CN111465639A - Laminated film, release film, and laminate - Google Patents

Laminated film, release film, and laminate Download PDF

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Publication number
CN111465639A
CN111465639A CN201880079992.8A CN201880079992A CN111465639A CN 111465639 A CN111465639 A CN 111465639A CN 201880079992 A CN201880079992 A CN 201880079992A CN 111465639 A CN111465639 A CN 111465639A
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layer
film
fluorine atom
laminated
laminated film
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CN111465639B (en
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大关阳介
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/005—Presence of halogenated polymer in the release coating
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane
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    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention provides a laminated film having excellent releasability from an adhesive layer having strong adhesiveness such as a silicone adhesive. The laminated film is characterized in that a layer A and a layer B are laminated in this order on at least one side of a polymer film, both the layer A and the layer B contain fluorine atoms, and the fluorine atom content ratio of the layer B is greater than the fluorine atom content ratio of the layer A.

Description

Laminated film, release film, and laminate
Technical Field
The present invention relates to a laminated film, and more particularly to a laminated film having releasability.
Background
In recent years, there have been increasing numbers of automobiles equipped with liquid crystal panels. In such vehicle-mounted applications, exposure to high and low temperatures for a long period of time is also frequent, and a high degree of weather resistance and heat resistance is also required for the adhesive for bonding the panel constituent members. As an adhesive suitable for these requirements, a silicone adhesive having strong adhesiveness is attracting attention.
The silicone adhesive is used as an adhesive layer and is in the form of a tape (film), and is generally stored in a state in which one side or both sides thereof are covered with a release film before use, and the release film is peeled off at the time of use. However, a silicone adhesive (adhesive layer) having strong adhesiveness has a problem that it is strongly adhered to a widely used release film coated with an organic silicone and it is difficult to peel the release film at the time of use.
As a method for exhibiting peelability from a molded article formed by molding a molding resin such as a silicone resin composition, a fluorinated silicone material having a fluorine substituent is proposed (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2011-201035
Disclosure of Invention
Problems to be solved by the invention
However, when a fluorinated silicone material is used as the release layer, the following problems are observed to occur: the adhesiveness between the polymer film and the release layer becomes insufficient, and interlayer peeling occurs, or the release layer is not uniformly formed, and the peelability to the adherend is deteriorated.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a release film having excellent releasability from an adhesive layer having strong adhesiveness such as a silicone adhesive.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the above problems can be solved by forming a laminated film in which a layer a and a layer B are laminated in this order on at least one surface of a polymer film, so that each layer contains fluorine atoms and the fluorine atom content ratio of the two layers is controlled, and the present invention has been 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, wherein both the a layer and the B layer contain fluorine atoms, and the fluorine atom content ratio of the B layer is larger than the fluorine atom content ratio of the a layer.
The present invention also provides a laminated film comprising a polymer film and, laminated on at least one side thereof, an a layer and a B layer in this order, wherein the B layer contains fluorine atoms and has a normal peel force of 100mN/cm or less as measured by the following method.
< measurement of Normal peeling force >
A tape (No 5413 tape, No. 3M Japan L approved) with a silicone adhesive was adhered to the surface of the layer B of the laminate film, and a 180 ℃ peel test was carried out at a peel speed of 0.3M/min.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a laminated film having excellent releasability from an adhesive layer having strong adhesiveness such as a silicone adhesive can be obtained.
Drawings
Fig. 1 is a schematic view of a laminated film of the present invention.
Fig. 2 is a schematic view showing a state where a silicone pressure-sensitive adhesive layer is peeled off in a laminated film of the conventional art (a) and the present invention (b).
Detailed Description
The embodiment of the laminated film of the present invention will be described in more detail below.
As illustrated in fig. 1, the laminated film of the present invention is a laminated film in which a layer a (undercoat layer) and a layer B (release layer) are laminated in this order on at least one surface of a polymer film.
The laminated film of the present invention will be described below in the order of a polymer film, an a layer (undercoat layer) and a B layer (release layer).
1. Polymer film
Examples of the polymer film to be a base material of the laminated film of the present invention include films obtained by forming a polymer such as polyethylene, polypropylene, polyester, polystyrene, polycarbonate, polyethersulfone, polyamide, polyimide, or the like into a film. Further, as long as the film can be made thin, a film (polymer blend) obtained by mixing these materials or a film (copolymer) obtained by compounding the structural units may be used.
The polymer film is not particularly limited as long as it is made into a film, and may be an unstretched film or a stretched film, and 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 flatness.
The thickness of the polymer film constituting the laminated film in the present invention is not particularly limited as long as it is within a range in which the film can be formed, and is preferably 5 μm or more and 1000 μm or less, more preferably 10 μm or more or 500 μm or less, and further preferably 15 μm or more or 200 μm or less.
Among the above-exemplified films, the biaxially stretched polyester film is particularly preferable because the polyester film is excellent in physical properties such as heat resistance, flatness, optical properties, and strength.
The polyester film may be a single layer, or may be 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 a homopolyester or a copolyester. The homopolyester is preferably a polyester obtained by polycondensing an aromatic dicarboxylic acid and an aliphatic diol. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2, 6-naphthalenedicarboxylic acid, and examples of the aliphatic diol include ethylene glycol, diethylene glycol, 1, 4-butanediol, and 1, 4-cyclohexanedimethanol.
Examples of typical homopolypolyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate (PBT). On the other hand, as the dicarboxylic acid component of the copolyester, there may be mentioned one or two or more species selected from isophthalic acid, phthalic acid, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, etc., and as the diol component, there may be mentioned one or two or more species selected from ethylene glycol, diethylene glycol, propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, etc.
Among them, in the present invention, it is preferable that: usually 60 mol% or more, preferably 80 mol% or more of polyethylene terephthalate comprising ethylene terephthalate units.
In the present invention, an undercoat layer (undercoat layer) may be provided on the surface of the polymer film in order to impart antistatic properties, blocking properties by bleeding of a compound or oligomer (bleed-out or plating) to the surface of the film, light transmittance of the film, and adhesion to the a layer (undercoat layer) described later.
The aforementioned substrate layer may be formed by any one of: an in-line coating method for forming an underlayer while forming a polymer film, and an off-line coating method for separately forming an underlayer on a film formed.
The substrate layer may be formed on at least one surface of the polymer film. When the layers are formed on both sides, the same substrate layer may be formed on both sides, or different substrate layers may be formed on the respective surfaces. The substrate layer may be any of a layer containing an organic substance, a layer containing an inorganic substance, and a layer containing a mixture of an organic substance and an inorganic substance.
Layer A (undercoat)
In the present invention, the polymer film has a layer a (undercoat layer) on at least one surface thereof.
< construction of layer A >
The a layer usually contains fluorine atoms. This not only has adhesion between the layer a and the layer B described later, but also exhibits light releasability between the layer B and a pressure-sensitive adhesive layer as an adherend when used as a release film, and enables easy peeling of the adherend.
The method for containing a fluorine atom in the a layer is not limited as long as at least the a layer contains a compound containing a fluorine atom. Specifically, a low molecular weight compound containing a fluorine atom, a resin containing a fluorine atom, and the like can be mentioned. Among them, a resin containing a fluorine atom is preferably used, and the resin is particularly preferably curable.
Further, when the release film is used as a release film, the B layer is laminated on the a layer, whereby the release force to an adherend can be reduced and the release film can have a light release property. The inventors speculate that: when the a layer is not laminated on the laminated film, the adherend (pressure-sensitive adhesive) follows the peeling direction even when the laminated film is peeled, and therefore a larger force is required for peeling from the adherend, and peeling (re-peeling) is difficult (fig. 2 (a)). On the other hand, as shown in the present invention, it is presumed that: when the a layer containing fluorine atoms is laminated on the laminated film, the a layer has relative flexibility, and therefore, the a layer functions in a cushioning manner at the time of peeling, and deformation of the adherend is suppressed, and therefore, the a layer can be peeled from the adherend with a smaller force and is easily peeled (light peeling) (fig. 2 (b)).
< fluorine atom content ratio in layer A >
The a layer contains a material containing a fluorine atom, and from the viewpoint of adhesion and light peeling properties, the fluorine atom content (atomic number fraction) thereof is preferably 50ppm or more, more preferably 500ppm or more, further preferably 1000ppm or more, and particularly preferably 50000ppm or more, based on the entire a layer. On the other hand, the upper limit is not particularly limited, but is preferably less than 900000ppm, more preferably 800000ppm or less, and still more preferably 700000ppm or less.
The fluorine atom content ratio of the a layer can be confirmed by analyzing the vicinity of the polymer thin film constituting the undercoat layer of the laminated thin film in the depth direction by sputter etching, for example, by X-ray photoelectron spectroscopy (XPS). The fluorine atom content ratio of the layer a can also be quantified by using a material (such as fluorinated silicone) whose fluorine atom content ratio is known in advance as a reference. In addition, the ratio of fluorine to all elements except hydrogen and helium was defined as the fluorine atom content ratio when confirmed by XPS method.
By setting the fluorine atom content ratio of the a layer to the above range, the B layer (release layer) containing fluorine atoms can be uniformly coated when provided on the a layer by a coating method, and the adhesion between the a layer and the B layer after coating and lamination can be improved.
When the fluorine atom content ratio is achieved as described above for the entire a layer, the resin used for the a layer may be a resin containing a fluorine atom alone or may be a resin containing no fluorine atom (non-fluorinated resin) in combination.
The layer a may have a composition in which the fluorine atom content is inclined in the thickness direction. The same applies to the B layer described later.
< resin containing fluorine atom >
Examples of the resin containing a fluorine atom used in the present invention include resins containing a fluorine atom in a side chain portion of a resin skeleton. Specific examples of the resin containing a fluorine atom include, in addition to the fluorinated silicone resin, fluorocarbon resins such as polytetrafluoroethylene, and other various resins subjected to a fluorination treatment, and among these, the fluorinated silicone resin is preferable from the viewpoint of peelability.
The fluorinated silicone resin may be a curable resin or a non-curable resin, and may be used without particular limitation. Among them, a curable fluorinated silicone resin is preferable in that a stronger layer is formed. The fluorinated silicone resin may be a solvent-based resin, a solventless resin, or a resin obtained by mixing these components. In general, a functional group capable of forming a crosslinked structure by reaction (curing) such as an alkenyl group or a hydrosilyl group is bonded to a curable fluorinated silicone resin.
Examples of the curable fluorinated silicone resin include KP-911 and X-70-201S available from shin-Etsu chemical Co., Ltd, FS1265-300CS, FS1265-1000CS, FS1265-10000CS, BY24-900, BY24-903, Syl-off 3062, and Q2-7785 available from Dow Corning Toray Co., Ltd, and L td..
The fluorine atom content (atomic number fraction) of the fluorinated silicone resin is usually about several thousand ppm to several tens%.
< resin containing no fluorine atom >
The resin containing no fluorine atom (non-fluorinated resin) used in the present invention includes silicone resin, polyolefin resin, acrylic resin, and the like, and among these, a resin containing a fluorine atom is preferable, and a silicone resin is particularly preferable from the viewpoint of compatibility with a fluorinated silicone resin (in the present invention, a silicone resin containing no fluorine atom is sometimes referred to as "non-fluorinated silicone resin"). The non-fluorinated resin may be either a curable resin or a non-curable resin, or both may be used in combination. Similarly to the curable fluorinated silicone resin, a functional group capable of forming a crosslinked structure by reaction (curing), such as an alkenyl group or a hydrosilyl group, is generally bonded to the non-curable fluorinated silicone resin.
Curable non-fluorinated silicone resin
The curable non-fluorinated silicone resin may be a solvent-based or solvent-free type.
Specific examples of the curable non-fluorinated silicone resin include KNS-3051, KNS-320-316, KNS-3002, KNS-3300, X-62-1387, KS-3656, KS-837, X-62-2829, KS-3650, KS-847-847-776, KS-776-774, KS-3703-3601, KS-830-62-2825, X-62-9201 3951, KM-768, X-52-6015, KF-2005, X-62-7205, X-62-7028-62-7052, X-62-7622, X-62-7660, X-62-7655, Dow Corg Toray, SP7017, SP7015, SP7025, SP 700, SP7031, TC3, TC-4431, TC-44357, SRTC-44752, TC-752, TC-44357, TC-10, TC-449, TC-44357, TC-449, TC-44752, TC-752, TC-200, TC-44357, TC-449, TC-102, and the like.
Further, a heavy release additive may be added to the curable non-fluorinated silicone resin, and examples thereof include KS-3800 manufactured BY shin-Etsu chemical Co., Ltd., SD7292 manufactured BY Dow Corning Toray Co., L td., BY24-4980, and the like.
The curable non-fluorinated silicone may be used alone, or two or more different types may be used in combination. By mixing two or more kinds of curable non-fluorinated silicones, the curing reaction can be adjusted, the viscosity of the coating liquid for the layer a can be adjusted, and the wettability and reactivity of the layer B can be further improved. In this case, the solvent-free silicone may be mixed with each other, the solvent-based silicone may be mixed with each other, or the solvent-free silicone and the solvent-based silicone may be mixed. In particular, when the thickness of the layer a is increased in order to obtain a release film that is more easily peeled off, the solid content concentration of the coating liquid forming the layer a tends to be high. Therefore, there is a possibility that the viscosity of the coating liquid increases, the coating appearance deteriorates, and the thickness unevenness becomes large. Therefore, by mixing the solvent-free silicone with the solvent-based silicone, the viscosity of the coating liquid can be reduced, and a layer a having good coating appearance and small thickness variation can be formed.
Here, the "solventless silicone" is a silicone having a viscosity that can be applied without being diluted with a solvent, is formed of a short polysiloxane chain, and is a silicone having a relatively low molecular weight.
The viscosity of the solvent-free silicone is preferably less than 1000 mPas, more preferably 50 mPas or more or 900 mPas or less, and even more preferably 80 mPas or more or 800 mPas or less, when the viscosity is 100% concentration.
On the other hand, "solvent-type silicones" are silicones having a viscosity as high as the extent that coating cannot be performed without dilution with a solvent, and are silicones containing a higher molecular weight.
The viscosity of the solvent-based silicone is preferably 1000mPa · s or more, more preferably 2000mPa · s or more, or 20000mPa · s or less, and even more preferably 3000mPa · s or more, or 18000mPa · s or less when it is a 30% toluene solution.
Non-curable non-fluorinated silicone resin
By including a non-curable non-fluorinated silicone resin in the layer a, the controllability of the curing reaction can be improved, sufficient flexibility can be imparted to the layer a, and the storage stability of a laminate in which a laminate film and a pressure-sensitive adhesive layer are laminated is also improved. The non-curable non-fluorinated silicone resin may be any of the non-fluorinated silicone resins listed above and having no reactive functional group, without any particular limitation. Specifically, organopolysiloxanes represented by the following general formula (I) are preferable.
R3SiO(R2SiO)mSiR3……(I)
(wherein R represents a monovalent hydrocarbon group of the same or different type having no aliphatic unsaturated bond, and m represents a positive integer.)
The mixing ratio by mass of the curable silicone resin (total of fluorinated and non-fluorinated) to the non-curable non-fluorinated silicone resin is preferably in the range of 1: 1000-1000: 1, more preferably in the range of 1: 100-100: 1, more preferably in the range of 1: 50-50: 1, in the above range. Particularly preferably in the range of 1: 20-20: 1, particularly preferably 1: 1-20: 1.
the thickness of the A layer is preferably 10nm to 100 μm, more preferably 20nm to 10 μm, and still more preferably 50nm to 1 μm. A particularly preferable range is 80nm or more and 800nm or less.
If the film thickness is too thin as less than 10nm, not only the adhesion between the a layer and the B layer is deteriorated, but also the releasability between the silicone adhesive layer and the B layer of the laminate film tends to be deteriorated. On the other hand, when the film thickness of the a layer is too thick, the amount of the material used increases, and it is difficult to obtain an effect corresponding to the increase in the amount.
Layer B (mold release layer)
< construction of layer B >
As a material for forming the B layer (release layer), the same fluorine atom-containing resin as described for the a layer (undercoat layer) can be used in the same manner. Among these, from the viewpoint of releasability from an adherend, a fluorinated silicone resin is preferable, and a curable fluorinated silicone resin is particularly preferable. By using a curable fluorinated silicone resin for the B layer (release layer), a release film having stable releasability from 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 a plurality of materials such as a mixture with a curable non-fluorinated silicone resin.
The coating liquid for forming the B layer particularly preferably contains a fluorine-based solvent containing a fluorine atom for the purpose of improving wettability with respect to the a layer.
If the film thickness of the B layer is too thin, the effect of the present invention may be difficult to obtain, while if it is too thick, the effect corresponding to the increase in the amount of the material may be difficult to obtain.
The lower limit of the film thickness of the B layer is preferably 5nm or more, more preferably 10nm or more, and particularly preferably 20nm or more. The upper limit is preferably 50 μm or less, more preferably 1 μm or less, and particularly preferably 500nm or less.
< fluorine atom content ratio in layer B >
The laminated film of the present invention has a B layer (release layer) formed on an a layer (primer layer). The material suitable for the B layer is the same as the material described in the description of the a layer, but from the viewpoint of adhesion and light peelability, the content of fluorine atoms per unit volume contained in the B layer must be higher than that contained in the a layer.
In the present invention, the lower limit of the fluorine atom content (atomic number fraction) in the B layer measured by SIMS method or the like is preferably 3000ppm or more, more preferably 5000ppm or more, still more preferably 10000ppm or more, and particularly preferably 20000ppm or more. On the other hand, the upper limit is not particularly limited, but is preferably 900000ppm or less, more preferably 800000ppm or less, and particularly preferably 700000ppm or less.
The fluorine atom content ratio of the B layer can be confirmed by, for example, Secondary Ion Mass Spectrometry (SIMS) or X-ray photoelectron spectroscopy (XPS) on the surface of the release layer of the laminated film. The fluorine atom content ratio of the B layer can also be quantified by using a material (such as fluorinated silicone) whose fluorine atom content ratio is known in advance as a reference. In addition, the ratio of fluorine to all elements except hydrogen and helium was defined as the fluorine atom content ratio when confirmed by XPS method.
Although the description has been made above with respect to the case where the a layer and the B layer having different fluorine atom content ratios are sequentially laminated, the structure substantially equivalent to the laminated structure of the a layer and the B layer may be obtained by processing the layers so that the fluorine atom content ratios in the layers have an inclined structure (composition forming an inclination) in the thickness direction in one lamination step. Examples of the method include the following: a method in which a resin containing fluorine atoms and a resin containing no fluorine atoms are diluted with a solvent to prepare a coating solution, and the coating solution is applied to at least one surface of a polymer film and dried, whereby the resin containing fluorine atoms is concentrated on the surface of a layer to prepare a layer having an inclined structure in the thickness direction. In the case of the lamination step, the method is not necessarily limited to the method of laminating the a layer and the B layer in a stepwise manner, and the interface between the two layers may not be obvious, and the present invention includes the case where the surface side of one layer is the B layer and the polymer film side is the a layer, and the substantially same structure is provided.
In this way, by making the a layer and the B layer have an inclined structure, it is also expected to improve the adhesion substantially at the interface between the a layer and the polymer thin film and at the interface between the a layer and the B layer. Further, since the fluorine atom content ratio on the surface of the B layer can be increased, the content of the resin containing fluorine atoms in the entire laminated film can be suppressed to be low, and the light peelability can be further improved in some cases.
4. Fluorine atom content ratio
In the present invention, from the viewpoint of adhesion and light peelability, both layers a and B contain fluorine atoms and also methyl siloxane ions (CH) in a proportion equal to the silicone resin forming the base material of each layer3SiO2 -) The content ratio of (b) is preferably in a specific relationship.
That is, the ratio of the fluorine ion content to the methylsiloxane ion content in the B layer calculated by SIMS or the like ([ F ]-]/[CH3SiO2 -]) (hereinafter, abbreviated as "fluorine atom content ratio") is preferably larger than the fluorine atom content ratio of the a layer.
In addition, the fluorine atom content ratio of each of the a layer and the B layer is preferably 1 or more and 1000 or less, and the B layer is preferably 3 or more and 5000 or less.
The lower limit of the fluorine atom content ratio in the B layer is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more. The upper limit is preferably 3000 or less, and more preferably 1000 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, further preferably 2 times or more, particularly preferably 3 times or more, and most preferably 5 times or more, the fluorine atom content ratio of the a layer, from the viewpoint of light peelability from the silicone pressure-sensitive adhesive layer. On the other hand, the upper limit is not particularly limited, but from the viewpoint of adhesion between the a layer and the B layer, the upper limit is preferably 1000 times or less, and more preferably 100 times or less.
In the present invention, from the viewpoint of light peelability from the silicone pressure-sensitive adhesive layer, the fluorine atom content (atomic number fraction) in the B layer is preferably 1.1 times or more, more preferably 1.5 times or more, further preferably 2 times or more, particularly preferably 3 times or more, and most preferably 5 times or more the fluorine atom content (atomic number fraction) in the a layer. On the other hand, the upper limit is not particularly limited, but is preferably 1000 times or less, and more preferably 100 times or less, from the viewpoint of adhesion between the a layer and the B layer.
Here, the "fluorine atom content ratio (atomic number fraction)" refers to the ratio of fluorine atoms to the layer. When both the a layer and the B layer are substantially made of silicone resin (including fluorinated, non-fluorinated, curable, and non-curable), the ratio of the a layer to the B layer is the same value with respect to the "fluorine atom content ratio" and the "fluorine atom content ratio (atomic number fraction)".
By setting the fluorine atom content ratio of the B layer to the above range, sufficient adhesion between the a layer and the B layer can be obtained, and good releasability between the B layer and the silicone pressure-sensitive adhesive layer can be exhibited.
Further, by making the fluorine atom content ratio and/or fluorine atom content ratio of the B layer higher than that of the a layer, sufficient adhesion between the a layer and the B layer can be obtained, and good releasability between the B layer and the silicone pressure-sensitive adhesive layer can be stably exhibited.
The fluorine atom content ratio or fluorine atom content ratio of the a layer and the B layer may be calculated by analyzing the structure of the coating agent by nuclear magnetic resonance spectroscopy (NMR) or may be determined by Secondary Ion Mass Spectrometry (SIMS) or X-ray electron spectroscopy (XPS) after the layer formation.
In the measurement by the SIMS method or the XPS method, the fluorine atom content ratio of each layer may be quantified based on a material (such as fluorinated silicone) whose fluorine atom content ratio is known in advance.
When fluorine atoms are not uniformly present in each of the a layer and the B layer (for example, in the case of the above-described inclined structure), the fluorine atom content ratio per unit volume obtained by dividing the total amount of fluorine atoms contained in each layer by the volume of each layer, which is measured by the SIMS method or the like, may be set as the fluorine atom content ratio in each of the a layer and the B layer.
< other compounding Agents >
As for the a layer and the B layer, the coating liquid having the curable non-fluorinated silicone resin and the curable fluorinated silicone resin preferably contains a crosslinking agent, a catalyst, and a reaction initiator (reaction accelerator). A commercially available coating material containing a curable silicone resin may contain a crosslinking agent and a catalyst from the beginning.
In the formation of the a layer and the B layer, a crosslinking agent is preferably contained in order to react with a reactive functional group contained in the resin to form a crosslinked structure, examples of the crosslinking agent include vinyl siloxane, organosiloxane having a hydrosiloxane site, and the like, and specific examples of the crosslinking agent include SP7297, 7560, 3062A, 3062B, 3062C, 3062D, and the like, manufactured by Dow Corning Toray co., L td..
The crosslinking agent may contain a site having a fluorine substituent, and a silane coupling agent having a fluorinated substituent or the like may be used.
In addition, in forming the a layer and the B layer, a catalyst that promotes an addition reaction is preferably contained, and among them, a platinum catalyst is preferably contained. Examples of the platinum catalyst include platinum compounds such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, complexes of chloroplatinic acid with olefins, and complexes of chloroplatinic acid with alkenylsiloxanes; platinum black, platinum-supporting silica, and platinum-supporting activated carbon. The platinum catalyst may be used in 1 kind or in combination of 2 or more kinds.
Specific examples of the catalyst include CAT P L-50T manufactured by shin-Etsu chemical Co., Ltd, SRX212P, NC-25 and FS XK-3077 manufactured by Dow Corning Toray Co., Ltd, L td., and the like.
Examples of other additives that can be blended in the layer a and the layer B include alkyl (meth) acrylates having an ester group with 1 to 20 carbon atoms, acrylic resins, olefin resins, and the like. Among them, a silane coupling agent having a fluorinated substituent is preferable.
5. Physical Properties of the laminated film of the present invention
< Normal peeling force >
The normal peel force of the laminated film of the present invention is preferably 100mN/cm or less.
When the laminated film is used as a release film, the lower the normal peeling force is, the less force may be required for peeling from the adhesive layer. Therefore, the release film can be peeled from the laminate in which the pressure-sensitive adhesive layer is laminated, and defects such as peeling failure and deformation of the pressure-sensitive adhesive layer in a production process for attaching the pressure-sensitive adhesive layer to various members can be suppressed. Among them, the laminated film of the present invention is suppressed in the above-mentioned problems and has low peelability even when it is an adhesive layer having strong adhesiveness such as a silicone adhesive. In addition, as the release film, in the laminate having the release films on both surfaces of the pressure-sensitive adhesive layer, the release film on the undesired side can be prevented from peeling.
From this viewpoint, the normal peel force is preferably 70mN/cm or less, more preferably 40mN/cm or less, particularly preferably 35mN/cm or less, and most preferably 30mN/cm or less. On the other hand, the lower limit is not particularly limited, but from the viewpoint of the storage stability of a laminate in which a laminate film and a pressure-sensitive adhesive layer are laminated, the lower limit is preferably 1mN/cm or more, and more preferably 3mN/cm or more.
Examples of the method of reducing the normal peeling force include a method of adjusting the fluorine atom content ratio in the a layer and the B layer. The normal peel force was measured by the method described in the examples below.
6. Laminated structure
The laminated film of the present invention may have a structure in which the polymer film has an a layer on one surface side or both surfaces and a B layer is provided on the a layer. Further, if necessary, another layer may be interposed between the polymer film and the layer a or between the layer a and the layer B.
Examples of the other layer include an antistatic layer having antistatic properties, and an oligomer blocking layer for blocking bleeding (bleeding, deposition) of the compound or oligomer to the surface of the film.
The layer such as the antistatic layer or the oligomer blocking layer may be formed by any of an in-line coating method in which the layer is formed simultaneously with the formation of the polymer film and an off-line coating method in which the layer is formed on the polymer film formed in a separate step.
The thickness of the entire 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.
7. The method for producing a 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 formed by forming polyethylene, polypropylene, polyester, polystyrene, polycarbonate, or another polymer material into a film shape can be used.
Hereinafter, a method for producing a polyester film will be described as an example.
As a method for producing the polyester film used in the present invention, the following method is preferable: the molten sheet extruded from the die is cooled and solidified by a cooling roll using the polyester raw material such as polyethylene terephthalate to obtain an unstretched sheet. In this case, in order to improve the planarity of the sheet, it is preferable to improve the adhesion between the sheet and the rotary cooling drum by an electrostatic application method and/or a liquid coating method.
The obtained unstretched sheet may be used as it is, but is preferably stretched at least uniaxially, more preferably biaxially. By stretching the polyester film uniaxially or more, good mechanical strength and dimensional stability can be obtained. In addition, when used as a release film, when an adherend (pressure-sensitive adhesive layer) is laminated to produce a pressure-sensitive adhesive sheet with a laminated film, occurrence of defects at the time of bonding can be suppressed.
The stretching conditions are not particularly limited, and for example, a uniaxially stretched polyester film is obtained by stretching an unstretched sheet at 70 to 145 ℃ to 2 to 6 times in the longitudinal direction (longitudinal direction) by a roll stretching method, then stretched at 80 to 160 ℃ to 2 to 6 times in the direction (width direction) perpendicular to the previous stretching direction by a tenter, and further heat-treated at 150 to 250 ℃ for 1 to 600 seconds, thereby obtaining a biaxially stretched film.
In this case, the following method is more preferable: in the heat treatment zone and/or the cooling zone at the heat treatment outlet, the relaxation is 0.1-20% along the longitudinal direction and/or the width direction.
(2) Formation of layer A (undercoat) and layer B (Release layer)
The method for forming the layer a and the layer B is not limited, and the layer a and the layer B may be formed by a co-extrusion method or the like, but a method based on coating is preferable.
The number of applications of the layer a and the layer B may be 1 or 2 or more. When the layer a and the layer B are formed by setting the number of coating times to 2 or more, different coating liquids may be applied. Among them, at least any coating liquid must contain fluorine atoms.
The coating method may be an on-line coating method or an off-line coating method, and a coating technique such as that shown in "coating method" (original kazaki, reign, Maki bookshop, 1979) may be used.
For example, as the coating head, a knife coater, a blade coater, a bar coater, a blade coater, a squeeze coater, an impregnation coater, a reverse roll coater, a roll-fed roll coater, a gravure coater, a roll-lick roll coater, a casting coater, a spray coater, a curtain coater, a calendar coater, an extrusion coater, and the like can be exemplified.
The coating liquid for forming the a layer and the B layer has a solid content mass concentration of preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and still more preferably 0.1 mass% or more. On the other hand, the upper limit is preferably 90% by mass or less, more preferably 50% by mass or less, and particularly preferably 20% by mass or less.
The solvent used for dilution may be a polar solvent or a nonpolar solvent. Further, a fluorine solvent having a fluorine atom may be used. Further, 2 or more of the above solvents may be used in combination. In particular, in the coating liquid for forming the B layer, it is preferable to contain a fluorine solvent having a fluorine atom for the purpose of improving wettability with respect to the a layer.
Examples of the polar solvent include alcohols such as ethanol and (isopropyl) alcohol; esters such as methyl acetate, ethyl acetate, (iso) propyl acetate, (iso) butyl acetate, (iso) pentyl acetate, ethyl lactate, and ethyl benzoate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol, and diisobutyl ketone; glycols such as ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether; n-methyl-2-pyrrolidone, N-dimethylformamide, tetrahydrofuran, acetonitrile, and the like.
Examples of the nonpolar solvent 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; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and cyclooctane; dioxane, and the like. Examples of the fluorine solvent include hydrofluoroethers, m-bis (trifluoromethyl) benzene, and tridecafluorooctane.
As a method for forming these layers, the following method can be exemplified: as the coating liquid, a coating liquid having a fluorine atom content ratio corresponding to each layer after coating/drying is prepared in advance and used.
Further, by using a curable non-fluorinated silicone resin and mixing it with a fluorinated material in a predetermined amount to prepare a coating liquid having a composition corresponding to the a layer/B layer, and then coating/drying it, a desired a layer and/or B layer containing fluorine atoms can be formed. This method is preferable because a release film having a layer a/a layer B with a specific fluorine atom content ratio can be produced more easily.
In addition, these a layer and B layer can be formed by applying the a layer and drying, and then applying the B layer and drying, and in the present invention, the a layer and the B layer can be formed by a wet coating method in which the a layer is applied and then the B layer is applied, and then drying is performed, whereby shortening of the production process and improvement of energy efficiency can also be expected.
As another method, there is a method of: the method of applying a mixture of a curable fluorinated silicone resin and a curable non-fluorinated silicone resin to form a layer a and then applying a solution containing a curable fluorinated silicone resin as a main component as a layer B is more preferable because a release film can be stably produced.
Further, as another method, a non-fluorinated resin may be formed in advance by coating, and then carbon tetrafluoride (CF) may be used4) Plasma treatment a dry process to produce the fluorinated layer. Among them, this method requires a chamber for plasma treatment, and is therefore suitable for mass production.
In the case of using so-called inline coating, which is coating in the step of producing a polymer film, as the method for producing a laminated film of the present invention, both the a layer and the B layer may be applied inline, or only the a layer may be applied inline and the B layer may be applied offline.
When both the a layer and the B layer are provided by off-line coating, they can be formed continuously by the "substrate film take-up and take-up step" of 1 time, or can be formed sequentially by the "substrate film take-up and take-up step" of plural times, and the former is a particularly preferable method because the production process is simple and the production can be performed at a lower cost.
Further, it is preferable that the amount of heat applied to the thin film when the a layer is formed is smaller than the amount of heat applied when the B layer is formed, because the deterioration of the planarity of the thin film when the B layer is formed can be suppressed, and the occurrence of uneven coating of the B layer can be effectively prevented.
8. Method for utilizing laminated film
The laminated film of the present invention has excellent releasability, and therefore can be provided, for example, as an adhesive sheet with a laminated film having a structure in which the laminated film and an adhesive layer are laminated. In particular, the laminated film of the present invention has excellent releasability even with a silicone adhesive having strong adhesiveness, and therefore can be provided as, for example, an adhesive sheet with a laminated film having a structure in which the laminated film and an adhesive layer formed of a silicone adhesive are laminated.
The method of using the laminated film is not limited to the above-described method. For example, since the laminated film contains fluorine atoms, it is excellent in water resistance, water repellency, oil resistance, oil repellency, antifogging property, antifouling property, chemical resistance, corrosion resistance and the like, and thus, there are exemplified a printed substrate, an optical member protective film, a film for building materials, a film for agriculture, a highly water repellent film, a film for packaging, a cosmetic film, a surface protective film and the like. In the case of the application in which the surface of the layer B is used as the outermost surface, an adhesive layer, a heat-sealing layer, or the like may be provided on the surface of the polymer film opposite to the surface having the layer a and the layer B.
< Silicone adhesive >
Examples of the silicone adhesive include addition reaction type, peroxide curing type, and condensation reaction type silicone adhesives. Among them, an addition reaction type silicone adhesive is preferably used from the viewpoint of being capable of curing at a low temperature in a short time. These addition reaction type silicone adhesives are cured when an adhesive layer is formed on a 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 aforementioned addition reaction type silicone adhesive can be cured as required in the following manner: a catalyst such as a platinum catalyst is added to a silicone resin solution diluted with a solvent such as toluene, the mixture is uniformly stirred and then applied to a support, and the mixture is cured at 100 to 130 ℃/1 to 5 minutes.
If necessary, a crosslinking agent or an additive for controlling the adhesive strength may be added to the addition reaction type silicone adhesive, or the support may be subjected to a primer treatment before the adhesive layer is formed.
Commercially available silicone resins used in the addition reaction type silicone ADHESIVE include SD4580PSA, SD4584PSA, SD4585PSA, SD 4587L PSA, SD4560PSA, SD4570PSA, SD4600FCPSA, SD4593PSA, DC7651ADHESIVE, DC7652ADHESIVE, L TC-755, and L TC-310 (all manufactured by Dow Corning CoryCo., and &lTtTtranslation = L "&ggggTtL/T gTtTtT td.), KR-3700, KR-3701, X-40-3237-1, X-40-3340, X-40-3291-1, X-40-3229, X-40-3323, X-40-3306, X-40-3270-1 (all manufactured by shinko Junyaku chemical industries, AS 001, AS-3265, AS-014, Moales AS-004, Moales industries, Moire R-004, and others (all manufactured by Mooney industries).
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples. In the following examples, the raw materials referred to as "addition molding" are all referred to as "curability".
(1) Evaluation method
(1-1) Normal peeling force
A silicone adhesive tape (No 5413 tape, 50mm wide, manufactured by 3MJ apan L input) was attached to the surface of the B layer (release layer) of the laminate film at 23 ℃ and placed in a peel tester, and the normal peel force was measured at a peel speed of 0.3 m/min and a peel angle of 180 ℃.
(1-2) fluorine atom content ratio and fluorine atom content ratio
The fluorine atom content ratio in the A layer and the B layer was evaluated by TOF-SIMS (U L VAC-PHI, manufactured by Inc., TRIF V).
Use of Au as the primary ion3+The acceleration voltage was set to 30 kV.
In order to evaluate the fluorine atom content ratio per unit volume, etching with Ar gas (voltage: 5kV, current: 2nA, etching rate: 20 nm/min (in terms of PET film)) was carried out for 0 minute, 1 minute, 2 minutes, and 3 minutes, and anions ("F") detected at each etching time were measured-And CH3SiO2 -") was averaged and was taken as the fluorine atom content ratio per unit volume (" F-”/“CH3SiO2 -”)。
The value of [ fluorine atom content ratio in layer B ]/[ fluorine atom content ratio in layer a ] is defined as the ratio of the fluorine atom content ratio. This value has the same meaning as the result of XPS measurement of the fluorine atom content ratio (atomic number fraction) of each of the a layer and the B layer and calculation of the ratio of the values of the respective layers.
[ example 1]
(coating liquid 1)
The following compositions were mixed and diluted so that the solid content concentration reached 4 mass% using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio 1: 1) to prepare "coating solution 1".
< composition of coating liquid 1 >
Addition-type organosiloxane (KS-847, product of shin-Etsu chemical Co., Ltd.): 67 parts by mass
0.7 part by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
100 parts by mass of addition type fluorinated silicone (Dow Corning Toray Co., L td., Syl-off 3062)
0.5 part by mass of a crosslinking agent (Dow Corning Toray Co., L td., Syl-off 3062A)
0.5 part by mass of a platinum catalyst (FSXK-3077, manufactured by Dow Corning Toray Co., L td.)
(coating liquid 2)
The following compositions were mixed, and the mixture was diluted with FS diluent (manufactured by shin-Etsu chemical Co., Ltd.)/ethyl acetate 1: 1 (mass ratio) was diluted so that the solid content concentration reached 0.5 mass%, thereby preparing "coating solution 2".
< composition of coating liquid 2 >
Addition-type fluorinated silicone (X-70-201S, product of shin-Etsu chemical Co., Ltd.): 100 parts by mass
0.5 part by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
(preparation of laminated film)
A PET film ("T100-38" manufactured by Mitsubishi chemical corporation, thickness 38 μm) was used as a polymer film, the coating solution 1 was applied to the polymer film by a bar coater (No. 4bar), and the resin of the layer A was cured by drying in a dryer at 150 ℃ for 30 seconds to prepare a polymer film having a layer A (undercoat layer).
The coating liquid 2 was further applied to the layer a of the polymer film having the layer a (undercoat layer) by a bar coater (No4bar), and the resin of the layer B was cured by drying in a dryer at 150 ℃ for 30 seconds, thereby producing a laminated film having the layer B (release layer) provided on the layer a (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 liquid 2 was set to 4 mass%.
Since the coating liquid 2 was applied using the same bar coater as in example 1, the thickness of the B layer was increased as compared with example 1 by increasing the solid content concentration.
Comparative example 1
A laminated film substantially composed only of a polymer film and a B layer (release layer) was produced in the same manner as in example 1, except that the a layer (undercoat layer) was not formed on the polymer film and only the coating solution 2 was applied by a bar coater (No4 bar).
Comparative example 2
A laminated film was produced in the same manner as in comparative example 1, except that the solid content concentration of coating liquid 2 was set to 4 mass%.
Since the coating liquid 2 was applied using the same bar coater as in comparative example 1, the thickness of the B layer was increased as compared with comparative example 1 by increasing the solid content concentration.
Comparative example 3
A laminated film substantially composed only of a polymer film and a layer a (undercoat layer) was produced in the same manner as in example 1, except that the coating solution 2 was not applied to the layer a (undercoat layer) and the layer B (release layer) was not formed.
Comparative example 4
(coating liquid 3)
Coating liquid 3 was prepared according to the following composition.
< composition of coating liquid 3 >
Addition-type organosiloxane (KS-847H, product of shin-Etsu chemical Co., Ltd.): 67 parts by mass
0.7 part by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
The composition was diluted with a mixed solvent of n-hexane and MEK (mass ratio 1: 1) so that the solid content concentration reached 4 mass%.
(preparation of laminated film)
The coating liquid 3 was applied to a polymer film by a bar coater (No4bar), and dried in a dryer at 150 ℃ for 30 seconds to form an A layer (undercoat layer).
Next, coating liquid 2 was applied to the A layer (undercoat layer) by a bar coater (No4 bar). However, since the coating liquid 2 is not uniformly applied to the layer a (undercoat layer), a dot-like or line-like (mesh-like) phenomenon (repulsion) occurs, and thus the layer B (release layer) cannot be formed.
Comparative example 5
A laminated film was produced in the same manner as in comparative example 4 except that the solid content concentration of the coating liquid 2 was set to 4 mass% in the layer B (release layer). However, since the "coating liquid 2" is not uniformly applied to the layer a (undercoat layer), a phenomenon (repulsion) of dots or lines (mesh shape) occurs, and thus the layer B (release layer) cannot be formed.
[ example 3]
(coating liquid 4)
The following compositions were mixed and diluted so that the solid content concentration reached 4 mass% using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio 1: 1) to prepare "coating solution 4".
< composition of coating liquid 4 >
Addition-type organosiloxane (KS-847, product of shin-Etsu chemical Co., Ltd.): 133 parts by mass
1.3 parts by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
100 parts by mass of addition type fluorinated silicone (Dow Corning Toray Co., L td., Syl-off 3062)
0.5 part by mass of a crosslinking agent (Dow Corning Toray Co., L td., Syl-off 3062A)
0.5 part by mass of a platinum catalyst (FSXK-3077, manufactured by Dow Corning Toray Co., L td.)
(preparation of laminated film)
A laminated film was produced in the same manner as in example 1 except that the coating solution 4 was applied to a polymer film in place of the coating solution 1 and cured to obtain an a layer (undercoat layer), and the coating solution 2 diluted so that the solid content concentration became 2 mass% was applied to the obtained a layer (undercoat layer).
[ example 4]
(coating liquid 5)
The following compositions were mixed and diluted so that the solid content concentration reached 4 mass% using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio 1: 1) to prepare "coating solution 5".
< composition of coating liquid 5 >
Addition-type organosiloxane (KS-847, product of shin-Etsu chemical Co., Ltd.): 200 parts by mass
2.0 parts by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
100 parts by mass of addition type fluorinated silicone (Dow Corning Toray Co., L td., Syl-off 3062)
0.5 part by mass of a crosslinking agent (Dow Corning Toray Co., L td., Syl-off 3062A)
0.5 part by mass of a platinum catalyst (FSXK-3077, manufactured by Dow Corning Toray Co., L td.)
(preparation of 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).
[ example 5]
(coating liquid 6)
The following compositions were mixed and diluted so that the solid content concentration reached 4 mass% using a mixed solvent of isopropyl ether and ethyl acetate (mass ratio 1: 1) to prepare "coating solution 6".
< composition of coating liquid 6 >
Addition-type organosiloxane (KS-847, product of shin-Etsu chemical Co., Ltd.): 267 parts by mass
2.0 parts by mass of a platinum catalyst (CAT-P L-50T, product of shin-Etsu chemical Co., Ltd.)
100 parts by mass of addition type fluorinated silicone (Dow Corning Toray Co., L td., Syl-off 3062)
0.5 part by mass of a crosslinking agent (Dow Corning Toray Co., L td., Syl-off 3062A)
0.5 part by mass of a platinum catalyst (FSXK-3077, manufactured by Dow Corning Toray Co., L td.)
(preparation of 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).
(3) Evaluation of the results
The fluorine atom content ratio of the a layer (undercoat layer) and the B layer (release layer) of the obtained laminated film, and the normal peel force using a silicone adhesive tape were measured. The results are shown in table 1 below.
Therefore, the following steps are carried out: in examples 1 and 2, since the layer a (undercoat layer) and the layer B (release layer) defined in the present invention were formed on the PET film, good releasability was obtained as compared with comparative examples 1 and 2 obtained using a film in which only the layer B (release layer) was present.
In particular, the laminated film of example 1 obtained the same level of peelability as that of the release film of example 2 (the concentration of coating liquid 2 was "4 mass%") in which the B layer (release layer) was thicker than that of example 1, even though the thickness of the B layer (release layer) was formed thin (the concentration of coating liquid 2 was "0.5 mass%"). From this result, it was found that a release film having excellent releasability from a silicone adhesive can be produced with a smaller amount of a fluorine-based material.
Further, it is judged that: the release films of examples 3 to 5 in which the fluorine atom content ratio of the a layer (undercoat layer) was smaller than that of example 1 also obtained release properties at the same level as that of the release film of example 1, and a release film having excellent release properties with respect to a silicone adhesive could be produced using a smaller amount of a fluorine-based material.
In order to evaluate the fluorine atom content ratio of each layer, the fluorine atom content ratio by TOF-SIMS was measured for the samples of comparative example 3 (only a layer) and comparative example 2 (only B layer), and the values were determined for the a layer and the B layer, respectively. As a result, it was confirmed that the layer B contained a larger proportion of fluorine atoms per unit volume than the layer a.
Since the compositions of the coating liquids were the same, the values were set to the fluorine atom content ratios of the respective layers in examples 1 and 2 and comparative example 1. Further, the fluorine atom content ratio of the a layer 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.
It should be noted that: the fluorine atom content ratio of the a layer is the largest at the surface (the etching time in TOF-SIMS is 0 minute), and the longer the etching time (that is, the closer to the PET film side of the base material), the smaller the etching time, and an inclined structure in which the fluorine atom content ratio on the surface side is increased can be formed. The values shown in table 1 are average values in the thickness direction.
[ Table 1]
Figure BDA0002534313760000241
Description of the reference numerals
1 Polymer film
2A layer (undercoat)
3B layer (demoulding layer)
4 Silicone adhesive layer

Claims (12)

1. A laminated film comprising a polymer film and, laminated on at least one surface thereof, an A layer and a B layer in this order,
the two layers of the layer A and the layer B contain fluorine atoms, and the fluorine atom content ratio of the layer B is greater than that of the layer A.
2. The laminate film according to claim 1, wherein a content ratio of fluorine atoms in the B layer to a content ratio of fluorine atoms in the a layer is 1.1 times or more.
3. A laminated film comprising a polymer film and, laminated on at least one surface thereof, an A layer and a B layer in this order,
the layer B contains fluorine atoms, and has a normal peel force of 100mN/cm or less as measured by the following method,
measurement of Normal peeling force:
a tape with a silicone adhesive was adhered to the surface of the layer B of the laminate film, and a 180 ℃ peel test was carried out at a peel speed of 0.3M/min, the tape being a No5413 tape manufactured by 3M Japan L approved, or a 50mm wide tape.
4. A laminated film according to any one of claims 1 to 3, wherein the polymer film is a biaxially stretched polyester film.
5. A laminated film according to any one of claims 1 to 4, wherein the A and B layers contain a fluorinated silicone resin.
6. A 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.
7. A laminated film according to any one of claims 1 to 6, wherein the layers A and B are layers formed by curing a curable fluorinated silicone resin.
8. The laminated film according to any one of claims 5 to 7, wherein fluorine ions (F) in measurement using time-of-flight secondary ion mass spectrometry (TOF-SIMS)-) Containing the methylsiloxane ion (CH) in a ratio3SiO2 -) Ratio of content ([ F ]-]/[CH3SiO2 -]) The A layer is 1 to 1000 inclusive, and the B layer is 3 to 5000 inclusive.
9. The laminate film according to any one of claims 1 to 8, wherein the A layer has a fluorine atom content ratio, that is, an atomic number fraction of 50ppm or more and less than 900000ppm, and the B layer has a fluorine atom content ratio, that is, an atomic number fraction of 3000ppm or more and 900000ppm or less.
10. A release film using the laminated film according to any one of claims 1 to 9.
11. A laminate comprising the release film according to claim 10 and an adhesive layer laminated thereon.
12. The laminate according to claim 11, wherein an adhesive layer is provided on the surface of the B layer on the side not in contact with the a layer.
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