JP6711195B2 - Laminates, films and sheets - Google Patents

Description

The present invention relates to a heat-sealable adhesive resin composition, and a laminate, a film and a sheet using the adhesive resin composition.

A polychlorotrifluoroethylene (PCTFE) film has high chemical resistance and excellent water vapor barrier properties, and is therefore used as a package in the fields of medical care and IT.

When the PCTFE film is used as a package in these fields, it is usually used as a laminate having another thermoplastic resin film to impart heat sealability and good handleability. However, since a fluororesin such as PCTFE has good releasability and non-adhesiveness, it is difficult to bond it to other materials.

As an example of a technique for adhering a fluororesin such as PCTFE to another material, Patent Document 1 discloses a technique for obtaining a laminate of a fluororesin and polyethylene, polyvinyl chloride, or the like. However, the bonding technique according to the present technology is a dry lamination method, and in this method, there is a problem of residual solvent because an organic solvent is used and a problem that the process is complicated and costly because a drying process is required.

Patent Document 2 discloses a technique for obtaining a laminate of a specific polyamide resin and a specific fluorine-containing ethylenic polymer by coextrusion molding.

Special table 2013-503760 gazette International Publication No. 2001/058686

When the PCTFE film is used as a package in these fields, it is considered that the heat-sealing property can be imparted by forming a laminate with a polyolefin film such as polypropylene (PP). In the past, including the technology disclosed in U.S. Pat. No. 5,096,097, there has been no adhesive resin capable of adhering to both PCTFE and PP. In addition, in various applications such as packaging, particularly in food applications, retort treatment for sterilization may be performed. In this case, it is desired that the adhesive strength and the shape are sufficiently maintained (no deformation or shrinkage) even after the heat treatment of the retort treatment.

The present invention is an adhesive resin composition that can easily bond a fluorine-containing resin and polypropylene by heat fusion, has excellent shape retention in heat treatment, and maintains high adhesive strength even after heat treatment, It is an object to provide a laminate, a film and a sheet using the adhesive resin composition.

The present inventors have found that the adhesive resin composition containing a specific amount of a specific polypropylene and a specific amount of polyethylene retains its shape even after the heat treatment in the adhesion between PCTFE and PP, resulting in deformation, shrinkage, etc. It has been found that there is no problem and the high adhesive strength can be maintained.
That is, the gist of the present invention is as follows [1] to [7].

[1] An adhesive resin composition containing the following component (A) and component (B), and 30 to 60% by weight of the component (A) with respect to the total amount thereof.
Component (A): Propylene/Propylene/Ethylene Block Copolymer Component (B): Epoxy Group Polyethylene

[2] The adhesive resin composition according to [1], wherein the bending elastic modulus of the component (A) is 200 to 700 MPa.

[3] The adhesive resin composition according to [1] or [2], wherein the component (B) is an ethylene/glycidyl (meth)acrylate copolymer.

[4] A laminate having a layer containing a fluorine-containing resin, a layer made of the adhesive resin composition according to any one of [1] to [3], and a layer containing polypropylene in this order.

[5] The laminate according to [4], which contains polychlorotrifluoroethylene as the fluorine-containing resin.

[6] A film containing the laminate according to [4] or [5].

[7] A sheet including the laminate according to [4] or [5].

According to the present invention, it is possible to easily bond the fluorine-containing resin and polypropylene by heat fusion, excellent shape retention in heat treatment, an adhesive resin composition that maintains high adhesive strength even after heat treatment, A laminate, a film and a sheet using the adhesive resin composition are provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is limited to the following description unless it exceeds the gist thereof. is not. In this specification, when the expression "to" is used, it is used as an expression including numerical values or physical properties before and after the expression. Further, hereinafter, the monomer unit contained in the copolymer may be simply referred to as “unit”. For example, when a propylene-based monomer unit is referred to as a “propylene unit”, and an ethylene-based monomer unit and an α-olefin-based monomer unit are referred to as an “ethylene unit” and an “α-olefin unit”, respectively. There is.

[Adhesive resin composition]
The adhesive resin composition of the present invention is characterized by containing the following components (A) and (B), and 30 to 60% by weight of the component (A) with respect to the total amount thereof.
Component (A): Propylene/Propylene/Ethylene Block Copolymer Component (B): Epoxy Group Polyethylene

[Mechanism of action]
In the present invention, the component (B) polyethylene having an epoxy group (hereinafter sometimes referred to as “epoxidized polyethylene”) exhibits adhesiveness with a fluorine-containing resin such as polychlorotrifluoroethylene (PCTFE). By including the epoxidized polyethylene as the component (B), it is possible to secure the adhesiveness with the fluorine-containing resin layer. In the case of PCTFE, for example, a functional group on the PCTFE side such as a carbonyl group obtained by a surface treatment such as corona treatment and an epoxy group in the component (B) react with each other to form a mixture of PCTFE and the component (B). It is presumed that this is due to the formation of a strong chemical bond between the two.

However, only the epoxidized polyethylene as the component (B) has insufficient adhesiveness with polypropylene. This is because polyethylene having an epoxy group and polypropylene are incompatible. In some cases, the flexibility of polyethylene as the component (B) may enter into the irregularities of polypropylene due to the anchoring effect and develop adhesive strength, but the surface state is reconstructed by melting and crystallization of epoxidized polyethylene during heat treatment. , The anchor effect disappears, and the adhesive strength drops significantly. Further, the heat resistance is insufficient only with the component (B), and it is difficult to maintain the shape after the heat treatment.

Therefore, in order to impart adhesiveness and heat resistance to polypropylene to the component (B) and maintain the adhesive strength after the heat treatment, a component that connects the epoxidized polyethylene and the polypropylene layer is necessary. It is considered that the addition of a polypropylene resin as a component for that purpose is effective, but a propylene/ethylene random copolymer or a propylene homopolymer has a weak affinity with epoxidized polyethylene and is difficult to exhibit adhesive strength. Therefore, in the present invention, in order to increase the affinity between the epoxidized polyethylene and the polypropylene, the propylene/propylene/ethylene block copolymer of the component (A) having a higher ethylene content in the propylene-based copolymer is used. The propylene/propylene/ethylene block copolymer of the component (A) serves as a bridge connecting the epoxidized polyethylene of the component (B) and the polypropylene layer, and high adhesive strength can be obtained.

According to the adhesive resin composition of the present invention, a fluorine-containing resin film such as PCTFE is bonded with high strength by the component (B) epoxidized polyethylene, and the component (A) propylene/propylene/ethylene block copolymer is used. Since the epoxidized polyethylene and the polypropylene film are connected to each other, they can be bonded by heat fusion, have excellent shape retention after heat treatment, and can maintain good adhesive strength even after heat treatment.

[Component (A)]
In the present invention, the “propylene/propylene/ethylene block copolymer” of the component (A) means that propylene and a comonomer used as necessary are polymerized in the first step, and then propylene and ethylene and necessary comonomer are used in the second step. It means a copolymer obtained by multistage polymerization, in which a comonomer used according to the above is polymerized. Hereinafter, the block polymerized in the first step may be referred to as a "propylene block", and the block polymerized in the second step may be referred to as a "propylene ethylene block". In the adhesive resin composition of the present invention, the ethylene component in the propylene/propylene/ethylene block copolymer serves as a bridge connecting the epoxidized polyethylene of component (B) and the polypropylene layer, and high adhesive strength can be obtained. ..

The propylene block of the propylene/propylene/ethylene block copolymer may be a homopolymer block of propylene, or a copolymer block of propylene and ethylene and/or another α-olefin, A propylene/ethylene copolymer block, a propylene/α-olefin copolymer block or a propylene homopolymer block having a propylene unit content of 90% by weight or more is preferable, and a propylene/ethylene copolymer weight is particularly preferable. It is a united block. When the propylene block is a propylene/α-olefin copolymer block, the α-olefin forming the propylene/α-olefin copolymer block is one of α-olefins having about 4 to 20 carbon atoms. Alternatively, two or more kinds may be mentioned.

When the propylene/ethylene block of the propylene/propylene/ethylene block copolymer is a propylene/ethylene/α-olefin copolymer block (“α-olefin” here means α-olefin other than propylene). As the α-olefin constituting this, one or more kinds of α-olefins having about 4 to 20 carbon atoms can be mentioned, and of these, 1-butene and 1-octene are preferable.

The propylene/propylene/ethylene block copolymer of the component (A) is a copolymerization component of an unsaturated compound other than the above α-olefin, for example, a vinyl ester such as vinyl acetate, within a range that does not impair the effects of the present invention. It may be a copolymer contained as.

The content ratio of the propylene block and the propylene/ethylene block contained in the propylene/propylene/ethylene block copolymer is not limited, but the propylene block is 50 to 80% by weight and the propylene/ethylene block is 20 to 50% by weight. Is preferred. When the content ratio of the propylene block is within the above range, the effect of improving the adhesiveness with polypropylene is excellent, and the heat resistance is also excellent. From this viewpoint, the more preferable ranges of the content ratios of the propylene block and the propylene/ethylene block are 55 to 70% by weight of the propylene block and 30 to 45% by weight of the propylene/ethylene block.

The propylene/propylene/ethylene block copolymer as the component (A) preferably has a flexural modulus of 200 to 700 MPa. When the bending elastic modulus is 700 MPa or less, the affinity with the component (A) tends to be good. On the other hand, when the bending elastic modulus is 200 MPa or more, the retort resistance (heat resistance) tends to be good. From these viewpoints, the bending elastic modulus of the propylene/propylene/ethylene block copolymer of the component (A) is more preferably 220 to 680 MPa, further preferably 250 to 650 MPa. The flexural modulus of the propylene/propylene/ethylene block copolymer is a value measured according to JIS K7203 (1995).

The flexural modulus of the propylene/propylene/ethylene block copolymer can be controlled by adjusting the content ratio of the propylene block and the propylene/ethylene copolymer block and the comonomer amount.

The MFR (melt flow rate) of the propylene/propylene/ethylene block copolymer of the component (A) used in the present invention is preferably 0.5 to 100 g/10 minutes, and is 1 to 50 g/10 minutes. Is more preferable. If the MFR of the propylene/propylene/ethylene block copolymer is more than the above lower limit, the moldability tends to be good, and if it is less than the above upper limit, the molding may become difficult. The MFR of the propylene/propylene/ethylene block copolymer is a value measured at 230° C. under a load of 2.16 kg according to JIS K7210.

The component (A) in the present invention can be obtained as a commercial product. As examples of commercially available products, appropriate products are selected from "NOVATEC (registered trademark) PP", "WELNEX (registered trademark)" and "ZELAS (registered trademark)" manufactured by Mitsubishi Chemical Co., Ltd. be able to.

Only one kind of these propylene/propylene/ethylene block copolymers may be used, or two or more kinds having different kinds and compositions of the copolymerization components, physical properties and the like may be mixed and used.

[Component (B)]
The epoxidized polyethylene as the component (B) is not particularly limited as long as the content of the ethylene unit having an epoxy group is 50% by weight or more, and may be a copolymer of ethylene and a compound having an epoxy group. Alternatively, polyethylene may be graft-modified with a compound having an epoxy group.

From the viewpoint of reactivity, glycidyl (meth)acrylate is preferable as the compound having an epoxy group used for the production of epoxidized polyethylene.

The epoxidized polyethylene may contain a copolymerization component having an ethylenic double bond in addition to ethylene, and examples of such a copolymerization component include alkyl (meth)acrylate, acrylonitrile, α-olefin, and conjugated diene. Is mentioned. Among these, from the viewpoint of good polymerization reactivity as a raw material monomer for epoxidized polyethylene, methyl (meth)acrylate, butyl (meth)acrylate, ethyl (meth)acrylate, vinyl acetate, styrene, butadiene, acrylonitrile, and propylene. At least one selected from the group consisting of is preferable, and methyl acrylate and/or vinyl acetate is more preferable.

The content of the epoxy group in the epoxidized polyethylene is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, and further preferably 3 to 10% by weight. It is preferable that the content of the epoxy group is more than the above lower limit, since the adhesiveness to the fluorine-containing resin such as PCTFE becomes more excellent. When the content of the epoxy group exceeds the above upper limit, the production may be difficult.

From the viewpoint of moldability, the content of ethylene units in the epoxidized polyethylene is preferably 40 to 99% by weight, more preferably 50 to 90% by weight, and 60 to 85% by weight. Is more preferable, and the content of copolymerization components such as methyl acrylate and vinyl acetate other than ethylene and glycidyl (meth)acrylate is preferably 0 to 40% by weight, more preferably 5 to 35% by weight. More preferably 10 to 30% by weight.

The MFR (melt flow rate) of the epoxidized polyethylene of the component (B) used in the present invention is preferably 0.1 to 100 g/10 minutes, preferably 1 to 75 g/10 minutes, and 2 to 50 g. It is more preferably /10 minutes. If the MFR of the epoxidized polyethylene is more than the above lower limit, the moldability tends to be good, and if it is less than the above upper limit, the molding is difficult. The MFR of the epoxidized polyethylene is a value measured according to JIS K7210 at 190° C. and a load of 2.16 kg.

The component (B) in the present invention can be obtained as a commercial product. Examples of commercially available products include "BONDFAST" manufactured by Sumitomo Chemical Co., Ltd., which is an ethylene-glycidyl methacrylate (GMA) copolymer, and "LOTADER" manufactured by Arkema.

These epoxidized polyethylenes may be used alone or in combination of two or more having different ethylene unit content, copolymerization component, physical properties and the like.

[Amount of adhesive resin composition]
The adhesive resin composition of the present invention contains 30 to 60% by weight of the component (A) based on the total amount of the component (A) and the component (B). When the amount of the component (A) is less than 30% by weight, it is difficult to maintain the shape after the heat treatment. Further, when the amount of the component (A) is more than 60% by weight, the adhesive force to the fluorine-containing resin such as PCTFE after the heat treatment is significantly reduced. From the above viewpoint, the adhesive resin composition of the present invention preferably contains the component (A) in an amount of 35 to 55% by weight, and preferably 40 to 50% by weight, based on the total amount of the component (A) and the component (B). It is more preferable to contain.

[Other ingredients]
In the adhesive resin composition of the present invention, in addition to the above-mentioned components, other optional additives and resins, etc. according to various purposes within the range of not significantly impairing the effects of the present invention (hereinafter, these are referred to as “other components It is referred to as "."). As the other components, only one kind may be used, or two or more kinds may be used in optional combination and ratio.

As the additive, an auxiliary additive component generally used for polyolefin, specifically, process oil, neutralizing agent, processing aid, plasticizer, crystal nucleating agent, impact modifier, flame retardant, flame retardant aid. , Cross-linking agents, cross-linking aids, antistatic agents, lubricants, fillers, compatibilizers, heat stabilizers, weather resistance stabilizers (antioxidants, light stabilizers, UV absorbers, etc.), anti-fog agents, slip agents, Examples include anti-blocking agents, antibacterial agents, carbon black, colorants (pigments, dyes, etc.), and the like.

Of these, flame retardants are roughly classified into halogen flame retardants and non-halogen flame retardants, but non-halogen flame retardants are preferable, and specifically, metal hydroxides, phosphorus flame retardants, nitrogen-containing compounds. Examples thereof include (melamine-based and guanidine-based) flame retardants and inorganic compounds (borate, molybdenum compound) flame retardants. Examples of the heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides.

The filler is roughly classified into an organic filler and an inorganic filler. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir shell, and bran, and modified products thereof. Further, as the inorganic filler, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite and carbon fibers.

When these additives are used, the content is not limited, but the content in the adhesive resin composition of the present invention is usually 0.01% by weight or more, preferably 0.1% by weight or more, and It is desirable that the amount is usually 5% by weight or less, preferably 2% by weight or less. When the adhesive resin composition of the present invention is used as a masterbatch, these additives may be contained in a concentration of 2 to 50 times, preferably 3 to 30 times the above-mentioned content.

Specific examples of resins used as other components include polyphenylene ether resins; polycarbonate resins; polyamide resins such as nylon 66 and nylon 11; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; and polystyrene. Examples thereof include acrylic/methacrylic resins such as styrene resins and polymethylmethacrylate resins.

When the adhesive resin composition of the present invention contains these other resins, the content thereof is preferably 30 parts by weight or less based on 100 parts by weight of the total of the components (A) and (B). ..

[Method for producing adhesive resin composition]
The adhesive resin composition of the present invention can be obtained by mixing the component (A), the component (B), and other components used as necessary by a known method. For example, a melt-kneading method using a single-screw or twin-screw extruder and a dry blending method may be mentioned.

[Laminate]
The laminate of the present invention comprises a layer containing a fluorine-containing resin (hereinafter sometimes referred to as “fluorine-containing resin layer”) and a layer comprising the adhesive resin composition of the present invention (hereinafter, “adhesive layer of the present invention”. And a layer containing polypropylene (hereinafter sometimes referred to as “PP layer”) in this order.

[Adhesive layer]
The thickness of the adhesive layer of the present invention contained in the laminate of the present invention is preferably 5 μm or more in order to obtain sufficient adhesive strength. The thickness of the adhesive layer of the present invention is more preferably 7.5 μm or more, further preferably 10 μm or more. On the other hand, the upper limit of the thickness of the adhesive layer is not particularly limited, but is usually 3,000 μm or less, preferably 2,500 μm or less.

[Fluorine-containing resin layer]
Examples of the fluorine-containing resin contained in the fluorine-containing resin layer include, but are not limited to, ethylene/chlorotrifluoroethylene (ECTFE), ethylene/tetrafluoroethylene copolymer, fluorinated ethylene/propylene copolymer, and perfluoroalkoxyethylene. , Polychlorotrifluoroethylene (PCTFE) homopolymers or copolymers, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene, and their copolymers and blends. Among these, PCTFE is preferable because it is particularly excellent in chemical resistance and water vapor barrier property.

The thickness of the fluorine-containing resin layer is not particularly limited and is appropriately determined depending on the use, the resin type, the required characteristics, etc., but is usually 10 to 500 μm, preferably 15 to 450 μm.

As the fluorine-containing resin, a film-shaped product can be obtained as a commercial product. Examples of commercially available PCTFE films include those manufactured by Honeywell Inc and Daikin Industries, Ltd.

[PP layer]
Polypropylene (PP) forming the PP layer is a propylene-based resin having a propylene content of 50% by weight or more. Specifically, propylene homopolymer (propylene homopolymer), propylene/ethylene random copolymer, propylene/butene random copolymer, propylene/ethylene/hexene random copolymer, propylene/ethylene/octene random copolymer. Examples include propylene-based polymers such as propylene/butene/hexene random copolymers, propylene/butene/octene random copolymers, propylene/hexene/octene random copolymers, and propylene/propylene/ethylene block copolymers. Propylene homopolymer (propylene homopolymer), propylene/ethylene random copolymer, propylene/butene random copolymer, propylene/MFR (230° C., 2.16 kg) 0.1 to 30 g/10 min. Ethylene/hexene random copolymer, propylene/ethylene/octene random copolymer, propylene/butene/hexene random copolymer, propylene/butene/octene random copolymer, especially propylene homopolymer (propylene homopolymer), propylene -Ethylene random copolymer and propylene-butene random copolymer are preferably used.

The thickness of the PP layer is not particularly limited and may be appropriately determined depending on the application, resin type, required characteristics, etc., but is usually 5 to 500 μm, preferably 10 to 300 μm.

As the PP layer, a film-shaped product can be obtained as a commercial product. The PP film that can be used in the present invention may be a conventionally used non-stretch cast film. Known unstretched cast films include those manufactured by Futamura Chemical Co., Ltd. and Toyobo Co., Ltd., for example.

[Other layers]
In addition to the fluorine-containing resin layer, the adhesive layer and the PP layer of the present invention, the laminate of the present invention may further have other layers laminated thereon. The other layers are not particularly limited. For example, a polycarbonate resin; a resin layer made of styrene resin such as polystyrene (GPPS), high-impact polystyrene (HIPS), styrene-acrylonitrile graft copolymer (ABS resin), or an olefin polymer other than propylene resin, Other thermoplastic resin layers such as polyphenylene ether resin, polyoxymethylene homopolymer, polyoxymethylene copolymer and other polyoxymethylene resin, polymethylmethacrylate resin and other acrylic/methacrylic resin, etc. From the viewpoint of adhesiveness between the fluorine-containing resin layer and the PP layer by the adhesive layer of the invention, the fluorine-containing resin layer and the PP layer are laminated via the adhesive layer of the present invention, and the fluorine-containing resin layer and the adhesive layer of the present invention, It is preferable that no other layer is provided between the PP layer and the adhesive layer of the present invention.

[Method of manufacturing laminated body]
As a method for producing the laminate of the present invention, various conventionally known methods can be adopted. For example, individual molten resin melted by an extruder is supplied to a multilayer die and laminated in the die by inflation molding by coextrusion method, film molding or sheet molding by T-die molding, container molding by blow molding, melting. There is co-injection molding in which the individual resins are injected into the same mold with a time lag. In addition, extrusion lamination by coextrusion with a single resin or another resin to the adherend, or during extrusion lamination, the adherend is subjected to corona discharge treatment or flame treatment before lamination, and the adherend and the present invention immediately before lamination. A method of subjecting the adhesive surface of the adhesive layer to ozone treatment is also used. In particular, it is preferable to perform surface treatment such as corona treatment and plasma treatment on the adhesive surface of the fluorine-containing resin layer (adhesive layer side of the present invention) from the viewpoint of improving adhesiveness. Further, a lamination method such as heat lamination or heat sealing of the adhesive layer film of the present invention obtained by coextrusion with a single resin or another resin and an adherend film can be used.

The conditions of the film, sheet and blow molding by these coextrusions are not particularly limited, but it is preferable to mold at a die temperature of 180 to 250°C. Further, the conditions for extrusion lamination molding are not particularly limited, but it is preferable to mold at a die temperature in the range of 280 to 320° C., and the lamination method by heat lamination or heat sealing is not particularly limited. However, it is preferable that the lamination temperature is 160 to 220° C.

[Films and sheets]
The laminate of the present invention can be used as a film or sheet. The manufacturing method is not particularly limited as long as it is a known molding method such as extrusion molding, injection molding, or heat press molding. The total thickness of the sheet made of the laminate of the present invention is preferably 200 to 5,000 μm. The total thickness of the film made of the laminate of the present invention is preferably 30 to 200 μm.

[Use]
A laminate using the adhesive resin composition of the present invention, as well as a film and a sheet formed from the laminate, are obtained by fusing a fluorine-containing resin layer such as PCTFE and a PP layer together with food, medical care, IT, It can be suitably used as a film for packaging materials such as sundries and industrial parts. Moreover, these can be made into a bag shape and used suitably as a packaging bag.

According to the adhesive resin composition of the present invention, in applications such as foods, the packaging film or the packaging bag made of the laminate of the present invention is subjected to retort treatment, for example, heat treatment at 120 to 130° C. for about 30 to 40 minutes. Even if it is applied, its shape and adhesive strength can be sufficiently maintained.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist. The values of various production conditions and evaluation results in the following examples have meaning as preferable values of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the value of the above-mentioned upper limit or the lower limit. It may be a range defined by a value of the following embodiment or a combination of the values of the embodiments.

<Evaluation Method of Film or Sheet Made of Adhesive Resin Composition>
(Retort processing)
Each laminate of the PCTFE film and the adhesive resin film, and the PP film and the adhesive resin film was put into a high temperature and high pressure cooking and sterilization tester (manufactured by Hisaka Seisakusho Co., Ltd., RCS-40RTGN type) and then pressurized. The ambient temperature was raised to 0° C. and maintained at that temperature for 20 minutes. Then, it cooled to about 40 degreeC, the said laminated body was taken out from the tester, and the state was adjusted for 24 hours in 23 degreeC/50%RH atmosphere.

(Measurement of adhesive strength after retort treatment)
After the retort treatment, each laminate was cut into a strip having a width of 15 mm, a 180° peel test was performed, and an adhesive strength was measured. A universal tester (Tensilon universal tester, manufactured by Orientec Co., Ltd.) was used as a measuring instrument, and the peeling speed was 300 mm/min. When the adhesive strength is 5 N/10 mm or more, it can be determined that the adhesive strength is sufficiently strong.

(Shape retention after retort treatment)
Regarding the laminate of the PCTFE film and the adhesive resin film, the shape of each laminate after the retort treatment was observed and evaluated according to the following criteria.
◯: The adhesive resin layer is not melted and is not deformed or has a small deformation.
Δ: The adhesive resin layer is not melted but is contracted.
X: The adhesive resin layer is melted and largely deformed.

<Raw material for film/adhesive resin composition>
[PCTFE film]
・Neotron PCTFE film (thickness 15 μm) manufactured by Daikin Industries, Ltd.
[PP film]
Two-layer film obtained by laminating a biaxially stretched PET film (thickness 12 μm) and a non-stretched PP cast film (thickness 20 μm) by a dry lamination method (the PP film side was used as an adhesive surface).

[Raw material of adhesive resin composition]
(Component (A))
A-1: Propylene/Propylene/Ethylene block copolymer (WELNEX (registered trademark) "RFG4VM" manufactured by Japan Polypro Co., Ltd.)
MFR (23° C., load 2.16 kg): 6.0 g/10 min Flexural modulus (JIS K7203 (1995)): 280 MPa
a-1 (for comparative example):
Propylene/ethylene random copolymer (Novatec (registered trademark) PP "FW4B" manufactured by Japan Polypro Co., Ltd.)
MFR (230°C, load 2.16kg): 7.0g/10min

(Component (B))
B-1:
Ethylene/glycidyl methacrylate/methyl acrylate copolymer (“BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd.)
Content of glycidyl methacrylate unit: 3% by weight
Methyl acrylate unit content: 27% by weight
MFR (190°C, load 2.16 kg): 7.0 g/10 minutes

[Example 1]
As an adhesive resin composition, 50% by weight of “BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd. and 50% by weight of “RFG4VM” (propylene/propylene/ethylene block copolymer) manufactured by Nippon Polypro Co., Ltd. are twin screw extruders manufactured by Technovel Co., Ltd. "KZW15-45MG-NH" melted and kneaded at a cylinder temperature of 200°C, a screw rotation speed of 300 rpm, and a discharge rate of 5 kg/h, and a spacer having a thickness of 85 mm × 85 mm × 2 mm at a molding temperature of 200°C and a molding pressure of 5 MPa. Was used to perform hot press molding. Then, it was cooled at a cooling temperature of 30° C. and a cooling pressure of 5 MPa to obtain a 2 mm thick adhesive resin film. The adhesive resin film and the PCTFE film were laminated so that the corona-treated surfaces were in contact with each other, and heat sealing was performed under the conditions of a temperature of 240° C., a pressure of 3 kgf/cm ² , a time of 2 seconds, and a seal bar of 10 mm×300 mm. Then, the above-mentioned retort treatment and evaluation were performed. Moreover, the same test was performed using the PP film.

[Comparative Example 1]
The test was performed in the same manner as in Example 1 except that 100% by weight of “BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd. was used as the adhesive resin composition.

[Comparative example 2]
The test was performed in the same manner as in Example 1 except that 75% by weight of “BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd. and 25% by weight of “RFG4VM” manufactured by Japan Polypro Co., Ltd. were used as the adhesive resin composition.

[Comparative Example 3]
The test was performed in the same manner as in Example 1 except that 25% by weight of “BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd. and 75% by weight of “RFG4VM” manufactured by Japan Polypro Co., Ltd. were used as the adhesive resin composition.

[Comparative Example 4]
The test was performed in the same manner as in Example 1 except that 50% by weight of “BONDFAST7M” manufactured by Sumitomo Chemical Co., Ltd. and 50% by weight of “FW4B” manufactured by Japan Polypro Co., Ltd. were used as the adhesive resin composition.

The results obtained in the above Examples and Comparative Examples are summarized in Table 1.

The following can be seen from Table-1.
In the peeling test after the heat treatment, Example 1 showed good adhesive strength for both the PCTFE film and the PP film and had a good appearance.
On the other hand, Comparative Examples 1 and 2 showed good adhesive strength in the peeling test after the heat treatment, but they were deformed by the heat treatment because the amount of epoxidized polyethylene was too much, and a good appearance was not obtained. Further, in Comparative Example 3, since the amount of epoxidized polyethylene is small, the adhesive strength with the PCTFE film cannot be obtained. Furthermore, in Comparative Example 4, since random polypropylene having a low affinity with epoxidized polyethylene was applied, the adhesive strength with the PCTFE film cannot be obtained.

Considering the above examples and comparative examples in contrast, the adhesive resin composition satisfying the constitution of the present invention has sufficient adhesive strength even after heat treatment, and retains its shape after heat treatment. It turns out that it is excellent.

The adhesive resin composition of the present invention has a sufficient adhesive strength even after the heat treatment in the adhesion between the fluorine-containing resin such as PCTFE and PP, and also has a good shape retention, and is therefore excellent in appearance. .. Therefore, the laminate of the present invention using the adhesive resin composition of the present invention is useful as a packaging film for foods, medical care, IT, miscellaneous goods, industrial parts, etc., or as a bag-shaped packaging bag. is there.

Claims (4)

A layered body having a layer containing a fluorine-containing resin, a layer made of an adhesive resin composition, and a layer containing polypropylene in this order,
The fluorine-containing resin is polychlorotrifluoroethylene,
The adhesive resin composition comprises the following components (A) and component (B), the laminate is an adhesive resin composition component (A) is containing from 40 to 60% by weight relative to the total amount thereof.
Component (A): a propylene/propylene/ethylene block copolymer having a propylene block content of 50 to 80% by weight and a propylene/ethylene block content of 20 to 50% by weight. Ethylene block copolymer Component (B): ethylene/glycidyl (meth)acrylate copolymer The laminate according to claim 1, wherein the bending elastic modulus of the component (A) is 200 to 700 MPa. Film comprising a laminate according to claim 1 or 2. Sheets containing laminate according to claim 1 or 2.