JP2000218752A - Multiplayer film and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film which shows low extensibility even when it is used at high temperature and high tensile strength and mold release properties. SOLUTION: This multilayer film is a three-layer film consisting of a poly 4-methyl-1-pentene resin layer, an adhesive resin layer and a heat-resistant resin layer laminated in that order on the surface side or a five-layer film consisting of the heat-resistant resin layer as a core, on both sides of which the adhesive resin layer and the poly 4-methyl-1-pentene resin layer are laminated. The heat-resistant resin is of such a nature that a heat-deformation temperature which is measured under 4.6 (kg/cm2) load is at lest 130 deg.C and a yield point stress at 140 deg.C is at least 100 (kg/cm2). Especially a polymer alloy is desirably acceptable which is a mixture of non-crystalline resin with at least 130 deg.C glass transition point and a crystalline resin with at least 170 deg.C melt point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a multilayer film having excellent physical properties such as heat resistance, chemical resistance and electrical insulation.
More specifically, the present invention relates to a multilayer film that can be widely used for applications such as a heat-resistant film, a release film, and an electric insulating film, and an application thereof.

[0002]

2. Description of the Related Art Conventionally, when a molded product of a thermosetting resin, a vulcanized rubber, or a cross-linkable adhesive, a heat-reactive thin film or a ceramic thin film is manufactured, a release film or a release paper is incorporated in a manufacturing process. It is becoming common to be manufactured in.

[0003] A typical release film or release paper is a so-called silicone-coated film or silicone-coated paper, which is formed on a base material such as a plastic film or clay-coated paper by a silicone resin. And cured and fixed with a silicone resin. There are two types of silicone resins used: thermosetting and ultraviolet curing.However, even if the type of resin or the curing method is changed, it is difficult to completely cure and adhere the coating, It is difficult to transfer to a product with which the coating comes into contact.

As another release film, a fluorine resin film represented by polytetrafluoroethylene or a tetrafluoroethylene / perfluoroalkylvinyl ether copolymer has been used. These fluorine-based resin films have a melting point of 200 ° C. or higher, are chemically stable and have excellent chemical resistance, and have an inactive surface, and thus have release properties. It is an excellent material as a release film. However, due to the above-mentioned properties, the formation of the film is not easy,
Further, the film forming apparatus is required to have corrosion resistance and, furthermore, the resin is expensive, so that its use in a wide range was naturally limited.

As another release film, poly-4-
Methyl-1-pentene resin films are known. This film has a high melting point, excellent releasability, and non-migration properties to products that come into contact with it, and is less expensive than fluororesin films. Used as a mold film. However, the poly 4-methyl-1-pentene resin has 2
Although it has a high melting point of about 30 ° C., its glass transition point is 40 to 50 ° C., so if the film is used under tension at a temperature higher than the glass transition point, the film may be deformed. there were.

When used under such severe conditions, a urethane type or epoxy type reactive adhesive is used, and a biaxially stretched polyester film having heat resistance and a composite film manufactured by dry lamination are used. The system is used. However, there is still a need for better dimensional stability at high temperatures,
Also, the high cost involved in the production of the composite film was unavoidable.

[0007]

Accordingly, in the present invention, a film used in a field requiring heat resistance and releasability has excellent releasability. No release agent is transferred to the product
Another object of the present invention is to provide an inexpensive film having sufficient tensile strength and dimensional stability even when used under heating conditions.
Another object of the present invention is to provide an inexpensive film having characteristics such as heat resistance, release properties, chemical resistance, and electrical insulation.

[0008]

That is, the present invention provides, in order from the surface side, a surface layer made of poly-4-methyl-1-pentene resin, an intermediate adhesive layer made of an adhesive resin, and a support layer made of a heat-resistant resin. A laminated multilayer film and a surface layer composed of poly-4-methyl-1-pentene resin are laminated on both sides of a support layer composed of the above-mentioned heat-resistant resin via an intermediate adhesive layer composed of an adhesive resin. To a multilayer film.

Here, the heat resistant resin is 4.6 (k)
g / cm ² ) The heat distortion temperature measured under load is 130 ° C.
As described above, the yield point stress at 140 ° C. is 100 (kg).
/ Cm ² ) or more.

The heat-resistant resin is preferably a polymer alloy composed of a combination of an amorphous resin having a glass transition point of 130 ° C. or higher and a crystalline resin having a melting point of 170 ° C. or higher. For example, polyphenylene oxide resin And a polyamide alloy or a polybutylene terephthalate resin, a polymer alloy composed of a polyarylate resin and a polyamide resin or a polyethylene terephthalate resin, and a polymer alloy composed of a polycarbonate resin and a polyethylene terephthalate resin or a polyamide resin. Particularly, a polymer alloy comprising 20 to 95% by weight of a polyphenylene oxide resin and 5 to 80% by weight of a polyamide resin is desirable.

It is preferable to use, as the adhesive resin, a modified product obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof to an olefin polymer, since a multilayer film in which each layer is firmly adhered can be obtained. .

This multilayer film is suitable as a heat-resistant film, a release film, an electric insulating film, etc. because of its low tensile elongation and high strength even at high temperatures.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The multilayer film according to the present invention is basically composed of a surface layer made of poly-4-methyl-1-pentene resin, an intermediate adhesive layer made of an adhesive resin, and a heat-resistant resin. As a three-layer structure that is laminated and integrated in the order of the support layer, or as the improved structure described above,
With a support layer made of a heat-resistant resin as the center, an intermediate adhesive layer made of an adhesive resin and poly 4-methyl-
It has a five-layer laminated structure in which surface layers made of 1-pentene resin are laminated and integrated. Next, the resin constituting each layer, the layer configuration, and its applied technology will be specifically described.

[0014] copolymerizing the poly 4-methyl-1-pentene resin forming the front surface layer surface layer, a homopolymer of 4-methyl-1-pentene, or 4-methyl-1-pentene with α- olefin It is united. Here, the α-olefin to be copolymerized with 4-methyl-1-pentene is an olefin having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 1-decene, 1
-Undecene, 1-dodecene, 1-tetradecene, 1-
Hexadecene, 1-octadecene, etc., which may be used alone or in combination of two or more. The α-olefin is contained in the copolymer in an amount of 0 to
It is desirable to contain 20 mol%, preferably 0 to 15 mol%.

The poly-4-methyl-1-pentene resin only needs to have a sufficient flowability for forming a film and a molecular weight that indicates a sufficient mechanical strength as a film. ) Is 0.5-20
0, preferably in the range of 5 to 120 (g / 10 minutes). The MFR is ASTM D-12.
This is a value measured under a load of 5 kg at 260 ° C. in accordance with No. 38.

Such a poly-4-methyl-1-pentene resin can be produced by a known method by using a Ziegler-Natta catalyst or a metallocene catalyst. Furthermore, this surface layer can be mixed with other resins, elastomers, additives, fillers, and the like, to the poly-4-methyl-1-pentene resin without departing from the object of the present invention.

The adhesive resin for forming the middle between contact adhesive layer intermediate layer, the surface layer made of the surface side of the poly-4-methyl-1-pentene resin, and both the support layer made from the opposite side of the heat-resistant resin Is a resin that exhibits adhesiveness to the layer and has extrudability.

Such adhesive resins include carboxylic acid groups, acid anhydride groups, carbonyl groups, hydroxyl groups, amide groups,
An olefin resin having a polar group such as an imide group can be used. The olefin-based resin having a polar group is a copolymer of a monomer having a polar group and an α-olefin, and is a random copolymer, an alternating copolymer, a graft copolymer, and a block copolymer of both monomers. Any copolymer form of the above may be used. The olefin resin having a polar group may be a polymer obtained by modifying an olefin polymer by means such as oxidation.

Among the above-mentioned adhesive resins, a random copolymer of ethylene and an unsaturated carboxylic acid or a derivative thereof, an ionomer resin obtained by cross-linking the random copolymer with a metal ion, or an unsaturated carboxylic acid or a derivative thereof is converted into an olefin polymer. A graft copolymer obtained by graft copolymerization is preferred.

Here, specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, sorbic acid, and nadic acid. (Endocis-bicyclo [2,2,1] hept-5
-Ene-2,3-dicarboxylic acid).

The derivatives of α, β-unsaturated carboxylic acids include unsaturated carboxylic acid anhydrides, esters, imides, amides, acid halides, epoxides, etc. Specifically, methyl acrylate, acryl Ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,
Glycidyl methacrylate, maleic anhydride, itaconic anhydride, citraconic anhydride, hymic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like can be mentioned.

Among these unsaturated carboxylic acids or derivatives thereof, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, nadic acid and nadic anhydride are preferred, and acrylic acid and maleic anhydride are particularly preferred.
These unsaturated carboxylic acids and derivatives thereof can be used alone or in combination of two or more.

Examples of a random copolymer of ethylene and an unsaturated carboxylic acid or a derivative thereof, which are one of preferred adhesive resins, include ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer and ethylene / methacrylic acid. -Methyl methacrylate copolymer can be mentioned.
Further, an ionomer resin obtained by cross-linking the above copolymer with metal ions can also be used.

A particularly preferred adhesive resin is a graft copolymer. Examples of the olefin polymer serving as the backbone polymer of the graft copolymer include those having 2 to 1 carbon atoms.
And α-olefin homopolymers and copolymers of the α-olefins. As the α-olefin, ethylene, propylene, 1-butene, 1-
Pentene, 3-methyl-1-butene, 1-hexene, 4
-Methyl-1-pentene, 1-heptene, 1-octene, 1-decene and the like can be used. Among these, ethylene homopolymer, propylene homopolymer,
Copolymer of ethylene with a small amount of propylene, 1-butene, 1-hexene, 1-octene, etc., copolymer of propylene with a small amount of ethylene, 1-butene, etc., 4-methyl-1
A homopolymer of -pentene, a copolymer of 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms, and the like are preferable as the backbone polymer.

Preferred examples of the graft copolymer include acrylic acid-grafted polyethylene, methacrylic acid-grafted polyethylene, maleic anhydride-grafted polyethylene,
Maleic anhydride-grafted polypropylene, maleic anhydride-grafted poly-4-methyl-1-pentene, and the like can be given.

The graft copolymer can be produced by polymerizing a monomer having a polar group, for example, an unsaturated carboxylic acid or a derivative thereof in the presence of an olefin polymer serving as a backbone polymer. At this time, by allowing a radical initiator such as an organic or inorganic peroxide to coexist, the copolymerization can be advanced with high grafting efficiency. Further, this copolymerization reaction can be performed in a solution state or a molten state.

The content of the unsaturated carboxylic acid or its derivative in the adhesive resin is 0.01 to 10% by weight, preferably 0.05 to 5% by weight. In the multilayer film according to the present invention, in the case of increasing the adhesive strength between the layers and forming a strong multilayer film, the content of the unsaturated carboxylic acid or a derivative thereof is set to be high, and the adhesive strength between the layers is so increased. If not necessary, the content may be set small. The content of the required unsaturated carboxylic acid or derivative thereof can be adjusted by changing the polymerization conditions at the time of copolymerization, or a high-content copolymer is produced in advance, and then the unmodified polymer is prepared. It can also be blended and diluted to adjust to the desired unsaturated carboxylic acid or derivative content.

In the present invention, the blend of the high-content graft copolymer and the unmodified polymer described above is used as a method for adjusting the content of the unsaturated carboxylic acid or a derivative thereof to a desired content, and the adhesive resin is modified. This is important as a method for improving the quality of the adhesive resin layer. Particularly in the latter case, the properties of the adhesive resin layer such as flexibility, heat resistance, and impact resistance can be changed depending on the properties of the unmodified polymer used. For example, when poly-4-methyl-1-pentene is used as the diluent polymer, the heat resistance is improved, and the adhesion to the poly-4-methyl-1-pentene resin of the surface layer is also increased. On the other hand, when an ethylene / α-olefin copolymer or the like having physical properties as an elastomer is blended, flexibility, adhesion, and impact resistance are improved. Other resins, elastomers, additives and the like can be added to the layer made of the adhesive resin without departing from the object of the present invention.

Support Layer The support layer in the present invention plays a role in compensating for the lack of tensile strength of the poly-4-methyl-1-pentene resin layer at a high temperature, and is 4.6 (kg / cm ² ). The heat distortion temperature measured under load is 130 ° C. or higher and 140 ° C.
A layer obtained from a heat-resistant resin composed of a resin having a yield point stress of 100 (kg / cm ² ) or more, more preferably 150 (kg / cm ² ) or more, and still more preferably 200 (kg / cm ² ) or more. It is. Here, the heat distortion temperature is a value measured according to ASTM D648, and the yield point stress is a value measured according to ASTM D-882. In addition, this multilayer film under high temperature,
When using with high tension, 18.6 (kg / c
m ² ) It is more preferable to use a resin whose heat distortion temperature measured under a load is 130 ° C. or higher.

Accordingly, such a support layer may be used in a high temperature environment in which the multilayer film according to the present invention is used, for example, in a high temperature environment.
It is a layer made of a heat-resistant resin exhibiting a heat-resistant tensile strength capable of responding to a demand that the multilayer film itself does not deform even when a high tensile or winding tension is applied at 20 to 200 ° C. In addition, the resin constituting such a support layer has a high fluidity at a molding temperature of poly 4-methyl-1-pentene resin, generally 260 to 320 ° C., in a production method by co-extrusion molding of a multilayer film described later. In a die with a poly-4-methyl-1-pentene resin having

Examples of the support resin meeting the above conditions include amorphous resins such as polycarbonate resin, polyphenylene oxide resin, polysulfone resin and polyarylate resin, and crystalline resins such as polyamide resin and polyester resin. Heat-resistant resins represented by alloys of the amorphous resin and the crystalline resin can be given.

Preferred examples of the support resin include an amorphous resin having a glass transition point (Tg) of 130 ° C. or more and a melting point (Tg).
m) is a polymer alloy comprising a crystalline resin having a temperature of 170 ° C. or higher. Here, Tg is a value obtained by a dilatometry method, and Tm is a value obtained from a melting peak temperature in DSC measurement. In this polymer alloy, the amorphous resin has a function of preventing the multilayer film from being deformed under tension at a high operating temperature due to its high glass transition point, and the crystalline resin has a high fluidity. And contribute to improvement of chemical resistance. Usually, a compatibilizing agent is added as a third component to improve the compatibility between the two, thereby enabling microdispersion of the two morphologically.

Specific examples of preferred polymer alloys include the following combinations. (A) Polyphenylene oxide resin (Tg; 210)
C.) and polyamide resin (Tm of nylon-6: 220)
C., Tm of nylon-6,6; 260 ° C.) (b) Polymer alloy mainly containing polyphenylene oxide resin and polybutylene terephthalate resin (Tm; 221 ° C.)

(C) Mixture of terephthalic acid and isophthalic acid Polyarylate resin (Tg; 193 ° C.) obtained from phthalic acid and bisphenol A, nylon-6, nylon-6,6, nylon-11, nylon-12 , Nylon 6,10, nylon-6,12, nylon-MXD6
(D) Polymer alloys containing the same polyarylate resin and polyethylene terephthalate resin as main components

(E) Polysulfone resin (Tg; 189)
° C) and polyethylene terephthalate resin (Tm; 256)
(G) a polymer alloy containing a polycarbonate resin (Tg; 150 ° C.) and a polyethylene terephthalate resin as main components. (G) A polymer alloy containing a polycarbonate resin and a polyamide resin as main components.

Among these, a polymer alloy containing a polyphenylene oxide resin and a polyamide resin as main components is preferable from the viewpoint of balance between heat resistance, tensile strength, and fluidity. Hereinafter, the polymer alloy containing the polyphenylene oxide resin and the polyamide resin as main components will be described in detail.

This polymer alloy is alloyed with a polyphenylene oxide resin, a polyamide resin and, if necessary, a compatibilizing agent for increasing the mutual compatibility and increasing the dispersibility. Such resin compositions are already commercially available, for example, Noryl GTX-60
13, GTX-600, GTX-910 (Nippon GE Plastics Co., Ltd.), Iupiace NX7000, Rennie NX5000 (Mitsubishi Gas Chemical Co., Ltd.) and the like. Also, the manufacturing method is disclosed in
60266, 10-114857.

Next, one method for producing the polymer alloy will be described. The polyphenylene oxide resin is a polymer produced by subjecting a phenol compound represented by the following general formula to an oxidative coupling reaction in the presence of an oxidative coupling catalyst and oxygen.

[0039]

Embedded image

Here, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group and a substituted hydrocarbon group. At least one of them is a hydrogen atom. Examples of R _{1 to} R ₅ include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxymethyl, hydroxyethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenylethyl, phenyl,
Examples include groups such as methylphenyl, ethylphenyl, chlorophenyl, dimethylphenyl, and benzyl.

Examples of the compound represented by the above general formula include phenol, o, m or p-cresol, 2,6
-, 2,5-, 2,4- or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-
Diphenylphenol, 2,6-diethylphenol,
2-methyl-6-ethylphenol, 2,3,5- or 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol and 2-methyl-6 Allyl phenol and the like can be mentioned. These phenol compounds may be used alone or in combination of two or more.

Further, the above-mentioned phenol compound may be copolymerized with a dihydric phenol such as bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone or a polyhydric phenol.

Particularly preferred phenol compounds are 2,6
-Dimethylphenol homopolymer, and a copolymer of 2,6-dimethylphenol and a small amount of 3-methyl-6-t-butylphenol or 2,3,6-trimethylphenol.

The polyamide resin is an aliphatic or aromatic thermoplastic resin having an amide group (—CONH—) in the polymer main chain. Examples thereof include nylon-4, nylon-6, nylon-6,6, nylon-12, nylon-6,9, and nylon-6,10. A polyamide obtained from terephthalic acid and trimethylhexamethylenediamine; a polyamide obtained from adipic acid and azelaic acid; and a polyamide obtained from 2,2-bis (p-aminocyclohexyl) -propane; terephthalic acid and 4,4'-diaminodicyclohexylmethane Can also be used. Further, 66 which is a copolymer of nylon-6,6 and nylon-6
/ 6 nylon or 6/12 nylon copolymer.

The above polymer alloy (4.6 (k)
g / cm ² ) The yield point stress 100 (kg / c) at a heat deformation temperature of 130 ° C. or higher measured under a load and 140 ° C.
m ² ) In order to impart physical properties of not less than ² m ² ), a favorable mixing ratio of the polyphenylene oxide resin and the polyamide resin in the composition is as follows.
It is desirable that the amount of polyamide resin is in the range of 0 to 95, preferably 30 to 80% by weight, and the amount of polyamide resin is in the range of 5 to 80, preferably 20 to 70% by weight. Within this mixing range, a composition having excellent extrudability, heat resistance, and mechanical strength can be obtained.

In order to improve the compatibility between the polyphenylene oxide resin and the polyamide resin and enhance the dispersibility, a compatibilizing agent is added as necessary when mixing. Any compatibilizer can be used if the compatibility of each other is improved,
Although the kind is not limited, a saturated or unsaturated carboxylic acid is preferable. Examples of the carboxylic acid include:
Maleic anhydride, maleic acid, fumaric acid, itaconic acid,
Citric acid, malic acid, succinic acid, methylsuccinic acid, succinic anhydride, adipic acid, sebacic acid and the like.

By melt-kneading a polyphenylene oxide resin, a polyamide resin and a compatibilizer,
A polymer alloy is obtained, which is a composition of a polyphenylene oxide resin and a polyamide resin uniformly dispersed in each other. In melt kneading, it is desirable to use a single or twin screw extruder.

The composition of the polyphenylene oxide resin and the polyamide resin includes a rubber-like polymer, a modified product thereof, a styrene-based resin, a rubber-modified styrene-based resin, etc. in order to improve the impact resistance, workability and the like. Can be appropriately blended.

Examples of the rubbery polymer include polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / diene copolymer, polyisoprene, polyisobutylene, polyacrylate, polyurethane and the like. Can be mentioned. Further, as a modified product of the rubber-like polymer, there is a polymer obtained by modifying the above-mentioned rubber polymer with an unsaturated dicarboxylic acid or a derivative thereof. As the unsaturated dicarboxylic acid or its derivative, maleic acid, fumaric acid, chloromaleic acid,
Examples thereof include cis-4-cyclohexene-1,2-dicarboxylic acid, anhydrides, esters, amides, and imides thereof. Among these, maleic acid and maleic anhydride are preferred.

As the styrene resin, polystyrene,
Styrene / α-methylstyrene copolymer, styrene / acrylonitrile copolymer, styrene / acrylonitrile / diene copolymer and the like are exemplified. Examples of the rubber-modified styrene resin include butadiene rubber-modified polystyrene, butadiene rubber-modified styrene-acrylonitrile copolymer, acrylic rubber-modified polystyrene, acrylic rubber-modified styrene-acrylonitrile copolymer, and ethylene-propylene copolymer-modified polystyrene. And ethylene / methyl methacrylate copolymer-modified polystyrene.

The polymer alloy containing polyphenylene oxide resin and polyamide resin as described above as main components is excellent in physical properties such as mechanical strength, solvent resistance, heat resistance and the like, and supports three to five-layer films. It is suitable as a material for forming a body layer. In particular, since this polymer alloy has a low elongation and a large yield point stress, it shows high resistance to deformation, and is preferably used as a support to be used under high-temperature and high-load conditions. You can do it.

The above-described method for producing a polymer alloy containing a polyphenylene oxide resin and a polyamide resin as main components can be similarly carried out for other polymer alloys. In particular, in order to develop physical properties in which the heat distortion temperature measured under a 4.6 (kg / cm ² ) load is 130 ° C. or more and the yield point stress at 140 ° C. is 100 (kg / cm ² ) or more, It is desirable that the alloy be formed in the composition ratio described below.

(A) In the alloy of a polyphenylene oxide resin and a polybutylene terephthalate resin, the polyphenylene oxide resin is 20 to 95, preferably 30 to
~ 80% by weight, polybutylene terephthalate resin is 5 ~
80, preferably 20 to 70% by weight.

(B) In an alloy of a polyarylate resin and a polyamide resin or a polyethylene terephthalate resin, the polyarylate resin is 40 to 95, preferably 60 to 95.
The composition of the polyamide resin or polyethylene terephthalate resin is 5 to 60% by weight, preferably 10 to 40% by weight.

(C) In a polymer alloy of a polysulfone resin and a polyethylene terephthalate resin, the composition of the polysulfone resin is 40 to 95% by weight, and the composition of the polyethylene terephthalate resin is 5 to 60% by weight.

(D) In the alloy of the polycarbonate resin and the polyethylene terephthalate resin, the polycarbonate is 60 to 95, preferably 70 to 90% by weight, and the polyethylene terephthalate resin is 5 to 40, preferably 10 to 10% by weight.
３０30% by weight.

(E) In an alloy of a polycarbonate resin and a polyamide resin, the polycarbonate resin is 55 to 9
5, preferably 60 to 90% by weight;
４５45, preferably 10-40% by weight.

[0058] The multilayer film according to the multi-layer full I le arm present invention, the surface layer from the surface side consisting of poly-4-methyl-1-pentene resin, an intermediate adhesive layer comprising an adhesive resin, a support made of a heat-resistant resin It is a three-layer film laminated in the order of layers. In this film,
The layer made of poly-4-methyl-1-pentene resin on the front side is used as a functional layer exhibiting heat resistance, release properties, electrical insulation and transparency, and the layer made of heat-resistant resin on the back side is heat-resistant. It functions as a support layer having excellent properties and mechanical strength. Accordingly, the layer structure may be a layer thickness corresponding to the function, and usually 10 to 100 μm for both layers.
Since the layer made of the intermediate adhesive resin is a layer provided as a function of joining the surface layer and the support layer, the layer may have a layer thickness according to the required adhesive strength, and usually has a thickness of 5 to 50.
μm.

This three-layer film is made of poly-4-methyl-1
-It can be produced by applying or extrusion laminating an adhesive resin between a film made of a pentene resin and a film made of a heat-resistant resin, and joining both layers. However, in order to manufacture more efficiently and inexpensively, and to increase the adhesive strength between the layers, it is necessary to use a separate extruder for each resin constituting the surface layer, the intermediate adhesive layer, and the support layer. Most preferred is a method of manufacturing by so-called co-extrusion, in which the layers are melted and extruded, and each layer is joined by a die lip.

The three-layer film itself can be used as a release film, a heat-resistant film, an electric insulating film, a metal-deposited film, and the like. Also, by joining a substrate to the support layer side of this film via an adhesive layer,
It is possible to provide a laminated material for the same application which further strengthens the strength and stabilizes the shape, and expands the application. As the base material, woven fabric, nonwoven fabric, paper, plywood, metal foil, etc. can be used, and as the adhesive layer, any adhesive can be used as long as it can bond both the support layer and the base material,
The adhesive resin described above can also be used.

Further, another multilayer film according to the present invention comprises a surface layer made of poly-4-methyl-1-pentene resin, an intermediate adhesive layer made of an adhesive resin, a support layer made of a heat-resistant resin, and an adhesive resin. Intermediate adhesive layer made of poly 4-
It is a five-layer film laminated in the order of a surface layer made of methyl-1-pentene resin. Each layer is basically composed of the aforementioned 3
It has the same function as each layer of the layer film, but since it has a layer configuration that is plane-symmetric around the support layer,
It has excellent morphological stability as a film, sheet, or tape. Because of these features, the five-layer film can be suitably used as a release film, a heat-resistant film, an electrical insulating film, a metal-deposited film, and the like.

In these three-layer and five-layer films, various coating agents or undercoating agents are applied on the outer surface of the layer made of poly-4-methyl-1-pentene resin on the surface side, so that the surface hardness and the like can be improved. Surface modification such as surface gloss can be achieved, and surface protection or surface decoration can be achieved by means such as coloring or metal deposition. The surface can be further covered with another coating agent or a top coating agent. By these methods, the multilayer film according to the present invention can further expand its use.

[0063]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. First, the resin commonly used here will be described.

(A) Poly-4-methyl-1-pentene resin (PMP) A copolymer of 4-methyl-1-pentene and 1-decene, having a 1-decene content of 3% by weight and a density of 0 .835
(G / cm ³ ) and MFR is 26 (g / 10 minutes).

(B) Adhesive resin (MAN-PO-1) Maleic anhydride-grafted polyethylene obtained by graft copolymerizing maleic anhydride onto high-density polyethylene (graft ratio: 2.1 (g / 100 g-polymer), density; 0.9
60 (g / cm ³ ), MFR: 1.2 (g / 10 minutes))
10% by weight, 85% by weight of the same poly (4-methyl-1-pentene) resin as in (a), and 5% by weight of an ethylene / propylene random copolymer are first dry-blended and then 27%.
The mixture was supplied to a 40 mmφ single screw extruder set at 0 ° C., kneaded, and granulated.

(C) Adhesive resin (MAN-PO-2) Using the same maleic anhydride-grafted polyethylene as described above, maleic anhydride-grafted polyethylene 2.5% by weight, poly-4-methyl-1-pentene resin 95.5 Pellets consisting of 2.0% by weight of an ethylene / propylene random copolymer were obtained in the same manner as in (b).

(D) Polyphenylene oxide / polyamide polymer alloy (PPO) A composition mainly composed of a polyphenylene oxide resin and a nylon-6 resin, using a product of Nippon GE Plastics Co., Ltd. (trade name: Noryl GTX6013). did. The density is 1.07 (g / cm ³ ), 4.6 (kg / cm ³ )
cm ² ) The heat distortion temperature (HDT) under load is 175 ° C.
The yield point stress at 140 ° C. is 340 (kg / cm ² )
Met.

The adhesive strength was determined by measuring the width of the film by 30 mm.
And 300 (mm / min) using a tensile tester
It was shown by the adhesive force when peeled at 180 ° at a pulling speed of. The tensile test was performed at 20 ° C. and 65% RH in accordance with ASTM D-882.

Example 1 Three extruders (40 mm each)
φ) was prepared, polyphenylene oxide / polyamide polymer alloy (PPO) was supplied to the first extruder, and the extruder tip was set at 310 ° C. to plasticize the resin. The adhesive resin (MAN-PO-1) was supplied to the second extruder, and the extruder tip was set at 260 ° C. to plasticize the resin. A poly-4-methyl-1-pentene resin (PMP) was supplied to the third extruder, and the extruder tip was set at 260 ° C. to plasticize the resin. The plasticized resin is led to a distribution adapter and passed through a T-die set at a temperature of 300 ° C. to pass through PMP / MAN-PO-1 / PPO / MAN-PO.
A five-layer film having a layer configuration of -1 / PMP was taken.

The obtained five-layer coextruded film had a total thickness of 12
0 μm, and the layer configuration is PMP (20 μm) / MAN-PO
-1 (20 μm) / PPO (40 μm) / MAN-PO
-1 (20 μm) / PMP (20 μm). Table 1 shows the physical properties of the film.

The adhesion between the PMP layer and the MAN-PO-1 layer and the adhesion between the MAN-PO-1 layer and the PPO layer were both strong and non-peelable. When a load of 3 (kg / 30 mm width) was applied at 140 ° C., the film elongation was as small as 3%. Therefore, it was found that the film had performance as a release film and a release belt that could be used at high temperatures.

Example 2 Example 1 was the same as Example 1 except that the adhesive resin (MAN-PO-1) supplied to the second extruder was replaced with the adhesive resin (MAN-PO-2). The same operation was performed to obtain a five-layer coextruded film having the same layer structure.

Table 1 shows the physical properties of this film. P
The adhesion between the MP layer and the MAN-PO-2 layer was strong and non-peelable. The adhesive strength between the MAN-PO-2 layer and the PPO layer was 500 (g / 30 mm width), which was sufficient for practical use. The yield point stress at 140 ° C. is 2
90 (kg / cm ² ) and 3 (kg / 3
(0 mm width), the elongation of the film was as small as 3%. Therefore, it was found that the film had performance as a release film and a release belt that could be used at high temperatures.

Comparative Example 1 The procedure of Example 1 was repeated, except that the adhesive resin was not used, to obtain a coextruded PMP / PPO / PMP film having two layers and three layers.
The total thickness is 120 μm, and the layer structure is PMP (40 μm) / P
PO (40 μm) / PMP (40 μm). The physical properties of the film are also shown in Table 1, and the adhesive strength between the PMP layer and the PPO layer was as small as 10 (g / 30 mm width).

(Comparative Example 2) Poly-4 was added to a 65 mmφ extruder.
-Methyl-1-pentene resin (PMP) is supplied, and the resin temperature at the tip of the extruder is set to 290 ° C. to plasticize the resin.
It was extruded from a T-die set at 290 ° C. to obtain a PMP monolayer film having a thickness of 120 μm. The physical properties of the film are shown in Table 1, and the yield point stress at 120 ° C. was 50 (kg / kg).
cm ^2), the addition tensile elongation were measured under a load of 3 at 140 ° C. (kg / 30 mm width) was 1000% or more.

[0076]

[Table 1]

[0077]

The multilayer film according to the present invention has a three-layer structure comprising a surface layer made of poly-4-methyl-1-pentene resin / an intermediate adhesive layer made of an adhesive resin / a support layer made of a heat-resistant resin. Film and poly 4-methyl-1
-Composed of a surface layer composed of a pentene resin / an intermediate adhesive layer composed of an adhesive resin / a support layer composed of a heat-resistant resin / an intermediate adhesive layer composed of an adhesive resin / a surface layer composed of poly-4-methyl-1-pentene resin By adopting the layer configuration of the five-layer film thus obtained, a film having heat resistance, release property, electrical insulation and transparency was obtained. In particular, since the multilayer film has a low elongation even at high temperatures and maintains high strength, it is suitable for applications used under tension under high temperatures, especially for release films. I understood.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toru Sawai 9th Kitatone, Sowa-cho, Sarushima-gun, Ibaraki Pref.

Claims (11)

[Claims] 1. A surface layer comprising a poly-4-methyl-1-pentene resin, an intermediate adhesive layer comprising an adhesive resin,
A support layer made of a heat-resistant resin is laminated in this order. Here, the heat-resistant resin has a heat deformation temperature of 130 ° C. or higher measured under a load of 4.6 (kg / cm ² ) and a yield point at 140 ° C. A multilayer film, which is a resin exhibiting a stress of 100 (kg / cm ² ) or more. 2. A surface layer made of poly-4-methyl-1-pentene resin is laminated on the surface side with an intermediate adhesive layer made of an adhesive resin on both sides of a support layer made of a heat-resistant resin as a center. Here, the heat-resistant resin is 4.6 (k)
g / cm ² ) The yield point stress 100 (kg / c) at a heat deformation temperature of 130 ° C. or higher measured under a load and 140 ° C.
m ² ) A multilayer film characterized by being a resin showing the above. 3. The heat-resistant resin has a glass transition point of 130.
3. The multilayer film according to claim 1, which is a polymer alloy comprising an amorphous resin having a melting point of 170 ° C. or higher and a crystalline resin having a melting point of 170 ° C. or higher. 4. The multilayer film according to claim 1, wherein said heat-resistant resin is a polymer alloy comprising a polyphenylene oxide resin and a polyamide resin or a polybutylene terephthalate resin. 5. The heat-resistant resin comprises 20 to 95% by weight of a polyphenylene oxide resin and 5 to 5% of a polyamide resin.
3. The multilayer film according to claim 1, which is a polymer alloy comprising 80% by weight. 6. The multilayer film according to claim 1, wherein said heat-resistant resin is a polymer alloy comprising a polyarylate resin and a polyamide resin or a polyethylene terephthalate resin. 7. The multilayer film according to claim 1, wherein the heat-resistant resin is a polymer alloy comprising a polycarbonate resin and a polyethylene terephthalate resin or a polyamide resin. 8. The multilayer according to claim 1, wherein said adhesive resin is a modified product obtained by graft copolymerizing an unsaturated carboxylic acid or a derivative thereof to an olefin polymer. the film. 9. The multilayer film according to claim 1, wherein each of the layers is formed by lamination by a coextrusion method. 10. A laminate comprising a multilayer film according to claim 1, wherein a substrate layer is further laminated via an adhesive layer outside a support layer made of a heat-resistant resin. 11. A release film comprising the multilayer film according to claim 1.