WO2019117059A1 - Layered film, release film, and layered body - Google Patents

Abstract

Provided is a layered film having excellent peeling characteristics with respect to an adhesive layer, such as a silicone adhesive, that has strong adhesion. This layered film is formed by layering an A layer and a B layer in the stated order on at least one side of a polymer film, the layered film being characterized in that both the A layer and the B layer contain fluorine atoms, and the B layer contains a higher proportion of fluorine atoms than the A layer.

Description

Laminated film, release film and laminate

The present invention relates to a laminated film, and more particularly to a laminated film having releasability.

In recent years, automobiles equipped with liquid crystal panels are increasing. In such automotive applications, the material is often exposed to high temperature or low temperature for a long time, and high pressure resistance and heat resistance are also required for the pressure-sensitive adhesive to which the panel component members are bonded. As a pressure-sensitive adhesive compatible with this, a silicone pressure-sensitive adhesive that is strongly adhesive has attracted attention.
The silicone pressure-sensitive adhesive is used in the form of a tape (film) as a pressure-sensitive adhesive layer, but before use, it is usually stored in a state where one or both sides are covered with a release film. It is used after peeling the mold film. However, a strongly adhesive silicone pressure-sensitive adhesive (adhesive layer) adheres strongly to a widely used organosilicone-coated release film, and there is a problem that the release film becomes difficult to peel off during use.

A fluorinated silicone material having a fluorine substituent has been proposed as a method for expressing the releasability from a molded article formed by molding of a mold resin such as a silicone resin composition. (Patent Document 1)

JP, 2011-201035, A

However, when a fluorinated silicone material is used as the release layer, the adhesion between the polymer film and the release layer is insufficient to cause delamination, and the release layer is not uniformly formed. In some cases, problems such as deterioration of the releasability to the adherend occurred.
This invention is made in view of the said situation, and makes it a subject to provide the release film which has the peelability excellent with respect to the adhesive layer which has strong adhesiveness, such as a silicone adhesive. .

In order to solve the above-mentioned problems, as a result of intensive investigations by the present inventors, the inventors of the present invention included fluorine atoms in each layer of a laminated film in which an A layer and a B layer were laminated in this order on at least one side of a polymer film. By controlling the fluorine atom content ratio of both layers, it was found that the above problems could be solved, and the present invention was completed.
That is, the gist of the present invention is a laminated film in which an A layer and a B layer are laminated in this order on at least one surface of a polymer film, and both layers of the A layer and B layer contain fluorine atoms. And it is a laminated film characterized by the fluorine atom content rate of B layer being more than the fluorine atom content rate of A layer.

Further, the gist of the present invention is a laminated film in which an A layer and a B layer are laminated in this order on at least one surface of a polymer film, and the B layer contains a fluorine atom and is measured by the following method It is a laminated film characterized in that the normal peeling force at the time is 100 mN / cm or less.
<Measurement of normal peeling force>
A tape with a silicone pressure sensitive adhesive (3M Japan, No. 5413 tape, 50 mm width) is laminated to the surface of layer B of the laminated film, and a 180 ° peel test is carried out under the conditions of a peel speed of 0.3 m / min.

According to the present invention, it is possible to obtain a laminated film having excellent releasability to a pressure-sensitive adhesive layer such as a silicone pressure-sensitive adhesive.

It is the schematic of the laminated film of this invention. It is a schematic diagram which shows the peeling state of the silicone adhesive layer in the laminated film of a prior art (a) and this invention (b).

Hereinafter, the embodiment of the laminated film of the present invention will be described more specifically.
The laminated film of the present invention is a laminated film in which an A layer (undercoat layer) and a B layer (releasing layer) are laminated in this order on at least one side of a polymer film, as illustrated in FIG.
The laminated film of the present invention will be described below in the order of the polymer film, the A layer (undercoat layer) and the B layer (releasing layer).

1. Polymer Film As a polymer film to be a base material of the laminated film of the present invention, a film in which a polymer such as polyethylene, polypropylene, polyester, polystyrene, polycarbonate, polyether sulfone, polyamide, polyimide is formed in a film shape can be mentioned. . Further, as long as film formation is possible, it may be a mixture of these materials (polymer blend) or a composite of constituent units (copolymer).
The polymer film is not particularly limited as long as it is formed into a film, and may be a non-stretched film or a stretched film, but is preferably a stretched film stretched in a uniaxial direction or a biaxial direction. Among them, a biaxially stretched film is more preferable from the viewpoint of balance of mechanical properties and planarity.

The thickness of the polymer film constituting the laminated film in the present invention is not particularly limited as long as the film can be formed as a film, but is preferably 5 μm to 1000 μm, and more preferably 10 μm to 500 μm, More preferably, it is 15 μm or more or 200 μm or less.

Among the films exemplified above, polyester films are preferable because they are excellent in physical properties such as heat resistance, planarity, optical properties, strength and the like, and among them, biaxially stretched polyester films are particularly preferable.
The polyester film may be a single layer or a multilayer film (laminated film) having two or more layers having different properties.
In the present invention, the polyester used for the polyester film may be homopolyester or copolyester. The homopolyester is preferably one obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of aliphatic glycols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like. Be

Examples of representative homopolyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT) and the like. On the other hand, examples of the dicarboxylic acid component of the copolyester include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like, and ethylene as a glycol component One or more of glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, neopentyl glycol and the like can be mentioned.

Among them, in the present invention, polyethylene terephthalate in which 60 mol% or more, preferably 80 mol% or more is ethylene terephthalate units is preferable.
In the present invention, the surface of the polymer film is provided with antistatic properties, sealing properties of bleeding of the compound or oligomer onto the film surface (bleed, plate out), light transmittance of the film, or the after-mentioned A subbing layer (base coat layer) may be provided in order to improve the adhesion to the A layer (undercoat layer).

The subbing layer may be formed by either an in-line coating method in which the subbing layer is formed simultaneously with the formation of the polymer film, or an off-line coating method in which the subbing layer is separately formed on the film having been formed.
When the undercoat layer is provided, it may be formed on at least one side of the polymer film. When forming on both sides, the same undercoating layer may be formed on both sides, or different undercoating layers may be formed on each side. The undercoat layer may be any of a layer formed of an organic substance, a layer formed of an inorganic film, and a layer formed of a mixture of an organic substance and an inorganic substance.

2. A layer (undercoat layer)
In the present invention, an A layer (undercoat layer) is provided on at least one side of the polymer film.
<Configuration of layer A>
The A layer usually contains a fluorine atom. As a result, not only the adhesion between layer A and layer B described below is obtained, but when used as a release film, light releasability between layer B and the pressure-sensitive adhesive layer, which is an adherend, is expressed, and adhesion is achieved. It can make the body easy to peel off.
There is no limitation on the method of containing a fluorine atom in the layer A, and it is sufficient if at least a compound containing a fluorine atom is contained in the layer A. Specifically, low molecular weight compounds containing a fluorine atom, resins containing a fluorine atom, and the like can be mentioned. Among them, it is preferable to use a resin containing a fluorine atom, and in particular, the resin is preferably curable.
Furthermore, when using it as a release film, by laminating | stacking B layer on A layer, the peeling force with respect to a to-be-adhered body becomes small, and it can have light peelability. According to the present inventor, when the layer A is not laminated on the laminated film, the adherend (adhesive) is also followed in the peeling direction at the time of peeling of the laminated film. A large force was required, and it was estimated that peeling was difficult (heavy peeling) (FIG. 2 (a)). On the other hand, as in the present invention, when an A layer containing fluorine atoms is laminated on the laminated film, the A layer acts like a cushion at the time of peeling because the A layer has relative flexibility, and the adherend It is assumed that the object can be peeled off from the adherend with a smaller force because it is suppressed from being deformed, and it becomes easy to peel off (light peeling) (FIG. 2 (b)).

<Fluorine atom content of layer A>
The layer A contains a material containing a fluorine atom, and the fluorine atom content (fraction of atoms) is preferably 50 ppm or more, more preferably 500 ppm or more as the whole layer A, from the viewpoint of adhesion and light removability. 1,000 ppm or more is more preferable, and 50,000 ppm or more is particularly preferable. On the other hand, the upper limit is not particularly limited, but preferably less than 900,000 ppm, more preferably 800,000 ppm or less, and still more preferably 700,000 ppm or less.
The fluorine atom content ratio of the layer A is confirmed by performing, for example, depth direction analysis by sputter etching in the vicinity of the polymer film in the undercoat layer constituting the laminated film by X-ray photoelectron spectroscopy (XPS method) Can. The fluorine atom content ratio of the layer A can also be quantified by using a material (fluorinated silicone etc.) known in advance as the fluorine atom content ratio as a reference. In the case of confirmation by the XPS method, the ratio of fluorine to all elements except hydrogen and helium was taken as the fluorine atom content ratio.

By setting the fluorine atom content of layer A in the above range, layer B (releasing layer) containing fluorine atoms can be uniformly coated on layer A by the coating method, and after coating or lamination. The adhesion between layer A and layer B can also be enhanced.
In addition, if it becomes said fluorine atom content ratio as whole A layer, even if resin used for A layer is resin containing only a fluorine atom, it mixes and uses resin (non-fluorinated resin) which does not contain a fluorine atom. It is also good.

In the layer A, the composition may have a fluorine atom content ratio inclined in the thickness direction. The same applies to the B layer described later.

<Resin containing fluorine atom>
As a resin containing a fluorine atom used for this invention, resin which contains a fluorine atom in the side chain part of resin frame | skeleton is mentioned. Specific examples of the resin containing a fluorine atom include fluorine-containing hydrocarbon resins such as polytetrafluoroethylene in addition to fluorinated silicone resins, and various other resins subjected to a fluorination treatment. Among these, among them, A fluorinated silicone resin is preferred from the viewpoint of releasability.

As the fluorinated silicone resin, both curable and non-curable ones can be used without particular limitation. Among them, curable fluorinated silicone resins are preferable in that they form a stronger layer. In addition, the fluorinated silicone resin may be a solvent type, a non-solvent type, or a mixture thereof. The curable fluorinated silicone resin usually has a functional group such as an alkenyl group or a hydrosilyl group which can form a crosslinked structure upon reaction (curing).

As the curable fluorinated silicone resin, KP-911 and X-70-201S manufactured by Shin-Etsu Chemical Co., Ltd .; FS1265-300CS and FS1265-1000CS, FS1265-10000CS and BY24-900 manufactured by Toray Dow Corning Co., Ltd. , BY24-903, Syl-off 3062, Q2-7785 and the like.
The fluorine atom content ratio (atomic number fraction) of the fluorinated silicone resin is generally several thousand ppm to several tens percent.

<Resin not containing fluorine atom>
Examples of the fluorine-free resin (non-fluorinated resin) used in the present invention include silicone resins, polyolefin resins, acrylic resins and the like, and among these, resins containing fluorine atoms, particularly fluorinated silicone resins From the viewpoint of compatibility, silicone resins are preferred (in the present invention, silicone resins containing no fluorine atom may be referred to as "non-fluorinated silicone resins"). Further, as the non-fluorinated resin, either a curable one or a non-curable one may be used, or both may be used in combination. As in the case of the curable fluorinated silicone resin, functional groups capable of forming a crosslinked structure upon reaction (curing), such as an alkenyl group or a hydrosilyl group, are also bonded to the non-curable fluorinated silicone resin.

The curable non-fluorinated silicone resin The curable non-fluorinated silicone resin may be a solvent type or a non-solvent type.
Specific examples of the curable non-fluorinated silicone resin include KNS-3051, KNS-320A, KNS-316, KNS-3002, KNS-3300, X-62-1387, and KS-3656 manufactured by Shin-Etsu Chemical Co., Ltd. , KS-837, X-62-2829, KS-3650, KS-847, KS-847T, KS-847H, KS-776L, KS-776A, KS-774, KS-3703T, KS-3601, KS-830E , X-62-2825, X-62-9201-A, X-62-9201 B, KM 3951, KM-768, X-52-6015, KF-2005, X-62-7205, X-62-7028-A , X-62-7028-B, X-62-7052, X-62-7622, X-62-7660, X-62-7655; Dow Corning's SP7017, SP7015, SP7025, SP7031, LTC1006L, LTC1063L, LTC1036M, LTC1056L, SRX357, SRX211, SRX345, SRX370, LTC300B, LTC300B, LTC355A, LTC755A, LTC755A, LTC750A, LTC761, LTC8561, LTC851 And the like.
In addition, a heavy release additive may be added to the curable non-fluorinated silicone resin, for example, KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd .; SD7292 manufactured by Toray Dow Corning Co., Ltd., BY24 -4980 etc. can be mentioned.

The above-mentioned curable non-fluorinated silicones may be used alone or in combination of two or more different ones. Adjusting the curing reaction, adjusting the viscosity of the coating solution of layer A, and further enhancing the wettability and reactivity of layer B by mixing two or more curable non-fluorinated silicones. Can. At that time, the non-solvent type silicones may be mixed with each other, or the solvent type silicones may be mixed with each other, or the non-solvent type silicone and the solvent type silicone may be mixed. In particular, when the film thickness of the A layer is increased in order to obtain a lighter release film, the solid concentration of the coating solution forming the A layer tends to be high. As a result, the viscosity of the coating solution may be increased, which may cause problems such as deterioration of the coat appearance and increase in thickness unevenness. Therefore, by mixing the non-solvent type silicone and the solvent type silicone, the viscosity of the coating solution can be reduced, and an A layer having a good coat appearance and a small thickness deviation can be formed.

Here, the "solvent-free silicone" is a silicone having a viscosity that can be applied without dilution in a solvent, is composed of short polysiloxane chains, and is a silicone having a relatively low molecular weight.
The viscosity of the solvent-free silicone is preferably less than 1000 mPa · s alone when it is 100% concentration, and more preferably 50 mPa · s or more or 900 mPa · s or less, and more preferably 80 mPa · s or more or 800 mPa · s. It is further preferred that

On the other hand, "solvent-type silicone" is a silicone having a viscosity high enough to be coated unless diluted with a solvent, and is a silicone having a relatively high molecular weight.
The viscosity of the solvent type silicone is preferably 1000 mPa · s or more when made into a 30% toluene solution, and more preferably 2000 mPa · s or more and 20000 mPa · s or less, and more preferably 3000 mPa · s or more or 18000 mPa · s or less It is further preferred that

By including the non-curable non-fluorinated silicone resin in the non-curable non-fluorinated silicone resin A layer, the controllability of the curing reaction can be improved, and sufficient flexibility is also imparted to the A layer, and The storage stability of the laminate laminated with the pressure-sensitive adhesive layer also becomes good. As the non-curable non-fluorinated silicone resin, it is possible to use the non-fluorinated silicone resin listed above without specifically limiting the silicone resin having no reactive functional group. Specifically, organopolysiloxanes represented by the following general formula (I) are preferable.
R ₃ SiO (R ₂ SiO) _m SiR ₃ ...... (I)
(Wherein R is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and m is a positive integer)

The mass mixing ratio of the curable silicone resin (total of fluorinated and non-fluorinated) and non-curable non-fluorinated silicone resin is preferably in the range of 1: 1000 to 1000: 1, 1: 100 to It is more preferably in the range of 100: 1, and still more preferably in the range of 1:50 to 50: 1. Particularly preferred is in the range of 1:20 to 20: 1, and preferably 1: 1 to 20: 1.

The film thickness of the layer A is preferably 10 nm to 100 μm, more preferably 20 nm to 10 μm, and still more preferably 50 nm to 1 μm. A particularly preferable range is 80 nm or more and 800 nm or less.
When the film thickness is excessively thin such as less than 10 nm, not only the adhesion between the layer A and the layer B is deteriorated, but also the peelability between the silicone pressure-sensitive adhesive layer and the layer B is deteriorated. . On the other hand, when the film thickness of layer A is too thick, the amount of material used increases, and it is difficult to obtain an increase in the effect commensurate with the increase in the amount of material used.

3. B layer (release layer)
<Configuration of layer B>
As a material for forming the B layer (releasing layer), a resin containing a fluorine atom similar to that described in the above-mentioned A layer (undercoat layer) can be used in the same manner. Among them, in view of releasability from the adherend, a fluorinated silicone resin is preferable, and in particular, a curable fluorinated silicone resin is preferable. By using a curable fluorinated silicone resin for the B layer (releasing layer), a releasing film having stable releasability with respect to the silicone pressure-sensitive adhesive layer can be obtained.

The layer B may be formed of a curable fluorinated silicone resin alone, or a mixture of a plurality of materials may be used, such as mixing with a curable non-fluorinated silicone resin.
The coating solution for forming the layer B particularly preferably contains a fluorine-containing solvent containing a fluorine atom for the purpose of enhancing the wettability to the layer A.

If the thickness of the layer B is too thin, the effects of the present invention may be difficult to obtain, while if it is too thick, it may be difficult to obtain an increase in the effect commensurate with the increase in the amount of material used. .
5 nm or more is preferable, as for the minimum of the film thickness of B layer, 10 nm or more is more preferable, and 20 nm or more is especially preferable. Moreover, 50 micrometers or less are preferable, as for the upper limit, 1 micrometer or less is more preferable, and 500 nm or less is especially preferable.

<Fluorine atom content ratio of layer B>
In the laminated film of the present invention, the B layer (releasing layer) is formed on the A layer (undercoat layer). The material suitable for the layer B is the same as that described in the description of the layer A, but from the viewpoint of adhesion and light removability, the fluorine atom content ratio per unit volume contained in the layer B is It is necessary to include more than A layer.

In the present invention, the lower limit of the fluorine atom content ratio (atomic number fraction) contained in the layer B measured by the SIMS method or the like is preferably 3,000 ppm or more, more preferably 5,000 ppm or more, 10,000 ppm or more is more preferable, and 20,000 ppm or more is particularly preferable. The upper limit is not particularly limited, but is preferably 900,000 ppm or less, more preferably 800,000 ppm or less, and particularly preferably 700,000 ppm or less.
The fluorine atom content ratio of the layer B can be confirmed by, for example, the surface of the release layer of the laminated film by secondary ion mass spectrometry (SIMS method) or X-ray photoelectron spectroscopy (XPS method). The fluorine atom content ratio of the layer B can also be quantified by using a material (fluorinated silicone etc.) known in advance as the fluorine atom content ratio as a reference. In the case of confirmation by the XPS method, the ratio of fluorine to all elements except hydrogen and helium was taken as the fluorine atom content ratio.

The case where layers A and B having different fluorine atom content ratios are sequentially stacked has been described above, but the fluorine atom content ratio in the layer has a sloped structure in the thickness direction in one lamination step (tilted composition In some cases, it is possible to take a structure substantially equivalent to the above-described laminated structure of the A layer and the B layer. For example, a resin containing fluorine atoms and a resin not containing fluorine atoms are diluted in a solvent to form a coating solution, and the coating solution is coated on at least one surface of a polymer film and dried to obtain a resin containing fluorine atoms. There is a method of concentrating on the surface of the layer to form a layer having a sloped structure in the thickness direction. When such a lamination process can be taken, it is not necessarily limited to a means for sequentially laminating the A layer and the B layer in a stepwise manner, and the interface between the two layers does not necessarily have to be clear. The surface side in the layer is a layer B and the side of a polymer film is an layer A, and if they have substantially the same structure, they are included in the present invention.
As described above, by forming the layer A and the layer B into a sloped structure, it is also expected to improve the adhesion of the interface between the layer A and the polymer film and the interface between the layer A and the layer B. Furthermore, since the fluorine atom content ratio of the B layer surface can be increased, the light releasability may be further improved while suppressing the content of the resin containing a fluorine atom in the entire laminated film to a low level.

4. Fluorine atom content ratio In the present invention, from the viewpoint of adhesion and light releasability, in addition to the layers A and B containing fluorine atoms, the content ratio is the silicone which is the base material of each layer It is preferable to have a specific relationship with the content ratio of methyl siloxane ion (CH ₃ SiO ₂ ⁻ ) of the resin.
That is, the ratio ([F ⁻ ] / [CH ₃ SiO ₂ ⁻ ]) of the fluorine ion content ratio to the methyl siloxane ion content ratio contained in the B layer calculated by SIMS method etc. (hereinafter, “fluorine atom content ratio” Is abbreviated to be greater than the fluorine atom content ratio of the A layer.

The fluorine atom content ratio of each of the layer A and the layer B is preferably 1 or more and 1,000 or less in the layer A and 3 or more and 5,000 or less in the layer B.
The lower limit of the fluorine atom content ratio of the layer B is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. Further, the upper limit thereof is preferably 3,000 or less, and more preferably 1,000 or less.

The fluorine atom content ratio of the layer B is preferably 1.1 times or more, more preferably 1.5 times or more, of the fluorine atom content ratio of the layer A from the viewpoint of light removability with the silicone pressure-sensitive adhesive layer. It is more preferably 2 times or more, particularly preferably 3 times or more, and most preferably 5 times or more. On the other hand, the upper limit is not particularly limited, but it is preferably 1000 times or less, more preferably 100 times or less from the viewpoint of the adhesion between layer A and layer B.
In the present invention, the fluorine atom content ratio (atomic number fraction) in the layer B is 1 of the fluorine atom content ratio (atomic number fraction) in the layer A from the viewpoint of light removability with the silicone pressure-sensitive adhesive layer. The ratio is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, particularly preferably 3 or more, and most preferably 5 or more. On the other hand, the upper limit is not particularly limited, but it is preferably 1000 times or less, more preferably 100 times or less from the viewpoint of the adhesion between layer A and layer B.
Here, "fluorine atom content ratio (atomic number fraction)" means the ratio of fluorine atoms to the layer concerned. In the case where each of layer A and layer B is substantially composed of silicone resin (including fluorinated, non-fluorinated and curable, non-curable), the above-mentioned "fluorine atom content ratio" and With respect to the “fluorine atom content ratio (atomic number fraction)”, the ratio of the layer A to the layer B is a similar value.

By setting the fluorine atom content ratio of the layer B to the above range, sufficient adhesion is obtained between the layer A and the layer B, and good peelability between the layer B and the silicone pressure-sensitive adhesive layer is expressed. Can.
Further, when the fluorine atom content ratio and / or the fluorine atom content ratio of the layer B is higher than that of the layer A, sufficient adhesion between the layer A and the layer B can be obtained, and the layer B and the silicone pressure-sensitive adhesive layer are good. Peelability can be stably expressed.

The fluorine atom content ratio or fluorine atom content ratio of the layer A or layer B can be calculated by structural analysis of the coating agent by nuclear magnetic resonance spectrum (NMR) method, or secondary ion may be formed after layer formation. It can be quantified by mass spectrometry (SIMS method) or X-ray electron spectroscopy (XPS method).
In the measurement by the SIMS method or the XPS method, the fluorine atom content ratio of each layer can also be quantified on the basis of a material (fluorinated silicone etc.) in which the fluorine atom content ratio is known in advance.
When fluorine atoms are not uniformly present in each of layer A and layer B (for example, in the case of the above-described inclined structure), the total amount of fluorine atoms contained in each layer is measured by the SIMS method or the like. The fluorine atom content ratio per unit volume divided by the volume of the layer A may be the fluorine atom content ratio of each of the A layer and the B layer.

<Other ingredients>
With regard to the layer A and the layer B, it is preferable that the coating solution having the curable non-fluorinated silicone resin and the curable fluorinated silicone resin contain a crosslinking agent, a catalyst, and a reaction initiator (reaction accelerator) . In addition, in the coating material containing a curable silicone resin, a crosslinking agent and a catalyst may be contained from the beginning.

In forming the layer A and the layer B, it is preferable that a crosslinking agent be included to react with reactive functional groups contained in the resin to form a crosslinked structure. Examples of the crosslinking agent include vinyl siloxane and organosiloxane having a hydrosiloxane moiety. Specific examples of the crosslinking agent include SP7297, 7560, 3062A, 3062B, 3062C, 3062D, etc. manufactured by Toray Dow Corning.
The crosslinking agent may contain a site having a fluorine substituent, or a silane coupling agent having a fluorinated substituent may be used.

In addition, in forming the layer A and the layer B, it is preferable that a catalyst that accelerates the addition type reaction be contained, and among them, a platinum catalyst is preferably contained. Examples of platinum catalysts include chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid and olefin, platinum-based compounds such as complexes of chloroplatinic acid and alkenyl siloxane, platinum black, platinum-supported silica, platinum-supported activated carbon Is illustrated. The platinum catalyst may be used alone or in combination of two or more.
Further, specific examples of the catalyst include CAT PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., SRX 212 manufactured by Toray Dow Corning Co., Ltd., SRX 212 P, NC-25, FS XK-3077 and the like.

Examples of other additives that can be added to layer A and layer B include (meth) acrylic acid alkyl esters having 1 to 20 carbon atoms in the ester group, acrylic resins, olefin resins, and the like. Among them, silane coupling agents having a fluorinated substituent are preferable.

5. Physical Properties of Laminated Film of the Present Invention <Normal Peeling Force>
The normal-state peeling force of the laminated film of the present invention is preferably 100 mN / cm or less.
When the laminated film is used as a release film, the lower the normal-state peeling power, the smaller the force required for peeling from the pressure-sensitive adhesive layer. Therefore, the release film is peeled from the laminate on which the pressure-sensitive adhesive layer is laminated, and defects such as peeling failure in the production process such as sticking the pressure-sensitive adhesive layer to various members and deformation of the pressure-sensitive adhesive layer are suppressed. Can. Among the above, the laminate film of the present invention can suppress the above problems and have low releasability even if it is a pressure-sensitive adhesive layer having strong adhesiveness such as a silicone pressure-sensitive adhesive. Moreover, it is possible to prevent the phenomenon in which the release film on the unintended side peels off in a laminate having release films on both sides of the pressure-sensitive adhesive layer as the release film.
From this point of view, the normal peel force is preferably 70 mN / cm or less, more preferably 40 mN / cm or less, particularly preferably 35 mN / cm or less, and most preferably 30 mN / cm or less. preferable. On the other hand, the lower limit is not particularly limited, but it is preferably 1 mN / cm or more, more preferably 3 mN / cm or more, from the viewpoint of storage stability of a laminate obtained by laminating a laminate film and an adhesive layer.

As a method of lowering the normal peeling force, a method of adjusting the fluorine atom content ratio of the layer A or the layer B can be mentioned. In addition, normal-state peeling force shall be measured by the method as described in the Example mentioned later.

6. Lamination Configuration The laminate film of the present invention may have a configuration in which an A layer is provided on one side or both sides of a polymer film, and a B layer is provided on the A layer. Also, if necessary, another layer may be interposed between the polymer film and the A layer, or between the A layer and the B layer.
Other layers may include an antistatic layer having antistatic properties, an oligomer sealing layer for sealing a compound on the film surface and bleeding of an oligomer (bleed, plate out), and the like.

The layers such as the antistatic layer and the oligomer sealing layer may be formed either by in-line coating, which is simultaneously formed with a polymer film, or off-line coating, which is separately formed on the formed polymer film. Can be adopted.

The total thickness of the laminated film in the present invention is preferably 5 μm or more and 1250 μm or less, more preferably 10 μm or more and 500 μm or less, and still more preferably 10 to 200 μm or less.

7. Method of Producing Laminated Film of the Present Invention <Production Method>
(1) Polymer Film As the polymer film to be a base material of the laminated film of the present invention, as described above, a film in which polyethylene, polypropylene, polyester, polystyrene, polycarbonate and other polymer materials are formed into a film is used .

Hereinafter, the method for producing a polyester film will be described by way of example.
As a method for producing the polyester film used in the present invention, it is preferable to use a polyester raw material such as the above-mentioned polyethylene terephthalate, and to solidify the molten sheet extruded from the die by cooling with a cooling roll to obtain an unstretched sheet. . At this time, in order to improve the planarity of the sheet, it is preferable to enhance the adhesion between the sheet and the rotary cooling drum by an electrostatic application adhesion method and / or a liquid application adhesion method.

The obtained unstretched sheet can be used as it is, but at least uniaxial stretching is preferable, and biaxial stretching is more preferable. By stretching the polyester film uniaxially or more, good mechanical strength and dimensional stability can be obtained. Moreover, when using as a release film, when laminating | stacking a to-be-adhered body (adhesive layer) and manufacturing an adhesive sheet with a laminated film, generation | occurrence | production of the malfunction at the time of bonding can be suppressed.
The stretching conditions are also not particularly limited, and for example, the unstretched sheet is stretched 2 to 6 times at 70 to 145 ° C. in the longitudinal direction (longitudinal direction) by roll stretching to obtain a uniaxially stretched polyester film, and then using a tenter A biaxially stretched film is obtained by stretching 2 to 6 times at 80 to 160 ° C. in the direction perpendicular to the previous stretching direction (width direction) and further performing heat treatment at 150 to 250 ° C. for 1 to 600 seconds.
At this time, a method of relaxing by 0.1 to 20% in the longitudinal direction and / or the width direction in the heat treatment zone and / or the cooling zone of the heat treatment outlet is more preferable.

(2) Formation of layer A (undercoat layer) and layer B (release layer) The method for forming layer A and layer B is not limited, and may be formed by coextrusion or the like. Is preferred.
The number of times of application of the layer A and the layer B may be one, or two or more. In the case of forming the layer A and the layer B by setting the number of times of application twice or more, different coating solutions may be applied. However, it is necessary that at least one of the coating solutions contains a fluorine atom.

The coating method may be in-line coating or off-line coating, and, for example, a coating method as shown in "Coating method" (Yuji Harazaki, published by Tsuji Shoten, 1979) can be used.
For example, as a coating head, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnating coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater And extrusion coaters and the like.

0.01 mass% or more is preferable, as for solid content mass concentration of the coating liquid which forms A layer and B layer, 0.05 mass% or more is more preferable, 0.1 mass% or more is more preferable. On the other hand, as an upper limit, 90 mass% or less is preferable, 50 mass% or less is more preferable, and 20 mass% or less is especially preferable.
The solvent for dilution may be a polar solvent or a nonpolar solvent. Alternatively, a fluorine solvent having a fluorine atom may be used. Furthermore, two or more of the above solvents may be mixed and used. In particular, the coating solution for forming the layer B preferably contains a fluorine solvent having a fluorine atom for the purpose of enhancing the wettability to the layer A.
As a polar solvent, alcohols such as ethanol and (iso) propyl alcohol, methyl acetate, ethyl acetate, ethyl acetate (iso) propyl, acetate (iso) butyl acetate, esters of acetate (iso) pentyl acetate, ethyl lactate, ethyl benzoate and the like , Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, diisobutyl ketone, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. Glycols, N-methyl-2-pyrrolidone, N, N-dimethylformamide, tetrahydrofuran, acetonitrile and the like.
Examples of nonpolar solvents include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, hydrocarbons having a branched structure such as isohexane, isooctane and isononane, cyclohexane and cyclo Examples thereof include alicyclic hydrocarbons such as heptane and cyclooctane, and dioxane. As the fluorine solvent, hydrofluoroethers, metaxylene hexafluoride, tridecafluorooctane and the like can be mentioned.

As a method for forming these layers, there is exemplified a method of preparing a coating liquid having a fluorine atom content ratio corresponding to each layer after coating and drying as a coating liquid, and using the same. it can.
In addition, a curable non-fluorinated silicone resin is mixed with a predetermined amount of a fluorinated material to prepare a coating solution having a composition corresponding to the A layer / B layer, and then applied and dried. It is possible to form an A layer and / or a B layer containing a desired fluorine atom. This method is preferable because a release film having a predetermined fluorine atom content ratio A layer / B layer can be produced more easily.
The layer A and the layer B can be formed by coating and drying the layer A and then coating and drying the layer B. In the present invention, the layer B is coated following the coating of the layer A. Then, it can be formed by a wet coating method in which drying is performed thereafter, which can also be expected to shorten the production process and improve energy efficiency.

Alternatively, layer A is formed by applying a mixture of a curable fluorinated silicone resin and a curable non-fluorinated silicone resin, and then a solution comprising a curable fluorinated silicone resin as a main component as layer B There is a method of coating and forming, and this method is more preferable because a release film can be stably produced.
As yet another method, a non-fluorinated resin can be previously formed by coating and then a fluorinated layer can be formed by a dry process such as carbon tetrafluoride (CF ₄ ) plasma treatment. However, this method is suitable for large-scale production because it is necessary to provide a chamber for plasma processing.

In the case of using so-called in-line coating which is coated in the step of producing a polymer film as a method of producing the laminated film of the present invention, both A layer and B layer may be in-line coating, or only A layer may be in-line coating The layer B may be coated off-line.
When both the layer A and the layer B are provided by off-line coating, even if they are continuously formed in one "substrate film unwinding-rewinding step", a plurality of "substrate film unwinding--" The former may be sequentially formed through the winding process, but the former is a particularly preferable method because the manufacturing process becomes simple and the manufacturing cost can be reduced.
Furthermore, by setting the amount of heat applied to the film at the time of forming the A layer lower than the amount of heat applied at the time of forming the B layer, it is possible to suppress the deterioration of film planarity at the time of forming the B layer, and also the occurrence of coating unevenness of the B layer. It is preferable because it can be effectively prevented.

8. Method of Using Laminated Film Since the laminated film of the present invention has excellent releasability, it can be provided, for example, as a laminated film-attached pressure-sensitive adhesive sheet having a configuration formed by laminating the laminated film and the adhesive layer. In particular, since the laminated film of the present invention has excellent releasability even for a silicone adhesive having strong adhesiveness, for example, a structure formed by laminating the laminate film and an adhesive layer made of a silicone adhesive. Can be provided as a laminated film-attached pressure-sensitive adhesive sheet.
However, the method of using the laminated film is not limited to such a method of use. For example, since the laminated film contains a fluorine atom, the print is excellent in water resistance, water repellency, oil resistance, oil repellency, antifogging, antifouling, chemical resistance, corrosion resistance, etc. Substrates, optical member protective films, films for construction materials, films for agriculture, highly water repellent films, films for packaging, cosmetic films, surface protective films and the like can be mentioned. In the case where the B layer surface is used as the outermost surface, an adhesive layer, an adhesive layer, a heat seal layer, etc. may be provided on the polymer film on the side opposite to the side having the A layer and the B layer. .

<Silicone adhesive>
As a silicone adhesive, an addition reaction type, a peroxide curing type, or a condensation reaction type silicone adhesive etc. are mentioned, for example. Among them, from the viewpoint of being curable in a low temperature and short time, an addition reaction type silicone pressure sensitive adhesive is preferably used. These addition reaction type silicone pressure sensitive adhesives are cured when forming the pressure sensitive adhesive layer on the support.
When an addition reaction type silicone adhesive is used as the silicone adhesive, the silicone adhesive may contain a catalyst such as a platinum catalyst.
For example, the above-mentioned addition reaction type silicone pressure-sensitive adhesive is coated on a support after stirring the silicone resin solution diluted with a solvent such as toluene, if necessary, uniformly by adding a catalyst such as a platinum catalyst. And cure at 100 to 130 ° C./1 to 5 minutes.
In addition, if necessary, a crosslinker, an additive for controlling adhesion, or the like may be added to the addition reaction type silicone pressure-sensitive adhesive, or the support may be subjected to a primer treatment before the formation of the pressure-sensitive adhesive layer. It is also good.

Commercially available silicone resins used for the addition reaction type silicone adhesive include SD4580PSA, SD4584PSA, SD4585PSA, SD4587LPSA, SD4560PSA, SD4570PSA, SD4600FCPSA, SD4593PSA, DC7651ADHESIVE, DC7652ADHESIVE, LTC-755, LTC-310 (all of which are Toray Dow) Corning Inc.), KR-3700, KR-3701, X-40-3237-1, X-40-3240, X-40-3291-1, X-40-3229, X-40-3323, X-40 -3306, X-40-3270-1 (all from Shin-Etsu Chemical Co., Ltd.), AS-PSA001, AS-PSA002, AS-PSA003, AS-PSA004, AS-PSA 05, AS-PSA012, AS-PSA014, PSA-7465 (all manufactured by Arakawa Chemical Industries, Ltd.), TSR1512, TSR1516, TSR1521 (all manufactured by Momentive Performance Materials, Inc.), and the like.

Hereinafter, the present invention will be more specifically described using examples, but the present invention is not limited by the following examples. In addition, the raw material described as "addition type" in the following examples all mean "hardenable".

(1) Evaluation method (1-1) Normal peeling force
Under an environment of 23 ° C., a tape with a silicone pressure-sensitive adhesive (No. 5413 tape manufactured by 3M Japan Co., Ltd., 50 mm width) was attached to the surface of the layer B (release layer) of the laminated film, and set in a peeling tester. The normal peeling force was measured under the conditions of a peeling speed of 0.3 m / min and a peeling angle of 180 °.

(1-2) Fluorine Atom Content Ratio, Fluorine Atom Content Ratio Ratio The fluorine atom content ratio in the A layer and the B layer was evaluated using TOF-SIMS (TRIF V, manufactured by ULVAC-PHI, Inc.).
Au ³⁺ was used as a primary ion, and the acceleration voltage was 30 kV.
In order to evaluate the fluorine atom content ratio per unit volume, etching with Ar gas (voltage: 5 kV, current: 2 nA, etching rate: 20 nm / min (PET film conversion)) is performed for 0 min, 1 min, 2 min, 3 min, Fluorine atom content ratio per unit volume (“F ⁻ ” / “CH ₃ ”) obtained by averaging the ratio of the counts of anions (“F ⁻ ” and “CH ₃ SiO ₂ ⁻ ”) detected during the etching time of SiO ₂ ^- ") and the.
Further, the value of [the fluorine atom content ratio of the layer B] / [the fluorine atom content ratio of the layer A] was taken as the ratio of the fluorine atom content ratio. This value has the same meaning as the result of calculating the ratio of the values of each layer by measuring the fluorine atom content ratio (atomic number fraction) of each of layer A and layer B using XPS.

Example 1
(Coating solution 1)
The following composition was mixed, and diluted with a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1: 1) to a solid content concentration of 4 mass% to prepare “coating liquid 1”.

<Coating solution 1 composition>
Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 67 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department

(Coating solution 2)
The following composition is mixed, diluted with a mixed solvent of FS thinner (manufactured by Shin-Etsu Chemical Co., Ltd.) / Ethyl acetate = 1: 1 (mass ratio) to a solid content concentration of 0.5 mass%, Coating solution 2 "was prepared.

<Coating solution 2 composition>
Addition type fluorinated silicone (Shin-Etsu Chemical Co., Ltd., X-70-201S): 100 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.5 parts by mass

(Creating laminated film)
A PET film ("T100-38" manufactured by Mitsubishi Chemical Corporation, 38 μm thick) is used as a polymer film, and the coating solution 1 is coated on the polymer film by a bar coater (No. 4 bar), in an oven at 150 ° C. For 30 seconds to cure the resin of layer A, and a polymer film having layer A (undercoat layer) was formed.
The coating solution 2 is further applied by a bar coater (No. 4 bar) on the layer A of the polymer film having the layer A (undercoat layer), and dried in an oven at 150 ° C. for 30 seconds to obtain a resin of the layer B Was cured to produce a laminated film in which the B layer (release layer) was provided on the A layer (undercoat layer).

Example 2
A laminated film was produced in the same manner as in Example 1 except that the solid content concentration of the coating solution 2 was 4% by mass.
In addition, since the coating liquid 2 is apply | coated using the same bar coater as Example 1, the thickness of B layer becomes large compared with Example 1 by making solid content concentration high.

Comparative Example 1
A polymer film was prepared in substantially the same manner as in Example 1, except that only the coating solution 2 was applied by a bar coater (No. 4 bar) without forming the layer A (undercoat layer) on the polymer film. A laminated film consisting only of B and B layers (releasing layers) was produced.

Comparative Example 2
A laminated film was produced in the same manner as in Comparative Example 1 except that the solid content concentration of the coating solution 2 was 4% by mass.
In addition, since the coating liquid 2 is apply | coated using the same bar coater as the comparative example 1, the thickness of B layer becomes large compared with the comparative example 1 by making solid content concentration high.

Comparative Example 3
In the same manner as in Example 1 except that the layer B (releasing layer) was not formed without applying the coating solution 2 on the layer A (undercoat layer), substantially a polymer film and A laminated film consisting only of layer A (undercoat layer) was produced.

Comparative Example 4
(Coating solution 3)
Coating solution 3 was prepared with the following composition.
<Coating solution 3 composition>
Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847H): 67 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass The above composition is a mixture of n-hexane and MEK It diluted with solvent (mass ratio = 1: 1) so that solid content concentration might be 4 mass%.

(Creating laminated film)
The coating solution 3 was coated on a polymer film by a bar coater (No. 4 bar) and dried in an oven at 150 ° C. for 30 seconds to provide an A layer (undercoat layer).
Next, it was tried to apply the coating solution 2 by a bar coater (No. 4 bar) on the layer A (undercoat layer). However, the coating solution 2 is not uniformly applied on the layer A (undercoat layer), and a phenomenon (repelling) occurs in the form of spots or lines (mesh), so that the layer B (release layer) Could not form.

Comparative Example 5
With regard to the B layer (release layer), a laminated film was to be produced in the same manner as in Comparative Example 4 except that the solid content concentration of the coating liquid 2 was 4 mass%. However, the “coating solution 2” is not uniformly applied on the layer A (undercoat layer), and a phenomenon (repelling) occurs in the form of spots or lines (mesh), so that the layer B (release layer) ) Could not form.

[Example 3]
(Coating solution 4)
The following composition was mixed, and diluted with a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1: 1) to a solid content concentration of 4 mass% to prepare “coating liquid 4”.
<Coating solution 4 composition>
Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 133 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 1.3 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department

(Creating laminated film)
The above was diluted to a solid content concentration of 2% by mass on an A layer (undercoat layer) obtained by applying and curing the coating solution 4 instead of the coating solution 1 on a polymer film A laminated film was produced in the same manner as in Example 1 except that the coating solution 2 was applied.

Example 4
(Coating solution 5)
The following composition was mixed, and diluted with a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1: 1) to a solid content concentration of 4 mass% to prepare “coating liquid 5”.
<Coating solution 5 composition>
Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 200 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 2.0 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department

(Creating laminated film)
A laminated film was produced in the same manner as in Example 3 except that the coating solution 5 was applied instead of the coating solution 4 to form a layer A (undercoat layer) on the polymer film.

[Example 5]
(Coating solution 6)
The following composition was mixed, and diluted with a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1: 1) to a solid content concentration of 4 mass% to prepare “coating liquid 6”.
<Coating solution 6 composition>
Addition type organosilicone (Shin-Etsu Chemical Co., Ltd., KS-847): 267 parts by mass Platinum catalyst (Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 2.0 parts by mass Addition type fluorinated silicone (Toray Dow Corning Co., Ltd.) Syl-off 3062): 100 parts by mass Crosslinking agent (Toray Dow Corning, Syl-off 3062A): 0.5 parts by mass Platinum catalyst (Toray Dow Corning, FSX K-3077): 0.5 parts Department

(Creating laminated film)
A laminated film was produced in the same manner as in Example 3, except that the coating solution 6 was applied instead of the coating solution 4 to form a layer A (undercoat layer) on the polymer film.

(3) Evaluation of the result About the obtained laminated film, the fluorine atom content ratio of A layer (undercoat layer) and B layer (releasing layer), and the normal-state peeling force using a silicone adhesive tape were measured. The results are shown in Table 1 below.
In Examples 1 and 2, since the A layer (undercoat layer) and the B layer (releasing layer) defined in the present invention were formed on the PET film, a film of only the B layer (releasing layer) was used. It was found that better releasability can be obtained compared to Comparative Examples 1 and 2.

In particular, in the laminated film of Example 1, the thickness of the layer B (releasing layer) is formed thin (the concentration of the coating solution 2 is “0.5 mass%”), compared to the example 1 The releasability of the same level as that of the release film of Example 2 (the concentration of the coating solution 2 is “4% by mass”) in which the layer B (release layer) is thick is obtained. From this, it has been found that it is possible to produce a release film having excellent releasability to a silicone adhesive with a smaller amount of fluorine-based material.
In addition, the release films of Examples 3 to 5 in which the fluorine atom content ratio of the layer A (undercoat layer) is smaller than that of Example 1 also provide the same level of releasability as the release film of Example 1. It has been found that it is possible to produce a release film having excellent releasability with respect to a silicone pressure sensitive adhesive, with a smaller amount of fluorine-based material.

In addition, in order to evaluate the fluorine atom content ratio of each layer, the fluorine atom content ratio by TOF-SIMS is measured for the samples of Comparative Example 3 (only A layer) and Comparative Example 2 (only B layer), It is the value of the layer. As a result, it was confirmed that the content of fluorine atoms per unit volume was higher in layer B than in layer A.
In addition, since the composition of the coating liquid is the same, this value was used as the value of the fluorine atom content ratio of each layer in Examples 1 and 2 and Comparative Example 1. Furthermore, the fluorine atom content ratio of the layer A in Examples 3 to 5 was calculated from the raw material composition ratio based on the value of the fluorine atom content ratio in Example 1.
The fluorine atom content of layer A is the largest on the surface (etching time 0 minutes in TOF-SIMS) and decreases as the etching time becomes longer (that is, the closer to the substrate PET film side), the fluorine on the surface side It is considered that a graded structure in which the atomic content ratio increases is formed. The values shown in Table 1 are average values in the thickness direction.

1 Polymer film 2 A layer (undercoat layer)
3 B layer (release layer)
4 Silicone adhesive layer

Claims (12)

A laminated film in which an A layer and a B layer are laminated in this order on at least one side of a polymer film,
A laminated film characterized in that both of the layer A and the layer B contain fluorine atoms, and the content of fluorine atoms in the layer B is higher than that in the layer A. The laminated film according to claim 1, wherein the content of fluorine atoms in the layer B is 1.1 or more times the content of fluorine atoms in the layer A. A laminated film in which an A layer and a B layer are laminated in this order on at least one side of a polymer film,
The laminated film characterized in that the layer B contains a fluorine atom, and the normal-state peeling force at the time of measurement by the following method is 100 mN / cm or less.
<Measurement of normal peeling force>
A tape with a silicone pressure sensitive adhesive (3M Japan, No. 5413 tape, 50 mm width) is laminated to the surface of layer B of the laminated film, and a 180 ° peel test is carried out under the conditions of a peel speed of 0.3 m / min. The laminated film according to any one of claims 1 to 3, wherein the polymer film is a biaxially stretched polyester film. The laminated film according to any one of claims 1 to 4, wherein the layer A and the layer B contain a fluorinated silicone resin. The laminated film according to any one of claims 1 to 5, wherein the layer A contains a non-fluorinated silicone resin and a fluorinated silicone resin. The laminated film according to any one of claims 1 to 6, wherein the layer A and the layer B are layers formed by curing a curable fluorinated silicone resin. Time-of-flight secondary ion mass spectrometer (TOF-SIMS) fluoride ions when measured using a (F ^-) content and methylsiloxane ion _(CH 3 SiO ₂ ^-) ratio of content ^([F -] / _[CH 3 SiO ₂ ^-]) is 1 or more than 1,000 in the a layer, laminated film according to any one of claims 5-7, characterized in that the layer B is 3 to 5,000. The fluorine atom content ratio (atomic number fraction) of the A layer is 50 ppm or more and less than 900,000 ppm, and the fluorine atom content ratio (atomic number fraction) of the B layer is 3,000 ppm or more and 900,000 ppm or less The laminated film according to any one of 1 to 8. A release film using the laminated film according to any one of claims 1 to 9. The laminated body on which the release film and adhesive layer of Claim 10 were laminated | stacked. The laminate according to claim 11, wherein a pressure-sensitive adhesive layer is provided on the side of the layer B not in contact with the layer A.

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