JP7270376B2 - Adhesive resin composition, fluorine-based resin adhesive film, laminate, and method for producing laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to an adhesive resin composition, a fluororesin adhesive film, a laminate, and a method for producing a laminate.

Film laminates with high barrier properties are used as packaging materials for foods, pharmaceuticals, and the like. For example, Patent Document 1 discloses a modified polyolefin obtained by radically polymerizing an epoxy group-containing acrylic acid ester or derivative thereof, a polyolefin, and an aromatic vinyl monomer during melt-kneading, and a modified polyolefin having a density of 0.0. An adhesive resin composition comprising polyethylene of 940 cm ³ or less and a styrenic thermoplastic elastomer is disclosed.

Patent Document 2 describes an adhesive resin composition containing a polyolefin resin, a compound having an intramolecular unsaturated bond, and an epoxy compound.
Patent Document 3 describes a resin composition for extrusion lamination comprising an ethylene polymer and an epoxy-modified diene copolymer that is liquid at 25°C.
Patent Document 4 describes a laminate using a resin composition suitable for co-extrusion molding, which has adhesiveness between an olefin resin composed of an olefin resin, a rubber-like polymer, and an acrylic graft copolymer, and a fluorine resin. It is

JP 2015-117281 A JP-A-2000-103914 Japanese Patent Application Laid-Open No. 2003-63226 JP-A-2000-15754

However, in the technique described in Patent Document 1, melt-kneading is performed in the presence of a radical polymerization initiator, so the initiator remains in the finally produced adhesive resin composition. Therefore, when stored for a long period of time, the properties of the resin itself may change significantly.

Moreover, in Patent Document 1, an epoxy group is partially introduced into a resin by polymerization. In this case, the adhesion of the resin does not appear unless the temperature is near the melting temperature of the resin. For this reason, there is a problem that the adhesiveness required for applications requiring adhesion or fusion bonding under lower temperature conditions and in a shorter time cannot be obtained.

The technique described in Patent Document 2 uses an epoxidized vegetable oil as the epoxy compound. Fatty acids such as linolenic acid, which is the main component of soybean oil and linoleic acid, which is the main component of linseed oil, described in Patent Document 2 have a molecular weight of about several hundred. For this reason, there is a problem in that when it is formed into a film, it bleeds immediately, easily causing poor adhesion.

In the technique described in Patent Document 3, the ethylene polymer accounts for 98.5-99.9 parts by mass. Therefore, there is a problem that it does not adhere to polypropylene and cannot be used as an adhesive resin for extrusion lamination to a polypropylene substrate or co-extrusion with polypropylene.
In addition to the above, the adhesive resins described in Patent Documents 1 to 3 all have the problem of insufficient adhesiveness to fluorine-based resins.

The technique described in Patent Document 4 is said to have adhesiveness with fluorine-based resins and olefin-based resins. It is produced by reacting an olefin polymer with a radical polymerizable monomer. For this reason, there is no reactive group with engineering plastic resins having amino groups, carboxyl groups, and hydroxyl groups at the ends, such as polyamide resins and polyester resins. rice field.

The present invention has been made in view of the above circumstances, and is an adhesive resin composition that is suitably used for bonding fluorine-based resins, and is a material other than fluorine-based resins or a fluorine-based resin and a fluorine-based resin. An object of the present invention is to provide an adhesive resin composition for the purpose of bonding with.

That is, the present invention employs the following configurations.
[1] An adhesive resin composition comprising a polyethylene resin (A) containing at least a butene-containing ethylene polymer, a styrene elastomer (B), and an epoxidized polybutadiene (C).
[2] According to [1], wherein the polyethylene resin (A) is a mixture of an ethylene-butene 1 copolymer (A1) and a polyethylene resin (A2) different from the polyethylene resin (A1). adhesive resin composition.
[3] Polyethylene having a density of 0.900 g/cm ³ or more and 0.930 g/cm ³ or less of the polyethylene resin (A2) (excluding those corresponding to the ethylene-butene 1 copolymer (A1)) The adhesive resin composition according to [2], which is a system resin.
[4] The content of the polyethylene resin (A) is 50 parts by mass or more and 80 parts by mass or less, the content of the styrene elastomer (B) is 20 parts by mass or more and 50 parts by mass or less, and the polyethylene resin ( The content of the epoxidized polybutadiene (C) with respect to 100 parts by mass of the total amount of A) and the styrene elastomer (B) is 0.1 parts by mass or more and 0.9 parts by mass or less, according to [1]. Adhesive resin composition.
[5] The content of the ethylene-butene 1 copolymer (A1) is 3 parts by mass or more and 22 parts by mass or less, the content of the polyethylene resin (A2) is 32 parts by mass or more and 72 parts by mass or less, and the styrene-based The content of the epoxidized polybutadiene (C) is 0.1 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of 20 parts by mass or more and 50 parts by mass or less of the elastomer (B). The adhesive resin composition according to [2] or [3].
[6] The epoxidized polybutadiene (C) is 1,2-polybutadiene into which epoxy is partially introduced, and has a number average molecular weight of 500 or more and 4,000 or less of [1] to [5]. The adhesive resin composition according to any one.
[7] Any one of [1] to [6], wherein the styrene elastomer (B) is a styrene-ethylene-butylene-styrene copolymer having a styrene content of 8% by mass or more and 20% by mass or less. The adhesive resin composition according to 1.
[8] A single-layer fluororesin adhesive film formed from the adhesive resin composition according to any one of [1] to [7].
[9] A laminate having a layer formed from the adhesive resin composition according to any one of [1] to [7].
[10] A method for manufacturing a laminate according to [9], which method includes any one of the following (1) to (3).
(1) A step of melt extruding a layer formed from the adhesive resin composition to obtain a fluororesin adhesive film having a single-layer structure, and laminating films on both sides of the fluororesin adhesive film and thermocompression bonding. A method for producing a laminate, comprising the step of obtaining a laminate by
(2) A step of melt extruding a layer formed from the adhesive resin composition onto a film serving as a base material to obtain a laminate of a base material/adhesive layer; A method for producing a laminate, comprising a step of laminating layers/laminating materials and thermocompression bonding to obtain a laminate.
(3) A method for producing a laminate, comprising a step of simultaneously melt extruding a resin that is a raw material for a base material and the adhesive resin composition.

According to the present invention, there is provided an adhesive resin composition that is suitably used for bonding fluorine-based resins, and has adhesiveness for the purpose of bonding between fluorine-based resins or between a fluorine-based resin and a material other than a fluorine-based resin. A resin composition can be provided.

It is a schematic sectional drawing of the laminated body of this invention. 1 is a schematic diagram of a tensile strength measuring device in an example. FIG.

The present invention will be described below based on preferred embodiments.

<Adhesive resin composition>
The adhesive resin composition of the present invention is used for bonding fluorine-based resins. For example, it can be suitably used for adhesion between films when fluororesin films are laminated together, or adhesion between films when fluororesin films and films other than fluororesins are laminated.

The adhesive resin composition of the present invention comprises a polyethylene resin (A) (hereinafter referred to as "component (A)") containing at least a butene-containing ethylene polymer, a styrene elastomer (B) (hereinafter referred to as "component (B)”) and epoxidized polybutadiene (C) (hereinafter referred to as “component (C)”).
Although the reason why the adhesive resin composition of the present invention is suitably used for adhesion of fluororesin and good adhesion of fluororesin films is not clear, it is speculated as follows.
Epoxidized polybutadiene of component (C), which is a component that exhibits adhesive strength due to the action of the butene-containing ethylene-based polymer contained in the polyethylene-based resin of component (A), which constitutes the "sea" phase of the adhesive composition. , and is uniformly dispersed in the adhesive composition without unevenly dispersing in the styrene-based elastomer of the component (B). It is presumed that this enables development of high adhesive strength based on the component (C).
Each component will be specifically described below.

<<Component (A)>>
Component (A) is the main ingredient in the adhesive resin composition of the present invention.
Component (A), a polyethylene resin containing at least a butene-containing ethylene polymer, is either an ethylene polymer alone containing a butene monomer as a copolymerization component, or an ethylene containing a butene monomer as a copolymerization component. It is not limited as long as it is a composition of a polymer and other polyethylene resins.

As the component (A), the polyethylene resin containing at least the butene-containing ethylene polymer, the butene content in the component (A) is preferably 0.1 mol % or more and 5 mol % or less, and 0.3 mol % or more and 4 mol % or less is more preferable.
If the butene content in component (A) is below the above lower limit, there is a risk that stable adhesive strength cannot be maintained. .
As the butene-containing ethylene-based polymer contained in component (A), an ethylene-butene 1 copolymer (hereinafter referred to as "component (A1)") is preferable.

The content of butene 1 in the component (A1) is preferably 5 mol % or more and 25 mol % or less, more preferably 10 mol % or more and 20 mol % or less.
When the butene 1 content is at least the above lower limit, good adhesive strength can be imparted to the formed adhesive layer. Moreover, when the butene 1 content is equal to or less than the above upper limit, stable moldability can be imparted.

Examples of the component (A1) include Tafmer (registered trademark) of Mitsui Chemicals, Inc., Excellen FX (registered trademark) of Sumitomo Chemical Co., Ltd., Engage (registered trademark) of Dow Chemical Company, and the like.

When the component (A) is a composition of an ethylene polymer containing a butene monomer as a copolymerization component and another polyethylene resin, the other polyethylene resin may be a linear low-density It is preferably one or more selected from polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
The other polyethylene-based resins may be biomass polyethylene, petroleum-derived polyethylene, or a mixture of the two.

The other polyethylene-based resin is preferably polyethylene polymerized with a metallocene-based catalyst. Among them, ethylene-α olefin copolymers such as C6-LLDPE and C8-LLDPE polymerized with a metallocene catalyst; long-chain branched polyethylene and the like are preferable examples.
A polyethylene-based resin polymerized by a metacelone-based catalyst tends to have a narrow molecular weight distribution. For this reason, it is thought that low-molecular-weight components that can inhibit adhesion are small, and high adhesiveness can be obtained when used as an adhesive.

In addition, considering moldability and adhesiveness, it is preferable to use low-density polyethylene (LDPE) or long-chain branched polyethylene as the other polyethylene-based resin.
By applying various polyethylene-based resins as the other polyethylene-based resins, it is possible to adjust the properties of the adhesive resin composition, adhesiveness, moldability, and the like. Component (A) is preferably a composition of an ethylene-based polymer containing a butene monomer as a copolymerization component and a polyethylene-based resin other than that.

The density of the ethylene polymer containing the butene monomer contained in component (A) as a copolymerization component is preferably 0.850 g/cm ³ or more and 0.910 g/cm ³ or less, and 0.860 cm ³ or more and 0.890 g/cm 3 or more. cm ³ or less is preferred.
Further, the density of the other polyethylene-based resin is preferably 0.900 g/cm ³ or more and 0.930 g/cm ³ or less, more preferably 0.905 cm ³ or more and 0.925 g/cm ³ or less. When the density of the other polyethylene-based resin is equal to or less than the above upper limit, hardening of the adhesive layer to be formed can be suppressed, and flexibility can be imparted, so high adhesive strength can be maintained.

The content of component (A) in the adhesive composition is preferably 50 parts by mass or more and 80 parts by mass or less, and 52 parts by mass or more and 75 parts by mass or less, based on a total of 100 parts by mass of components (A) and (B). is preferred.
When the content of component (A) is at most the above upper limit, curing of the adhesive layer to be formed can be suppressed, and high adhesive strength can be maintained.

In the adhesive composition of the present invention, the butene-containing ethylene-based polymer contained in component (A) is a component having excellent affinity with component (C).
Moreover, when the component (A) contains a polyethylene-based resin other than the butene-containing ethylene-based polymer, the butene-containing ethylene-based polymer is preferably a component compatible with the other polyethylene-based resin. The adhesive resin composition of the present invention thereby uniformly disperses the component (C) in the resin component (A), which is the main component, in the adhesive layer formed from the adhesive resin composition. It is possible.

The butene-containing ethylene polymer contained in the component (A) is an ethylene-butene 1 copolymer (A1), and the component (A) is a polyethylene resin (A2) different from (A1) and (A1). In the case of a mixture with, the content of component (A1) is 3 parts by mass or more and 22 parts by mass or less in a total of 100 parts by mass of component (A) [(A1) + (A2)] and component (B) is preferable, and 5 parts by mass or more and 20 parts by mass or less is more preferable. The content of component (A2) is preferably 32 parts by mass or more and 72 parts by mass or less, preferably 35 parts by mass or more and 70 parts by mass, based on a total of 100 parts by mass of component (A) [(A1) + (A2)] and component (B). Part by mass or less is more preferable.
When the content of the component (A1) is equal to or less than the above upper limit, the elastic modulus of the formed adhesive layer is not excessively increased, and high adhesive strength can be maintained.

<<Component (B)>>
In this embodiment, component (B) is a component that imparts adhesiveness to the adhesive layer.
In the present embodiment, examples of the styrene-based elastomer component include block copolymers having hard segments made of polystyrene or the like and soft segments made of polyethylene, polybutadiene, polyisoprene, or the like. Styrene-based polymers that can be used for styrene-based elastomers include aromatic olefin-aliphatic olefin copolymers such as styrene-butadiene copolymers, styrene-isoprene copolymers, and styrene-ethylene copolymers. .

In this embodiment, the styrene-based elastomer is a styrene-ethylene-butylene-styrene copolymer (SEBS) obtained by hydrogenating a styrene-butylene-styrene copolymer (SBS) to completely ring-open the unsaturated bonds in the molecule. ) is preferred.
The styrene content is preferably 8% by mass or more and 20% by mass or less, more preferably 10% by mass or more and 16% by mass or less.
When the styrene content is equal to or less than the above upper limit, hardening of the resin can be suppressed, and a decrease in adhesiveness can be suppressed.

In this embodiment, the component (B) includes, for example, Dynalon manufactured by JSR Corporation, Tuftec H series manufactured by Asahi Kasei Chemicals Corporation, Kraton G Polymer manufactured by Kraton Polymer Co., Ltd., and the like.

The content of component (B) in the adhesive composition is 20 parts by mass or more and 50 parts by mass based on a total of 100 parts by mass of component (A) [or component (A1) + component (A2)] and component (B). 22 parts by mass or more and 49 parts by mass or less is more preferable, 30 parts by mass or more and 48 parts by mass or less is even more preferable, and 35 parts by mass or more and 48 parts by mass or less is particularly preferable.
When the content of the component (B) is equal to or less than the above upper limit, it is possible to suppress a decrease in tensile strength and prevent a decrease in adhesive strength when an adhesive layer is formed.

In the present embodiment, the total amount of component (A) [or component (A1)+component (A2)] and component (B) is 100 parts by mass.

<<Component (C)>>
In this embodiment, component (C) is epoxidized polybutadiene, preferably epoxidized polybutadiene, which is partially epoxidized butadiene. In this embodiment, partially epoxidized 1,2-polybutadiene is particularly preferred.
In this embodiment, the epoxy group in the component (C) is compatible with the fluorine component of the fluororesin and can adhere to the fluororesin. Since it has an epoxy group, the inclusion of the component (C) enables adhesion to metal materials.

Examples of component (C) that can be used in the present embodiment include liquid polybutadiene JP-100 and JP-200 available from Nippon Soda Co., Ltd., and ADEKA CIZER BF-1000 available from Adeka Corporation.
Component (C) preferably has a number average molecular weight of 500 to 4,000, more preferably 800 to 2,500.
When the number average molecular weight of component (C) is equal to or less than the above upper limit, it is possible to suppress a decrease in adhesiveness due to solid state at room temperature, and to prevent a decrease in adhesiveness.
In the present invention, the number average molecular weight is a polystyrene-equivalent value measured by GPC (gel permeation chromatography).

Moreover, it is preferable to use liquid epoxidized polybutadiene as the component (C).
In the present embodiment, the content of component (C) is preferably 0.1 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of component (A) and component (B), and 0.3 More preferably, the amount is not less than 0.7 parts by mass and not more than 0.7 parts by mass.
When the content of the component (C) is equal to or less than the above upper limit, it is possible to reduce the amount of low-molecular-weight components in the adhesive composition that cause adhesion inhibition.

The adhesive resin composition of the present embodiment contains component (A), component (B) and component (C).
The adhesive resin composition of this embodiment is considered to form a so-called sea-island structure in which the component (A) corresponds to the "sea" and the components (B) and (C) correspond to the "islands". Further, component (C) is compatible with the butene-containing ethylene polymer contained in component (A), so that component (C) can be uniformly dispersed in the adhesive resin composition. In addition, component (C) can be uniformly dispersed in the adhesive resin composition by making component (C) compatible with component (B). Since the component (C) that exhibits adhesive strength is dispersed more uniformly throughout the adhesive layer, it is believed that the adhesive layer can exhibit high adhesive strength.
Furthermore, it is presumed that the epoxy groups in component (C) are protected by components (A) and (B), thereby suppressing ring-opening of the epoxy groups due to moisture.

According to the adhesive resin composition of the present embodiment, fluororesins can be adhered to each other or fluororesin and other materials can be adhered without using other adhesives, anchor coating agents, or the like. Therefore, the amount of solvent used can be reduced, and the environmental load can be reduced.

<Fluorine resin adhesive film>
The present invention provides a fluororesin adhesive film and laminate formed from the adhesive resin composition of the present invention.
The fluororesin adhesive film of the present invention is a single-layer film formed from the adhesive resin composition of the present invention. In the present embodiment, the term "film" refers to a flat molded body having a spread in the surface direction that can be molded by melt molding. things).

<Method for producing fluorine-based resin adhesive film>
The manufacturing method of the single-layer fluororesin adhesive film is not particularly limited, and it can be manufactured by a single-layer extrusion method using an inflation molding method or a T-die molding method.

<Laminate>
The laminate of the present invention is obtained by laminating a layer comprising the adhesive resin composition of the present invention on at least one side of a substrate.
FIG. 1 shows a schematic diagram of a cross section of the laminate of the present invention. A laminate 1 shown in FIG.

Examples of fluorine-based resin materials for forming the fluorine-based resin film 11 include polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). ), tetrafluoroethylene/hexafluoropropylene/perfluoroalkyl vinyl ether (EPA), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorofluoroethylene (PCTFE), chlorotrifluoroethylene/ Ethylene copolymer (ECTFE), a mixture of one or more of these, and the like can be used.

The adhesive layer 10 can be formed using the adhesive resin composition of the present invention.

The resin film 12 may be the fluorine-based resin film described above, or may be a resin film other than this. Examples of resin materials for resin films other than fluorine-based resin films include polypropylene, polyethylene terephthalate, and polyester.

<Method for manufacturing laminate>
The laminate of the present invention is preferably produced by any one of the following laminate production methods (1) to (3).
(1) A step of melt extruding a layer formed from the adhesive resin composition to obtain a fluororesin adhesive film having a single-layer configuration, and laminating films on both sides of the fluororesin adhesive film and thermocompression bonding. A method for producing a laminate, comprising the step of obtaining a laminate by
(2) a step of melt extruding a layer formed from the adhesive resin composition onto a film serving as a substrate to obtain a laminate of substrate/adhesive layer; A method for producing a laminate, comprising a step of laminating layers/laminating materials and thermocompression bonding to obtain a laminate.
(3) A method for producing a laminate, comprising a step of simultaneously melt extruding a resin that is a raw material for a base material and the adhesive resin composition.

The laminate can be produced by a co-extrusion method such as an inflation molding method or a T-die molding method.
In the above manufacturing method (2), when using the T-die molding method, a method such as extrusion lamination in which resin is extruded onto the base material or sand lamination method in which resin is extruded between the base material and the lining material is used. can be
The base material from which the adhesive resin composition of the present invention is extruded may be either the above-mentioned fluororesin material or a resin material other than the fluororesin, but the resin material other than the fluororesin is more preferable.
When a resin material other than a fluororesin is used as the base material, the fluororesin is set and laminated as a matching material to form a resin material other than the fluororesin, an adhesive layer, and a fluororesin. can produce a laminated film.

In the production method of (3) above, when the resin is extruded in a structure of two or more layers using a co-extrusion method, for example, the adhesive resin composition of the present invention is arranged on the surface layer side, and the fluorine By setting and laminating the system resin, it is possible to finally form a laminate of three or more layers having a layer structure adjacent to the fluororesin.
For example, when using a fluororesin that has a melting point of 200° C. or less and can be melt-extruded, such as an acid-modified ethylene-tetrafluoroethylene copolymer, it is simultaneously used as an adjacent layer of the adhesive resin composition of the present invention by a coextrusion method. It may be melt extruded.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

Component (A), component (B) and component (C) shown in Table 1 were each mixed at the compounding ratio shown in Table 1 to prepare an adhesive resin composition.

In Table 1, each abbreviation means the following materials. Moreover, the numerical value in [ ] is a compounding quantity (mass part).
"Component (A2)-1" ... Excellen GMH GH030 (metallocene polymerized long-chain branched polyethylene, ρ = 0.912 g/cm ³ , Tm = 101°C, MFR = 0.5 g/10 min (190°C, 2.16 kgf ) Made by Sumitomo Chemical Co., Ltd.)
"Component (A2)-2" ... Petrothene 175K (low density polyethylene, ρ = 0.922 g/cm ³ , Tm = 109°C, MFR = 0.6 g/10 min (190°C, 2.16 kgf) Tosoh Corporation ) made)
"Component (A1)-1"... ethylene-butene 1 copolymer (ρ = 0.864 g/cm ³ , Tm = 41°C, MFR = 3.6 g/10 min (190°C, 2.16 kgf), ethylene content 80 mol%, butene 1 content 20 mol%)
"Component (A1)-2"... ethylene-butene 1 copolymer (ρ = 0.885 g/cm ³ ,
Tm = 66°C, MFR = 3.6 g/10 min (190°C, 2.16 kgf), ethylene content 90 mol%, butene 1 content 10 mol%)
“Component (B)-1”: styrene content 12% by mass, ρ=0.890 g/cm ³ , MFR=4.5 g/10 min (230° C., 2.16 kgf)
"Component (B)-2": styrene content 13% by mass, ρ = 0.900 g/cm ³ , MFR = 22 g/10 min (230°C, 5 kgf)
“Component (C)-1”: 1,2-epoxidized polybutadiene, ρ=0.99 g/cm ³ , Mn=1,000
"Component (C)-2" ... 1,2-epoxidized polybutadiene, Mn = 1,300

(Production example 1)
The adhesive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 6 shown in Table 1 were heated and melt-mixed, and then formed into a film by a T-die extruder to form a melt-mixed film having a thickness of 50 μm. It was produced as a single adhesive layer film (melt-blended film 10).

≪Peel strength measurement≫
The peel strength measurement will be described with reference to FIG.
Using the produced melt-mixed film 10, the following laminates 1 to 4, which are laminated in the order of fluororesin film 11, melt-mixed film 10, and adherend film 12 in the order of three layers, are formed into strips with a length of 50 mm and a width of 15 mm. It was cut out and used as a test piece.
Furthermore, the top and bottom of each of them was sandwiched between PTFE sheets having a film thickness of 50 μm, and 10 mm from the edge of this test piece was heat-sealed. The heat sealing conditions were a sealing temperature of 240° C., a pressure of 0.4 MPa, and a heating time of 3 seconds.

After that, the upper and lower PTFE sheets are removed, the fluororesin film 11 is gripped with the gripper 22 so that it is on the pulling side, the adherend film 12 is gripped and fixed with the gripper 20, and the fluororesin film 11 is removed. , in the tensile direction indicated by reference numeral 21, and the peel strength was measured.
Measurement was performed at a tensile speed of 300 mm/min and a width of 15 mm.
The fluorine-based film, the melt-mixed film, and the adhered film used in the test, and the order of lamination are as follows.

[Laminate]
Laminate 1; MAH-ETFE/adhesive layer (study resin)/PP
Laminate 2; PCTFE/adhesive layer (study resin)/PP
Laminate 3; PCTFE/adhesive layer (study resin)/PCTFE
Laminate 4; PCTFE/adhesive layer (study resin)/PET

Each abbreviation in Laminates 1 to 4 means the following materials.
MAH-ETFE: fluorine-based resin film. Fluon LH-8000 (ρ=1.75 g/cm ³ , Tm=180° C., MFR=4 g/10 min (230° C., 2.16 kgf), manufactured by Asahi Glass Co., Ltd.) is used by making a 50 μm film using an in-house extruder. .
PP: Polypropylene film. SunAllomer PS522M (ρ = 0.9 g/cm ³ , MFR = 4.9 g/10 min (230°C, 2.16 kgf) was made into a 50 µm film by an in-house extruder and used.
PCTFE: Polychlorofluoroethylene film DF0050-C1. (51 μm) (manufactured by Daikin Industries, Ltd.) was purchased and used.
PET... Polyethylene terephthalate film. A polyester film E5001 (250 μm, untreated) (manufactured by Toyobo Co., Ltd.) was purchased and used.

The peel strength and peel appearance of laminates 1 to 4 are shown in Table 2 below.

Each description regarding "exfoliation appearance" means the following states.
Interfacial delamination: Delamination occurred between the adhesive layer and the fluororesin film (interface).
- Adhesive layer cohesive failure: Peeling occurs inside the adhesive layer, leaving part of the adhesive on the adhered film.
• PP fracture: The adhesive strength was very strong and the test piece was not peeled off, and was fractured at the center of the test piece.
・ PCTFE tensile side edge breakage: The adhesive strength was very strong and did not peel off, and the test piece was broken at the base.
· PCTFE breakage: The adhesive strength was very strong and the test piece was broken at the center without peeling.

From the results shown in Table 2, according to the present invention (Examples 1 to 12), the adhesive strength is improved by mixing polyethylene resin, ethylene-butene 1 copolymer, styrene elastomer, and epoxidized polybutadiene. I was able to confirm that.
In Comparative Example 1, in which PE alone was used, the peel strength was very low because it did not adhere not only to the fluororesin but also to the polypropylene.
Comparative Example 2, in which only epoxidized polybutadiene was blended with PE, exhibited a higher peel strength than Comparative Example 1, in which only PE was used. Peel strength and peel appearance were not as good as 1-12.
In Comparative Example 3 in which no styrene-based elastomer was added, laminate 3 having the same upper and lower covering materials exhibited peel strength equal to or greater than that of Examples 1 to 12, but laminates 1 and 2 having different upper and lower covering materials , 4, the peel strength was lower than that of Examples 1-12.
Moreover, in Comparative Examples 4 and 5, in which the styrene elastomer was not added, the peel strength was high in the laminates 1 and 2, and values similar to those of Examples 1 to 12 were shown. In Comparative Example 5, the peel strength of laminates 3 and 4 was low.
In Comparative Example 6, in which no epoxidized polybutadiene was added, the peel strength of Laminate 4 was very high, but in Laminates 1-3, the peel strength did not reach Examples 1-12.

1: Laminate, 11: Fluorinated resin, 10: Adhesive layer, 12: Resin film, 21: Tensile direction, 20, 22: Gripper

Claims (6)

At least, a polyethylene resin (A) containing a butene-containing ethylene polymer, a styrene elastomer (B) and an epoxidized polybutadiene (C) ,
The polyethylene resin (A) is a mixture of an ethylene-butene 1 copolymer (A1) and a polyethylene resin (A2) different from the polyethylene resin (A1),
The styrene-based elastomer (B) is a styrene-ethylene-butylene-styrene copolymer having a styrene content of 8% by mass or more and 20% by mass or less,
The epoxidized polybutadiene (C) is obtained by partially introducing epoxy into 1,2-polybutadiene, and has a number average molecular weight of 500 or more and 4,000 or less,
The content of the polyethylene resin (A) is 50 parts by mass or more and 80 parts by mass or less, the content of the styrene elastomer (B) is 20 parts by mass or more and 50 parts by mass or less, and the polyethylene resin (A) The adhesive resin composition, wherein the content of the epoxidized polybutadiene (C) is 0.1 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of the styrene elastomer (B). The density of the polyethylene resin (A2) (excluding those corresponding to the ethylene-butene 1 copolymer (A1)) is a polyethylene resin having a density of 0.900 g/cm ³ or more and 0.930 g/cm ³ or less. The adhesive resin composition according to claim 1 , wherein The content of the ethylene-butene 1 copolymer (A1) is 3 parts by mass or more and 22 parts by mass or less, the content of the polyethylene resin (A2) is 32 parts by mass or more and 72 parts by mass or less, and the styrene elastomer (B The content of the epoxidized polybutadiene (C) is 0.1 parts by mass or more and 0.9 parts by mass or less with respect to 100 parts by mass of the total amount of 20 parts by mass or more and 50 parts by mass or less. Or the adhesive resin composition according to 2 . A single-layer fluororesin adhesive film formed from the adhesive resin composition according to any one of claims 1 to 3 . A laminate having a layer formed from the adhesive resin composition according to any one of claims 1 to 3 . 6. The method for producing a laminate according to claim 5 , wherein the method for producing a laminate according to any one of the following (1) to (3).
(1) A step of melt extruding a layer formed from the adhesive resin composition to obtain a fluororesin adhesive film having a single-layer configuration, and laminating films on both sides of the fluororesin adhesive film and thermocompression bonding. A method for producing a laminate, comprising the step of obtaining a laminate by
(2) a step of melt extruding a layer formed from the adhesive resin composition onto a film serving as a substrate to obtain a laminate of substrate/adhesive layer; A method for producing a laminate, comprising a step of laminating layers/laminating materials and thermocompression bonding to obtain a laminate.
(3) A method for producing a laminate, comprising a step of simultaneously melt extruding a resin that is a raw material for a base material and the adhesive resin composition.

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