containing organosilicon compound (D), a mixture of two or more different glycidyl group-containing organosilicon compounds (D) can be used. When used as a mixture, an embodiment containing a monoacetoxy compound in which one of R ² in the above formula [Chemical Formula 10] is an acetoxy group is preferable, and 50 mol% or more based on the total amount of the glycidyl group-containing organosilicon compound (D) An embodiment containing a monoacetoxy compound is more preferable. Further, an embodiment containing a diacetoxy compound in which two of R ² in the formula [Chemical Formula 10] are acetoxy groups is preferable, and an embodiment containing 30 mol% or more of a diacetoxy compound based on the total amount of the glycidyl group-containing organosilicon compound (D). Is more preferable. By using the mixture of such an aspect, it becomes more excellent in the adhesiveness of a base film and a release layer. In addition, the adhesiveness in an environment affected by an organic solvent is superior.

  The mold release agent composition in this invention contains the said alkenyl group containing organosilicon compound (C) and the said glycidyl group containing organosilicon compound (D), and those content ratio satisfy | fills following formula [Equation 2].

Y ¹ in the above formula [Equation 2] represents the total number of moles of X ¹ groups derived from the alkenyl group-containing organosilicon compound (C) in the release agent composition, and Y ² is in the release agent composition. This represents the total number of moles of X ² groups derived from the glycidyl group-containing organosilicon compound (D). By setting the content ratio as described above, the mold release property is excellent and the adhesion between the base film and the release layer is excellent. In addition, the adhesiveness in an environment affected by an organic solvent is superior. In the release agent composition, if Y ¹ is too large with respect to Y ^2, the adhesion between the base film and the release layer tends to improve, there is a tendency that poor releasability. On the other hand, the release agent composition, if Y ² is too large with respect to Y ^1, tend to poor adhesion. From such a viewpoint, the ratio of Y ¹ and Y ² is preferably Y ¹ : Y ² = 70: 30 to 30:70, more preferably Y ¹ : Y ² = 60: 40 to 40:60. is there.

  In the present invention, the total content of the alkenyl group-containing organosilicon compound (C) and the glycidyl group-containing organosilicon compound (D) in the release agent composition is the solid content of the release agent composition. It is preferably 0.5% by mass or more and 4.0% by mass or less based on the weight. By making content into the said numerical range, the adhesive improvement effect of a base film and a mold release layer can be made higher. Moreover, the improvement effect of the adhesiveness in the environment where it was corroded by the organic solvent can be made higher. When there is too little content, the adhesive improvement effect tends to become low. On the other hand, when there is too much content, there exists a tendency for the improvement effect of a mold release property to become low. Furthermore, problems such as a short pot life of the release agent composition and contamination of the drying process in the coating process are likely to occur. From such a viewpoint, the total of the content of the alkenyl group-containing organosilicon compound (C) and the content of the glycidyl group-containing organosilicon compound (D) is more preferably 0.8% by mass or more and 3.5% by mass. %, Particularly preferably 1.0% by mass or more and 2.5% by mass or less. Moreover, in this invention, the silane coupling agent different from said alkenyl group containing organosilicon compound (C) and glycidyl group containing organosilicon compound (D) is further added in the range by which the effect of this invention is not impaired. can do.

<Platinum catalyst (E)>
The platinum-based catalyst (E) in the present invention is a catalyst for promoting the addition polymerization of the main agent (A) and the crosslinking agent (B), and a known catalyst can be used for such addition polymerization. Examples of such platinum-based catalyst (E) include chloroplatinic acid, chloroplatinic acid alcohol solutions and aldehyde solutions, chloroplatinic acid complexes with various olefins or vinyl siloxanes, and the like.

  The addition amount of the platinum-based catalyst (E) may be an amount usually used as a catalyst amount, but the amount of platinum metal is preferably 1 to 1000 ppm, more preferably 100 parts by mass of the main agent (A). When the addition amount is 10 to 300 ppm, the strength of the release layer is increased, and it is economically excellent.

<Base film>
In the present invention, a thermoplastic resin film having flexibility and heat resistance is used as the base film. Preferable examples of the polymer constituting the thermoplastic resin film include polyesters such as polyethylene terephthalate and polyethylene naphthalate, aliphatic polyamides, aromatic polyamides, polyethylene, and polypropylene. Of these, polyester is preferable.

  The polyester in the present invention comprises a dicarboxylic acid component as the first component and a glycol component as the second component. Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4,4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like. In particular, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of excellent mechanical properties of the base film. Examples of the glycol component include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, polyethylene glycol, and the like. . In particular, ethylene glycol is preferable from the viewpoint of excellent rigidity of the base film.

  The polyester may be a copolyester obtained by copolymerizing the dicarboxylic acid component or the glycol component as a third component. As the third component, a copolymer component different from the dicarboxylic acid component selected as the first component or the glycol component selected as the second component can be selected. Further, the third component may include a trifunctional or higher polyvalent carboxylic acid component or a polyol component. In this case, the copolymerization amount is within a range in which the obtained polyester is substantially linear (for example, 5 mol). % Or less, more preferably 3 mol% or less). As the polyester in the present invention as described above, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable.

  Such a polyester can be produced by a conventional method. When the intrinsic viscosity of the polyester (intrichlorophenol at 35 ° C.) is 0.45 (unit: dl / g) or more, the rigidity of the film is high. It is preferable because of its excellent mechanical properties. The polyester includes inorganic fine particles such as silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, titanium oxide, and barium sulfate, crosslinked silicone resin, crosslinked polystyrene resin, crosslinked acrylic resin, urea resin, and melamine resin. The organic fine particle which consists of heat resistant polymers, such as, can be improved, and slipperiness can be improved or transparency can be adjusted. In addition, other resins such as polyethylene, polypropylene, ethylene / propylene copolymer, olefinic ionomer, stabilizers, antioxidants, ultraviolet absorbers, fluorescent brighteners, and the like can be contained as necessary.

  The base film in the present invention is preferably a biaxially stretched film. Such a biaxially stretched film can be produced by a conventionally known method. For example, in the case of a biaxially stretched film made of polyester, after drying the polyester, it is melted in an extruder at a temperature of Tm to (Tm + 70) ° C. (where Tm represents the melting point of the polyester (unit: ° C.)), Extruded from a die (for example, T-die, I-die, etc.) onto a rotating cooling drum, rapidly cooled at 20 to 90 ° C. to produce an unstretched film, and then the unstretched film is converted into (Tg-10) to (Tg + 70). ) At a temperature of ° C. (where Tg represents the glass transition temperature of the polyester (unit: ° C.)) 2.5 to 8.0 times, preferably 2.9 to 5.0 times, more preferably 3 in the longitudinal direction. The film is stretched at a magnification of 2 to 4.0 times, and 2.5 to 8.0 times, preferably 3.1 to 5.2 times, more preferably 3.4 to 4.2 times in the transverse direction. 1-60 at a temperature of 180-250 ° C. as required It can be prepared by between heat set. The thickness of the base film in the present invention is preferably 5 μm or more and 250 μm or less, more preferably 20 μm or more and 150 μm or less, and particularly preferably 30 μm or more and 100 μm or less from the viewpoint of excellent mechanical properties and handling properties.

  In the present invention, when at least one treatment selected from the group consisting of corona treatment and plasma treatment is applied to the surface of the base film on which the release layer is provided, the adhesion between the base film and the release layer is further improved. It is preferable because it can be used. Moreover, in this invention, the aspect which does not have the anchor coat layer formed by the apply | coating method etc. is preferable in the surface which provides a release layer in a base film. By setting it as such an aspect, the foreign material in a mold release layer can further be reduced.

<Manufacturing method>
In the present invention, the main component (A), the crosslinking agent (B), the alkenyl group-containing organosilicon compound (C), the glycidyl group-containing organosilicon compound (D), and the platinum-based catalyst (E) are the constituent components. A release layer is formed by applying a release agent composition (hereinafter sometimes referred to as a coating solution) included as at least one surface of the base film.

  Such a coating liquid comprises the above main agent (A), crosslinking agent (B), alkenyl group-containing organosilicon compound (C), glycidyl group-containing organosilicon compound (D), platinum-based catalyst (E), stirring blades and the like. It can manufacture by using and mixing uniformly. As the coating liquid for application, the coating liquid obtained by mixing may be used as it is, but it is uniform to use a coating liquid that is diluted with an appropriate organic solvent and adjusted to have an appropriate viscosity. From the viewpoint that a release layer having a good appearance can be obtained.

  As a coating method for coating the coating liquid on the base film, any known coating method can be applied. For example, gravure roll coating method, reverse roll coating method, die coating method, kiss coating method, reverse kiss coating method, offset gravure method A coating method, a Mayer bar coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, a doctor blade method, and the like can be applied alone or in combination. Further, for the purpose of improving the stability of the coating appearance such as repelling, the coating liquid can contain a slight amount of a surfactant.

  As a condition for drying and curing the coating film obtained by applying the coating liquid to the base film, it is preferable to heat at a temperature of 100 ° C. or higher and 180 ° C. or lower for a time of 10 seconds or longer and 120 seconds or shorter. It is more preferable to heat at a temperature of 160 ° C. or lower for 20 seconds to 90 seconds, and it is particularly preferable to heat at a temperature of 130 ° C. to 150 ° C. for 30 seconds to 60 seconds. By adopting drying conditions as described above, the strength of the release layer can be increased. Moreover, the adhesiveness of a base film and a mold release layer can be made higher. Furthermore, the adhesiveness in the environment affected by the organic solvent can be made higher.

  In the present invention, the thickness of the release layer is preferably 0.03 μm or more and 0.5 μm or less. When the thickness of the release layer is in the above numerical range, the release property is more excellent. It is also preferable from the viewpoint of productivity. If the thickness is too thick, the productivity tends to be inferior. On the other hand, when the thickness is too thin, the releasability tends to be inferior. From such a viewpoint, the thickness of the release layer is more preferably 0.05 μm or more and 0.4 μm or less, and particularly preferably 0.07 μm or more and 0.3 μm or less. The thickness of the release layer can be adjusted by any known method such as appropriately adjusting the concentration of the coating liquid and the wet coating amount when applying the coating liquid.

  Hereinafter, the present invention will be further described with reference to examples. Each characteristic value was measured by the following method.

(1) Peeling force A polyester adhesive tape (manufactured by Nitto Denko Corporation: trade name NO.31B) is lightly bonded to the release layer surface of the release film using a rubber roll, and then uniform using a 5 kg metal roller. The sample for evaluating the peeling force under the condition of heating without pressure and under the condition without heating is in an environment at a temperature of 23 ° C. The sample for evaluating the peeling force under a condition with heating is in an environment of a temperature of 70 ° C. , Each was left for 20 hours. A strip-shaped sample having a width of 25 mm was cut out from the release film after being left, and bonded to the aluminum support plate with a double-sided tape so that the base film side of the release film was on the aluminum support plate side. The obtained sample was set in a tensile tester, and the peeling force between the polyester adhesive tape and the release layer was measured by a 180 ° peeling method. It implemented about five strip-shaped samples of 25 mm width, and made those average values the peeling force (unit: g / 25mm).
In the present invention, it is preferable that the peeling force under the condition with heating is within 3 times the peeling force under the condition without heating.

(2) Adhesiveness After forming a release film, as a aging treatment, a sample for evaluating the adhesiveness during normal aging was evaluated for adhesiveness over time at a temperature of 23 ° C. and a relative humidity of 55% RH. The samples to be tested were left for 24 hours in an environment of a temperature of 60 ° C. and a relative humidity of 90% RH. Next, the sample after the aging treatment was subjected to a rub-off test by strongly rubbing the release layer surface 10 times with the thumb. At this time, the thumb was thoroughly wiped with gauze preliminarily containing ethanol and degreased before carrying out the above operation. About the obtained sample after the rub-off test, the state of the release layer in the portion rubbed with the thumb was visually observed and judged according to the following criteria.
○: No cloudiness is observed in the release layer by visual observation.
Δ: Some cloudiness was observed in the release layer visually.
X: Cloudiness was observed in the release layer visually.
Furthermore, the cellophane adhesive tape was affixed to the part rubbed with the thumb, and the degree of catch when peeling it was evaluated according to the following criteria.
○: There is no catch when the cellophane adhesive tape is peeled off.
Δ: When the cellophane adhesive tape is peeled off, there is a slight catch.
X: There is a catch when the cellophane adhesive tape is peeled off.
XX: When the cellophane adhesive tape is peeled off, there is a strong catch (a catch equivalent to a part having no release layer).

(3) Adhesion in an environment affected by an organic solvent The release layer surface of the release film was evaluated by rubbing using a fastness tester. For the rubbing part of the fastness tester, five layers of standard cotton cloth were used. The standard cotton cloth was impregnated with each organic solvent, and the release layer surface was rubbed with the solvent. Here, the rubbing conditions were as follows.
Material of rubbing part: 5 layers of standard cotton cloth (gold width 3) for fastness test Load: 100 gf / 20 mm
Number of scratches: 10 reciprocations Organic solvent used: Methyl ethyl ketone, toluene, ethanol, ethyl acetate Impregnation amount of organic solvent: 2 ml
With respect to the solvent-rubbed portion of the release layer, the peeling force was measured for five strip-shaped samples having a width of 25 mm by the same method as the peeling force under the condition (1) without heating. The peel strength after rubbing (unit: g / 25 mm) was used. The above operation was performed for each organic solvent.
Then, the value of the peel force after solvent rubbing was calculated by dividing the value of the peel strength after solvent rubbing by the value of the peel force obtained without heating in the above (1). The rate of change was evaluated according to the following criteria.
○: Change rate is 1.5 or less △: Change rate is more than 1.5 and less than 3 ×: Change rate is 3 or more

(4) Residual adhesion rate Uniform load using a polyester adhesive tape (manufactured by Nitto Denko Corporation: trade name: NO.31B) on a cold rolled stainless steel plate (SUS304) according to JIS G 4305 using a 2 kg rubber roller The peel strength after being attached and maintained for 30 seconds was measured by a 180 ° peel method to obtain a basic adhesive strength (f0) (unit: g / 25 mm). Next, a new polyester pressure-sensitive adhesive tape (manufactured by Nitto Denko Corporation: trade name: NO.31B) was pressure-bonded to the release layer surface of the release film with a uniform load using a 2 kg rubber roller, and maintained for 30 seconds. The polyester adhesive tape was peeled off. After the peeled polyester adhesive tape was bonded to the cold rolled stainless steel plate with a uniform load using a 2 kg rubber roller, the peeling force between the polyester adhesive tape and the cold rolled stainless steel plate was 180 °. The residual adhesive strength (f) (unit: g / 25 mm) was measured by a peeling method. From the basic adhesive force (f0) and the residual adhesive force (f) obtained as described above, the residual adhesive rate was determined by the following formula.
Residual adhesion rate = (f / f0) × 100
Said operation was implemented 5 times and those average values were made into the residual adhesive rate (unit:%).
In the present invention, the residual adhesion rate is preferably 85% or more. When the residual adhesive rate is less than 85%, for example, when the release film is wound and stored in a roll shape, the components constituting the release layer are transferred to the surface of the base film in contact with the release layer (rear transfer) ) And the properties of the release layer such as wettability and releasability may be poor.

[Production Example 1]
65 parts by mass of vinyltrimethoxysilane and 35 parts by mass of γ-glycidoxypropyltrimethoxysilane were mixed to obtain silicon compound S1. In the silicon compound S1, the number of moles of vinyl group: number of moles of glycidyl group = 75: 25.

[Production Example 2]
35 parts by mass of vinyldimethoxymonoacetoxysilane and 65 parts by mass of γ-glycidoxypropyldimethoxymonoacetoxysilane were mixed to obtain silicon compound S2. In the silicon compound S2, the number of moles of vinyl group: number of moles of glycidyl group = 45: 55.

[Production Example 3]
10 parts by mass of vinyltrimethoxysilane, 20 parts by mass of vinyldimethoxymonoacetoxysilane, 35 parts by mass of γ-glycidoxypropyldimethoxymonoacetoxysilane, and 35 parts by mass of γ-glycidoxypropylmonomethoxydiacetoxysilane By mixing, a silicon compound S3 was obtained. In the silicon compound S3, the number of moles of vinyl group: number of moles of glycidyl group = 42: 58.

[Production Example 4]
Vinyl trimethoxysilane was used as it was to obtain silicon compound S4. In the silicon compound S4, the number of moles of vinyl group: number of moles of glycidyl group = 100: 0.

[Production Example 5]
γ-glycidoxypropyltrimethoxysilane was used as it was to obtain silicon compound S5. In the silicon compound S5, the number of moles of vinyl group: number of moles of glycidyl group = 0: 100.

[Example 1]
Addition reaction type silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KS-847T) (solid content concentration 30% by mass, toluene 70% by mass as a volatile component). ) To 100 parts by mass, 1400 parts by mass of toluene was added and diluted to a solid content concentration of 2.0% by mass. Next, 0.6 parts by mass of the silicon compound S1 obtained in Production Example 1 and 1.0 part by mass of a platinum-based catalyst (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name PL-50T) were added, and the coating liquid (solid content) Concentration 2.1 mass%) was obtained.
In addition, content of silicon compound S1 in the coating liquid obtained in Example 1 was 1.9 mass% on the basis of the solid content weight of the coating liquid.
The obtained coating solution was applied to one side of a 38 μm thick biaxially stretched polyester film by a reverse gravure method so that the coating amount was 6 g / m ² and dried at 140 ° C. for 30 seconds to form a coating film. It was cured to obtain a release film on which a release layer having a thickness of 0.1 μm was formed. The properties of the obtained release film are shown in Table 1.

[Example 2]
Using a biaxially stretched polyester film with a thickness of 38 μm with a surface energy of 54 mN / m or more applied to one side as a base film, a coating solution is applied to the surface subjected to the corona treatment to form a release layer. A release film was obtained in the same manner as in Example 1 except that the film was formed. The properties of the obtained release film are shown in Table 1.

[Example 3]
A release film was obtained in the same manner as in Example 1 except that the silicon compound S2 obtained in Production Example 2 was used instead of the silicon compound S1. The properties of the obtained release film are shown in Table 1.

[Example 4]
A release film was obtained in the same manner as in Example 3 except that the amount of silicon compound S2 added was 0.3 parts by mass. The properties of the obtained release film are shown in Table 1.
In addition, the solid content concentration of the coating liquid obtained in Example 4 was 2.1 mass%, and the content of the silicon compound S2 was 1.0 mass% based on the solid content weight of the coating liquid. .

[Example 5]
A release film was obtained in the same manner as in Example 1 except that the silicon compound S3 obtained in Production Example 3 was used instead of the silicon compound S1. The properties of the obtained release film are shown in Table 1.

[Comparative Example 1]
A release film was obtained in the same manner as in Example 1 except that the silicon compound S1 was not added. The properties of the obtained film are shown in Table 1.
In addition, the solid content concentration of the coating liquid obtained in Comparative Example 1 was 2.1% by mass.

[Comparative Example 2]
A release film was obtained in the same manner as in Example 1 except that the silicon compound S4 obtained in Production Example 4 was used instead of the silicon compound S1. The properties of the obtained release film are shown in Table 1.

[Comparative Example 3]
A release film was obtained in the same manner as in Example 1 except that the silicon compound S5 obtained in Production Example 5 was used instead of the silicon compound S1. The properties of the obtained release film are shown in Table 1.

  The release films obtained in Examples 1 to 5 were excellent in releasability, excellent in adhesion between the base film and the release layer, and excellent in adhesion in an environment affected by an organic solvent. It was. Moreover, as a result of performing foreign material inspection using the polarizing plate about the 1 m x 1 m sample, the foreign material was not confirmed by the release layer of the release film obtained in Examples 1-5.

  The release film obtained in Comparative Example 1 does not contain both the alkenyl group-containing organosilicon compound (C) and the glycidyl group-containing organosilicon compound (D), and the adhesion between the base film and the release layer And poor adhesion in an environment affected by an organic solvent.

  Comparative Example 2 is an experimental example that does not contain the glycidyl group-containing organosilicon compound (D). When the addition amount of the alkenyl group-containing organosilicon compound (C) was such that the adhesion between the base film and the release layer was sufficient, the release property was inferior. Further, the residual adhesive rate was low, that is, the release layer was easily transferred to the back surface.

  The release film obtained in Comparative Example 3 does not contain the alkenyl group-containing organosilicon compound (C), and the adhesion between the base film and the release layer, and the adhesion in an environment affected by an organic solvent. It was inferior in nature.

Claims (2)

Hydrogen poly having at least one hydrogen atom directly bonded to a silicon atom in one molecule and a main agent (A) composed of polysiloxane having at least two unsaturated groups in one molecule on at least one surface of the base film Crosslinker (B) made of siloxane, alkenyl group-containing organosilicon compound (C) represented by the following formula [Chemical Formula 1], glycidyl group-containing organosilicon compound (D) represented by the following Formula [Chemical Formula 2], and platinum-based A release film having a release layer obtained by applying a release agent composition containing a catalyst (E) as a constituent component, the alkenyl group-containing organosilicon compound (C) in the release agent composition A release film in which the content ratio of the glycidyl group-containing organosilicon compound (D) satisfies the following formula [Equation 1].

(Wherein, X ¹ represents an alkenyl group, X ² represents a glycidyl group or a hydrocarbon group having a glycidyl group, or a glycidoxy group or a hydrocarbon group having a glycidoxy group, and R ¹ and R ² represent an alkoxy group and an acyloxy group, respectively. A hydrolyzable group selected from a group, halogen, or an alkyl group, and a and b each represent an integer of 1 to 3.

(In the formula, Y ¹ represents the total number of moles of X ¹ groups derived from the alkenyl group-containing organosilicon compound (C) in the release agent composition, and Y ² represents a glycidyl group in the release agent composition. This represents the total number of moles of X ² groups derived from the contained organosilicon compound (D).)   The sum of the content of the alkenyl group-containing organosilicon compound (C) and the content of the glycidyl group-containing organosilicon compound (D) is 0.5% by mass or more based on the solid content weight of the release agent composition. The release film according to claim 1, which is 0.0 mass% or less.