JP2017222748A - Resin film, method for producing the same, laminate, and method for adjusting releasability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film that enables the releasability of a polymer layer of interest to be easily adjusted.SOLUTION: In the resin film including a base layer and an outer layer containing cyclic olefin-based resin, the surface halogen element concentration of the outer layer is adjusted to 0.07 atom% or more. The surface halogen element concentration may be a surface chlorine concentration. The surface chlorine concentration is around 0.1 to 2 atom%. In the resin film, an intermediate layer including a chlorine-containing resin may be interposed between the base layer and the outer layer. The weight per unit area of the outer layer may be 3 g/mor less. The cyclic olefin-based resin may be a cyclic olefin-based copolymer. The chlorine-containing resin may be a vinylidene chloride-based polymer.SELECTED DRAWING: None

Description

  The present invention relates to a resin film useful for release in various fields such as foods, pharmaceuticals, chemicals, optical members, and electrical / electronic materials, a production method thereof, a laminate, and a release property adjusting method.

  In general, a method of using a release film as a supporting substrate for forming a polymer layer is known. The release film is required to have the property of being peelable from the polymer layer after the target polymer layer is formed, that is, the release property. If this releasability is insufficient, when the release film is peeled off from the target polymer layer, the polymer layer may remain on the release film or the polymer layer may be destroyed. On the other hand, if the releasability is too high, floating occurs between the release film and the polymer layer during the formation or storage of the polymer layer, or the separation from the polymer layer is not necessary in the processing step that does not require the release film to be peeled off. The problem that a mold film peels will generate | occur | produce and a mold release film cannot play the role as a support base material.

For example, as a release film that exhibits good release properties with respect to an ion exchange layer containing an ion exchange resin, Japanese Patent No. 5300240 (Patent Document 1) is laminated on a plastic substrate and is composed of a chlorine-containing resin. A laminated film composed of the first layer formed and the second layer laminated on the first layer and made of a cyclic olefin resin is disclosed. In this document, the adhesion between the plastic substrate and the second layer is improved by interposing a first layer made of a chlorine-containing resin between the plastic substrate and the second layer. In the examples, the coating amount of the coating solution for forming the second layer is 3.3 g / m ² (dry thickness 3 μm) or 5 g / m ² (dry thickness 5 μm).

  In JP-A-2015-218276 (Patent Document 2), a release layer formed of a resin composition containing a cyclic olefin-based resin and a chlorine-containing resin is laminated on at least one surface of a base material layer. A laminated film is disclosed. In this document, by combining a cyclic olefin-based resin and a chlorine-containing resin, it has appropriate peelability and adhesion to the electrolyte membrane and electrode membrane of a solid polymer fuel cell, and an adhesive layer such as an easy-adhesion layer is provided. It can adhere to a general-purpose substrate film without interposing.

  However, in these patent documents, the chlorine-containing resin is recognized as an adhesive resin between the cyclic olefin-based resin and the base material, and it is not assumed that the release property of the release layer is controlled. For example, in the release film of the Example of patent document 1, although there exists a tendency for mold release property to be too high depending on a use, it is difficult to control mold release property by cyclic olefin resin. Moreover, in the release film of patent document 2, in order to improve the adhesive force of a base material layer and a release layer, since a chlorine containing resin is mix | blended, there exists a tendency for a release property to be too low.

Japanese Patent No. 5300240 (Claim 1, paragraphs [0009] and [0012], Examples) JP-A-2015-218276 (Claims, paragraphs [0013] and [0018])

  Therefore, the objective of this invention is providing the resin film which can adjust mold release property easily with respect to the target polymer layer, its manufacturing method, a laminated body, and the mold release property adjusting method.

  Another object of the present invention is to provide a resin film that can be easily peeled from a polymer such as an ion exchange layer containing an ion exchange resin when necessary, and can be prevented from being peeled when peeling such as storage is unnecessary. It is providing the manufacturing method, a laminated body, and the adjustment method of mold release property.

  Still another object of the present invention is to provide a resin film capable of achieving both high releasability with respect to the ion exchange layer and its own stability (adhesion between the base material layer and the surface layer), a production method thereof, a laminate, and a release It is to provide a method of adjusting sex.

  Another object of the present invention is to provide a resin film that can be easily thinned by coating, a method for producing the same, a laminate, and a method for adjusting mold release properties.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have adjusted the surface halogen element concentration of the surface layer to 0.07 Atom% or more in a resin film including a base material layer and a surface layer containing a cyclic olefin resin. By making it possible to easily adjust the releasability for the target polymer layer, in particular, when an intermediate layer containing a chlorine-containing resin is interposed between the base material layer and the surface layer, surprisingly, Although the surface layer solvent is a poor solvent for the intermediate layer chlorine-containing resin, and the intermediate layer solvent is a poor solvent for the surface layer cyclic olefin resin, it is derived from the chlorine-containing resin in the production process. As a result, it was found that chlorine in the intermediate layer was transferred from the intermediate layer to the surface layer, and the releasability of the surface layer could be controlled, and the present invention was completed.

That is, the resin film of the present invention is a resin film including a base material layer and a surface layer containing a cyclic olefin resin, and the surface halogen element concentration of the surface layer is 0.07 Atom% or more. The surface halogen element concentration may be a surface chlorine concentration. The surface chlorine concentration is about 0.1 to 2 Atom%. In the resin film of the present invention, an intermediate layer containing a chlorine-containing resin may be interposed between the base material layer and the surface layer. The halogen element present on the surface of the surface layer may be chlorine derived from a chlorine-containing resin contained in the intermediate layer (liquid composition for forming the intermediate layer). The weight per unit area of the surface layer may be 3 g / m ² or less. The surface layer may contain a chlorine-containing resin. The cyclic olefin resin may be a cyclic olefin copolymer. The chlorine-containing resin may be a vinylidene chloride polymer. The base material layer may contain at least one selected from the group consisting of polyolefin, polyvinyl alcohol polymer, polyester, polyamide, polyimide, and cellulose derivative.

  The manufacturing method of the said resin film including the surface layer formation process of coating the liquid composition containing cyclic olefin resin and forming a surface layer is also contained in this invention. Furthermore, the present invention includes an intermediate layer forming step in which a liquid composition containing a chlorine-containing resin is coated on a base material layer to form an intermediate layer, a cyclic olefin resin is included on the intermediate layer, and chlorine The manufacturing method of the said resin film including the surface layer formation process which coats the liquid composition which does not contain containing resin and forms a surface layer is also included.

  The laminated body containing the said resin film and the ion exchange layer laminated | stacked on the surface layer of this resin film and containing an ion exchange resin is also contained in this invention.

  The present invention also includes a method of adjusting the releasability of the surface layer by adjusting the surface halogen element concentration of the surface layer in a resin film including a base material layer and a surface layer containing a cyclic olefin-based resin. In this method, an intermediate layer containing a chlorine-containing resin is interposed between the base material layer and the surface layer, and the surface of the surface layer is formed by the chlorine-containing resin contained in the liquid composition for forming the intermediate layer. The chlorine concentration may be adjusted.

  In the present specification and claims, the “surface layer” of the resin film means an outermost layer on at least one surface side regardless of the surface or the back surface of the resin film.

  In the present invention, in the resin film including the base material layer and the surface layer containing the cyclic olefin-based resin, the surface halogen element concentration of the surface layer is adjusted to 0.07 Atom% or more. The moldability can be easily adjusted. In particular, a polymer such as an ion exchange layer containing an ion exchange resin can be easily peeled when necessary, and the peeling can be suppressed when peeling such as during storage is unnecessary. Furthermore, when an intermediate layer containing a chlorine-containing resin is interposed between the base material layer and the surface layer, the releasability to the ion exchange layer and its own stability (adhesion between the base material layer and the surface layer) are enhanced. Can be compatible. Such a resin film can be easily thinned by coating. Therefore, it can be wound on a roll, can be continuously manufactured in a roll-to-roll manner, and has high productivity.

[Base material layer]
The resin film of the present invention includes a base material layer. The base material layer can improve the dimensional stability of the resin film. In particular, even when tension is applied in the roll-to-roll method, it can suppress elongation, and it is exposed to high temperatures by the drying process and thermocompression bonding process. However, it is preferably formed of a material having high heat resistance and high dimensional stability from the viewpoint of maintaining high dimensional stability and suppressing peeling from the target polymer layer. It may be formed of a synthetic resin having a rate of 100 to 1000 MPa. The elastic modulus may be, for example, about 120 to 1000 MPa, preferably about 150 to 1000 MPa, and more preferably about 200 to 1000 MPa. When the elastic modulus is too small, the dimensional stability of the resin film is lowered, and there is a possibility that peeling between the surface layer and the polymer layer occurs in the production by the roll-to-roll method.

As such a synthetic resin, for example, various thermoplastic resins and thermosetting resins can be used, but a thermoplastic resin is preferable from the viewpoint of flexibility that can be manufactured by a roll-to-roll method. Examples of the thermoplastic resin include polyolefin (polypropylene resin, cyclic polyolefin, etc.), polyvinyl alcohol polymer, polyester, polyamide, polyimide, polycarbonate, polyphenylene ether, polyphenylene sulfide, cellulose derivatives (cellulose ester such as cellulose acetate). Etc. These thermoplastic resins can be used alone or in combination of two or more. In the present invention, since the surface layer or the intermediate layer is excellent in adhesion to the base material layer, these thermoplastic resins are reactive groups and polar groups (side chains formed of reactive groups, etc.) for improving adhesion. ) Is preferably substantially absent. Among these thermoplastic resins, at least one selected from the group consisting of polyolefins, polyvinyl alcohol polymers, polyesters, polyamides, polyimides and cellulose derivatives (particularly selected from the group consisting of polyolefins, polyesters, polyimides and cellulose esters). At least one kind) is preferred, and polyester and polyimide are particularly preferred from the viewpoint of excellent balance between heat resistance and flexibility. Furthermore, as the polyester, poly C _2-4 alkylene arylate resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) can be preferably used. Examples of the polyimide include thermoplastic polyimide, polyetherimide, and polyamideimide.

  The base material layer may be formed of a stretched film from the viewpoint of improving the film strength of the resin film. The stretching may be uniaxial stretching, but biaxial stretching is preferred from the viewpoint that the film strength can be improved. The stretching ratio may be, for example, 1.5 times or more (for example, 1.5 to 6 times), preferably 2 to 5 times, more preferably about 3 to 4 times, in the longitudinal and transverse directions, respectively. It is. If the draw ratio is too low, the film strength tends to be insufficient.

  The base material layer may contain a conventional additive. Examples of conventional additives include fillers, lubricants (waxes, fatty acid esters, fatty acid amides, etc.), antistatic agents, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), flame retardants, viscosity adjustments Agents, thickeners, antifoaming agents and the like. The ratio of the synthetic resin in the base material layer is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more (for example, 95 to 100% by weight) with respect to the whole base material layer. Also good.

  The surface smoothness of the base material layer is not particularly limited as long as the surface layer can be formed by coating, but the arithmetic average roughness Ra based on JIS B0601 may be 1 μm or less, preferably 100 nm or less (for example, 10 to 10 nm). 100 nm) or so.

  The surface of the base material layer may be subjected to a surface treatment in order to improve adhesion with the surface layer or the intermediate layer. Examples of the surface treatment include conventional surface treatments such as corona discharge treatment, flame treatment, plasma treatment, ozone and ultraviolet irradiation treatment. Of these, corona discharge treatment is preferred.

  The base material layer is an easy-adhesion layer formed of a conventional adhesive resin (for example, when the base material layer is a polyester resin, adhesion of a low molecular weight polyester resin, aliphatic polyester resin, amorphous polyester resin, etc.) An easy-adhesion layer formed of an adhesive resin or the like, or may not substantially have an easy-adhesion layer. Among these, the surface layer or the intermediate layer has excellent adhesion to the base material layer, and even if the base material layer does not have the easy adhesion layer, the base material does not have the easy adhesion layer because it has high adhesion. A layer is particularly preferred. Therefore, in this invention, the layer structure of a resin film can be simplified and it can also reduce in thickness by using the base material layer which does not have an easily bonding layer.

  The average thickness of a base material layer is 1-300 micrometers, for example, Preferably it is 5-200 micrometers, More preferably, it is about 10-100 micrometers (especially 20-80 micrometers). If the thickness of the base material layer is too large, it will be difficult to produce by roll-to-roll method, and if it is too thin, dimensional stability and transportability by roll-to-roll method will deteriorate and wrinkles will be mixed. There is a fear.

[Surface]
The resin film of the present invention further includes a surface layer. This surface layer contains a cyclic olefin resin and has a surface halogen element concentration of 0.07 Atom% or more. In the present invention, since the surface halogen element concentration of the surface layer is 0.07 Atom% or more, the releasability of the surface layer containing the cyclic olefin resin can be adjusted by adjusting the halogen element concentration.

  Examples of the halogen element contained on the surface of the surface layer include chlorine, bromine and iodine. These halogen elements can be used alone or in combination of two or more. Of these, chlorine is preferred because it is easy to handle and easy to adjust the releasability.

  The form of the halogen element contained on the surface may be either a simple substance or a compound. From the viewpoint of excellent releasability and durability, halogen-containing resin (especially chlorine-containing resin) or its Monomeric or oligomeric forms are preferred. The halogen element (especially chlorine) may be a halogen element derived from the raw material of the surface layer, but may be a halogen element derived from the raw material of the base material layer or the intermediate layer. It may be chlorine derived from a chlorine-containing resin contained in the liquid composition for forming the.

  The surface halogen element concentration (especially surface chlorine concentration) of the surface layer may be adjusted to a range of 0.07 Atom% or more depending on the type of the target polymer layer. If the surface halogen element is too small, it becomes difficult to adjust the releasability by the halogen element. In particular, the surface halogen element concentration (especially surface chlorine concentration) of the surface layer can be selected from a range of about 0.07 to 10 Atom%, and when the polymer layer is an ion exchange layer containing an ion exchange resin, for example, 0.07 to 5 Atom. %, Preferably 0.1 to 4 Atom% (for example, 0.1 to 2 Atom%), more preferably about 0.1 to 3 Atom% (particularly 0.5 to 1.5 Atom%). If the surface halogen element is too large, the releasability may be deteriorated too much. In the present specification and claims, surface halogen element concentration (especially surface chlorine concentration) can be measured based on X-ray photoelectron spectroscopy (or ESCA analysis: Electron Spectroscopy for Chemical Analysis). It can measure by the method as described in the below-mentioned Example.

(Chlorine-containing resin)
As long as the surface layer has a surface halogen element concentration of 0.07 Atom% or more, the form of the halogen element is not particularly limited. However, the surface layer may contain a chlorine-containing resin. When forming a surface layer on a material layer, it is preferable to contain chlorine containing resin from the point which can improve adhesiveness with a base material layer.

  The chlorine-containing resin may be a chlorinated resin such as chlorinated polyethylene or chlorinated polypropylene, but is usually a polymer having a chlorine-containing monomer as a polymerization component. Examples of the chlorine-containing monomer include a vinyl chloride monomer and a vinylidene chloride monomer. These chlorine-containing monomers can be used alone or in combination of two or more. Among these, vinylidene chloride monomer is preferable from the viewpoint of adhesion to the base material layer or the intermediate layer (particularly the base material layer).

  The chlorine-containing resin may contain other copolymerizable units other than chlorine-containing monomer units. Examples of polymerization components (copolymerizable monomers) for forming other copolymerizable units include vinyl ester monomers such as vinyl acetate and vinyl propionate; diene monomers such as butadiene and isoprene; (meth) acrylic Ethyl unsaturated carboxylic acids such as acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid and angelic acid; methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters such as butyl acrylate, (meth) acrylic acid hydroxyalkyl esters, (meth) acrylic acid esters such as glycidyl (meth) acrylate; vinyl cyanide monomers such as (meth) acrylonitrile, etc. It is done. These copolymerizable monomers can be used alone or in combination of two or more. Among the copolymerizable monomers, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile and the like are generally used.

  The proportion of other copolymerizable units (copolymerizable monomers) may be such that it does not impair the properties of the chlorine-containing resin, and is usually 0.1 to 50% by weight (for example, 0.1% by weight) based on the entire chlorine-containing resin. 3 to 25% by weight), preferably 0.5 to 20% by weight, and more preferably about 1 to 15% by weight (for example, 3 to 10% by weight).

  Examples of the chlorine-containing resin include a vinyl chloride polymer [a vinyl chloride monomer homopolymer (polyvinyl chloride), a vinyl chloride copolymer (vinyl chloride-vinyl acetate copolymer, vinyl chloride- (meth) acrylic). Acid ester copolymer, etc.)], vinylidene chloride polymer [vinylidene chloride homopolymer (polyvinylidene chloride), vinylidene chloride copolymer (vinylidene chloride-vinyl chloride copolymer, vinylidene chloride-vinyl acetate copolymer) Polymer, vinylidene chloride- (meth) acrylic acid copolymer, vinylidene chloride- (meth) acrylic acid ester copolymer, vinylidene chloride- (meth) acrylonitrile copolymer, etc.)] and the like. These chlorine-containing resins can be used alone or in combination of two or more.

  Among these chlorine-containing resins, from the viewpoint of improving the adhesion to the base material layer or the intermediate layer (particularly the base material layer), a vinylidene chloride polymer (particularly, vinylidene chloride such as vinylidene chloride-vinyl chloride copolymer). Based copolymer). In the vinylidene chloride-vinyl chloride copolymer, the ratio (molar ratio) of vinylidene chloride units to vinyl chloride units is, for example, the former / the latter = 99/1 to 5/95, preferably 97/3 to 10/90, Preferably it is about 95 / 5-50 / 50. The vinylidene chloride polymer may not contain an emulsifier, a surfactant and the like contained in the aqueous emulsion.

  The number average molecular weight of the chlorine-containing resin is, for example, 10,000 to 500,000, preferably 20,000 to 250,000, more preferably 25,000 to 100,000 in terms of polystyrene in gel permeation chromatography (GPC). It may be about 000.

  The ratio of the chlorine-containing resin is not particularly limited as long as the surface chlorine concentration is 0.07 Atom% or more. However, from the viewpoint of the release property of the resin film, for example, 0.1 to 10 parts by weight (for example, 0.15 to 5 Parts by weight), preferably 0.2 to 3 parts by weight (eg 0.2 to 1 part by weight), more preferably about 0.3 to 0.8 parts by weight (particularly 0.4 to 0.6 parts by weight). is there. If the proportion of the chlorine-containing resin is too small, when forming the surface layer on the base material layer, the adhesion between the two layers may be lowered, and if too much, the release property of the resin film may be lowered. .

(Cyclic olefin resin)
Cyclic olefin resin should just contain the cyclic olefin unit as a repeating unit at least. The polymerization component (monomer) for forming the cyclic olefin unit is a polymerizable cyclic olefin having an ethylenic double bond in the ring, and is a monocyclic olefin, a bicyclic olefin, a tricyclic or more polycyclic Can be classified into olefins.

Examples of monocyclic olefins include cyclic C _4-12 cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.

Examples of the bicyclic olefin include 2-norbornene; norbornenes having a C _1-2 alkyl group such as 5-methyl-2-norbornene, 5,5-dimethyl-2-norbornene, and 5-ethyl-2-norbornene. Norbornenes having an alkenyl group such as 5-ethylidene-2-norbornene; norbornenes having an alkoxycarbonyl group such as 5-methoxycarbonyl-2-norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene; Norbornenes having a cyano group such as cyano-2-norbornene; norbornenes having an aryl group such as 5-phenyl-2-norbornene and 5-phenyl-5-methyl-2-norbornene; octalin; 6-ethyl-octahydro _{C 1-2} alkyl group such as naphthalene -Octalin compound having others.

  Examples of the polycyclic olefin include dicyclopentadiene; 2,3-dihydrodicyclopentadiene, methanooctahydrofluorene, dimethanooctahydronaphthalene, dimethanocyclopentadienonaphthalene, methanooctahydrocyclopentadienaphthalene, and the like. Derivatives thereof; adducts of cyclopentadiene and tetrahydroindene, etc .; 3-pentamers of cyclopentadiene, and the like.

  These cyclic olefins can be used alone or in combination of two or more. Of these cyclic olefins, bicyclic olefins are preferred because they are excellent in the balance between the releasability and flexibility of the resin film. The ratio of bicyclic olefins (particularly norbornenes) to the whole cyclic olefins (cyclic olefins for forming cyclic olefin units) may be 10 mol% or more, for example, 30 mol% or more, preferably 50 It is at least mol%, more preferably at least 80 mol% (particularly at least 90 mol%), and it may be a bicyclic olefin alone (100 mol%). In particular, when the ratio of the tricyclic or higher polycyclic olefin is increased, it becomes difficult to use for production in a roll-to-roll system.

As typical bicyclic olefins, for example, norbornene (2-norbornene) which may have a substituent, octaline (octahydronaphthalene) which may have a substituent, and the like can be exemplified. Examples of the substituent include a methyl group, an ethyl group, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a cyano group, an amide group, and a halogen atom. These substituents may be used alone or in combination of two or more. Of these substituents, a nonpolar group such as a methyl group or an ethyl group is preferable because it does not impair the releasability of the resin film. Among these bicyclic olefins, norbornenes such as norbornene and norbornene having a C _1-2 alkyl group (particularly norbornene) are particularly preferable.

  The cyclic olefin resin may contain at least a cyclic olefin unit as a repeating unit. From the viewpoint of adhesion to a base material layer or an intermediate layer and mechanical properties, a cyclic olefin copolymer (cycloolefin copolymer). Is preferred. The cyclic olefin copolymer may be a copolymer of cyclic olefin units containing different types of cyclic olefin units, or may be a copolymer of cyclic olefin units and other copolymerizable units. Among these copolymers, a copolymer of a cyclic olefin unit and another copolymerizable unit is preferable from the viewpoint of excellent balance between the adhesion and mechanical properties, and a cyclic olefin unit and a chain olefin are used as repeating units. A copolymer containing units is particularly preferred.

  The chain olefin unit may be a chain olefin unit generated by ring-opening of a cyclic olefin, but from the viewpoint of easily controlling the ratio of the cyclic olefin unit and the chain olefin unit, the chain olefin is used as a polymerization component. The unit to do is preferable.

Examples of the chain olefin include ethylene, propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-nonene, Examples thereof include chain C _2-12 olefins such as 1-decene, 1-undecene and 1-dodecene. These chain olefins can be used alone or in combination of two or more. Among these chain olefins, α-chain C _2-3 olefins are preferable and ethylene is particularly preferable from the viewpoint that the halogen element concentration can be suppressed.

  The ratio (molar ratio) between the cyclic olefin unit and the chain olefin unit can be selected, for example, from the range of the former / the latter = 1/99 to 99/1, for example, the former / the latter = 30/70 to 95/5. The ratio is preferably 50/50 to 90/10 (for example, 55/45 to 80/20), more preferably about 60/40 to 75/25 (especially 65/35 to 70/30). When the ratio of the cyclic olefin unit is too small, the heat resistance is lowered, and when it is too much, the mechanical characteristics are also easily lowered.

  The cyclic olefin-based resin may contain other copolymerizable units in addition to the cyclic olefin unit and the chain olefin unit. Examples of the polymerization component (copolymerizable monomer) for forming other copolymerizable units include the copolymerizable monomers exemplified in the section of the chlorine-containing resin. The said copolymerizable monomer can be used individually or in combination of 2 or more types.

  The ratio of the other copolymerizable units is preferably within a range that does not impair the releasability of the resin film, and is, for example, 10 mol% or less with respect to the total of olefin units (for example, the total of cyclic olefin units and chain olefin units). , Preferably 5 mol% or less, more preferably 1 mol% or less.

  The number average molecular weight of the cyclic olefin-based resin is, for example, 10,000 to 100,000, preferably about 20,000 to 80,000 in terms of polystyrene in gel permeation chromatography (GPC) (solvent: toluene). . If the molecular weight is too small, the film-forming property is liable to be lowered, and if it is too large, the viscosity is increased, so that the handleability is liable to be lowered.

  The glass transition temperature (Tg) of the cyclic olefin-based resin is, for example, 50 to 350 ° C., preferably 80 to 300 ° C., more preferably 100 to 250 ° C. (particularly 130 to 200 ° C.) in a method based on JIS K7121-1087. Degree. If the glass transition temperature is too low, the heat resistance is low, so that peeling failure from the polymer layer is likely to occur, and if it is too high, production may be difficult. In the present specification and claims, the glass transition temperature can be measured using a differential scanning calorimeter (DSC). For example, a differential scanning calorimeter (“DSC6200” manufactured by SII NanoTechnology Co., Ltd.) may be used and measured in accordance with JIS K7121 under a nitrogen stream at a heating rate of 10 ° C./min.

  The cyclic olefin-based resin may be a resin obtained by addition polymerization or a resin obtained by ring-opening polymerization (ring-opening metathesis polymerization or the like). The polymer obtained by ring-opening metathesis polymerization may be a hydrogenated hydrogenated resin. The polymerization method of the cyclic olefin resin is a conventional method, for example, ring-opening metathesis polymerization using a metathesis polymerization catalyst, addition polymerization using a Ziegler type catalyst, addition polymerization using a metallocene catalyst (usually a metathesis polymerization catalyst). The ring-opening metathesis polymerization used) can be used. Specific polymerization methods include, for example, JP-A No. 2004-197442, JP-A No. 2007-119660, JP-A No. 2008-255341, Macromolecules, 43, 4527 (2010), Polyhedron, 24, 1269 (2005). ), J. Appl. Polym. Sci, 128 (1), 216 (2013), Polymer Journal, 43, 331 (2011). As the catalyst used for the polymerization, a conventional catalyst such as a catalyst synthesized by the method described in Macromolecules, 31, 3184 (1988), Journal of Organometallic Chemistry, 2006, Vol. 691, p.193 can be used.

(Characteristics of the surface layer)
The surface layer may contain conventional additives exemplified in the section of other resins and base material layers. Examples of other resins include chain olefin resins (polyethylene, polypropylene, etc.). In addition, organic or inorganic particles (particularly anti-blocking agents such as zeolite) may be included as long as the surface smoothness is not impaired. In particular, in the present invention, it is preferable that the releasability can be improved without containing a low molecular weight release agent such as a silicone compound, and it is preferable that the silicone compound is not substantially contained. The ratio of the cyclic olefin-based resin in the surface layer is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more (for example, 95 to 99.9% by weight) with respect to the entire surface layer. Also good.

The weight per unit area of the surface layer (the coating amount of the dry coating film or the dry coating amount) is not particularly limited and can be selected from the range of, for example, about 0.05 to 20 g / m ^2, but the surface is smooth and thin by coating. Can be formed, for example, 0.1 to 10 g / m ² , preferably 0.15 to 8 g / m ² , more preferably about 0.2 to 5 g / m ² (particularly 0.3 to 4 g / m ² ). It is.

  The average thickness of the surface layer is not particularly limited and can be selected, for example, from a range of about 0.01 to 100 μm, for example, 0.01 to 20 μm, preferably 0.03 to 15 μm, more preferably 0.05 to 10 μm (particularly 0 .1 to 5 μm). In the case of a coating film, the average thickness can be calculated based on the dry coating amount (solid content weight per unit area) and density of the surface layer.

Furthermore, when the resin film includes an intermediate layer containing a chlorine-containing resin and the liquid composition for forming the surface layer does not contain a halogen-containing compound (particularly a chlorine-containing resin), the weight per unit area of the surface layer is 3 g. / M ² or less, for example, 0.1 to 3 g / m ² , preferably 0.15 to 2.5 g / m ² , more preferably 0.2 to ² g / m ² (particularly 0.3 to 1 g / m ² ). The average thickness of the surface layer may be 2.5 μm or less, for example, 0.01 to 2.5 μm, preferably 0.03 to 2 μm (for example, 0.05 to 1.5 μm), more preferably 0.1 to 1. About 2 μm (particularly 0.3 to 1 μm). When the weight and thickness per unit area of the surface layer are too large, the amount of halogen element transferred from the intermediate layer to the surface of the surface layer is lowered, and it may be difficult to adjust the releasability of the resin film.

  The surface layer should just be located in the outermost surface of at least one of the resin film, may be formed in the one surface side of the base material layer, and may be formed in the both surfaces side of the base material layer.

[Middle layer]
The resin film of the present invention may further have an intermediate layer interposed between the base material layer and the surface layer. By interposing an intermediate layer, it is possible to achieve both a high level of releasability and its own stability (adhesion between the base layer and the surface layer). Excellent releasability even for ion exchange layers containing ion exchange resins with a unique structure with side chains containing low sulfonic acid groups (can be easily peeled off when necessary, peeled off when not needed Characteristic), and the stability of itself can be improved.

  The intermediate layer contains a chlorine-containing resin in order to improve the adhesion between the base material layer and the surface layer. As the chlorine-containing resin, the chlorine-containing resin exemplified in the section of the surface layer can be used. The preferable range of the monomer type and molecular weight is the same as that of the chlorine-containing resin in the surface layer.

  In order to adjust the adhesion, the intermediate layer may further contain a reactive adhesive component [an isocyanate compound, an imino group-containing polymer (polyethyleneimine, etc.)] in addition to the chlorine-containing resin. It is preferable to contain a system compound.

  The isocyanate compound may be a prepolymer or an oligomer having a terminal isocyanate group, but is usually a polyisocyanate such as an aliphatic isocyanate, an alicyclic isocyanate, an aromatic isocyanate, or a derivative thereof. Also good.

  Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like. Examples of the alicyclic isocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and hydrogenated tolylene diisocyanate. (Hydrogenated TDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), hydrogenated diphenylmethane-4,4′-diisocyanate (hydrogenated MDI), and the like. Examples of the aromatic isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), diphenylmethane-4,4'-diisocyanate (MDI), and the like.

  Examples of the isocyanate derivative include, for example, the above-mentioned isocyanate multimer [dimer (uretdione group-containing isocyanate), trimer (isocyanurate ring-containing isocyanate), pentamer, heptamer, etc.], Examples include modified products (such as allophanate-modified isocyanate, burette-modified isocyanate, urea-modified isocyanate, and carbodiimide-modified isocyanate), adducts of polyhydric alcohols and the above isocyanates, and the like.

  Of these isocyanate compounds, aromatic isocyanates such as TDI, MDI, XDI, and TMXDI and derivatives thereof are preferable.

  The proportion of the reactive adhesive component (particularly the isocyanate compound) is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the chlorine-containing resin. It may be a degree.

  The intermediate layer may contain a conventional additive exemplified in the section of the base material layer. The ratio of the chlorine-containing resin in the intermediate layer is, for example, 80% by weight or more, preferably 90% by weight or more, more preferably 95% by weight or more (for example, 95 to 99.9% by weight) with respect to the entire intermediate layer. May be.

The weight per unit area (dry coating amount) of the intermediate layer is not particularly limited, and can be selected, for example, from a range of about 0.01 to 10 g / m ² , for example, 0.02 to 5 g / m ² , preferably 0.8. 03~3g / ^{m 2,} more preferably from 0.05 to 1 g / ^{m 2} (especially 0.1 to 0.5 g / ^{m 2)} approximately.

  The ratio between the dry coating amount of the surface layer and the dry coating amount of the intermediate layer can be selected from the range of the former / the latter = 50/1 to 1/10, for example, 30/1 to 1/5, preferably 25/1. Is about 1/3, more preferably about 20/1 to 1/2 (particularly 10/1 to 1 / 1.5). If the ratio of the dry coating amount on the surface layer is too small, the release property of the resin film may be lowered. If the amount is too large, the polymer layer cannot be properly adhered and fixed, or the base material layer and the surface layer are separated. There is a possibility that it becomes easy to do.

  The average thickness of the intermediate layer is not particularly limited, and can be selected from a range of, for example, about 0.01 to 100 μm, for example, 0.01 to 20 μm, preferably 0.03 to 15 μm, more preferably 0.05 to 10 μm (particularly 0.1 to 5 μm).

[Production method of resin film]
The resin film of this invention should just include the surface layer formation process which coats the liquid composition containing cyclic olefin resin and forms a surface layer.

  When the resin film is formed of a base material layer and a surface layer, the resin film is obtained through a surface layer forming step of forming a surface layer by coating a liquid composition for forming the surface layer on the base material layer. It is done. Specifically, it can be produced by a method of coating (or casting) a liquid composition (coating agent) containing a cyclic olefin-based resin and a solvent on a base material layer, and then drying.

  As the coating method, conventional methods such as roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, die coater, gravure coater, screen coater method, spray method, spinner method and the like can be mentioned. It is done. Of these methods, the blade coater method, the bar coater method, the gravure coater method and the like are widely used.

  Examples of the solvent include water; alcohols such as ethanol, isopropanol, butanol, and cyclohexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; Cellosolves such as cellosolve and ethyl cellosolve; cellosolve acetates; esters such as methyl acetate, ethyl acetate and butyl acetate; aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; toluene and xylene Aromatic hydrocarbons; halogenated hydrocarbons such as dichloromethane and dichloroethane; aromatic oils such as solvent naphtha and the like. These solvents can be used alone or in combination of two or more.

  The solvent can be appropriately selected according to the components contained in the liquid composition. For example, when only the cyclic olefin-based resin is included, the solvent may be an aromatic hydrocarbon such as toluene. When the liquid composition contains a cyclic olefin resin and a chlorine-containing resin, the solvent may be a mixed solvent of aromatic hydrocarbons such as toluene and cyclic ethers such as tetrahydrofuran.

  The solid content concentration in the liquid composition is, for example, about 0.1 to 50% by weight, preferably about 1 to 30% by weight, and more preferably about 3 to 20% by weight (particularly 5 to 15% by weight).

  Drying may be natural drying, or the solvent may be evaporated by heating and drying. 50 degreeC or more may be sufficient as drying temperature, for example, 50-200 degreeC, Preferably it is 60-150 degreeC, More preferably, it is about 80-120 degreeC.

  On the other hand, when the resin film includes an intermediate layer, the resin film is formed on the base layer by coating a liquid composition for forming the intermediate layer to form the intermediate layer. Further, it is obtained through a surface layer forming step of coating the liquid composition for forming the surface layer to form the surface layer. Specifically, after coating a liquid composition containing a chlorine-containing resin and a solvent on a base material layer, and drying, a liquid composition containing a cyclic olefin-based resin and a solvent on the obtained intermediate layer After the product is coated, it can be produced by a method of drying.

  In the intermediate layer forming step, the same method as in the surface layer forming step can be used as a coating method and a drying method.

  As the solvent, the solvents exemplified as the solvent used in the surface layer forming step can be used. Of these solvents, solvents having high solubility in chlorine-containing resins are preferable. For example, ketones such as methyl ethyl ketone, cyclic ethers such as tetrahydrofuran, aromatic hydrocarbons such as toluene, etc. may be used. Particularly preferred is a mixed solvent of styrene, cyclic ethers and aromatic hydrocarbons. In the mixed solvent, the proportion of ketones and cyclic ethers is about 50 to 90% by weight, preferably about 60 to 80% by weight, based on the whole solvent. The proportion of the ketone is 5 to 50 parts by weight, preferably about 10 to 30 parts by weight, based on 100 parts by weight of the cyclic ether.

  In the surface layer forming step, as the coating method and the drying method, the same method as in the surface layer forming step of the resin film formed of the base material layer and the surface layer can be used.

  The liquid composition for forming the surface layer only needs to contain a cyclic olefin-based resin, and may further contain a halogen-containing compound such as a chlorine-containing resin. In the resin film in which the intermediate layer is interposed between the base material layer and the surface layer, the chlorine-containing resin in the intermediate layer can be transferred to the surface of the surface layer by adjusting the production conditions. Even if the halogen compound is not included, the surface halogen element concentration of the surface layer can be adjusted to 0.07 Atom% or more. Therefore, the resin composition for forming the surface layer may be a composition containing a cyclic olefin resin and not containing a halogen compound (particularly a chlorine-containing resin).

  Also as a solvent, the solvent illustrated as a solvent used at the surface layer formation process of the resin film formed with the base material layer and the surface layer can be utilized. Among the solvents, a solvent having high solubility in the cyclic olefin resin is preferable, and for example, aromatic hydrocarbons such as toluene are preferable. Although the solvent for forming the liquid composition for forming the surface layer and the solvent for forming the intermediate layer are different in this way, in the present invention, by selecting the solvent and adjusting the coating amount, Although the mechanism is unknown, surprisingly, the halogen element (especially chlorine) in the intermediate layer can be transferred to the surface layer.

[Laminate]
The laminate of the present invention includes the resin film and an ion exchange layer laminated on the surface layer of the resin film and containing an ion exchange resin.

  As the ion exchange resin, a conventional ion exchange resin used in a fuel cell or the like can be used. Among them, a cation exchange resin such as a strong acid cation exchange resin or a weak acid cation exchange resin is preferable. , Ion-exchange resin having sulfonic acid group, carboxyl group, phosphoric acid group, phosphonic acid group, etc. (In detail, sulfonic acid group, carboxyl group, phosphoric acid group, phosphonic acid group, etc. are introduced as electrolyte groups having electrolyte function. An ion exchange resin having a sulfonic acid group (an ion exchange resin into which a sulfonic acid group is introduced as an electrolyte group) is particularly preferable.

  As the ion exchange resin having a sulfonic acid group, various resins having a sulfonic acid group can be used. Examples of the various resins include polyolefins such as polyethylene and polypropylene, (meth) acrylic resins, styrene resins, polyacetals, polyesters, polycarbonates, polyamides, polyamideimides, polyimides, polyethers, polyetherimides, polyether ketones, Examples include polyetheretherketone, polysulfone, polyethersulfone, polyphenylene sulfide, and fluororesin.

Among the ion exchange resins having a sulfonic acid group, a fluorine resin having a sulfonic acid group, a sulfonated product of a crosslinked polystyrene, and the like are preferable. A polystyrene-graft-polyethylenetetrafluoroethylene copolymer having a sulfonic acid group, a polystyrene-graft. -Polytetrafluoroethylene copolymer etc. may be sufficient. Of these, a fluororesin having a sulfonic acid group (such as a fluorohydrocarbon resin in which at least some of the hydrogen atoms are substituted with fluorine atoms) is particularly preferable from the viewpoint of releasability. In particular, in a polymer electrolyte fuel cell, a fluororesin having a sulfonic acid group (or —CF ₂ CF ₂ SO ₃ H group) in the side chain, for example, [2- (2-sulfotetrafluoroethoxy) hexafluoropropoxy] A copolymer (such as a block copolymer) of trifluoroethylene and tetrafluoroethylene is preferably used.

  The ion exchange capacity of the ion exchange resin may be 0.1 meq / g or more, for example, 0.1 to 2.0 meq / g, preferably 0.2 to 1.8 meq / g, more preferably 0.3. It may be about ~ 1.5 meq / g (particularly 0.5 to 1.5 meq / g).

  As such an ion exchange resin, commercially available products such as “registered trademark: Nafion” manufactured by DuPont can be used. In addition, as an ion exchange resin, you may use the ion exchange resin etc. which are described in Unexamined-Japanese-Patent No. 2010-234570.

  The ion exchange layer may be, for example, an electrolyte membrane, an electrode membrane, or a membrane electrode assembly of a polymer electrolyte fuel cell. For example, the electrolyte membrane formed of the ion exchange resin, the ion exchange resin, and catalyst particles May be an electrode film.

  In the electrode film (catalyst layer or electrode catalyst film), the catalyst particles include a metal component having a catalytic action (particularly, a noble metal element such as platinum (Pt) or an alloy containing a noble metal), and is usually an electrode film for a cathode electrode. Contains platinum, and the electrode film for the anode electrode contains a platinum-ruthenium alloy. Furthermore, the catalyst particles are usually used as composite particles in which the metal component is supported on a conductive material (carbon material such as carbon black). In the electrode membrane, the ratio of the ion exchange resin is, for example, about 5 to 300 parts by weight, preferably about 10 to 250 parts by weight, and more preferably about 20 to 200 parts by weight with respect to 100 parts by weight of the catalyst particles.

  The ion exchange layer may also contain the conventional additives exemplified in the section of the base material layer, and include, for example, inorganic materials such as inorganic particles and inorganic fibers (carbonaceous material, glass, ceramics, etc.). Also good.

  The average thickness of the ion exchange layer is, for example, 1 to 500 μm, preferably 1.5 to 300 μm, and more preferably about 2 to 200 μm.

  The average thickness of the electrolyte membrane is, for example, about 1 to 500 μm, preferably about 5 to 300 μm, and more preferably about 10 to 200 μm.

  The average thickness of the electrode film is, for example, about 1 to 100 μm, preferably 2 to 80 μm, and more preferably about 2 to 50 μm.

  The manufacturing method of a laminated body is obtained by the method of drying, after coating the liquid composition for forming an ion exchange layer on the surface layer of a resin film.

  As a coating method and a drying method, the same method as the surface layer forming step of the resin film formed by the base material layer and the surface layer can be used.

Examples of the solvent include water, alcohols (C _1-4 alkanols such as methanol, ethanol, isopropanol, and 1-butanol), ketones (acetone, methyl ethyl ketone, etc.), ethers (dioxane, tetrahydrofuran, etc.), and sulfoxides. (Such as dimethyl sulfoxide). These solvents can be used alone or in combination of two or more. Among these solvents, water or a mixed solvent of water and C _1-4 alkanol is generally used from the viewpoint of handleability. The concentration of the solute (ion exchange resin, catalyst particles) in the solution is, for example, about 1 to 80% by weight, preferably 2 to 60% by weight, and more preferably about 3 to 50% by weight.

  In this invention, since the said resin film or the said laminated body is excellent in a softness | flexibility, the lamination process with such conveyance can be performed by a roll-to-roll system, and productivity can be improved. Furthermore, since the dimensional stability of the resin film is excellent due to the combination of the surface layer and the base material layer, the elongation due to the tension of the resin film is suppressed even in the roll-to-roll method. Therefore, the ion exchange layer can be wound up in a roll shape without peeling, and productivity can be improved.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The characteristics of the resin films obtained in Examples and Comparative Examples were evaluated by the following methods.

[Raw materials used]
Ion exchange resin solution: a solution of a perfluoropolymer having a sulfonic acid group in the side chain, “Nafion (registered trademark) DE2020CS” manufactured by DuPont, solid content of 20% by weight
Vinylidene chloride copolymer: “PVDC Resin R204” manufactured by Asahi Kasei Chemicals Corporation
Cyclic olefin resin: “TOPAS (registered trademark) 6015” manufactured by Polyplastics Co., Ltd., glass transition temperature of 158 ° C.
Biaxially stretched polyethylene terephthalate (PET) film: “Polyester film emblet S50” manufactured by Unitika Co., Ltd., thickness 50 μm, no adhesive layer Cellotape (registered trademark): “CT-24” manufactured by Nichiban Co., Ltd.

[Dry coating amount]
(Application amount of the resin film obtained in Examples 1 to 4 and Comparative Example 1)
The base material layer on which the intermediate layer was laminated was cut out into 10 cm × 25 cm, used as a sample, weighed, and then the intermediate layer was eluted from the base material layer with tetrahydrofuran, and then sufficiently wiped off. The weight of the sample was measured again, and the coating amount of the surface layer was calculated from the decrease in weight. In addition, a resin film having a surface layer formed on the intermediate layer laminated on the base material layer was cut into 10 cm × 25 cm as a sample, and after measuring the weight, the intermediate layer and the surface layer were separated from the base material layer with toluene and tetrahydrofuran. It peeled off enough. The weight of the sample was measured again, the total coating amount of the intermediate layer and the surface layer was calculated from the decrease in weight, and the coating amount of the surface layer was also calculated.

(Coating amount of the resin film obtained in Example 5)
The resin film on which the surface layer was formed was cut into a size of 10 cm × 25 cm, and the weight was measured. Then, the surface layer was eluted from the base material layer with toluene and tetrahydrofuran, and then sufficiently wiped off. The weight of the sample was measured again, and the coating amount of the surface layer was calculated from the decrease in weight.

[Surface chlorine concentration]
The surface chlorine concentration of the surface layer of the resin film was measured using an X-ray photoelectron spectrometer (“Physical Electronics PHI 5800 ESCA System” manufactured by ULVAC-PHI Co., Ltd.), Monochlorinated AlKα ray, X-ray incident angle 90 °, photoelectron detection The sum of the elements detected at an angle of 45 ° and an aperture of 800 μmφ was taken as 100% and calculated from the ratio of chlorine elements.

[Adhesion (adhesion to substrate layer)]
Paste the cellophane on the surface of the resin film, fully press-bond with a roller, cut to a width of 15 mm, let stand at 23 ° C., 50% RH for 1 hour or more, then fix the resin film, The peel strength was measured by a method of peeling 180 ° under the condition of 300 mm / min.

[Releasability (Peel strength of ion exchange layer)]
An ion exchange resin solution is coated on the surface layer of the resin film by the Mayer bar coating method, dried at a temperature of 100 ° C. for 3 minutes, and then heat-treated at a temperature of 160 ° C. for 10 minutes to obtain an ion exchange layer (thickness). 4 μm) was formed. A cellophane tape is affixed on the obtained ion exchange layer, and after sufficiently pressing with a roller, it is cut to a width of 15 mm, left at 23 ° C. and 50% RH for 1 hour or more, and then fixed with a resin film. The peel strength was measured by a method in which one end of the film was peeled 180 ° under the condition of 300 mm / min. If the peel strength is too large, when the ion exchange layer is peeled from the resin film, the ion exchange layer may remain on the resin film or the ion exchange layer may be destroyed.If the peel strength is too small, There is a risk that the ion exchange layer may be peeled off during storage or in a processing step that does not require peeling.

Examples 1 to 4 and Comparative Example 1
(Preparation of coating solution P)
Toluene, methyl ethyl ketone and tetrahydrofuran (toluene: methyl ethyl ketone: tetrahydrofuran (weight ratio) = 1.5: 1.5: 7) were mixed and stirred to prepare a uniform solvent (solvent). In this solvent, 100 parts by weight of vinylidene chloride polymer and 3 parts by weight of tolylene diisocyanate (TDI) were dissolved to obtain a coating solution P having a solid content concentration of 3% by weight.

(Preparation of coating solution C)
A cyclic olefin-based resin was added to toluene so as to have a solid concentration of 15% by weight, and dissolved by heating to obtain a coating solution C.

(Manufacture of resin film)
A biaxially stretched PET film was used as the base material layer, and one side of this film was subjected to corona discharge treatment. The coating liquid P was coated on the surface subjected to the corona discharge treatment by the Mayer bar coating method, and dried at a temperature of 100 ° C. for 1 minute to form an intermediate layer. Furthermore, the coating liquid C was coated on the intermediate layer by the Mayer bar coating method and dried at a temperature of 100 ° C. for 3 minutes to form a surface layer to obtain a resin film.

  By coating with different Mayer bars by such a method, resin films having coating amounts shown in Table 1 were obtained.

Example 5
(Preparation of coating solution D)
A mixed solvent of toluene and tetrahydrofuran (toluene / tetrahydrofuran = 70/30 (weight ratio)) so that 100 parts by weight of a cyclic olefin resin and 0.5 parts by weight of a vinylidene chloride polymer are 5% by weight in solid content. ), Heated to dissolve, and coating solution D was obtained.

(Manufacture of resin film)
A biaxially stretched PET film was used as the base material layer, and one side of this film was subjected to corona discharge treatment. The coating liquid D was coated on the surface subjected to the corona discharge treatment by the Mayer bar coating method and dried at a temperature of 100 ° C. for 1 minute to obtain a resin film. The coating amount of the surface layer of the obtained resin film was 0.3 g / m ² .

  Table 2 shows the results of evaluating the surface chlorine concentration and release properties of the resin films obtained in Examples 1 to 5 and Comparative Example 1.

  The resin films obtained in Examples 1 to 5 can be easily peeled off when attempting to peel off because the peel strength of the ion exchange layer is appropriate, and can be peeled off during storage or processing steps that do not require peeling. Showed no characteristics. On the other hand, since the resin film obtained in Comparative Example 1 has a small peel strength of the ion exchange layer, the ion exchange layer was peeled off during storage or in a processing step that does not require peeling.

  Furthermore, about the adhesiveness with respect to a base material layer, since the film obtained in Examples 1-4 and the comparative example 1 has peeled between a cellophane and a surface layer, the peeling strength of a base material layer and an intermediate | middle layer. In addition, it was determined that the peel strength between the intermediate layer and the surface layer exceeded 5.5 N / 15 mm, and the adhesive strength was high. On the other hand, in the film obtained in Example 5, the base material layer and the surface layer were peeled off, and the peel strength between the two layers was 0.4 N / 15 mm, which is compared with Examples 1 to 4 and Comparative Example 1. Adhesion decreased. However, since the releasability of the film obtained in Example 5 was 70 mN / 15 mm (0.07 N / 15 mm), it could be used without peeling off the surface layer for the ion exchange layer used in the Example. .

  The resin film of the present invention can be easily adjusted for releasability, so that it can be used as a release film in various fields such as foods, pharmaceuticals, chemicals, optical members, electrical / electronic materials, for example, release films for polymer layers. it can. In particular, a release film for producing a membrane electrode assembly (MEA) of a polymer electrolyte fuel cell, particularly an ion, because it has appropriate peelability and adhesion to the ion exchange layer. An electrolyte membrane and / or an electrode membrane containing an exchange resin can be laminated thereon to produce a MEA, which can be preferably used as a film for peeling from the MEA.

Claims (15)

  A resin film comprising a base material layer and a surface layer containing a cyclic olefin resin, wherein the surface layer has a surface halogen element concentration of 0.07 Atom% or more.   The resin film according to claim 1, wherein the surface halogen element concentration is a surface chlorine concentration.   The resin film according to claim 2, wherein the surface chlorine concentration is 0.1 to 2 Atom%.   The resin film according to any one of claims 1 to 3, wherein an intermediate layer containing a chlorine-containing resin is interposed between the base material layer and the surface layer.   The resin film according to claim 4, wherein the halogen element present on the surface of the surface layer is chlorine derived from a chlorine-containing resin contained in the intermediate layer. The resin film according to claim 1, wherein the weight per unit area of the surface layer is 3 g / m ² or less.   The resin film in any one of Claims 1-6 in which a surface layer contains chlorine containing resin.   The resin film according to claim 1, wherein the cyclic olefin resin is a cyclic olefin copolymer.   The resin film according to any one of claims 4 to 8, wherein the chlorine-containing resin is a vinylidene chloride polymer.   The resin film in any one of Claims 1-9 in which a base material layer contains at least 1 sort (s) selected from the group which consists of polyolefin, a polyvinyl alcohol-type polymer, polyester, polyamide, a polyimide, and a cellulose derivative.   The manufacturing method of the resin film in any one of Claims 1-10 including the surface layer formation process of coating the liquid composition containing cyclic olefin resin and forming a surface layer.   An intermediate layer forming step of forming an intermediate layer by coating a liquid composition containing a chlorine-containing resin on the base material layer, a liquid composition containing a cyclic olefin-based resin on the intermediate layer and not containing a chlorine-containing resin The manufacturing method of the resin film in any one of Claims 4-10 including the surface layer formation process which coats a thing and forms a surface layer.   The laminated body containing the resin film in any one of Claims 1-10, and the ion exchange layer which is laminated | stacked on the surface layer of this resin film, and contains an ion exchange resin.   A method of adjusting the releasability of the surface layer by adjusting the surface halogen element concentration of the surface layer in a resin film including a base material layer and a surface layer containing a cyclic olefin resin.   An intermediate layer containing a chlorine-containing resin is interposed between the base material layer and the surface layer, and the surface chlorine concentration of the surface layer is adjusted by the chlorine-containing resin contained in the liquid composition for forming the intermediate layer. 14. The method according to 14.