JP2019172961A - Adhesive resin composition, film for fluorine-based resin adhesion, laminate, and manufacturing method of laminate - Google Patents

Abstract

To provide an adhesive resin composition used for adhesion of a fluorine resin, and having an aim to adhere fluorine resins to each other, or the fluorine resins and a material other than the fluorine resins.SOLUTION: There is provided an adhesive resin composition containing at least a polyethylene resin containing a butene-containing ethylene polymer (A), a styrenic elastomer (B), and epoxidized polybutadiene (C).SELECTED DRAWING: None

Description

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

Film laminates with high barrier properties are used for packaging materials such as foods and pharmaceuticals. For example, Patent Document 1 discloses a modified polyolefin obtained by radical polymerization of an acrylic ester containing an epoxy group or a derivative thereof, a polyolefin, and an aromatic vinyl monomer in melt kneading, and a density of 0. An adhesive resin composition composed of polyethylene of 940 cm ³ or less and a styrene thermoplastic elastomer is described.

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 coextrusion molding having an adhesive property of an olefin resin and a fluororesin composed of an olefin resin, a rubber-like polymer, and an acrylic graft copolymer. Has been.

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

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

  Moreover, in patent document 1, the epoxy group is partially introduce | transduced into resin by superposition | polymerization. In this case, the adhesiveness of the resin does not appear unless it is near the melting temperature of the resin. For this reason, there exists a problem that the adhesiveness required by the use for which adhesion | attachment and a melt | fusion are calculated | required in a low-temperature condition and a short time cannot be obtained.

  In the technique described in Patent Document 2, epoxidized vegetable oil is used as an 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 hundreds. For this reason, there is a problem that when the film is formed, it immediately bleeds and easily causes poor adhesion.

In the technique described in Patent Document 3, the ethylene-based polymer accounts for 98.5 to 99.9 parts by mass. For this reason, there is a problem that it cannot be used as an adhesive laminate for extrusion lamination to a polypropylene base material or co-extrusion with polypropylene without adhering to polypropylene.
In addition to the above, all of the adhesive resins described in Patent Documents 1 to 3 have a problem that the adhesiveness with the fluorine-based resin is insufficient.

  The technique described in Patent Document 4 is that it has adhesiveness with a fluorine-based resin and an olefin-based resin, but has a functional group composed of a carboxylic acid or its anhydride group, an epoxy group, a hydroxyl group, and an isocyanate group. It is made by reacting an olefin polymer with a radical polymerization monomer. For this reason, for example, there is no reactive group with an engineering plastic resin having an amino group, a carboxyl group, or a hydroxyl group at the terminal, such as a polyamide resin or a polyester resin, so that there is a problem that adhesiveness with them is greatly reduced. It was.

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

That is, the present invention employs the following configuration.
[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] 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] The polyethylene resin (A2) (provided that ethylene - excluding those falling under 1 copolymer butene (A1)) density of, 0.900 g / cm ³ or more 0.930 g / cm ³ or less of polyethylene The adhesive resin composition according to [2], which is a system resin.
[4] The polyethylene resin (A) is contained in an amount of 50 to 80 parts by mass, the styrene elastomer (B) is contained in an amount of 20 to 50 parts by mass, 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-based elastomer (B) is 0.1 parts by mass or more and 0.9 parts by mass or less. 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 type The content of the epoxidized polybutadiene (C) with respect to a total amount of 100 parts by mass of the elastomer (B) of 20 parts by mass or more and 50 parts by mass or less is 0.1 parts by mass or more and 0.9 parts by mass or less. The adhesive resin composition according to [2] or [3].
[6] The epoxidized polybutadiene (C) is obtained by partially introducing an epoxy into 1,2-polybutadiene and having a number average molecular weight of 500 or more and 4,000 or less. The adhesive resin composition as described in 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. Adhesive resin composition as described in one.
[8] A film for adhering a fluororesin having a single layer structure, 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] The method for producing a laminate according to [9], wherein the laminate is any one of the following (1) to (3).
(1) A step in which a layer formed from the adhesive resin composition is melt-extruded to obtain a fluororesin adhesive film having a single layer structure, and a film is laminated on both sides of the fluororesin adhesive film and thermocompression bonded The manufacturing method of a laminated body which has a process which makes it let it obtain a laminated body.
(2) A step in which a layer formed from the adhesive resin composition is melt-extruded onto a film serving as a base material to obtain a laminate of a base material / adhesive layer, and a laminated material is further used as a base material / adhesive. The manufacturing method of a laminated body which has the process of making it laminate | stack so that it may become a layer / combination material, and thermocompression-bonding, and obtaining a laminated body.
(3) A method for producing a laminate, which includes a step of simultaneously melt-extruding a resin as a raw material for a substrate and the adhesive resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, it is the adhesive resin composition used suitably for adhesion | attachment of fluororesin, Comprising: The adhesiveness for the purpose of adhesion | attachment between fluororesins or between materials other than fluororesin A resin composition can be provided.

It is a schematic sectional drawing of the laminated body of this invention. It is a schematic diagram of the tensile strength measuring apparatus in an Example.

  Hereinafter, the present invention will be described based on preferred embodiments.

<Adhesive resin composition>
The adhesive resin composition of this invention is used for adhesion | attachment of a fluorine resin. For example, it can be suitably used for adhesion between films in the case of laminating fluorine resin films, or adhesion between films in the case of laminating a resin film other than a fluorine resin film and a fluorine resin.

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 details of the reason why the adhesive resin composition of the present invention is suitably used for adhesion of a fluorine resin and good adhesion of the fluorine resin film is not clear, it is presumed as follows.
Due to the action of the butene-containing ethylene polymer contained in the polyethylene resin of the component (A) that constitutes the “sea” phase of the adhesive composition, the epoxidized polybutadiene of the component (C), which is a component that exhibits adhesive strength, is obtained. It is considered that the component (B) is uniformly dispersed in the adhesive composition without being dispersed in the styrene-based elastomer. Thereby, it is estimated that the expression of the high adhesive force based on a component (C) is enabled.
Hereinafter, each component will be specifically described.

≪Component (A) ≫
A component (A) is a component used as a main material in the adhesive resin composition of this invention.
The polyethylene-based resin containing at least a butene-containing ethylene polymer as the component (A) is an ethylene-based polymer alone containing a butene monomer as a copolymer component, or ethylene containing a butene monomer as a copolymer component. The composition is not limited as long as it is a composition of a polymer and other polyethylene resins.

The polyethylene resin containing at least the butene-containing ethylene polymer of the component (A) preferably has a butene content in the component (A) of 0.1 mol% or more and 5 mol% or less, More preferably, it is at least 4 mol%.
If the butene content in the component (A) is less than or equal to the above lower limit value, stable adhesive strength may not be maintained, and if it is greater than or equal to the above upper limit value, good processability may not be obtained. .
The butene-containing ethylene polymer contained in the component (A) is preferably an ethylene-butene 1 copolymer (hereinafter referred to as “component (A1)”).

As the said component (A1), it is preferable that the content rate of butene 1 is 5 mol% or more and 25 mol% or less, and 10 mol% or more and 20 mol% or less are more preferable.
When the butene 1 content is not less than the above lower limit, good adhesive force can be imparted to the formed adhesive layer. Further, when the butene 1 content is not more than the above upper limit value, stable moldability can be imparted.

  Examples of the component (A1) include Tafmer (registered trademark) from Mitsui Chemicals, Exelen FX (registered trademark) from Sumitomo Chemical, Engage (registered trademark) from Dow Chemical Company, and the like.

In the case where the component (A) is a composition of an ethylene polymer containing a butene monomer as a copolymerization component and other polyethylene resins, the other polyethylene resins may be 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 polyethylene resin other than the above may be biomass polyethylene, petroleum-derived polyethylene, or a mixture of both.

The other polyethylene resin is preferably polyethylene polymerized with a metallocene catalyst. Among these, ethylene-α olefin copolymers such as C6-LLDPE and C8-LLDPE polymerized by a metallocene catalyst; long-chain branched polyethylene and the like are suitable examples.
Polyethylene resins polymerized with a metatheron catalyst tend to have a narrow molecular weight distribution. For this reason, there are few low molecular weight components which can become an adhesion inhibiting factor, and when using as an adhesive agent, it is thought that high adhesiveness is acquired.

In consideration of 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 resins as the other polyethylene resins, in addition to the properties and adhesiveness of the adhesive resin composition, molding processability and the like can be adjusted. The component (A) is preferably a composition of an ethylene polymer containing a butene monomer as a copolymerization component and another polyethylene resin.

The density of the ethylene polymer containing butene monomers contained in component (A) as a copolymerization component is preferably 0.850 g / cm ³ or more 0.910 g / cm ³ or less, 0.860Cm ³ or 0.890 g / cm ³ or less is preferable.
Further, as the density of other polyethylene resin is preferably 0.900 g / cm ³ or more 0.930 g / cm ³ or less, 0.905Cm ³ or 0.925 g / cm ³ or less is more preferable. When the density of the other polyethylene-based resin is not more than the above upper limit value, curing of the adhesive layer to be formed can be suppressed and flexibility can be imparted, so that high adhesive force can be maintained.

The content of the 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, in a total of 100 parts by mass of the component (A) and the component (B). Is preferred.
When content of a component (A) is below the said upper limit, hardening of the adhesive material layer to form can be suppressed and high adhesive force can be maintained.

In the adhesive composition of the present invention, the butene-containing ethylene polymer contained in the component (A) is a component having excellent affinity with the component (C).
Moreover, when a component (A) contains polyethylene-type resins other than a butene containing ethylene polymer, it is preferable that a butene containing ethylene polymer is a component compatible with other polyethylene resins. The adhesive resin composition of the present invention thereby uniformly disperses the component (C) in the resin component (A) as the main component in the adhesive layer formed from the adhesive resin composition. It is something that can be done.

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). Content of the 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 the component (A) [(A1) + (A2)] and the component (B). Is preferably 5 parts by mass or more and 20 parts by mass or less. The content of the component (A2) is preferably 32 parts by mass or more and 72 parts by mass or less, and preferably 35 parts by mass or more and 70 parts by mass, out of a total of 100 parts by mass of the component (A) [(A1) + (A2)] and the component (B). Less than the mass part is more preferable.
When the content of the component (A1) is not more than the above upper limit value, the elastic modulus of the formed adhesive layer is not excessively increased, and high adhesive force can be maintained.

≪Ingredient (B) ≫
In this embodiment, a component (B) is a component which provides adhesive force to an adhesive bond layer.
In the present embodiment, examples of the styrene elastomer component include a block copolymer having a hard segment made of polystyrene or the like and a soft segment made of polyethylene, polybutadiene, polyisoprene, or the like. Examples of the styrenic polymer that can be used for the styrenic elastomer include aromatic olefin-aliphatic olefin copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, and styrene-ethylene copolymer. .

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

  In this embodiment, examples of the component (B) include Dynalon from JSR Corporation, Tuftec H Series from Asahi Kasei Chemicals Corporation, and Kraton G Polymer from Kraton Polymer Corporation.

The content of the component (B) in the adhesive composition is 20 parts by mass or more and 50 parts by mass in 100 parts by mass in total of the component (A) [or component (A1) + component (A2)] and component (B). Part or less, preferably 22 parts by weight or more and 49 parts by weight or less, more preferably 30 parts by weight or more and 48 parts by weight or less, and particularly preferably 35 parts by weight or more and 48 parts by weight or less.
When content of a component (B) is below the said upper limit, the fall of the tensile strength when forming an adhesive bond layer can be suppressed, and the fall of adhesive strength can be prevented.

  In this embodiment, the sum total of the said component (A) [or (component (A1) + component (A2)] and the said component (B) shall be 100 mass parts.

≪Ingredient (C) ≫
In this embodiment, component (C) is epoxidized polybutadiene, and epoxidized polybutadiene obtained by partially epoxidizing butadiene is preferable. In this embodiment, a partially epoxidized 1,2-polybutadiene is particularly preferable.
In this embodiment, the epoxy group in the component (C) is compatible with the fluorine component of the fluororesin and can be bonded to the fluororesin. Since it has an epoxy group, it can be bonded to a metal material by including the component (C).

Examples of the component (C) that can be used in the present embodiment include liquid polybutadiene JP-100 and JP-200 manufactured by Nippon Soda Co., Ltd. and Adeka Sizer BF-1000 manufactured by Adeka Corporation.
The number average molecular weight of the component (C) is preferably 500 or more and 4,000 or less, and more preferably 800 or more and 2,500 or less.
When the number average molecular weight of the component (C) is not more than the above upper limit, it is possible to suppress a decrease in tackiness due to a solid state at room temperature, and to prevent a decrease in adhesiveness.
In the present invention, the number average molecular weight is a value in terms of polystyrene measured by GPC (gel permeation chromatography).

The component (C) is preferably liquid epoxidized polybutadiene.
In the present embodiment, the content of the 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 the component (A) and the component (B). More preferably, it is not less than 0.7 parts by mass.
When the content of the component (C) is not more than the above upper limit value, low molecular components in the adhesive composition that cause adhesion inhibition can be reduced.

The adhesive resin composition of this embodiment contains a component (A), a component (B), and a 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 “sea”, the component (B), and the component (C) each correspond to “island”. Furthermore, when the component (C) is compatible with the butene-containing ethylene polymer contained in the component (A), the component (C) can be uniformly dispersed in the adhesive resin composition. In addition, since component (C) is compatible with component (B), component (C) can be uniformly dispersed in the adhesive resin composition. Since the component (C) that exhibits adhesive force is uniformly dispersed throughout the adhesive layer, it is considered that the adhesive layer can exhibit high adhesive force.
Furthermore, it is speculated that the epoxy group in the component (C) is protected by the component (A) and the component (B), and the ring opening of the epoxy group due to moisture can be suppressed.

  According to the adhesive resin composition of the present embodiment, fluorine resins can be bonded to each other or fluorine resins and other materials without using other adhesives, anchor coating agents, or the like. For this reason, the usage-amount of a solvent can be reduced and an 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 this embodiment, the “film” is a flat molded body having a spread in the surface direction that can be molded by melt molding, and has an extremely thin thickness to a thick one (so-called sheet-like shape). Stuff).

<Production method of fluororesin adhesive film>
The production method of the fluorine-based resin adhesive film having a single layer structure is not particularly limited, and can be produced by a single layer extrusion method using an inflation molding method or a T-die molding method.

<Laminated body>
As for the laminated body of this invention, the layer which consists of the adhesive resin composition of this invention is laminated | stacked on the at least single side | surface of a base material.
A schematic diagram of a cross section of the laminate of the present invention is shown in FIG. The laminate 1 in FIG. 1 includes an adhesive layer 10, a fluorine resin film 11, and a resin film 12.

  Examples of the fluorine resin material for forming the fluorine 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 / An ethylene copolymer (ECTFE) and a mixture of one or more of these 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 above-mentioned fluorine-based resin film, or may be a resin film other than this. Examples of the resin material of the resin film other than the fluorine resin film include polypropylene, polyethylene terephthalate, and polyester.

<Method for producing laminate>
It is preferable to manufacture the laminated body of this invention with the manufacturing method of any one of following (1)-(3).
(1) A step in which a layer formed from the adhesive resin composition is melt-extruded to obtain a fluororesin adhesive film having a single layer structure, and a film is laminated on both sides of the fluororesin adhesive film and thermocompression bonded The manufacturing method of a laminated body which has a process which makes it let it obtain a laminated body.
(2) A step in which a layer formed from the adhesive resin composition is melt-extruded onto a film serving as a base material to obtain a laminate of a base material / adhesive layer, and a laminated material is further used as a base material / adhesive. The manufacturing method of a laminated body which has the process of making it laminate | stack so that it may become a layer / combination material, and thermocompression-bonding, and obtaining a laminated body.
(3) A method for producing a laminate, which includes a step of simultaneously melt-extruding a resin as a raw material for a substrate and the adhesive resin composition.

The laminate can be formed by a coextrusion method such as an inflation molding method or a T-die molding method.
In the production method of (2) above, if a T-die molding method is used, a method such as an extrusion laminating method in which a resin is extruded onto a base material or a sand laminating method in which a resin is extruded between a base material and a laminated material is used. May be.
The substrate for extruding the adhesive resin composition of the present invention may be any of the above-described fluorine-based resin materials or resin materials other than the fluorine-based resins, but resin materials other than the fluorine-based resins are more preferable.
When using a resin material other than the fluorine-based resin as the base material, the resin material other than the fluorine-based resin, the adhesive layer, the fluorine-based resin, Can be produced.

In the production method of (3) above, when extruding a resin with a structure of two or more layers using a coextrusion method, for example, the adhesive resin composition of the present invention is disposed on the surface layer side, and fluorine is disposed on the laminated material side of the surface layer. 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 having a melting point of 200 ° C. or less and capable of being melt-extruded, such as an acid-modified ethylene-tetrafluoroethylene copolymer, it can be simultaneously used as an adjacent layer of the adhesive resin composition of the present invention by a co-extrusion method. It may be melt extruded.

    EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

  Each of the component (A), the component (B) and the component (C) shown in Table 1 was mixed at a blending 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 (Sumitomo Chemical Co., Ltd.)
“Component (A2) -2”: Petrocene 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, and a melt mixed film having a thickness of 50 μm was formed. It was produced as an adhesive layer single layer film (melt mixed film 10).

≪Peel strength measurement≫
The peel strength measurement will be described with reference to FIG.
Using the manufactured melt-mixed film 10, the following laminates 1 to 4 laminated in three layers in the order of the fluororesin film 11, the melt-mixed film 10 and the adherent film 12 are formed into strips having a length of 50 mm and a width of 15 mm. It cut out and it was set as the test piece.
Furthermore, the upper and lower sides were sandwiched between PTFE sheets having a film thickness of 50 μm, and 10 mm from the end of the 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.

Thereafter, the upper and lower PTFE sheets are removed, and the fluororesin film 11 is gripped by the gripping tool 22 so that the fluororesin film 11 is on the tension side, the adherent film 12 is gripped and fixed by the gripping tool 20, and the fluororesin film 11 is fixed. The tensile strength and peel strength were measured in the tensile direction indicated by reference numeral 21.
Measurement was carried out at a tensile speed of 300 mm / min and a width of 15 mm.
The fluorine-based film, melt-mixed film, and adherent film used in the test are as follows.

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

Each abbreviation in the laminated bodies 1 to 4 means the following materials.
MAH-ETFE: Fluorine resin film. Fullon 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 it on a 50 μm film with our own extruder. .
PP: Polypropylene film. Sun Allomer PS522M (ρ = 0.9 g / cm ³ , MFR = 4.9 g / 10 min (230 ° C., 2.16 kgf)) was prepared on a 50 μm film using its own extruder.
PCTFE: polychlorofluoroethylene film DF0050-C1. (51 μm) (manufactured by Daikin Industries, Ltd.) is purchased and used.
PET: Polyethylene terephthalate film. Polyester film E5001 (250 μm, untreated) (manufactured by Toyobo Co., Ltd.) was purchased and used.

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

Each description regarding “peeling appearance” means the following state.
Interfacial peeling; peeling occurred between the adhesive layer and the fluororesin film (interface).
-Adhesive layer cohesive failure: peeling occurred inside the adhesive layer and a part of the adhesive remained on the film.
-PP rupture: The adhesive strength is very strong and does not peel off, but breaks at the center of the specimen.
-PCTFE pull-side edge break; adhesive strength is very strong and does not peel off, but breaks at the base of the specimen.
-PCTFE rupture; the adhesive strength is very strong and does not peel off, but breaks at the center of the specimen.

From the results shown in Table 2, according to the present invention (Examples 1 to 12), the adhesive strength is improved by mixing the polyethylene resin, the ethylene-butene 1 copolymer, the styrene elastomer, and the epoxidized polybutadiene. I was able to confirm.
In Comparative Example 1 in which PE was used alone, not only the fluorine-based resin but also polypropylene was not adhered, so that the peel strength was very low.
In Comparative Example 2 in which only epoxidized polybutadiene was blended with PE, the peel strength was higher than that of Comparative Example 1 alone, and the peel strength between PCTFE / PET was relatively high. The peel strength and peel appearance were not better than 1-12.
In Comparative Example 3 in which no styrenic elastomer was added, Laminate 3 having the same upper and lower deposition materials showed a peel strength equal to or greater than that of Examples 1 to 12, but Laminates 1 and 2 having different upper and lower deposition materials. 4, the peel strength was lower than in Examples 1-12.
Similarly, in Comparative Example 4 and Comparative Example 5 in which no styrene-based elastomer was added, the laminates 1 and 2 had high peel strength and showed values close to those of Examples 1 to 12, but Comparative Example 4 Then, the peel strength in the laminates 3 and 4 was low, and in Comparative Example 5, the peel strength in the laminate 4 was low, which did not reach Examples 1-12.
In Comparative Example 6 in which no epoxidized polybutadiene was added, the peel strength of the laminate 4 was very high, but in the laminates 1 to 3, the peel strength did not reach that of Examples 1 to 12.

  1: Laminated body, 11: Fluorine resin, 10: Adhesive layer, 12: Resin film, 21: Tensile direction, 20, 22: Gripping tool

Claims (10)

  An adhesive resin composition comprising at least a polyethylene resin (A) containing a butene-containing ethylene polymer, a styrene elastomer (B) and an epoxidized polybutadiene (C).   The adhesive property according to claim 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). Resin composition. The polyethylene-based resin (A2) (provided that ethylene - excluding those falling under 1 copolymer butene (A1)) density of, 0.900 g / cm ³ or more 0.930 g / cm ³ or less of the polyethylene resin The adhesive resin composition according to claim 2.   The polyethylene resin (A) content is 50 parts by mass or more and 80 parts by mass or less, the styrene elastomer (B) content is 20 parts by mass or more and 50 parts by mass or less, and the polyethylene resin (A) and The content of the epoxidized polybutadiene (C) with respect to 100 parts by mass of the total amount of the styrene-based elastomer (B) is 0.1 part by mass or more and 0.9 part by mass or less. The adhesive resin composition according to item.   The content of the ethylene-butene 1 copolymer (A1) is 3 to 22 parts by mass, the content of the polyethylene resin (A2) is 32 to 72 parts by mass, the styrene elastomer (B The content of the epoxidized polybutadiene (C) with respect to a total amount of 100 parts by mass of 20 parts by mass or more and 50 parts by mass or less is 0.1 parts by mass or more and 0.9 parts by mass or less. Or the adhesive resin composition of 3.   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 adhesive resin composition as described.   The adhesion according to any one of claims 1 to 6, wherein 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. Resin composition.   A film for adhering a fluorine-based resin having a single layer structure, which is formed from the adhesive resin composition according to any one of claims 1 to 7.   The laminated body which has a layer formed from the adhesive resin composition of any one of Claims 1-7. It is a manufacturing method of the laminated body of Claim 9, Comprising: The manufacturing method of any one laminated body of following (1)-(3).
(1) A step in which a layer formed from the adhesive resin composition is melt-extruded to obtain a fluororesin adhesive film having a single layer structure, and a film is laminated on both sides of the fluororesin adhesive film and thermocompression bonded The manufacturing method of a laminated body which has a process which makes it let it obtain a laminated body.
(2) A step in which a layer formed from the adhesive resin composition is melt-extruded onto a film serving as a base material to obtain a laminate of a base material / adhesive layer, and a laminated material is further used as a base material / adhesive. The manufacturing method of a laminated body which has the process of making it laminate | stack so that it may become a layer / combination material, and thermocompression-bonding, and obtaining a laminated body.
(3) A method for producing a laminate, which includes a step of simultaneously melt-extruding a resin as a raw material for a substrate and the adhesive resin composition.

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