TWI801466B - Laminated film, release film and laminate - Google Patents

Abstract

The present invention provides a laminated film having excellent peelability to an adhesive layer having strong adhesiveness such as a silicone adhesive. The laminated film is formed by sequentially laminating layer A and layer B on at least one side of a polymer film, and is characterized in that: the above-mentioned layer A and layer B contain fluorine atoms, and the fluorine atom content ratio of layer B is higher than that of layer A The fluorine atom content ratio.

Description

Laminated film, release film and laminate

The present invention relates to a laminated film, in particular to a laminated film with release properties.

In recent years, more and more automobiles are equipped with liquid crystal panels. In this kind of vehicle-oriented application, it is often exposed to high or low temperature for a long time, and high weather resistance and heat resistance are also required for the adhesive of the constituent members of the laminated panel. As an adhesive suitable for this, strong adhesive silicone adhesives have attracted attention.

Polysiloxane adhesives are made into tapes (films) using this as an adhesive layer. They are usually stored in a state of covering one or both sides with a release film before use, and the release film is used before use. Use with the film peeled off. However, the highly adhesive silicone adhesive (adhesive layer) strongly adheres to the release film coated with the widely used organopolysiloxane, making it difficult to peel off the release film during use.

A fluorinated silicone material having a fluorine substituent is disclosed as a method for expressing the releasability of a silicone resin composition and the like from a molded article including a molded resin. (Patent Document 1)

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-201035

However, when the fluorinated polysiloxane material is used as the release layer, it can be seen that the following adverse conditions occur: the adhesion between the polymer film and the release layer is insufficient, causing interlayer detachment, or uneven Forming a release layer degrades the detachability of the adherend.

The present invention was made in view of the above-mentioned circumstances, and an object of the present invention is to provide a release film having excellent peelability to an adhesive layer having strong adhesiveness such as a silicone adhesive.

In order to solve the above problems, the inventors of the present invention found, as a result of intensive research, that by making each layer of a laminated film in which a layer A and a layer B are sequentially laminated on at least one side of a polymer film contain fluorine atoms, and control the two The content ratio of fluorine atoms in the layer can solve the above-mentioned problems, and the present invention has been completed.

That is, the gist of the present invention is a laminated film, which is formed by sequentially laminating layer A and layer B on at least one side of a polymer film. It is characterized in that: the two layers of layer A and layer B contain fluorine atoms, and B The fluorine atom content ratio of the layer is higher than the fluorine atom content ratio of the A layer.

Also, the gist of the present invention is a laminated film, which is formed by sequentially laminating layer A and layer B on at least one side of a polymer film, characterized in that the layer B contains fluorine atoms, and is measured by the following method The normal peel force is below 100mN/cm.

<Measurement of Normal Peeling Force>

A tape with a silicone adhesive (manufactured by 3M Japan, No5413 tape, 50 mm wide) was attached to the surface of layer B of the laminated film, and a 180° peel test was performed at a peeling speed of 0.3 m/min.

According to the present invention, a laminated film having excellent releasability to an adhesive layer having strong adhesiveness such as a silicone adhesive can be obtained.

1: polymer film

2: A layer (undercoat)

3: B layer (release layer)

4: Silicone adhesive layer

Fig. 1 is a schematic diagram of a laminated film of the present invention.

Fig. 2 is a schematic view showing the peeling state of the silicone adhesive layer in the laminated film of the prior art (a) and the present invention (b).

Hereinafter, embodiments of the laminated film of the present invention will be described more specifically.

The laminated film of the present invention, as shown in Figure 1, is a laminated film in which layer A (undercoat layer) and layer B (release layer) are sequentially laminated on at least one side of the polymer film.

Hereinafter, the above-mentioned laminated film of the present invention will be described in order of the polymer film, A layer (undercoat layer) and B layer (release layer).

1. Polymer film

Examples of the polymer film to be the base material of the laminated film of the present invention include polyethylene, polypropylene, polyester, polystyrene, polycarbonate, polyether, polyamide, polyimide, etc. Molecules are formed into a film-like film. Moreover, as long as it can be formed into a film, it may be a mixture of these materials (polymer blend) or a composite of structural units (copolymer).

Also, the polymer film is not particularly limited as long as it is formed into a film, and may be an unstretched film or a stretched film, 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 the balance of mechanical properties or planarity.

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

Among the films exemplified above, polyester films are preferred because they are excellent in physical properties such as heat resistance, planarity, optical properties, and strength, and among them, biaxially stretched polyester films are particularly preferred.

The above-mentioned polyester film may be a single layer, or may be a multilayer film (laminated film) having two or more layers with different properties.

In the present invention, the polyester used in the polyester film may be a homopolyester or a copolymerized polyester. As the homopolyester, one obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol is preferable. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid, and examples of aliphatic diols include ethylene glycol, diethylene glycol, 1,4-butanediol, 1 , 4-cyclohexanedimethanol, etc.

As typical homopolyester, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), etc. can be illustrated. On the other hand, examples of the dicarboxylic acid component of the copolymerized polyester include isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid, adipic acid, and sebacic acid. One or more than two. As the diol component, one or more of ethylene 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 is preferably polyethylene terephthalate in which usually 60 mol% or more, preferably 80 mol% or more are ethylene terephthalate units.

In the present invention, for the surface of the polymer film, in order to impart antistatic properties, or to seal the formulation or oligomer to the surface of the film (escaping, precipitation), or to improve the light transmittance of the film, or to combine with the following For the adhesion of layer A (base coat), a base layer (base coat) can also be provided.

The base layer can be formed by any of the in-line coating method in which the base layer is formed simultaneously with the production of the polymer film, or the off-line coating method in which the base layer is separately formed on the film after film formation.

When the above-mentioned base layer is provided, it only needs to be formed on at least one side of the polymer film. When forming on both sides, the same underlayer may be formed on both sides, or different underlayers may be formed on each side. The base layer may be any of a layer containing an organic substance, a layer containing an inorganic film, or a layer containing a mixture of an organic substance and an inorganic substance.

2. A layer (base coat)

In the present invention, layer A (undercoat layer) is provided on at least one side of the polymer film.

<Composition of Layer A>

Layer A usually contains fluorine atoms. In this way, it not only has the adhesiveness between layer A and layer B described later, but also when it is used as a release film, it can show the light peelability between layer B and the adhesive layer as the adherend, and it is easy to peel off the adherend. body.

There is no limitation on the method of making layer A contain fluorine atoms, as long as the compound containing fluorine atoms is contained in layer A at least. Specifically, low-molecular-weight compounds containing fluorine atoms, resins containing fluorine atoms, and the like are exemplified. Among them, it is preferable to use a resin containing fluorine atoms, and it is particularly preferable that the resin is curable.

Furthermore, when used as a release film, by laminating the B layer on the A layer, the peeling force to the adherend becomes small, and it can have light peelability. The inventors of the present invention speculate that when the layer A is not laminated on the laminated film, the adherend (adhesive) also follows the peeling direction when the laminated film is peeled off, so a greater force is required to peel off the adherend, making it difficult to peel off. (heavy peeling) (Fig. 2(a)). On the other hand, it is speculated that when layer A containing fluorine atoms is laminated in the laminated film as in the present invention, layer A is relatively flexible, so layer A acts as a buffer when peeling off, and suppresses the deformation of the adherend. It can be peeled off from the adherend with less force, and it is easy to peel off (light peel) (Figure 2(b)).

<Content ratio of fluorine atoms in layer A>

The layer A contains a material containing fluorine atoms, and its fluorine atom content ratio (atomic fraction) is preferably 50 ppm or more, more preferably 500 ppm or more for the entire A layer from the viewpoint of adhesiveness or light peeling property. , and more preferably at least 1,000 ppm, particularly preferably at least 50,000 ppm. On the other hand, the upper limit is not particularly limited, but is preferably less than 900,000 ppm, more preferably 800,000 ppm or less, further preferably 700,000 ppm or less.

The fluorine atom content ratio of layer A can be confirmed, for example, by X-ray photoelectron spectroscopy (XPS method) in the undercoat layer constituting the laminated film, near the polymer film Depth direction analysis using sputter etching. The fluorine atom content ratio of the A layer can also be quantified by using a material (fluorinated polysilicon, etc.) whose fluorine atom content ratio is known in advance as a reference. In addition, when confirming by the XPS method, the ratio of fluorine to all elements obtained by removing hydrogen and helium was set as the fluorine atom content ratio.

By setting the fluorine atom content ratio of the A layer to the above range, the B layer (release layer) similarly containing fluorine atoms can be uniformly coated when it is placed on the A layer by a coating method, and it is also possible to Improve the adhesion between layer A and layer B after coating or lamination.

Furthermore, as long as the overall A-layer has the above-mentioned fluorine atom content ratio, the resin used for the A-layer may be a resin containing fluorine atoms alone, or may be mixed with a resin not containing fluorine atoms (non-fluorinated resin).

Furthermore, a composition in which the fluorine atom content ratio in the layer A is inclined in the thickness direction may be used. The same applies to the B layer described later.

<Resin containing fluorine atoms>

Examples of the fluorine atom-containing resin used in the present invention include resins containing fluorine atoms in the side chain portion of the resin skeleton. Specific examples of resins containing fluorine atoms include, in addition to fluorinated silicone resins, fluorinated hydrocarbon resins such as polytetrafluoroethylene, and various other fluorinated resins. From a viewpoint, a fluorinated silicone resin is preferable.

As the fluorinated silicone resin, curable or non-curable silicone resins can be used without any particular limitation. Among these, curable fluorinated polysiloxane resins are preferred in terms of forming a stronger layer. In addition, the fluorinated silicone resin may be a solvent type, a solvent-free type, or a mixture of these. On the curable fluorinated polysiloxane resin, there are usually bonded alkenyl groups or hydrosilyl groups, etc. A functional group that can form a crosslinked structure by reaction (hardening).

Examples of curable fluorinated silicone resins include: KP-911, X-70-201S manufactured by Shin-Etsu Chemical Co., Ltd.; FS1265-300CS, FS1265-1000CS, FS1265-10000CS manufactured by Toray Dow Corning Co., Ltd. BY24-900, BY24-903, Syl-off 3062, Q2-7785, etc.

Furthermore, the fluorine atom content rate (atomic fraction) of the fluorinated silicone resin is generally about several thousand ppm to several tens%.

<Resin without fluorine atoms>

As resins (non-fluorinated resins) not containing fluorine atoms used in the present invention, silicone resins, polyolefin resins, acrylic resins, etc. can be cited. Among them, resins containing fluorine atoms, especially fluorine From the viewpoint of the compatibility of fluorinated polysiloxane resins, polysiloxane resins are preferred (in the present invention, polysiloxane resins that do not contain fluorine atoms are sometimes referred to as "non-fluorinated polysiloxane resins") ). Also, as the non-fluorinated resin, either curable or non-curable resins may be used, or both may be used in combination. On the non-hardening fluorinated polysiloxane resin, like the curable fluorinated polysiloxane resin, there are usually bonded functions such as alkenyl or hydrosilyl groups that can form a cross-linked structure by reaction (hardening) base.

Hardening non-fluorinated silicone resin

As a hardening non-fluorinated polysiloxane resin, it can be solvent type or non-solvent type.

Specific examples of curable non-fluorinated silicone resins include KNS-3051, KNS-320A, KNS-316, KNS-3002, KNS-3300, and X-62-1387 manufactured by Shin-Etsu Chemical Co., Ltd. , KS-3656, 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- 9201B, KM3951, 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; SP7017, SP7015, SP7025, SP7031, LTC1006L, LTC1063L, LTC1036M, LTC1056L, SRX357, SRX211, SRX345, SRX370, LTC300B, L manufactured by Toray Dow Corning Co., Ltd. TC310, LTC355A, LTC759, LTC755, LTC750A, LTC752, LTC761, LTC856, LTC851, etc.

In addition, heavy release additives can also be added to the above-mentioned curable non-fluorinated polysiloxane resin. As examples, KS-3800 manufactured by Shin-Etsu Chemical Co., Ltd.; SD7292 manufactured by Toray Dow Corning Co., Ltd.; BY24-4980 etc.

In addition, the above-mentioned curable non-fluorinated polysiloxane may be used alone, or two or more different types may be used in combination. By mixing two or more types of hardening non-fluorinated polysiloxane, the hardening reaction can be adjusted, or the viscosity of the coating solution of layer A can be adjusted, or the wettability and reactivity of layer B can be improved. At this time, solvent-free polysiloxane may be mixed with each other, solvent-type polysiloxane may be mixed with each other, or solvent-free polysiloxane and solvent-type polysiloxane may be mixed. In particular, when the film thickness of layer A is thickened in order to obtain a release film that peels more lightly, there is a tendency for the solid content concentration of the coating liquid that forms layer A to become high. Therefore, there is a possibility that the viscosity of the coating liquid increases, the deterioration of the coating appearance, or the problem of increased thickness unevenness may occur. Therefore, by mixing the solvent-free polysiloxane with the solvent-type polysiloxane, the viscosity of the coating solution can be reduced, and a layer A with good coating appearance and less uneven thickness can be formed.

Here, "solvent-free polysiloxane" refers to a polysiloxane of a viscosity that can be applied even without being diluted with a solvent, and refers to a polysiloxane with a relatively low molecular weight including a short polysiloxane chain.

Regarding the viscosity of solvent-free polysiloxane, it is better to set the viscosity at 100% concentration as the monomer It is less than 1000mPa‧s, more preferably more than 50mPa‧s or less than 900mPa‧s, and more preferably more than 80mPa‧s or less than 800mPa‧s.

On the other hand, the so-called "solvent-type silicone" is a silicone with a relatively high viscosity that cannot be applied unless it is diluted with a solvent, and it includes a silicone with a relatively high molecular weight.

Regarding the viscosity of solvent-based polysiloxane, it is preferable that the viscosity when made into a 30% toluene solution is above 1000mPa‧s, more preferably above 2000mPa‧s or below 20000mPa‧s, and even more preferably above 3000mPa‧s Or below 18000mPa‧s.

Non-hardening non-fluorinated silicone resin

By containing a non-hardening non-fluorinated polysiloxane resin in the A layer, the controllability of the curing reaction can be improved, and sufficient flexibility can be imparted to the A layer, and the laminated film and the adhesive layer can be laminated. Storage stability is also good. As the non-hardening non-fluorinated silicone resin, silicone resins having no reactive functional groups among the non-fluorinated silicone resins listed above can be used without particular limitation. Specifically, an organopolysiloxane represented by the following general formula (I) is preferable.

R ₃ SiO(R ₂ SiO) _m SiR ₃ ...(I)

(In the formula, R is the same or different monovalent hydrocarbon groups without aliphatic unsaturated bonds, and m represents a positive integer)

The mass mixing ratio of hardening silicone resin (the sum of fluorinated and non-fluorinated) and non-hardening non-fluorinated silicone resin is preferably in the range of 1:1000~1000:1, more preferably 1: Within the range of 100~100:1, more preferably within the range of 1:50~50:1. Most preferably, it is in the range of 1:20~20:1, especially preferably 1:1~20:1.

The thickness of the layer A is preferably from 10 nm to 100 μm, more preferably from 20 nm to 10 μm, still more preferably from 50 nm to 1 μm. The preferred range is 80 nm or more and 800nm or less.

When the film thickness is too thin as less than 10 nm, not only the adhesion between the A layer and the B layer is deteriorated, but also the peelability between the silicone adhesive layer and the B layer of the laminated film tends to be deteriorated. On the other hand, when the film thickness of the A layer is too thick, the amount of material used increases, and it is difficult to obtain an increase in the effect commensurate with the increased amount of use.

3.B layer (release layer)

<Composition of Layer B>

As a material for forming the B layer (release layer), the same fluorine atom-containing resin as described in the above-mentioned A layer (undercoat layer) can be used in the same manner. Among these, a fluorinated silicone resin is preferable, and a curable fluorinated silicone resin is particularly preferable from the viewpoint of releasability with an adherend. By using a curable fluorinated silicone resin for the B layer (release layer), a release film having stable peelability to the silicone adhesive layer can be obtained.

The layer B may be formed of a curable fluorinated silicone resin alone, or may be a mixture of plural materials such as being mixed with a curable non-fluorinated silicone resin.

The coating solution for forming the B layer is particularly preferably a fluorine-based solvent containing a fluorine atom for the purpose of improving wettability to the A layer.

If the film thickness of the B layer is too thin, it may be difficult to obtain the effect of the present invention. On the other hand, if it is too thick, it may be difficult to obtain an increase in the effect corresponding to the increase in the amount of material used.

The lower limit of the thickness of the layer B is preferably at least 5 nm, more preferably at least 10 nm, and most preferably at least 20 nm. Also, the upper limit thereof is preferably not more than 50 μm, more preferably not more than 1 μm, and most preferably not more than 500 nm.

<Content ratio of fluorine atoms in layer B>

In the laminated film of the present invention, layer B (release layer) is formed on layer A (undercoat layer). The material of the layer B is preferably the same as that described in the description of the layer A above, but from the viewpoint of adhesion or easy peeling, the content ratio of fluorine atoms per unit volume contained in the layer B must be more than Layer A.

In the present invention, the lower limit of the fluorine atom content ratio (atomic fraction) contained in the B layer measured by SIMS (Secondary ion mass spectroscopy, secondary ion mass spectrometry) is preferably 3,000 ppm or more, more preferably Preferably, it is 5,000 ppm or more, More preferably, it is 10,000 ppm or more, Most preferably, it is 20,000 ppm or more. On the other hand, the upper limit is not particularly limited, but is preferably at most 900,000 ppm, more preferably at most 800,000 ppm, and most preferably at most 700,000 ppm.

The fluorine atom content ratio of the B layer can be confirmed on the surface of the release layer of the laminated film by secondary ion mass spectrometry (SIMS method) or X-ray photoelectron spectroscopy (XPS method), for example. The fluorine atom content ratio of the B layer can also be quantified by using a material (fluorinated polysilicon, etc.) whose fluorine atom content ratio is known in advance as a reference. In addition, when confirming by the XPS method, the ratio of fluorine to all elements obtained by removing hydrogen and helium was set as the fluorine atom content ratio.

In the above, the case where layer A and layer B having different fluorine atom content ratios are sequentially laminated has been described. When this kind of lamination step can be adopted, the interface between the two layers is clear.

This can also be expected to substantially improve the adhesiveness of the interface between the A layer and the polymer film, or the interface between the A layer and the B layer. Furthermore, since the fluorine atom content ratio on the surface of the B layer can be increased, the content of the fluorine atom-containing resin in the entire laminated film can sometimes be suppressed low, and the light peeling property can be further improved.

4. Fluorine atom content ratio

In the present invention, from the viewpoint of adhesiveness or light peeling property, it is preferable that except for the fluorine atoms contained in the two layers of A layer and B layer, the content ratio is the same as that of the polysiloxane resin used as the base material of each layer. There is a specific relationship in the content ratio of oxane ions (CH ₃ SiO ₂ ⁻ ).

That is, the ratio ([F − ]/[CH 3 SiO 2 − ]) of the fluorine ion content ratio contained in the B layer to the methylsiloxane ion content ratio ([F ⁻ ]/[CH ₃ SiO ₂ ⁻ ]) (hereinafter referred to simply as “ The fluorine atom content ratio") is preferably greater than the fluorine atom content ratio of the A layer.

Moreover, the fluorine atom content ratio of each of the A layer and the B layer is preferably from 1 to 1,000 in the A layer, and from 3 to 5,000 in the B layer.

The lower limit of the more preferable fluorine atom content ratio of the B layer is preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. Moreover, the upper limit is preferably 3,000 or less, more preferably 1,000 or less.

The fluorine atom content ratio of the B layer is preferably 1.1 times or more, more preferably 1.5 times or more, and still more preferably 1.5 times or more, from the viewpoint of light peelability from the silicone adhesive layer. More than 2 times, preferably more than 3 times, most preferably more than 5 times. On the other hand, although the upper limit is not particularly limited, it is preferably 1000 times or less, more preferably 100 times or less, from the viewpoint of the adhesiveness of the A layer and the B layer.

In the present invention, the fluorine atom content ratio (atomic fraction) in the B layer is preferably the fluorine atom content ratio (atomic fraction) in the A layer from the viewpoint of easy release from the silicone adhesive layer. ratio) of 1.1 times or more, more preferably 1.5 times or more, further preferably 2 times or more, especially preferably 3 times or more, most preferably 5 times or more. On the other hand, although the upper limit is not particularly limited, it is preferably 1000 times or less, more preferably 100 times or less, from the viewpoint of the adhesiveness of the A layer and the B layer.

Here, the "fluorine atom content ratio (atomic fraction)" refers to the ratio of fluorine atoms to the layer. When either layer A or layer B is substantially composed of polysiloxane resin (including fluorinated, non-fluorinated, hardened, and non-hardened), regarding the above-mentioned "fluorine atom content ratio" and "fluorine atom Content ratio (atomic fraction)", the ratio of A layer and B layer becomes the same value.

By setting the fluorine atom content ratio of the B layer within the above range, sufficient adhesion can be obtained between the A layer and the B layer, and good peelability between the B layer and the silicone adhesive layer can be exhibited.

In addition, since the fluorine atom content ratio and/or the fluorine atom content ratio of the B layer are higher than that of the A layer, sufficient adhesion between the A layer and the B layer can be obtained, and the good stability between the B layer and the silicone adhesive layer can be obtained. of stripping.

Furthermore, the fluorine atom content ratio or fluorine atom content ratio of the above-mentioned A layer and B layer is calculated by analyzing the structure of the coating agent by nuclear magnetic resonance (nuclear magnetic resonance, NMR) method, or after the layer is formed. It can also be quantified by secondary ion mass spectrometry (SIMS method) or X-ray photoelectron spectrometry (XPS method).

In the measurement by SIMS method or XPS method, the fluorine atom content ratio of each layer can also be quantified by using a material (fluorinated polysiloxane, etc.) whose fluorine atom content ratio is known in advance as a reference.

When the fluorine atoms are not uniformly present in each of the A layer and the B layer (for example, in the case of the above-mentioned inclined structure), it is only necessary to calculate the fluorine atoms contained in each layer measured by the SIMS method or the like. The fluorine atom content ratio per unit volume obtained by dividing the total amount by the volume of each layer may be used as the fluorine atom content ratio of each layer of the A layer and the B layer.

<Other compounds>

Regarding layer A and layer B, it is preferable to contain a crosslinking agent, a catalyst, and a reaction initiator ( reaction accelerator). Furthermore, commercially available coatings containing curable polysiloxane resins sometimes contain crosslinking agents or catalysts initially.

When forming the A layer and the B layer, in order to form a crosslinked structure by reacting with the reactive functional groups contained in the resin, it is preferable to contain a crosslinking agent. Examples of the crosslinking agent include organosiloxanes having vinylsiloxane or hydrogensiloxane moieties, and the like. Specific examples of the above-mentioned crosslinking agent include SP7297, 7560, 3062A, 3062B, 3062C, 3062D, etc. manufactured by Leador Corning Co., Ltd.

In addition, the crosslinking agent may include a site having a fluorine substituent, and a silane coupling agent having a fluorinated substituent may be used.

Also, when forming the A layer and the B layer, it is preferable to contain a catalyst for promoting the addition reaction, and it is preferable to contain a platinum catalyst among them. Examples of platinum catalysts include platinum-based compounds such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid and olefins, complexes of chloroplatinic acid and alkenyl siloxane, platinum black, Platinum-supported silicon oxide and platinum-supported activated carbon. A platinum catalyst can be used 1 type or in combination of 2 or more types.

Moreover, as a specific example of the said catalyst, CAT PL-50T by Shin-Etsu Chemical Co., Ltd., SRX212, SRX212P, NC-25, FS XK-3077 by Toray Dow Corning Co., Ltd. etc. are mentioned.

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

5. Physical properties of the laminated film of the present invention

<Normal peel force>

The normal peel force of the laminated film of the present invention is preferably 100 mN/cm or less.

When a laminated film is used as a release film, the lower the normal peel force, the less force is required to peel off the adhesive layer. Therefore, failure of peeling and deformation of the adhesive layer in the production steps such as peeling off the release film from the laminate with the adhesive layer and attaching the adhesive layer to various members can be suppressed. Among them, even if the laminated film of the present invention is an adhesive layer having strong adhesiveness such as a silicone adhesive, the above-mentioned disadvantages can be suppressed, and it has relatively low peelability. Also, as a release film, In a laminate having a release film on both sides of the adhesive layer, it is possible to prevent the peeling of the release film on the unintended side.

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, most preferably 30 mN/cm or less. 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 the laminate of the laminated film and the adhesive layer.

As a method of reducing the normal peeling force, methods such as adjusting the fluorine atom content ratio of the A layer and the B layer are mentioned. In addition, normal-state peeling force is measured by the method described in the Example mentioned later.

6. Laminated composition

The laminated film of the present invention may have a structure in which layer A is provided on one side or both sides of the polymer film, and layer B is provided on the layer A. In addition, other layers may be inserted between the polymer film and the A layer, or between the A layer and the B layer, as necessary.

Examples of other layers include an antistatic layer having antistatic properties, and an oligomer sealing layer that seals bleed (bleeding, precipitation) of formulations or oligomers onto the film surface, and the like.

Furthermore, the above-mentioned antistatic layer, oligomer sealing layer and other layers can also be formed by the in-line coating method formed at the same time as the polymer film is formed, or formed by other steps on the polymer film after film formation. Formed by any of the off-line coating methods.

The overall thickness of the laminated film of the present invention is preferably from 5 μm to 1250 μm, more preferably from 10 μm to 500 μm, and still more preferably from 10 to 200 μm.

7. Manufacturing method of laminated film of the present invention

<Manufacturing method>

(1) polymer film

As the polymer film used as the base material of the laminated film of the present invention, one formed by forming a film of ethylene, polypropylene, polyester, polystyrene, polycarbonate, and other polymer materials as described above can be used. membrane.

Hereinafter, it demonstrates taking the manufacturing method of a polyester film as an example.

As a method for producing the polyester film used in the present invention, it is preferable to use polyester raw materials such as the above-mentioned polyethylene terephthalate, and use a cooling roll to cool and solidify the melted sheet extruded from the die to obtain a polyester film. A method of stretching a sheet. At this time, in order to improve the planarity of the sheet, it is preferable to increase the adhesion between the sheet and the rotating cooling drum by electrostatic application bonding and/or liquid coating bonding.

The obtained unstretched sheet can also be used as it is, but it is preferably at least uniaxially stretched, more preferably biaxially stretched. Good mechanical strength and dimensional stability can be obtained by stretching the polyester film more than one axis. Also, when used as a release film, it is possible to suppress the occurrence of problems during lamination when the adherend (adhesive layer) is laminated to produce an adhesive sheet with a laminated film.

The stretching conditions are not particularly limited. For example, the unstretched sheet is stretched 2 to 6 times in the longitudinal direction (longitudinal direction) at 70 to 145° C. by a roll stretching method to obtain a uniaxially stretched polyester film, and then, using a tenter The machine stretches at 80~160°C to 2~6 times in the direction (width direction) at right angles to the previous stretching direction, and then heats at 150~250°C for 1~600 seconds to obtain a biaxially stretched film.

In this case, it is more preferable to relax 0.1 to 20% in the longitudinal and/or width direction in the heat treatment area and/or the clean area of the heat treatment outlet.

(2) Formation of A layer (undercoat layer) and B layer (release layer)

The method for forming the above-mentioned A layer and B layer is not limited, and may be formed by a co-extrusion method, but a coating method is preferred.

The number of times of coating of the said A layer and B layer may be 1 time, and may be 2 times or more. When forming the layer A and the layer B by setting the number of times of coating to 2 or more, different coating liquids can be coated. However, at least one of the coating liquids needs to contain fluorine atoms.

The coating method may be in-line coating or off-line coating. For example, the coating technique shown in "Coating Method" (Yuji Harasaki, Maki Shoten, 1979) can be used.

For example, as a coating head, an air knife coater, a knife coater, a rod coater, a knife coater, an extrusion coater, a dip coater, a reverse roll coater, Conveyor Coater, Gravure Coater, Touch Roll Coater, Casting Machine, Spray Coater, Curtain Coater, Calender Coater, Extrusion Coater, etc.

The solid content mass concentration of the coating solution for forming the A layer and the B layer is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, and still more preferably at least 0.1% by mass. On the other hand, the upper limit is preferably at most 90% by mass, more preferably at most 50% by mass, and most preferably at most 20% by mass.

The solvent used for dilution may be a polar solvent or a nonpolar solvent. In addition, a fluorine solvent having a fluorine atom can also be used. Furthermore, the said solvent can be used in mixture of 2 or more types. It is particularly preferable that the coating solution for forming the B layer contains a fluorine solvent having a fluorine atom for the purpose of improving the wettability of the A layer.

Examples of polar solvents include alcohols such as ethanol and isopropanol, and esters such as methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl lactate, and ethyl benzoate. , methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, diisobutyl ketone and other ketones, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and other glycols, N-methyl-2-pyrrolidone, N,N-dimethylformamide, Tetrahydrofuran, acetonitrile, etc.

烷等。作為氟溶劑，可列舉：氫氟醚類、六氟化間二甲苯、十三氟辛烷等。 Examples of non-polar solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, and octane; and branched hydrocarbons such as isohexane, isooctane, and isononane. Classes, cyclohexane, cycloheptane, cyclooctane and other alicyclic hydrocarbons, two

alkanes etc. Examples of the fluorine solvent include hydrofluoroethers, m-xylene hexafluoride, and tridecafluorooctane.

As a method for forming these layers, there can be exemplified a method of preparing in advance as a coating liquid a coating liquid having a ratio corresponding to the fluorine atom content of each layer after coating and drying, and using the same.

In addition, a hardening non-fluorinated polysiloxane resin can be used, mixed with a fluorinated material in a specific amount to prepare a coating solution corresponding to the composition of the A layer/B layer, and then apply and dry. This forms layer A and/or layer B containing the desired fluorine atoms. This method is preferable since it can manufacture the release film of A layer/B layer which has a specific fluorine atom content ratio more simply.

In addition, the A layer and the B layer can be formed by applying and drying the A layer and then applying and drying the B layer. However, in the present invention, the B layer can be coated by applying the A layer. , The wet coating method of subsequent drying can also be expected to shorten the production steps or improve energy efficiency.

As another method, a mixture of curable fluorinated polysiloxane resin and curable non-fluorinated polysiloxane resin is applied to form layer A, and then, as layer B, curable fluorinated polysiloxane is coated. The method of forming a solution of oxygen resin as the main component is more preferable because it can stably produce a release film.

Furthermore, as another method, it is also possible to form a non-fluorinated resin by coating in advance, and then to produce a fluorinated layer by a dry process such as carbon tetrafluoride (CF ₄ ) plasma treatment. However, this method needs to install a chamber for plasma processing, so it can be said that it is suitable for mass production.

As the manufacturing method of the laminated film of the present invention, it is used in the manufacture of polymer films In the case of the so-called in-line coating of the in-step coating, both the A layer and the B layer can be used for in-line coating, or only the A layer can be used for in-line coating, and the B layer can be set for off-line coating. coating.

In the case where the above-mentioned layer A and layer B are provided by off-line coating, it can be formed continuously by one "substrate film unwinding-coiling step", or it can be formed through multiple "substrate film unwinding-coiling steps" "Formed sequentially, but the former manufacturing steps are simple and can be manufactured at a lower cost, so it is the preferred method.

Furthermore, by making the heat applied to the film when forming the above-mentioned A layer lower than the heat applied when forming the above-mentioned B layer, the deterioration of the film planarity when forming the B layer can be suppressed, and it is also possible to effectively prevent the coating of the B layer from being uneven. It is produced equally, so it is better.

8. How to use laminated film

The laminated film of the present invention has excellent release properties, so it can be provided, for example, as an adhesive sheet with a laminated film having a structure in which the above laminated film and an adhesive layer are laminated. In particular, the laminated film of the present invention also has excellent release properties to a silicone adhesive having strong adhesiveness, so it can be used, for example, as a laminated film having the above-mentioned laminated film and an adhesive layer containing a silicone adhesive. Supplied as an adhesive sheet with a laminated film.

However, the utilization method of the laminated film is not limited to this utilization method. For example, since fluorine atoms are contained in the laminated film, it is excellent in water resistance, water repellency, oil resistance, oil repellency, anti-fogging property, anti-fouling property, chemical resistance, corrosion resistance, etc. Films, films for building materials, agricultural films, high water repellency films, packaging films, decorative films, surface protection films, etc. When the surface of layer B is used as the outermost surface, an adhesive layer, adhesive layer, heat-sealing layer, etc. can also be provided on the surface of the polymer film opposite to the surface having layers A and B.

<Polysilicone Adhesive>

Examples of silicone adhesives include addition reaction type, peroxide curing type, or condensation reaction type silicone adhesives. Among them, from the viewpoint of low-temperature short-time hardening In other words, an addition reaction type polysiloxane adhesive can be preferably used. Furthermore, the addition reaction polysiloxane adhesive is hardened on the support when the adhesive layer is formed.

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 adhesive can be coated on a support after adding a catalyst such as a platinum catalyst to a silicone resin solution diluted with a solvent such as toluene as needed and stirring in a uniform manner. Harden at 100~130°C/1~5 minutes.

Also, if necessary, a crosslinking agent or an additive for controlling the adhesive force may be added to the above-mentioned addition reaction silicone adhesive, or the above-mentioned support may be primed before forming the above-mentioned adhesive layer.

Examples of commercially available silicone resins used in the above-mentioned addition reaction silicone adhesive include: SD4580PSA, SD4584PSA, SD4585PSA, SD4587LPSA, SD4560PSA, SD4570PSA, SD4600FCPSA, SD4593PSA, DC7651ADHESIVE, DC7652ADHESIVE, LTC-755, LTC-310 (all manufactured by Toray Dow Corning), 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 made by Shin-Etsu Chemical Co., Ltd.), AS-PSA001, AS-PSA002, AS-PSA003, AS-PSA004, AS-PSA005, AS-PSA012 .

[Example]

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following Example. Furthermore, the raw materials described as "addition type" in the following examples are all Means "hardening".

(1) Evaluation method

(1-1) Normal peel force

In an environment of 23°C, attach a tape with silicone adhesive (manufactured by 3M Japan, No5413 tape, 50mm width) to the surface of layer B (release layer) of the laminated film, and set it on the peel tester . The normal peeling force was measured under the condition that the peeling speed was 0.3m/min and the peeling angle was 180°.

(1-2) Fluorine atom content ratio, ratio of fluorine atom content ratio

The fluorine atom content ratio in the A layer and the B layer was evaluated using TOF-SIMS (manufactured by ULVAC-PHI, TRIF V).

As primary ions, Au ³⁺ was used, and the acceleration voltage was set to 30 kV.

In order to evaluate the fluorine atom content ratio per unit volume, etch with Ar gas (voltage: 5kV, current: 2nA, etch rate: 20nm/min (PET film conversion)) was performed for 0min, 1min, 2min, and 3min, and each etched Average the ratio of the counted values of the anions ("F ^- " and "CH ₃ SiO ₂ ^- ") detected over time, and set the resultant as the fluorine atom content ratio per unit volume ("F ^- "/"CH ₃ SiO 2 - _2- ^" ).

Also, the value of [the fluorine atom content ratio of the B layer]/[the fluorine atom content ratio of the A layer] was defined as the ratio of the fluorine atom content ratio. This value has the same meaning as the result obtained by measuring the fluorine atom content ratio (atomic fraction) of each of the A layer and the B layer using XPS and calculating the ratio of the values of each layer.

[Example 1]

(coating liquid 1)

The following compositions were mixed and diluted using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1:1) so that the solid content concentration became 4% by mass to prepare "coating liquid 1".

<Composition of Coating Liquid 1>

Addition-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 67 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass

Addition-type fluorinated silicone (manufactured by Toray Dow Corning, Syl-off 3062): 100 parts by mass

Crosslinking agent (manufactured by Dow Corning Toray, Syl-off 3062A): 0.5 parts by mass

Platinum catalyst (manufactured by Toray Dow Corning, FSXK-3077): 0.5 parts by mass

(coating liquid 2)

The following composition was mixed and diluted with a mixed solvent of FS diluent (manufactured by Shin-Etsu Chemical Co., Ltd.)/ethyl acetate=1:1 (mass ratio) so that the solid content concentration became 0.5% by mass to prepare a "coating solution" 2".

<Composition of Coating Liquid 2>

Addition-type fluorinated silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-70-201S): 100 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.5 parts by mass

(production of laminated film)

Using a PET film ("T100-38" manufactured by Mitsubishi Chemical Corporation, thickness 38 μm) as a polymer film, the above-mentioned coating solution 1 was coated on the polymer film with a bar coater (No. Dry in an oven for 30 seconds to harden the resin of layer A to form a polymer film with layer A (undercoat layer).

Furthermore, the above-mentioned coating solution 2 was coated on the A layer of the polymer film having the above-mentioned A layer (undercoat layer) by a bar coater (No4 rod), and dried in an oven at 150° C. for 30 seconds to make B The resin of the layer is cured, thereby producing a laminated film in which the B layer (release layer) is 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 above-mentioned coating solution 2 was set to 4% by mass.

In addition, since the coating solution 2 was applied using the same bar coater as in Example 1, the thickness of the B layer was increased compared with Example 1 by increasing the solid content concentration.

[Comparative example 1]

In the same manner as in Example 1, substantially only Laminated film including polymer film and B layer (release layer).

[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 above-mentioned coating solution 2 was 4% by mass.

Furthermore, the same bar coater as that of Comparative Example 1 was used to coat the coating liquid 2, so the thickness of the layer B in Comparative Example 1 was larger than that of the B layer due to the increase in the solid content concentration.

[Comparative example 3]

Except that the above-mentioned coating solution 2 is not coated on the above-mentioned A layer (undercoat layer) and the B layer (release layer) is not formed, in the same manner as in Example 1, a polymer film consisting essentially only of a polymer film and A layer (undercoat layer) of the laminated film.

[Comparative example 4]

(coating liquid 3)

Coating solution 3 was prepared with the following composition.

<Composition of Coating Liquid 3>

Addition-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847H): 67 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 0.7 parts by mass

The said composition was diluted with the mixed solvent (mass ratio=1:1) of n-hexane and MEK so that solid content concentration might become 4 mass %.

(production of laminated film)

The above coating solution 3 was coated on the polymer film by a bar coater (No4 bar), and dried in an oven at 150° C. for 30 seconds to form a layer A (undercoat layer).

Next, the above-mentioned coating liquid 2 is to be coated on the above-mentioned A layer (undercoat layer) with a bar coater (No4 bar). However, the above-mentioned coating solution 2 was not uniformly applied on the above-mentioned A layer (undercoat layer), and a phenomenon (shrinkage) occurred in dots or lines (network), so the B layer (release layer) could not be formed. .

[Comparative Example 5]

About layer B (release layer), except having made the solid content concentration of the said coating liquid 2 into 4 mass %, it was going to manufacture a laminated film in the same manner as in the comparative example 4. However, "coating solution 2" was not uniformly applied on the above-mentioned A layer (undercoat layer), and a phenomenon (shrinkage) occurred in the form of dots or lines (network), so the B layer (release layer) could not be formed. ).

[Example 3]

(coating liquid 4)

The following composition was mixed and diluted so that the solid content concentration might become 4 mass % using the mixed solvent (mass ratio=1:1) of isopropyl ether and ethyl acetate, and "coating liquid 4" was prepared.

<Composition of Coating Solution 4>

Addition-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 133 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 1.3 parts by mass

Addition-type fluorinated silicone (manufactured by Toray Dow Corning, Syl-off 3062): 100 parts by mass

Crosslinking agent (manufactured by Dow Corning Toray, Syl-off 3062A): 0.5 parts by mass

Platinum catalyst (manufactured by Toray Dow Corning, FSXK-3077): 0.5 parts by mass

(made into laminated film)

On the A layer (undercoat layer) obtained by applying and curing the above-mentioned coating liquid 4 instead of the above-mentioned coating liquid 1 on the polymer film, the above-mentioned Except for the coating solution 2, a laminated film was produced in the same manner as in Example 1.

[Example 4]

(coating solution 5)

The following compositions were mixed and diluted using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1:1) so that the solid content concentration became 4% by mass to prepare "coating liquid 5".

<Composition of Coating Solution 5>

Addition-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 200 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 2.0 parts by mass

Addition-type fluorinated silicone (manufactured by Toray Dow Corning, Syl-off 3062): 100 parts by mass

Crosslinking agent (manufactured by Dow Corning Toray, Syl-off 3062A): 0.5 parts by mass

Platinum catalyst (manufactured by Toray Dow Corning, FSXK-3077): 0.5 parts by mass

(made into laminated film)

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

[Example 5]

(coating liquid 6)

The following compositions were mixed and diluted using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio = 1:1) so that the solid content concentration became 4% by mass to prepare "coating liquid 6".

<Composition of Coating Solution 6>

Addition-type organopolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KS-847): 267 parts by mass

Platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., CAT-PL-50T): 2.0 parts by mass

Addition-type fluorinated silicone (manufactured by Toray Dow Corning, Syl-off 3062): 100 parts by mass

Crosslinking agent (manufactured by Dow Corning Toray, Syl-off 3062A): 0.5 parts by mass

Platinum catalyst (manufactured by Toray Dow Corning, FSXK-3077): 0.5 parts by mass

(production of laminated film)

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

(3) Evaluation of results

For the obtained laminated film, the fluorine atom content ratio of the A layer (undercoat layer) and the B layer (release layer), and the normal peeling force using a silicone adhesive tape were measured. The results are shown in Table 1 below.

It can be seen that in Examples 1 and 2, the A layer (undercoat layer) and the B layer (release layer) specified in the present invention are formed on the PET film, so it is different from the film using only the B layer (release layer). In Comparative Examples 1 and 2, good peelability was obtained.

In particular, in the laminated film of Example 1, although the thickness of the B layer (release layer) was formed relatively thin (the concentration of the coating solution 2 was "0.5% by mass"), it was obtained with a layer B (release layer) thicker than the thickness of the layer B (release layer). The peelability of the release film of Example 2 of Example 1 (the concentration of the coating solution 2 is "4% by mass") is the same level. From this, it can be seen that a release film with excellent peelability to the silicone adhesive can be produced with a smaller amount of fluorine-based materials.

In addition, the release film of Examples 3 to 5 in which the fluorine atom content ratio of the A layer (undercoat layer) is lower than that of Example 1 also obtained the same level of peeling properties as the release film of Example 1. by A smaller amount of fluorine-based materials produces a release film with excellent peelability to silicone adhesives.

Furthermore, in order to evaluate the fluorine atom content ratio of each layer, the fluorine atom content ratio obtained by TOF-SIMS was measured for the samples of Comparative Example 3 (only A layer) and Comparative Example 2 (only B layer), and they were respectively referred to as A layer and The value of layer B. As a result, it was confirmed that the fluorine atom content ratio per unit volume of the B layer was higher than that of the A layer.

Moreover, since the composition of the coating liquid is the same, this value is made into the value of the fluorine atom content ratio of each layer of Example 1, 2 and Comparative Example 1. Furthermore, the fluorine atom content ratio of the A layer in Examples 3 to 5 is based on the value of the fluorine atom content ratio in Example 1, and calculated from the raw material composition ratio.

Furthermore, it is considered that the fluorine atom content ratio of layer A is the highest on the surface (TOF-SIMS etching time of 0 minutes), and the longer the etching time (that is, the closer to the substrate PET film side), the less, and the fluorine atom content on the surface side is formed. Slope structure with increasing ratio. The values shown in Table 1 are average values in the thickness direction.

1‧‧‧polymer film

2‧‧‧A layer (undercoat)

3‧‧‧B layer (release layer)

4‧‧‧polysiloxane adhesive layer

Claims (14)

A laminated film, characterized in that: it is formed by sequentially laminating layer A and layer B on at least one side of a polymer film, and the interface between layer A and layer B is clear, and the two layers of layer A and layer B contain fluorine atoms , and the fluorine atom content ratio of the B layer is higher than the fluorine atom content ratio of the A layer. The laminated film according to claim 1, wherein the content ratio of the fluorine atoms in the B layer is 1.1 times or more than the content ratio of the fluorine atoms in the A layer. A laminated film, characterized in that: it is formed by sequentially laminating layer A and layer B on at least one side of a polymer film, and the interface between layer A and layer B is clear, the above-mentioned layer B contains fluorine atoms, by the following Method The normal peeling force at the time of measurement is 100mN/cm or less. <Measurement of normal peeling force> A tape with a silicone adhesive (manufactured by 3M Japan, No5413 tape, 50mm wide) is attached to B of the laminated film On the surface of the layer, a 180°peel test was performed at a peeling speed of 0.3m/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 3, wherein the above-mentioned A layer and B layer contain fluorinated Silicone resin. The laminated film according to any one of claims 1 to 3, 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 3, wherein the above-mentioned layers A and B are layers formed by curing a curable fluorinated polysiloxane resin. The laminated film according to claim 5, wherein the content ratio of fluoride ion (F ^- ) and the content ratio of methylsiloxane ion (CH ₃ SiO ₂ ^- ) when measured by time-of-flight secondary ion mass spectrometer (TOF-SIMS) The ratio ([F ⁻ ]/[CH ₃ SiO ₂ ⁻ ]) is 1 to 1,000 in the A layer, and 3 to 5,000 in the B layer. The laminated film according to claim 6, wherein the content ratio of fluoride ion (F ^- ) and the content ratio of methylsiloxane ion (CH ₃ SiO ₂ ^- ) when measured by time-of-flight secondary ion mass spectrometer (TOF-SIMS) The ratio ([F ⁻ ]/[CH ₃ SiO ₂ ⁻ ]) is 1 to 1,000 in the A layer, and 3 to 5,000 in the B layer. The laminated film according to claim 7, wherein the content ratio of fluoride ion (F ^- ) and the content ratio of methylsiloxane ion (CH ₃ SiO ₂ ^- ) when measured by time-of-flight secondary ion mass spectrometer (TOF-SIMS) The ratio ([F ⁻ ]/[CH ₃ SiO ₂ ⁻ ]) is 1 to 1,000 in the A layer, and 3 to 5,000 in the B layer. The laminated film according to any one of claims 1 to 3, wherein the fluorine atom content ratio (atomic fraction) of the A layer is more than 50 ppm and less than 900,000 ppm, and the fluorine atom content ratio (atomic fraction) of the B layer is ) is not less than 3,000 ppm and not more than 900,000 ppm. A release film using the laminated film according to any one of Claims 1 to 11. A laminate, which is formed by laminating the release film and adhesive according to claim 12. The laminate according to Claim 13 is formed by providing an adhesive layer on the surface of the B layer which is not in contact with the above-mentioned A layer.

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