JP7404750B2 - laminate - Google Patents

Description

The present invention relates to a laminate.

Molded bodies made of fiber-reinforced composite materials are used in a wide range of applications, such as transportation equipment (vehicles (automobiles, railway cars, etc.), aircraft, etc.), building components, electronic devices, and the like. Accordingly, it is desired that complex shapes such as uneven shapes and deep drawing shapes can be applied to molding materials for manufacturing molded bodies made of fiber reinforced composite materials. However, there are various problems when applying a complex shape to a molding material.
For example, a molded body is produced by placing a molding material made of prepreg, which is a reinforced fiber sheet made of long-fiber reinforcing fibers impregnated with a thermosetting resin, between a pair of molds having a complex shape. It is manufactured by press-molding the material while heating it and curing the thermosetting resin.
However, because the reinforcing fiber sheet in the prepreg has difficulty following the shape of the mold, in the resulting molded product, the reinforcing fibers may be disordered at the corners of the complex shape, or the matrix resin, which does not have reinforcing fibers, may Accumulation may occur. As a result, the mechanical strength of the molded body may be insufficient at the corner portions. Furthermore, depending on the use, sufficient flame retardancy and chemical resistance are required.

Patent Document 1 describes a molding material that has excellent flame retardancy and chemical resistance and can produce a molded article that can be applied to a complicated shape, and includes at least one prepreg layer containing a reinforcing fiber sheet and a resin matrix; a laminate having at least one polymer layer containing a fluorine-containing polymer, wherein there is at least one interface where the prepreg layer and the polymer layer are in contact, and the surface of the polymer layer at the interface A laminate characterized by the presence of an adhesive functional group is described.

International Publication No. 2017/030190

The laminate described in Patent Document 1 has excellent flame retardancy and chemical resistance, and can be manufactured into a molded product to which a complicated shape can be applied, but there is still room for further improvement in interlayer adhesion.

An object of the present invention is to provide a laminate that has excellent adhesion between layers, has excellent flame retardancy and chemical resistance, and can produce a molded product that can be molded into a complicated shape.

The above problem is solved by the following configuration.
[1] A laminate having a thermoplastic elastomer layer and a polymer layer containing a fluoropolymer,
The thermoplastic elastomer layer and the polymer layer are laminated so as to be in contact with each other,
A laminate characterized in that an adhesive functional group is present on the surface of the polymer layer on the side that is in contact with the thermoplastic elastomer layer.
[2] Furthermore, it has a prepreg layer containing a fiber sheet and a resin matrix,
The laminate according to [1], wherein the prepreg layer is laminated so as to be in contact with a surface of the thermoplastic elastomer layer on a side opposite to the side in contact with the polymer layer.
[3] The laminate according to [2], wherein the resin matrix contains an uncured thermosetting resin or a thermoplastic resin.
[4] The laminate according to any one of [1] to [3], wherein the polymer layer is a film containing a fluoropolymer.
[5] The polymer layer according to any one of [1] to [4], wherein the polymer layer is a film containing a fluoropolymer and subjected to corona treatment on the surface of the film in contact with the thermoplastic elastomer. laminate.
[6] The adhesive functional group of [1] to [5], wherein the adhesive functional group is at least one selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group. The laminate according to any one of the above.
[7] The thermoplastic elastomer layer is made of a styrene thermoplastic elastomer, a vinyl chloride thermoplastic elastomer, an olefin thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer, a nitrile thermoplastic elastomer, or a polyamide thermoplastic elastomer. The laminate according to any one of [1] to [6], comprising at least one selected from the group consisting of a plastic elastomer, a chlorinated polyethylene, and a 1,2-polybutadiene thermoplastic elastomer.
[8] The laminate according to any one of [1] to [7], wherein the fluoropolymer has a melting point of 100 to 325°C.
[9] The laminate according to any one of [1] to [8], wherein the fluoropolymer has an oxygen index of 27 or more according to JIS K 7201-2:2007.
[10] Any one of [1] to [9], wherein the peel strength between the polymer layer and the thermoplastic elastomer layer is 10 N/cm or more, and the mode of failure is material failure of the polymer layer. 1. The laminate according to item 1.

According to the present invention, it is possible to provide a laminate that has excellent adhesion between layers, has excellent flame retardancy and chemical resistance, and can produce a molded product that can be molded into a complicated shape.

FIG. 1 is a cross-sectional view showing a first embodiment of the laminate of the present invention. FIG. 3 is a cross-sectional view showing a second embodiment of the laminate of the present invention. It is a sectional view showing a third embodiment of a laminate of the present invention. It is a sectional view showing a fourth embodiment of a laminate of the present invention. It is a sectional view showing a fifth embodiment of a laminate of the present invention. It is a sectional view showing a 6th embodiment of the layered product of the present invention. FIG. 3 is a cross-sectional view showing some steps in the method for manufacturing a molded body of the present invention.

The meanings of the following terms in this specification are as follows.
"Melting point" means the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC). In this specification, a differential scanning calorimeter (DSC device, manufactured by Seiko Instruments Inc.) was used to record the melting peak when the polymer was heated at a rate of 10°C/min, and the temperature corresponding to the maximum value ( ℃) is the melting point.
"Melt-formable" means exhibiting melt flowability.
"Showing melt flowability" means that there exists a temperature at which the melt flow rate is 0.1 to 1000 g/10 minutes at a temperature 20°C or more higher than the melting point of the resin under a load of 49N. .
"Melt flow rate" means melt mass flow rate (MFR) defined in JIS K 7210:1999 (ISO 1133:1997). In this specification, the melt flow rate is the mass of polymer flowing out in 10 minutes from a nozzle with a diameter of 2 mm and a length of 8 mm under specific temperature and load conditions using a melt indexer (manufactured by Techno Seven). (g) is determined by measuring.
"Film" and "sheet" refer to a relatively thin planar object as a "film" and a relatively thick planar object as a "sheet." However, their thickness is not limited, and the "film" may be a planar body with a thickness that can be called a sheet, and the "sheet" is a planar body with a thickness that can be called a film. It may be.
"Acid anhydride group" means a group represented by -C(=O)-OC(=O)-.
"Unit" means a part derived from a monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by processing the polymer.

Hereinafter, a mode for carrying out the present invention will be described, but the present invention is not limited to the embodiments described below, and various modifications can be made without departing from the gist of the present invention.

[Laminated body]
<First embodiment>
A first embodiment of the laminate of the present invention is a laminate 101 having a polymer layer 1 containing a fluoropolymer and a first thermoplastic elastomer layer 2, as shown in FIG.

In the laminate 101 shown in FIG. 1, the polymer layer 1 and the first thermoplastic elastomer layer 2 are laminated so as to be in contact with each other, and the side of the polymer layer 1 that is in contact with the first thermoplastic elastomer layer 2 A first adhesive functional group is present on the surface 1b.
Below, the polymer layer 1 and the first thermoplastic elastomer layer 2 will be explained in detail.

《Polymer layer 1》
The polymer layer 1 is a layer containing a fluoropolymer.
In the laminate 101 of this embodiment, the first adhesive functional group is present on the surface 1b of the polymer layer 1 on the side that is in contact with the first thermoplastic elastomer layer 2. Therefore, the peel strength between the polymer layer 1 and the first thermoplastic elastomer layer 2 is further improved.

The polymer layer 1 is preferably composed of a film containing the fluoropolymer (hereinafter sometimes referred to as "fluoropolymer film").
The polymer layer 1 may have a single-layer structure consisting of one of the above-mentioned fluoropolymer films, or may have a laminated structure consisting of two or more fluoropolymer films.

The lower limit of the thickness of the polymer layer 1 is usually 1 μm, preferably 5 μm, and more preferably 10 μm. Moreover, the upper limit of the thickness of the polymer layer 1 is usually 1000 μm, preferably 500 μm, and more preferably 300 μm. Furthermore, the thickness range of the polymer layer 1 is usually 1 to 1000 μm, preferably 5 to 500 μm, and more preferably 10 to 300 μm.
When the thickness of the polymer layer 1 is within this range, the flame retardance and chemical resistance of the molded product obtained by molding the laminate 101 will be better, and the moldability of the laminate 101 will be better. .

When the polymer layer 1 is composed of a fluoropolymer film, the thickness of the fluoropolymer film as a whole may be equal to or less than the thickness of the polymer layer 1, and is usually within the range of 1 to 1000 μm. The thickness is preferably 10 to 500 μm, more preferably 10 to 200 μm.

The fluoropolymer film is preferably produced by molding a molding material containing a melt-moldable fluoropolymer into a film shape by a known molding method (extrusion molding method, inflation molding method, etc.). .

(First adhesive functional group and second adhesive functional group)
The first adhesive functional group is an adhesive functional group imparted by surface treatment of the surface 1b of the polymer layer 1 in contact with the first thermoplastic elastomer layer 2, and an adhesive possessed by the fluoropolymer described later. Contains either one or both of the functional groups. Here, the adhesive functional group that the fluoropolymer has is not one introduced into the fluoropolymer by the surface treatment, but an adhesive functional group (hereinafter referred to as "secondary adhesive functional group") that the fluoropolymer itself has. ).

Examples of the surface treatment include corona discharge treatment, plasma treatment (excluding corona discharge treatment), plasma graft polymerization treatment, and wet etching treatment using metallic sodium. Among these surface treatments, the first thermoplastic property of the polymer layer 1 has the advantage that it does not use auxiliary materials such as chemicals, does not require additional processes such as cleaning, and can efficiently introduce adhesive functional groups to the surface. Corona discharge treatment, plasma treatment, or plasma graft polymerization treatment is preferred from the viewpoint of a high effect of improving the adhesion of the surface 1b in contact with the elastomer layer 2, and the surface 1b of the polymer layer 1 in contact with the first thermoplastic elastomer layer 2 is preferably subjected to a corona discharge treatment, a plasma treatment, or a plasma graft polymerization treatment. Plasma treatment or plasma graft polymerization treatment is more preferred since it has a higher effect of improving the adhesion of the side surface 1b.

As the surface treatment, plasma treatment is preferable since a large amount of adhesive functional groups can be introduced. Further, when introducing a carbonyl group-containing group to the surface 1b of the polymer layer 1 on the side that is in contact with the first thermoplastic elastomer layer 2, plasma treatment is preferable as the surface treatment. In plasma treatment, by setting the environment during discharge to be in the presence of oxygen, oxygen radicals or ozone are generated, and the surface of the polymer layer 1 in contact with the first thermoplastic elastomer layer 2 is efficiently A carbonyl group-containing group can be introduced into 1b.

As the plasma processing apparatus, a known processing system can be applied. As known treatment systems, those employing a capacitively coupled electrode system, a corona discharge electrode-plasma jet system, etc. have been proposed. In the capacitively coupled electrode method, at least one of a pair of electrodes is covered with a dielectric plate, and plasma is formed by applying a high voltage such as a pulse between the electrodes filled with a rare gas or the like. The surface of the film is treated by passing the film conveyed on a roll through the plasma. The film passes near one electrode or near the center between the electrodes, and basically both sides of the film are processed. The configuration of this type of system has been known for a relatively long time, and has been applied to surface treatments of various resin films. Note that since the distance between the electrodes needs to be several cm or less, it is difficult to process three-dimensional objects or large objects, but it is possible to process relatively large areas with objects shaped like films.

Normally, when plasma treatment is applied to the surface of a workpiece made of resin, polymer, glass, metal, etc., the surface of the workpiece made of these materials often becomes significantly hydrophilic and its adhesion improves. . The reason is as follows.
Due to the action of high-energy electrons (about 1 to 10 eV) generated by atmospheric pressure plasma discharge, the main chains and side chains of the bonds in the surface material (in the case of metals, the oxide layer or oil film on the surface) dissociate and become radicals. In addition, molecules of atmospheric gases such as air and moisture also dissociate and become radicals. Hydrophilic functional groups such as hydroxy groups, carbonyl groups, and carboxy groups are formed on the surface of the object to be treated by the recombination reaction between these two types of radicals. As a result, the free energy of the surface of the object to be treated increases, making it easier to adhere and bond it to other surfaces.

As a surface treatment that can introduce a wide variety of adhesive functional groups, including basic functional groups such as amide groups and amino groups, to the surface 1b of the polymer layer 1 on the side that is in contact with the first thermoplastic elastomer layer 2. In this method, a monomer having an adhesive functional group and an unsaturated double bond to be introduced is present in a plasma treatment system, and the first thermoplastic elastomer layer of the polymer layer 1 is further treated by high-energy ray irradiation. A surface treatment is known in which radical species generated on the surface 1b in contact with 2 are used as a trigger to initiate polymerization, and the monomers are graft-polymerized.
As the surface treatment using graft polymerization, plasma graft polymerization treatment is preferable because the combination of plasma treatment and graft polymerization allows a wider control range of the amount and type of adhesive functional groups introduced.
Examples of monomers used in plasma graft polymerization include acrylic acid, methacrylic acid, acrylamide, allylamine, and glycidyl methacrylate. By surface-treating the material using the monomer, adhesive functional groups such as carboxyl groups, amide groups, amino groups, and epoxy groups are added to the surface 1b of the polymer layer 1 in contact with the thermoplastic elastomer layer 2. It is possible to introduce

The second adhesive functional group is an adhesive functional group of a fluoropolymer having an adhesive functional group.
Details of the fluoropolymer having adhesive functional groups will be described later.

(Fluorine-containing polymer)
The fluoropolymer may be a fluoropolymer that has an adhesive functional group or a fluoropolymer that does not have an adhesive functional group.

The adhesive functional group in the fluoropolymer having an adhesive functional group is, for example, a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, or an isocyanate group. These adhesive functional groups may be used alone or in combination of two or more.

From the viewpoint of adhesiveness at the interface between the polymer layer 1 and the first thermoplastic elastomer layer 2, the adhesive functional group is either a terminal group of the main chain or a pendant group of the main chain of the fluoropolymer. Preferably present as one or both.
The adhesive functional group is preferably a carbonyl group-containing group from the viewpoint of adhesiveness at the interface.
The carbonyl group-containing group is, for example, a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, or an acid anhydride group.

The hydrocarbon group in the group having a carbonyl group between the carbon atoms of the hydrocarbon group is preferably an alkylene group having 2 to 8 carbon atoms. Here, the number of carbon atoms in the alkylene group is the number of carbon atoms not including carbon atoms in the carbonyl group. When the alkylene group has 3 or more carbon atoms, it may be linear or branched.
The haloformyl group is represented by -C(=O)-X (where X is a halogen atom). The halogen atom is preferably one or two selected from fluorine atoms and chlorine atoms, and more preferably fluorine atoms. That is, the haloformyl group is preferably a fluoroformyl group (also referred to as a "carbonyl fluoride group").
The alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 8 carbon atoms, and more preferably a methoxy group or an ethoxy group. When the alkoxy group has 3 or more carbon atoms, it may be linear or branched.

The content of the adhesive functional group in the fluoropolymer is preferably 10 to 60,000, more preferably 100 to 50,000, based on 1×10 ⁶ carbon atoms in the main chain of the fluoropolymer. The number is more preferably 100 to 10,000, and even more preferably 300 to 5,000.
When the content of the adhesive functional group is within the above range, the adhesiveness at the interface is more excellent.

The content of the adhesive functional group can be measured by nuclear magnetic resonance (NMR) analysis or infrared absorption spectrum analysis. For example, as described in JP-A No. 2007-314720, the proportion (mol%) of units having an adhesive functional group in all units constituting a fluoropolymer is determined by infrared absorption spectroscopy. From the ratio, the content of adhesive functional groups in the fluoropolymer can be calculated.

The fluoropolymer can be either a fluoropolymer that has a melting point or a fluoropolymer that does not have a melting point. The fluoropolymer having a melting point includes a fluoropolymer having a melting point but not within a specific range.

The fluorine-containing polymer contained in the polymer layer 1 is preferably a fluorine-containing polymer having the above melting point.
When the fluoropolymer has a melting point, the melting point is preferably 100 to 325°C, more preferably 105 to 260°C, even more preferably 110 to 220°C, and even more preferably 120 to 200°C.
When the melting point is within this range, the molded product obtained by molding the laminate 101 of the first embodiment has excellent adhesiveness at the interface between the polymer layer 1 and the first thermoplastic elastomer layer 2. , and the molded product has excellent heat resistance.

The melting point of the fluoropolymer can be adjusted by adjusting the type and proportion of units constituting the fluoropolymer, the molecular weight of the fluoropolymer, and the like. For example, the melting point tends to increase as the proportion of the unit (u1) described later increases.

As the fluoropolymer, a fluoropolymer that can be melt-molded is preferred from the viewpoint of easy production of a film.
As the fluoropolymer that can be melt-molded, any known fluoropolymer that can be melt-molded can be used.

Among the fluorine-containing polymers that can be melt-molded, those that do not have adhesive functional groups include, for example, tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), ethylene/tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), and ethylene/chlorotrifluoroethylene copolymer (ECTFE).
In these fluoropolymers, adhesive functional groups can be efficiently introduced by surface treatment of the surface 1b of the polymer layer 1. Therefore, ETFE, which is a fluoropolymer having a hydrogen atom bonded to a carbon atom, PVDF and the like are preferred.

Among the fluorine-containing polymers that can be melt-molded, those having adhesive functional groups (hereinafter sometimes simply referred to as "fluorine-containing polymers having adhesive functional groups") have adhesive functional groups. Examples include the above-mentioned fluoropolymers having one or both of a unit and an end group having an adhesive functional group. Examples of such fluoropolymers are PFA having an adhesive functional group, FEP having an adhesive functional group, and ETFE having an adhesive functional group.

The fluoropolymer in the polymer layer 1 is preferably a fluoropolymer having the adhesive functional group described above. By using the fluorine-containing polymer having the adhesive functional group, the adhesive strength between the polymer layer 1 and the first thermoplastic elastomer layer 2 can be further increased.

The fluorine-containing polymer having an adhesive functional group is prepared by adding a chain transfer agent or a polymerization initiator that copolymerizes the monomer having an adhesive functional group and brings about an adhesive functional group during monomer polymerization. It can be produced by a method such as polymerizing a monomer using a monomer. In particular, it is preferable to copolymerize a monomer having an adhesive functional group to produce a copolymer having the monomer unit to obtain a fluorine-containing polymer having an adhesive functional group. These methods can also be used in combination.

The monomer having an adhesive functional group is preferably a monomer having a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, or an isocyanate group. As the carbonyl group-containing group, acid anhydride groups and carboxy groups are preferred. Specifically, monomers having a carboxy group such as maleic acid, itaconic acid, citraconic acid, and undecylenic acid, itaconic anhydride (hereinafter also referred to as "IAH"), and citraconic anhydride (hereinafter also referred to as "CAH") ), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter also referred to as "NAH"), monomers having an acid anhydride group such as maleic anhydride, hydroxyalkyl vinyl ether, epoxyalkyl vinyl ether, etc. can be mentioned.

The chain transfer agent that provides the adhesive functional group is preferably a chain transfer agent having a carboxy group, an ester bond, a hydroxyl group, or the like. Specific examples include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol, and the like.

As the polymerization initiator that provides the adhesive functional group, peroxide-based polymerization initiators such as peroxycarbonate, diacyl peroxide, and peroxyester are preferred. Specific examples include di-n-propylperoxydicarbonate, diisopropylperoxycarbonate, tert-butylperoxyisopropyl carbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, etc. .

As a fluorine-containing polymer having an adhesive functional group derived from a monomer, a fluorine-containing polymer having superior adhesiveness between the surface 1b of the polymer layer 1 and the surface 2a of the first thermoplastic elastomer layer 2 is used. , the following fluoropolymer A is particularly preferred.
Fluorine-containing polymer A: a cyclic hydrocarbon monomer having a unit derived from tetrafluoroethylene (hereinafter also referred to as "TFE") or chlorotrifluoroethylene (hereinafter also referred to as "CTFE") and an acid anhydride group. A fluorine-containing polymer having a unit derived from an acid anhydride monomer (hereinafter also referred to as an "acid anhydride monomer") and a unit derived from a fluorine-containing monomer (excluding TFE and CTFE). Combined.
In addition, hereinafter, a unit derived from TFE or CTFE will be referred to as "unit (u1)", a unit derived from an acid anhydride monomer will be referred to as "unit (u2)", and a unit derived from the above fluorine-containing monomer will be referred to as "unit (u2)". Also written as "unit (u3)".

The acid anhydride monomers are, for example, IAH, CAH, NAH, and maleic anhydride. The acid anhydride monomer is preferably at least one selected from the group consisting of IAH, CAH, and NAH, and more preferably at least one selected from IAH and NAH. The acid anhydride monomers may be used alone or in combination of two or more.
When at least one selected from the group consisting of IAH, CAH, and NAH is used as the acid anhydride monomer, a special polymerization method required when using maleic anhydride (Japanese Patent Application Laid-Open No. 11-193312) The fluoropolymer A having an acid anhydride group can be easily produced without using any of the following. Further, when at least one selected from IAH and NAH is used as the acid anhydride monomer, the adhesiveness at the interface is further improved.

In the fluoropolymer A, a part of the acid anhydride group in the unit (u2) is hydrolyzed, and as a result, dicarboxylic acids (itaconic acid, citraconic acid, 5-norbornene) corresponding to the acid anhydride monomer are hydrolyzed. -2,3-dicarboxylic acid, maleic acid, etc.) units may be included. When the dicarboxylic acid unit is included, the content of the carboxylic acid unit is included in the content of the unit (u2).

When producing the fluoropolymer A, the concentration of the acid anhydride monomer during polymerization is preferably 0.01 to 5 mol%, and 0.05 to 3 mol% based on the total monomers. More preferably, 0.1 to 2 mol% is even more preferable. When the concentration of the acid anhydride monomer is within this range, the polymerization rate will be moderate.
As the acid anhydride monomer is consumed in polymerization, the consumed amount is continuously or intermittently fed into the polymerization tank to maintain the concentration of the acid anhydride monomer within the range. It is preferable to do so.

The fluorine-containing monomer constituting the unit (u3) is preferably a fluorine-containing compound having one polymerizable carbon-carbon double bond, such as fluoroolefins (vinyl fluoride, vinylidene fluoride, trifluoroethylene, Hexafluoropropylene (hereinafter also referred to as "HFP"), hexafluoroisobutylene, etc. (excluding TFE), CF ₂ = CFOR ^f1 (However, R ^f1 has 1 to 10 carbon atoms and an oxygen atom between carbon atoms. ) (hereinafter also referred to as "PAVE ^" ), CF ₂ ⁼ CFOR ^f2 SO ₂ (X ¹ is a halogen atom or _a hydroxyl group), ^CF ₂ =CFOR ^f3 CO ² (X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), CF ₂ =CF(CF ₂ ) _p OCF=CF ₂ (where p is 1 or 2) ), CH ₂ =CX ³ (CF ₂ ) _q X ⁴ (wherein, X ³ is a hydrogen atom or a fluorine atom, q is an integer from 2 to 10, and X ⁴ is a hydrogen atom or a fluorine atom. ) (hereinafter also referred to as "FAE"), fluorine-containing monomers having a ring structure (perfluoro(2,2-dimethyl-1,3-dioxole), 2,2,4-trifluoro-5-trifluoro methoxy-1,3-dioxole, perfluoro(2-methylene-4-methyl-1,3-dioxolane), etc.).

As the fluorine-containing monomer, at least one selected from the group consisting of HFP, PAVE, and FAE is preferable from the viewpoint of excellent moldability of the fluoropolymer A, bending resistance of the polymer layer, etc., and FAE and HFP are preferred. Either one or both of these are more preferred.

Examples _of PAVE _{are CF2 = CFOCF2CF3} , _{CF2 = CFOCF2CF2CF3} , _CF2 = _{CFOCF2CF2CF2CF3 ,} and _CF2 =CFO( _{CF2 ) 8F} . The PAVE is preferably CF ₂ =CFOCF ₂ CF ₂ CF ₃ (hereinafter also referred to as "PPVE").

Examples of FAE are _CH2 =CF( _CF2 ) _2F , _CH2 =CF( _CF2 ) _3F , _CH2 =CF( _CF2 ) _4F , _CH2 =CF( _CF2 ) _5F , CH ₂ =CF( _CF2 ) _8F , _CH2 =CF( _CF2 )2H, _CH2 =CF( _CF2 ) _3H , _CH2 =CF( _{CF2 ) 4H} , _CH2 =CF( _CF2) ) _5H , _CH2 =CF( _CF2 ) _8H , _CH2 =CH( _CF2 ) _2F , _CH2 =CH( _CF2 ) _3F , _CH2 =CH( _CF2 ) _4F , _CH2 =CH( _CF2 ) _5F , _CH2 =CH( _CF2 ) _6F , _CH2 =CH( _CF2 ) _8F , _CH2 =CH( _CF2 ) _2H , _CH2 =CH( _CF2 ) _3H , _CH2 =CH( _CF2 ) _4H , _CH2 =CH( _CF2 ) _5H , and _CH2 =CH( _CF2 ) _8H . The FAE ^is preferably _{CH 2 = CH (CF 2 ) q1 2} =CH( _CF2 ) _3F , _CH2 =CH( _CF2 ) _4F , _CH2 =CF( _CF2 ) _3H , _CH2 =CF( _CF2 ) _4H are more preferable, and _CH2 =CH (CF ₂ ) ₄ F (hereinafter also referred to as “PFBE”) and CH ₂ =CH(CF ₂ ) ₂ F (hereinafter also referred to as “PFEE”) are more preferred.

In addition to the units (u1) to (u3), the fluoropolymer A contains units derived from non-fluorine monomers (excluding acid anhydride monomers) (hereinafter referred to as units (u4)). ) may also be included.
The non-fluorine monomer is preferably a non-fluorine compound having one polymerizable carbon-carbon double bond, such as olefins (ethylene, propylene, 1-butene, etc.), vinyl esters (vinyl acetate, etc.), etc. Can be mentioned.
The non-fluorine monomers may be used alone or in combination of two or more.
As the non-fluorine monomer, ethylene, propylene, and 1-butene are preferable, and ethylene is particularly preferable, from the viewpoint of excellent mechanical strength of the fluororesin layer.

Preferred specific examples of the fluoropolymer A are TFE/NAH/PPVE copolymer, TFE/IAH/PPVE copolymer, TFE/CAH/PPVE copolymer, TFE/IAH/HFP copolymer, TFE/CAH /HFP copolymer, TFE/IAH/PFBE/ethylene copolymer, TFE/CAH/PFBE/ethylene copolymer, TFE/IAH/PFEE/ethylene copolymer, TFE/CAH/PFEE/ethylene copolymer, and TFE/IAH/HFP/PFBE/ethylene copolymer.

When the fluorine-containing copolymer A is a copolymer having ethylene units, the preferred ratio of each unit to the total amount of the unit (u1), the unit (u2), the unit (u3), and the unit (u4) is as follows. That's right.
The proportion of the unit (u1) is preferably 25 to 80 mol%, more preferably 40 to 65 mol%, even more preferably 45 to 63 mol%.
The proportion of units (u2) is preferably 0.01 to 5 mol%, more preferably 0.03 to 3 mol%, even more preferably 0.05 to 1 mol%.
The proportion of the unit (u3) is preferably 0.2 to 20 mol%, more preferably 0.5 to 15 mol%, and even more preferably 1 to 12 mol%.
The proportion of the unit (u4) is preferably 20 to 75 mol%, more preferably 35 to 50 mol%, even more preferably 37 to 55 mol%.

In the fluorine-containing copolymer A having ethylene units, if the ratio of each unit is within the above range, the flame retardance, chemical resistance, etc. of the polymer layer will be further excellent.
If the proportion of the units (u2) is within the above range, the amount of acid anhydride groups in the fluoropolymer A will be appropriate, and the adhesiveness at the interface between the polymer layer 1 and the thermoplastic elastomer layer 2 will be further improved. Excellent.
When the proportion of the units (u3) is within the above range, the moldability of the fluoropolymer A, the bending resistance of the polymer layer, etc. are further excellent.
The proportion of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the fluoropolymer A.

The fluoropolymer has a melt flow rate of 0.1 to 1000 g/10 min at a temperature 20° C. or more higher than the melting point of the fluoropolymer under a load of 21N. preferable.

The melt flow rate of the fluoropolymer under the conditions of 235° C. and a load of 21 N is preferably 0.5 to 100 g/10 minutes, more preferably 1 to 50 g/10 minutes, and even more preferably 2 to 30 g/10 minutes. . When the melt flow rate is at least the lower limit of the range, the fluoropolymer has excellent moldability, and the film containing the fluoropolymer has excellent surface smoothness and appearance. If the melt flow rate is below the upper limit of the range, the film containing the fluoropolymer will have excellent mechanical strength.

The fluorine-containing polymer having no melting point is a fluorine-containing elastomer containing a unit based on at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, and chlorotrifluoroethylene. Can be mentioned. Specific examples of the fluorine-containing elastomer include the tetrafluoroethylene/propylene copolymer described in JP-A-05-78539, etc., and the vinylidene fluoride/hexafluoropropylene described in JP-A-11-124482, etc. copolymers, vinylidene fluoride/hexafluoropropylene/tetrafluoroethylene copolymers, etc., and units based on tetrafluoroethylene and perfluoro(methyl vinyl ether) described in JP-A No. 2006-089720, etc. It is a fluorine-containing polymer.

Examples of the fluoropolymer that does not have the above-mentioned melting point or the fluoropolymer that has a melting point outside the above-mentioned range include a tetrafluoroethylene homopolymer, a modified tetrafluoroethylene polymer, and the like.

The oxygen index (OI) of the fluoropolymer according to JIS K 7201-2:2007 is preferably 27 or more. The oxygen index (OI) is an index of the minimum oxygen concentration (volume %) necessary for the fluoropolymer to sustain combustion, and the larger the index, the higher the flame retardancy. .

The film of the fluoropolymer is preferably a film obtained by molding a molding material containing a melt-formable fluoropolymer into a film.
The constituent material of the film may further contain a resin other than the fluoropolymer and additives within a range that does not impair the effects of the present invention.
The content of the fluoropolymer in the constituent materials of the film is preferably 50% by mass or more, more preferably 80% by mass or more, based on the total constituent materials of the film. The upper limit of the content of the fluoropolymer is usually 100% by mass.

(Method for producing fluoropolymer)
The fluoropolymer can be produced by a conventionally known production method. When producing a fluoropolymer by polymerizing monomers, a polymerization method using a radical polymerization initiator is preferred as the polymerization method.
Polymerization methods include bulk polymerization, solution polymerization using organic solvents (fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols, hydrocarbons, etc.), and aqueous media and appropriate organic solvents as necessary. Examples include a suspension polymerization method using an aqueous medium and an emulsion polymerization method using an aqueous medium and an emulsifier, and a solution polymerization method is preferred.

As the radical polymerization initiator, an initiator whose half-life is 10 hours and a temperature of 0 to 100°C is preferable, and an initiator whose temperature is 20 to 90°C is more preferable.
Examples of radical polymerization initiators include azo compounds (azobisisobutyronitrile, etc.), non-fluorinated diacyl peroxides (isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, etc.), peroxydicarbonates (diisopropyl peroxide, etc.) carbonate, etc.), peroxyesters (tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, etc.), fluorine-containing diacylperoxides ((Z(CF ₂ ) _r COO) ₂ (However, Z hydrogen atom, fluorine atom or chlorine atom, and r is an integer from 1 to 10), inorganic peroxides (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), etc. It will be done.

During polymerization of monomers, a chain transfer agent may be used to control the melt viscosity of the fluoropolymer.
Examples of chain transfer agents include alcohols (methanol, ethanol, etc.), chlorofluorohydrocarbons (1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, etc.) ), hydrocarbons (pentane, hexane, cyclohexane, etc.).

Examples of organic solvents used in the solution polymerization method include perfluorocarbons, hydrofluorocarbons, chlorohydrofluorocarbons, hydrofluoroethers, and the like. The number of carbon atoms is preferably 4 to 12.
Specific examples of perfluorocarbons include perfluorocyclobutane, perfluoropentane, perfluorohexane, perfluorocyclopentane, perfluorocyclohexane, and the like.
Specific examples of hydrofluorocarbons include 1-hydroperfluorohexane and the like.
Specific examples of chlorohydrofluorocarbons include 1,3-dichloro-1,1,2,2,3-pentafluoropropane.
Specific examples of hydrofluoroether include methyl perfluorobutyl ether, 2,2,2-trifluoroethyl 2,2,1,1-tetrafluoroethyl ether, and the like.

The polymerization temperature is preferably 0 to 100°C, more preferably 20 to 90°C.
The polymerization pressure is preferably 0.1 to 10 MPa [gage], more preferably 0.5 to 3 MPa [gage].
The polymerization time is preferably 1 to 30 hours.

The polymer layer is not limited to a polymer layer made of a fluoropolymer film, and the constituent materials of the polymer layer may include additives, resins other than the fluoropolymer, etc., in addition to the fluoropolymer, to the extent that the effects of the present invention are not impaired. May include.
Examples of resins other than fluoropolymers include polyester, polyolefin, styrene resin, urethane resin, polyoxymethylene, polyamide, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polyphenylene sulfide, polyphenylene ether, modified polyphenylene ether, and polyimide. , polyamideimide, polyetherimide, polysulfone, modified polysulfone, polyethersulfone, polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyarylate, polyethernitrile, phenolic resin, phenoxy resin, etc. .

As the additive, inorganic fillers are preferred.
The inorganic fillers include silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, Aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, Examples include glass beads, silica balloons, carbon black, carbon nanotubes, carbon nanohorns, graphite, carbon fibers, glass balloons, carbon balloons, wood flour, and zinc borate.
The inorganic fillers may be used alone or in combination of two or more.

The inorganic filler may be porous or non-porous.
The inorganic filler may be surface-treated with a surface-treating agent such as a silane coupling agent or a titanate coupling agent in order to improve dispersibility in the resin.

<<First thermoplastic elastomer layer 2>>
The first thermoplastic elastomer layer 2 is a layer containing a first thermoplastic elastomer.
Since the laminate of the present invention includes the first thermoplastic elastomer layer 2, the interlayer peel strength is further improved.

The first thermoplastic elastomer layer 2 is preferably composed of a film containing the first thermoplastic elastomer (hereinafter sometimes referred to as "thermoplastic elastomer film").
The first thermoplastic elastomer layer 2 may have a single layer structure consisting of one thermoplastic elastomer film, or may have a laminated structure consisting of two or more films.

The lower limit of the thickness of the first thermoplastic elastomer layer 2 is usually 1 μm, preferably 5 μm, and more preferably 10 μm. Moreover, the upper limit of the thickness of the first thermoplastic elastomer layer 2 is usually 1000 μm, preferably 500 μm, and more preferably 300 μm. Further, the thickness of the first thermoplastic elastomer layer 2 is generally 1 to 1000 μm, preferably 5 to 500 μm, and more preferably 10 to 300 μm.
When the thickness of the first thermoplastic elastomer layer is 1 μm or more, it is possible to form a film by a conventionally known method, and when it is 5 μm or more, film formation is stable. Moreover, when the thickness of the first thermoplastic elastomer layer 2 is 1000 μm or less, it can be wound up by a conventionally known method, and when it is 300 μm or less, stable winding is possible.

When the first thermoplastic elastomer layer 2 is composed of a thermoplastic elastomer film, the thickness of the thermoplastic elastomer film as a whole may be equal to or less than the thickness of the first thermoplastic elastomer layer 2, and usually , 1 to 1000 μm_, preferably 5 to 500 μm, and more preferably 10 to 300 μm.

The thermoplastic elastomer film can be formed by molding a molding material containing the first thermoplastic elastomer into a film shape by a known molding method (extrusion molding method, inflation molding method, etc.), or by molding the molding material containing the first thermoplastic elastomer into the polymer layer 1. It is preferable to manufacture by molding a molding material containing the first thermoplastic elastomer into a film shape.

The first thermoplastic elastomer is a styrene thermoplastic elastomer, a vinyl chloride thermoplastic elastomer, an olefin thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer, a nitrile thermoplastic elastomer, or a polyamide thermoplastic elastomer. At least one selected from the group consisting of elastomers, chlorinated polyethylene, and 1,2-polybutadiene thermoplastic elastomers is preferred, and polyurethane thermoplastic elastomers are particularly preferred. The first thermoplastic elastomer may be used alone or in combination of two or more.
When a polyurethane thermoplastic elastomer is used as the first thermoplastic elastomer, the adhesive strength between each layer of the laminate of the present invention can be particularly increased.

The first thermoplastic elastomer layer 2 may contain components other than the first thermoplastic elastomer as long as the effects of the present invention are not impaired.
Such components other than the first thermoplastic elastomer include additives, polymers other than the first thermoplastic elastomer (hereinafter sometimes referred to as "other polymers"), and the like.
The content of the first thermoplastic elastomer in the first thermoplastic elastomer layer is preferably 50% by mass or more, more preferably 80% by mass or more, and 90% by mass or more of the total mass of the first thermoplastic elastomer layer. More preferably, it is % by mass or more. The upper limit of the content of the first thermoplastic elastomer in the first thermoplastic elastomer layer is usually 100% by mass.
When the first thermoplastic elastomer layer has a laminated structure consisting of two or more sublayers, the first thermoplastic elastomer contained in each adjacent sublayer may be of the same type or different types. .

Examples of the additives include inorganic fillers. As the inorganic filler, those mentioned above can be used.

The other polymer is preferably a thermoplastic resin other than the first thermoplastic elastomer. Examples of such thermoplastic resins are polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide MXD6 (semi-aromatic polyamide). , polyethylene, polypropylene, polyvinyl acetate, poly(ethylene/vinyl acetate), polyvinyl alcohol, poly(ethylene/vinyl alcohol), polystyrene, polyvinylidene chloride, polyacrylonitrile, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyamide imides, polyetherimides, polysulfones and polyarylates.

"Mechanism of action"
Since the laminate 101 of this embodiment has the polymer layer 1 containing a fluoropolymer, a molded article with excellent flame retardancy and chemical resistance can be manufactured. Further, in the laminate 101 having the polymer layer 1 containing a melt-moldable fluorine-containing polymer, the moldability is improved as in the case of a laminate in which conventional thermoplastic resin sheets are arranged. Therefore, by using the laminate 101 of this embodiment, a molded body that can be molded into a complicated shape can be manufactured. Furthermore, in the laminate 101 of the present embodiment, by having the first adhesive functional group on the surface 1b of the polymer layer 1 that is in contact with the first thermoplastic elastomer layer 2, the polymer layer 1 has a first adhesive functional group. Adhesion at the interface between layer 1 and first thermoplastic elastomer layer 2 is improved.

<Second embodiment>
The second embodiment of the laminate of the present invention, as shown in FIG. This is a laminate 201 having a prepreg layer 3.

In the laminate 201 shown in FIG. 2, the polymer layer 1 and the first thermoplastic elastomer layer 2 are laminated so as to be in contact with each other. The first prepreg layer 3 is laminated so as to be in contact with the surface 2b of the first thermoplastic elastomer layer 2 on the side opposite to the side that is in contact with the polymer layer 1. A first adhesive functional group is present on the surface 1b of the polymer layer 1 on the side that is in contact with the first thermoplastic elastomer layer 2.

The polymer layer 1 and the first thermoplastic elastomer layer 2 of the laminate 201 of this embodiment are the same as the polymer layer 1 and the first thermoplastic elastomer layer 2 of the laminate 101 of the first embodiment, respectively. Therefore, the explanation will be omitted.
Below, the first thermoplastic elastomer layer 3 will be explained in detail.

《First prepreg layer 3》
The first prepreg layer 3 is a layer made of first prepreg.
The laminate 201 of this embodiment has improved mechanical strength by having the first prepreg layer 3.

The first prepreg layer 3 may have a single layer structure consisting of one prepreg sheet containing a fiber sheet and a resin matrix, or may have a laminated structure consisting of two or more prepreg sheets.

The lower limit of the thickness of each first prepreg layer 3 is usually 10 to 50 μm, preferably 20 to 40 μm. Further, the upper limit of the thickness of the first prepreg layer 3 is usually 200 to 600 μm, more preferably 300 to 550 μm. Furthermore, the thickness range of the first prepreg layer 3 is preferably 10 to 600 μm, more preferably 20 to 550 μm.

The fiber sheet includes, for example, a fiber bundle made of a plurality of fibers, a cloth made by weaving the fiber bundles, a unidirectional fiber bundle in which a plurality of fibers are aligned in one direction, and the unidirectional fiber bundle. unidirectional cloth, a combination of these, or a stack of multiple fiber bundles.
The fibers are preferably continuous long fibers with a length of 10 mm or more. However, the fibers do not need to be continuous over the entire length in the length direction or the entire width in the width direction of the fiber sheet, and may be separated along the way.

The fibers are, for example, inorganic fibers, metal fibers, or organic fibers.
Examples of the inorganic fibers are carbon fibers, graphite fibers, glass fibers, silicon carbide fibers, silicon nitride fibers, alumina fibers, silicon carbide fibers and boron fibers.
Examples of the metal fibers are aluminum fibers, brass fibers and stainless steel fibers.
Examples of the organic fibers are aromatic polyamide fibers, polyaramid fibers, polyparaphenylenebenzoxazole (PBO) fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers and polyethylene fibers.

The fibers may or may not be surface-treated.
The above-mentioned fibers may be used alone or in combination of two or more.
The fibers are preferably carbon fibers because they have a low specific gravity, high strength, and high elastic modulus.

The resin constituting the resin matrix (hereinafter sometimes referred to as "matrix resin") is one or both of a curable resin (such as a thermosetting resin or a photocurable resin) and a thermoplastic resin.
The matrix resin is preferably a curable resin from the viewpoint of adhesiveness with the thermoplastic elastomer layer, and particularly preferably a thermosetting resin from the viewpoint of productivity of the molded article.

The thermosetting resin includes a crosslinkable resin and a thermal polymerization initiator.
Examples of said crosslinkable resins are epoxy resins, unsaturated polyester resins, vinyl ester resins, phenolic resins, urea-melamine resins, polyimides, bismaleimide resins and cyanate ester resins.
The crosslinkable resin contained in the curable resin is preferably at least one selected from the group consisting of these crosslinkable resins. The crosslinkable resins may be used alone or in combination of two or more.
The thermal polymerization initiator can be selected from conventionally known thermal polymerization initiators depending on the curing conditions.
The thermal polymerization initiators may be used alone or in combination of two or more.
Furthermore, the thermosetting resin may further contain resins other than the crosslinkable resin, additives, etc. within a range that does not impair the effects of the present invention.

The photocurable resin includes a crosslinkable resin and a photopolymerization initiator.
Examples of the crosslinked resin include vinyl ester resin, unsaturated polyester resin, epoxy resin, spiroorthocarbonate resin, oxetane resin, and the like.
The crosslinkable resin contained in the photocurable resin is preferably at least one selected from the group consisting of these crosslinkable resins. The crosslinkable resins may be used alone or in combination of two or more.
The photopolymerization initiator can be selected from conventionally known photopolymerization initiators depending on the curing conditions.
The photopolymerization initiators may be used alone or in combination of two or more.
Further, the photocurable resin may further contain other resins, additives, etc. within a range that does not impair the effects of the present invention.

Examples of the thermoplastic resins are crystalline resins, amorphous resins and thermoplastic elastomers.
Examples of the crystalline resin include polyester resins (polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester, etc.), polyolefin resins (polyethylene (PE), polypropylene (PP), polybutylene, acid-modified polyethylene (m-PE), acid-modified polypropylene (m-PP), acid-modified polybutylene, etc.), polyoxymethylene (POM), polyamide (PA), polyarylene sulfide Resins (polyphenylene sulfide (PPS), etc.), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyethernitrile (PEN), and liquid crystal polymer (LCP) It is.
Examples of the amorphous resin include styrene resins (polystyrene (PS), acrylonitrile styrene (AS), acrylonitrile butadiene styrene (ABS), etc.), polycarbonate (PC), polymethyl methacrylate (PMMA), and polyvinyl chloride (PVC). ), unmodified or modified polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR) and phenoxy resins It is.
Examples of the thermoplastic elastomer are polystyrene elastomer, polyolefin elastomer, polyurethane elastomer, polyester elastomer, polyamide elastomer, polybutadiene elastomer, polyisoprene elastomer, and acrylonitrile elastomer.

The thermoplastic resin may be a fluoropolymer, but preferably a thermoplastic resin other than a fluoropolymer. Further, the thermoplastic resin may be a blend resin of a thermoplastic resin other than a fluoropolymer and a fluoropolymer. In this case, the proportion of the fluoropolymer in the blend resin is preferably less than 50% by mass, more preferably less than 20% by mass.

The thermoplastic resin is preferably at least one selected from the group consisting of these thermoplastic resins. The thermoplastic resins may be used alone or in combination of two or more.
Further, the thermoplastic resin may further contain other resins, additives, etc. within a range that does not impair the effects of the present invention.

"Mechanism of action"
Since the laminate 201 of this embodiment has the polymer layer 1 containing a fluoropolymer, it is possible to produce a molded article with excellent flame retardancy and chemical resistance. Further, in the laminate 201 having the polymer layer 1 containing a melt-moldable fluorine-containing polymer, the moldability is improved as in the case of a laminate in which conventional thermoplastic resin sheets are arranged. Therefore, by using the laminate 201 of this embodiment, a molded body that can be molded into a complicated shape can be manufactured. Furthermore, in the laminate 201 of this embodiment, by having the first adhesive functional group on the surface 1b of the polymer layer 1 that is in contact with the first thermoplastic elastomer layer 2, the polymer layer 1 has a first adhesive functional group. Adhesion at the interface between layer 1 and first thermoplastic elastomer layer 2 is improved.
Furthermore, since the laminate 201 of this embodiment includes the first prepreg layer 3 in addition to the polymer layer 1 and the first thermoplastic elastomer layer 2, the mechanical strength of the molded product is significantly improved. improves.

<Third embodiment>
The third embodiment of the present invention is a modification of the second embodiment described above, and as shown in FIG. This is a laminate 202 that further includes a membrane layer 4.

The polymer layer 1, first thermoplastic elastomer layer 2, and prepreg layer 3 are as described above.
The coating layer 4 is laminated so as to be in contact with the surface 2b of the polymer layer 1 on the side opposite to the side that is in contact with the first thermoplastic elastomer layer 2.

The surface 1c of the polymer layer 1 facing the coating layer 4 is provided with a first adhesive functionality, similar to the surface 1b of the polymer layer 1 facing the first thermoplastic elastomer layer 2. A group exists. Here, the first adhesive functional group present on the surface 1c of the polymer layer 1 facing the coating layer 4 and the first adhesive functional group present on the surface 1c of the polymer layer 1 facing the first thermoplastic elastomer layer 2 The first adhesive functional groups present on the surface 1b may be of the same type or different types.
The first adhesive functional group present on the surface 1c of the polymer layer 1 facing the coating layer 4 is an adhesive functional group introduced by surface treatment and an adhesive functional group possessed by the fluoropolymer. Either or both.

《Coating film layer 4》
The coating layer 4 is a layer obtained by applying a paint to the surface 1c of the polymer layer 1 on the side opposite to the side in contact with the first thermoplastic elastomer layer 2.
Since the first adhesive functional group is also present on the surface 1b of the polymer layer 1 opposite to the side in contact with the first thermoplastic elastomer layer 2, the bond between the coating layer 4 and the polymer layer 1 is The adhesive strength of the interface is improved compared to the case where the first adhesive functional group is not present.

The paint forming the coating layer usually contains a resin, a pigment, and a solvent.
The resin is preferably a fluororesin, a polyester resin, an acrylic resin, or the like, since the resin itself has high weather resistance and has excellent adhesion to the fluororesin film body.
Examples of the pigment include inorganic pigments, organic pigments, extender pigments, and the like.
Examples of the inorganic pigments include titanium oxide, carbon black, Bengara, iron black, and ultramarine. Examples include zinc white, yellow lead, chrome vermilion, cobalt blue, fired green, zinc sulfide, bronze powder, aluminum powder, pearl pigment, and the like.
The organic pigments include unnecessary azos, azo lakes, quinacridone red, carmine red, watching red, perylene red, anthraquinone, disazo orange, dinitroaniline orange, acetotron orange, disazo yellow, Hansa yellow, acetotron yellow, Examples include chlorinated phthalocyanine, phthalocyanine, industhrene blue, dioxazine violet, methyl violet, fluorescent pigments, and luminescent pigments.
Examples of the extender pigment include precipitated barium sulfate, calcium carbonate, alumina white, and clay.
Examples of the solvent include alcohols, ketones, esters, ethers, aromatic hydrocarbons, and the like.

Examples of methods for applying the paint include brushing, spray coating, and the like. The coating layer formed by these methods is preferably dried at 60 to 150°C for 2 to 30 seconds for the purpose of removing the solvent and for adhesion and curing with the fluororesin polymer.
Further, coating and drying may be carried out not only indoors but also outdoors, but it is also possible to achieve adhesion and hardening by evaporating the solvent in an atmosphere without particularly heating.

<Fourth embodiment>
The fourth embodiment of the present invention is a modification of the second embodiment described above, and as shown in FIG. 4, in addition to the polymer layer 1, first thermoplastic elastomer layer 2, and prepreg layer 3, This is a laminate 203 that further includes a second thermoplastic elastomer layer 2' and a second prepreg layer 3'.
The polymer layer 1, first thermoplastic elastomer layer 2, and prepreg layer 3 are as described above.
The second thermoplastic elastomer layer 2' is a layer similar to the first thermoplastic elastomer layer 2. The second thermoplastic elastomer layer 2' may differ from the first thermoplastic elastomer layer 2 without departing from the ranges described for the first thermoplastic elastomer layer 2.
The second prepreg layer is a layer similar to the first prepreg layer 3. The second prepreg layer 3' may differ from the first prepreg layer 3 without departing from the ranges described for the first prepreg layer 3.

Similarly to the surface 1b of the polymer layer 1 on the side facing the first thermoplastic elastomer layer 2, the surface 1d of the polymer layer 1 in contact with the second thermoplastic elastomer layer 2' has a One adhesive functional group is present. Here, the first adhesive functional group present on the surface 1d of the polymer layer 1 in contact with the second thermoplastic elastomer layer 2' and the first thermoplastic elastomer layer 2 of the polymer layer 1 The first adhesive functional group present on the surface 1b on the side opposite to the first adhesive functional group may be the same type of adhesive functional group or may be a different type of adhesive functional group.
The first adhesive functional group present on the surface 1d of the polymer layer 1 in contact with the second thermoplastic elastomer layer 2' is the adhesive functional group introduced by surface treatment and the fluorine-containing polymer. or both adhesive functional groups.

<Fifth embodiment>
The fifth embodiment of the present invention is a modification of the second embodiment described above, and as shown in FIG. It is 204.
Printing 5 is applied to a portion of the surface 1b of the polymer layer 1 on the side that is in contact with the first thermoplastic elastomer layer 2.

Furthermore, in the fourth embodiment described above, printing 5 may be applied to a part of the surface 1d of the polymer layer 1 on the side that is in contact with the second thermoplastic elastomer layer 2'.

《Printing 5》
The printing 5 is formed by printing a part of the surface 1b of the polymer layer 1 on the side that is in contact with the thermoplastic elastomer layer 2 by a conventionally known method. The area of the printing 5 is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less of the area of the surface 1b of the polymer layer 1 in contact with the first thermoplastic elastomer layer 2. The smaller the printed area, the better the peel strength between the first thermoplastic elastomer layer 2 and the polymer layer 1.
Further, a portion of the surface 1d of the polymer layer 1 on the side that is in contact with the second thermoplastic elastomer layer 2' may be printed. The area of the printing 5 is preferably 90% or less, more preferably 70% or less, even more preferably 50% or less of the area of the surface 1d of the polymer layer 1 in contact with the second thermoplastic elastomer layer 2'. The smaller the printed area, the better the peel strength between the second thermoplastic elastomer layer 2' and the polymer layer 1.

Materials used for printing typically include resins, pigments, and solvents.
The resin is preferably a fluororesin, a polyester resin, an acrylic resin, or the like, since the resin itself has high weather resistance and has excellent adhesion to the fluororesin film body.
Examples of the pigment include inorganic pigments, organic pigments, extender pigments, and the like.
Examples of the inorganic pigments include titanium oxide, carbon black, Bengara, iron black, ultramarine blue, zinc white, yellow lead, chrome vermilion, cobalt blue, fired green, zinc sulfide, bronze powder, aluminum powder, pearl pigment, etc. It will be done.
The organic pigments include unnecessary azos, azo lakes, quinacridone red, carmine red, watching red, perylene red anthraquinone, disazo orange, dinitroaniline orange, acetotron orange, disazo yellow, Hansa yellow, acetotron yellow, and chlorine. Examples include phthalocyanine, phthalocyanine, industhrene blue, dioxazine violet, methyl violet, fluorescent pigments, and luminescent pigments.
Examples of the extender pigment include precipitated barium sulfate, calcium carbonate, alumina white, and clay.
Examples of the solvent include alcohols, ketones, esters, ethers, aromatic hydrocarbons, and the like.

Examples of printing methods include gravure printing, screen printing, and inkjet printing.
Prints formed by these methods are preferably dried at 60 to 150° C. for 2 to 30 seconds in order to remove the solvent and improve adhesion to the polymer 1.

<Sixth embodiment>
The sixth embodiment of the present invention is a modification of the second embodiment described above, and as shown in FIG. 6, in addition to the polymer layer 1, the first thermoplastic elastomer layer 2, and the prepreg layer 3, The laminate 205 further includes a layer 6.
The clear coat layer 6 is laminated so as to be in contact with the surface 1e of the polymer layer 1 on the side opposite to the surface 1b on the side that is in contact with the first thermoplastic elastomer layer 2.
Printing 5 is applied to a portion of the surface 1e of the polymer layer 1 on the side that is in contact with the clear coat layer 6.

The surface 1e of the polymer layer 1 on the side in contact with the clear coat layer 6 has a first adhesive functional group, similar to the surface 1b of the polymer layer 1 on the side facing the first thermoplastic elastomer layer 2. exists. Here, the first adhesive functional group present on the surface 1e of the polymer layer 1 in contact with the clear coat layer 6 and the surface of the polymer layer 1 on the side facing the first thermoplastic elastomer layer 2 The first adhesive functional group present in 1b may be the same type of adhesive functional group or may be a different type of adhesive functional group.
The first adhesive functional group present on the surface 1e of the polymer layer 1 in contact with the clear coat layer 6 is an adhesive functional group introduced by surface treatment and an adhesive functional group possessed by the fluorine-containing polymer. Either or both.

《Printing 5》
The printing 5 is formed by printing on a part of the surface 1e of the polymer layer 1 on the side that is in contact with the clear coat layer 6 by a conventionally known method. The area of the printing 5 is preferably 90% or less, more preferably 70% or less, and even more preferably 50% or less of the area of the surface 1e of the polymer layer 1 in contact with the clear coat layer 6. The smaller the printed area, the better the peel strength between the clear coat layer 6 and the polymer layer 1.
The printing materials and method are the same as in the fifth embodiment described above.

《Clear coat layer 6》
The clear coat layer 6 is formed by applying a conventionally known clear paint to the surface 1e of the polymer layer 1 on the side opposite to the side in contact with the first thermoplastic elastomer layer 2.
Since the purpose of the coating is primarily to protect the underlying layer from deterioration, it is desirable that the coating be pigment-free and highly transparent.

The material used for the clear coat layer 6 usually includes a resin, a solvent, and an additive.
The resin is preferably a fluororesin, a polyester resin, an acrylic resin, or the like, since the resin itself has high weather resistance and has excellent adhesion to the fluororesin film body.
Examples of the solvent include alcohols, ketones, esters, ethers, aromatic hydrocarbons, and the like.
Examples of the additives include antioxidants, photooxidants, surfactants, water-soluble polymers, gelling agents, thickeners, antifoaming agents, and the like.
Examples of the photooxidant include hindered amine light stabilizers (HALS) (manufactured by ADEKA, ADEKA STAB LA series) that capture radicals generated by photooxidation.
When the clear coat layer contains an antioxidant or a photooxidant, it is possible to suppress not only ultraviolet deterioration of the organic pigment in the printing layer but also oxidation prevention.

Examples of clear coating methods include direct gravure coating, direct gravure reverse coating, micro gravure coating, comma coating, die coating, and spin coating.
The clear coat layer formed by these methods is preferably dried at 60 to 150° C. for 2 to 30 seconds in order to remove the solvent and improve adhesion to the polymer layer 1.

<Seventh embodiment>
The seventh embodiment of the present invention is a modification of the second embodiment described above, and in the laminate 201 shown in FIG. 2, the polymer layer 1 contains an ultraviolet absorber.
As the ultraviolet absorber, a conventionally known ultraviolet absorber can be used. Further, the content of the ultraviolet absorber in the polymer layer 1 can be appropriately set as long as it does not impede the effects of the present invention.
In the laminate 201 of this embodiment, since the polymer layer 1 contains the ultraviolet absorber, deterioration of the first thermoplastic elastomer layer 2 and the first prepreg layer due to ultraviolet rays can be suppressed.

<Eighth embodiment>
The eighth embodiment of the present invention is a modification of the second embodiment described above, and in the laminate 201 shown in FIG. 2, the polymer layer 1 contains a pigment.
As the pigment, a conventionally known pigment can be used. Further, the content of the pigment in the polymer layer 1 can be appropriately set as long as it does not impede the effects of the present invention.
In the laminate 201 of this embodiment, the polymer layer 1 can be colored by containing the pigment. Further, by using a pigment that functions as an ultraviolet scattering material, it is possible to suppress deterioration of the first thermoplastic elastomer layer 2 and the first prepreg layer due to ultraviolet rays.

<Ninth embodiment>
The ninth embodiment of the present invention is a modification of the second embodiment described above, and in the laminate 201 shown in FIG. The opposite surface has irregularities.
The irregularities on the surface 1a of the polymer layer 1 on the side opposite to the side in contact with the first thermoplastic elastomer layer 2 are usually provided during molding of the fluoropolymer film. Specifically, the unevenness can be imparted by using a roll having unevenness as a roll during molding of the fluoropolymer film.
In the laminate 201 of this embodiment, since the surface 1a of the polymer layer 1 has irregularities, the surface of the laminate becomes matte and the design is improved.

[Molded object]
The molded article of the present invention is characterized in that the laminate of the present invention is molded while being heated.
FIG. 7 is a cross-sectional view showing an example of the method for manufacturing a molded article of the present invention.
As shown in the first row of FIG. 7, the laminate 10, which has been produced in advance at a place other than the mold or which has been produced on the lower mold 34, is placed between the upper mold 32 and the lower mold 34 so as to be in contact with the lower mold 34. It is placed between a pair of molds 30 consisting of a lower mold 34.
Next, as shown in the second stage of FIG. 7, the laminate 10 is preheated while being sandwiched between the upper mold 32 and the lower mold 34.
Next, as shown in the third row of FIG. 7, the upper mold 32 and the lower mold 34 are clamped together, and the laminate 10 is pressure-molded while being heated to form a shape that follows the shape of the mold. A molded body 20 having the following is obtained.

A pair of molds 30 consisting of an upper mold 32 and a lower mold 34 are used to mold the laminate into a molded body having a desired shape. Since the laminate of the present invention can be molded into a complicated shape, a mold having a complicated shape can be used in the method for manufacturing a molded product of the present invention.
Examples of the mold having a complicated shape include a mold having an uneven shape, a deep drawing shape, and the like. The corner portions of the uneven shape and the deep drawn shape are preferably rounded portions having a predetermined radius of curvature. The radius of curvature of the R portion is preferably 0.1 to 10 mm, more preferably 1 to 6 mm, and even more preferably 2 to 5 mm, from the viewpoint of suppressing disorder of the reinforcing fibers and improving the appearance of the molded product.
Examples of the material for the mold include steel, and ultra-high alloys with high wear resistance are preferred. The mold may be subjected to surface treatment (surface nitriding treatment, etc.) from the viewpoint of wear resistance.

The preheating temperature may be, for example, the same temperature as the mold clamping temperature described later. The preheating temperature and the mold clamping temperature are the temperatures of the surface of the mold that is in contact with the laminate.
The preheating time is, for example, the time required for the heat of the mold to be sufficiently transmitted to the polymer layer of the laminate to soften it appropriately.

The temperature during mold clamping is preferably less than 400°C, preferably 100°C or more and 300°C or less, and more preferably 100°C or more and 220°C or less. If the temperature at the time of mold clamping is equal to or higher than the lower limit of the above range, the resulting molded product will have excellent heat resistance. If the temperature during mold clamping is below the upper limit of the above range, a general-purpose molding device can be used to produce the molded product, and if the resin matrix is a thermosetting resin, the polymer layer in the molded product Excellent adhesion at the interface between the fiber-reinforced resin layer and the fiber-reinforced resin layer.

When a fluoropolymer with a relatively low melting point is used and the resin matrix is a thermosetting resin, even if the temperature when molding the laminate is low, the polymer layer and thermoplastic elastomer layer in the molded product, and excellent adhesion at the interface between the thermoplastic elastomer layer and the fiber-reinforced resin layer. Therefore, when the melting point of the fluoropolymer is 120°C or more and 220°C or less, the temperature during mold clamping is preferably less than 220°C, and the melting point of the fluoropolymer is 120°C or more and 200°C or less. In this case, the temperature during mold clamping is more preferably lower than the melting point of the fluoropolymer.

Even if the temperature during mold clamping is lower than the melting point of the fluoropolymer when the melting point of the fluoropolymer is 120°C or higher and 200°C or lower, the thermoplastic elastomer layer and fiber reinforced resin layer, and the thermoplastic elastomer layer and A molded article having a peel strength of 10 N/cm or more with respect to the combined layer is obtained.

The pressure during mold clamping is preferably 10 MPa or less, more preferably 6 MPa or less, and even more preferably 3 MPa or less, from the viewpoint of suppressing disorder of reinforcing fibers and improving the appearance of the molded product. The pressure during mold clamping is preferably 0.01 MPa or more, more preferably 0.1 MPa or more, and still more preferably 0.5 MPa or more, from the viewpoint of making the laminate follow the shape of the mold and not leaving air bubbles in the molded product. preferable.

From the viewpoint of productivity, the mold clamping time is preferably 30 minutes or less, more preferably 15 minutes or less, and even more preferably 10 minutes or less. When the resin matrix is a thermosetting resin, the mold clamping time is preferably 5 minutes or more, more preferably 7 minutes or more, and even more preferably 10 minutes or more, from the viewpoint of curability of the thermosetting resin.

(Mechanism of action)
In the method for producing a molded article of the present invention described above, since the laminate of the present invention is used, it is possible to manufacture a molded article that has excellent flame retardancy and chemical resistance, and can be formed into a complex shape. . Moreover, since the obtained molded article contains a fluoropolymer, it has characteristics (water repellency, weather resistance, etc.) derived from the fluoropolymer.

(Application)
Examples of uses of the molded body include the following.
Electrical/electronic equipment (PCs, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (personal digital assistants such as electronic notebooks), video cameras, digital still cameras, (optical equipment, audio equipment, air conditioners, lighting equipment, entertainment supplies, toys, other home appliances, etc.) housings, internal parts (trays, chassis, etc.), internal parts cases, battery pack housings, mechanical parts, etc.
Building materials (panels), etc.
Automobile and motorcycle related parts, materials and outer panels: motor parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light wheels, suspension parts, various valves (exhaust gas valves, etc.), fuel-related, exhaust systems or intake systems. Pipes, air intake nozzles snorkels, intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine cooling water joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, cooling water sensors , oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, Turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, battery trays, AT brackets, Headlamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, spare tire cover, seat shell , solenoid bobbin, engine oil filter, ignition case, undercover, scuff plate, pillar trim, propeller shaft, wheel, fender, fascia, bumper, bumper beam, bonnet, aero parts, platform, cowl louver, roof, instrument panel, Spoilers, various modules, etc.
Aircraft-related parts, materials and skins: landing gear pods, winglets, spoilers, edges, rudders, elevators, faillings, ribs, etc.
Others: windmill blades, etc.
The molded product is particularly preferably used for aircraft parts, windmill blades, automobile outer panels, and housings, trays, and chassis of electronic devices.
Moreover, the molded body is particularly preferably used for the housing of a battery pack.

Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the examples described below, and various modifications can be made without changing the gist of the present invention. Among Examples 1 to 7, Examples 1 to 4 correspond to Examples, and Examples 5 to 7 correspond to Comparative Examples.

[Preparation of fluoropolymer and production of fluoropolymer film]
The abbreviations and their meanings are explained below.
Abbreviation Meaning TFE Unit based on tetrafluoroethylene PFBE Unit based on perfluorobutyl ethylene PFEE Unit based on perfluoroethyl ethylene E Unit based on ethylene IAH Unit based on itaconic acid

<Fluorine-containing polymer (1)>
A fluoropolymer having no adhesive functional group was purchased and used.
The units and proportions (molar ratio) constituting the fluoropolymer (1) were TFE/PFBE/E=60/1.4/40.
The melting point of the fluoropolymer (1) was 260°C, and the melt flow rate under a load of 49N was 10 to 13 g/10 minutes.

<Fluorine-containing polymer (2)>
A fluoropolymer having adhesive functional groups was synthesized and used.
Synthesis was performed in the same manner as in Example 1 of International Publication No. 2015/182702 to obtain a fluoropolymer (2).
The units (monomers) and proportions (molar ratio) constituting the fluoropolymer (2) are tetrafluoroethylene/itaconic anhydride/perfluoroethylethylene/ethylene = 58.5/0.1/2.4/39. Met.
The melting point of the fluoropolymer (2) was 245°C, and the melt flow rate under a load of 49N was 22 g/10 minutes.
The content of adhesive functional groups in the fluoropolymer (2) was 3000 per 1×10 ⁶ carbon atoms in the main chain.

<Fluoropolymer film (1)>
The purchased fluoropolymer (1) was extrusion-molded using a 30 mm diameter single screw extruder having a 750 mm width coat hanger die at a die temperature of 300 degrees to produce a film having a thickness of 25 μm.

<Fluoropolymer film (2)>
The synthesized fluoropolymer (2) was extruded using a 30 mm diameter single screw extruder having a 750 mm width coat hanger die at a die temperature of 300 degrees to produce a film with a thickness of 25 μm.

<Fluoropolymer film (3)>
Corona discharge treatment was performed on both sides of the fluoropolymer film (1) at a treatment density of 150 W·min/m ² in air.
The surface tension of the surface subjected to corona discharge treatment was 0.054 N/m.

<Fluoropolymer film (4)>
Corona discharge treatment was performed on both sides of the fluoropolymer film (2) at a treatment density of 150 W·min/m ² in air.
The surface tension of the surface subjected to corona discharge treatment was 90 N/m.

[Production of TPE sheet]
A thermoplastic polyurethane elastomer (Elastlan (registered trademark) S80A10 (pellet form, no lubricant), manufactured by BASF) was extruded at a die temperature of 300 degrees using a 30 mmφ single screw extruder equipped with a 750 mm width coat hanger die. A film having a thickness of 30 μm was prepared.

[Example 1]
Fluoropolymer film (3), TPE sheet, prepreg (pyrofil prepreg TR3110 381GMX, manufactured by Mitsubishi Chemical Corporation: thickness, 223 μm; reinforcing fiber, carbon fiber fabric (cloth); resin matrix, thermosetting resin) were stacked and heated using a heat press device (manufactured by Tester Sangyo Co., Ltd.) under conditions of a press temperature of 180° C., a press time of 10 minutes, and a surface pressure of 4.8 MPa to obtain a molded body.

(Peeling test)
The obtained molded body was cut into a size of 100 mm in length and 10 mm in width to prepare a test piece.
The polymer layer and the thermoplastic elastomer layer were peeled off to a position 50 mm from one end of the test piece in the length direction. Next, using a tensile testing machine (manufactured by Orientech Co., Ltd.), the test piece was peeled 180 degrees at a tensile speed of 50 mm/min with the center located 50 mm from one end in the length direction, and the maximum load was determined as the peel strength (N /cm). A higher peel strength indicates better adhesion between the polymer layer and the thermoplastic elastomer layer.
The material failure means A=destruction of the thermoplastic elastomer layer, D=not the destruction of the thermoplastic elastomer layer but peeling at the interface.
Table 1 shows the results of the peel test of the molded body.

[Examples 2 to 4]
A molded article was prepared in the same manner as in Example 1, except that the polymer layer and the base material were changed as shown in Table 1, and a peel test was conducted.
Note that the base material "aluminum" in Examples 3 and 4 indicates that aluminum foil (thickness: 200 μm) was used as the base material instead of prepreg.
Table 1 shows the results of the peel test of the molded body.

[Examples 5-7]
A molded article was prepared in the same manner as in Example 1 except that the thermoplastic elastomer layer was not used, the polymer layer and the base material were as shown in Table 1, and a peel test was conducted.
Table 1 shows the results of the peel test of the molded body.

[Explanation of results]
The molded bodies of Examples 1 to 4, which correspond to Examples, had a peel strength of 10 N/cm or more between the polymer layer and the thermoplastic elastomer layer, and had excellent adhesion.
On the other hand, the molded bodies of Examples 5 to 7, which correspond to comparative examples, had a peel strength of less than 10 N/cm between the polymer layer and the prepreg layer, and had poor adhesion.

The laminate of the present invention is useful as a material for molding members constituting transportation equipment (vehicles (automobiles, railway cars, etc.), aircraft, etc.), architecture, electrical/electronic equipment, etc.

10, 101, 201, 202, 203, 204, 205, 206 Laminate 1 Polymer layer 1a, 1b, 1c, 1d, 1e, 2a, 2b, 2'a, 2'b Surface 2 First thermoplastic elastomer Layer 2' Second thermoplastic elastomer layer 3 First prepreg layer 3' Second prepreg layer 4 Coating layer 5 Printing 6 Clear coat layer 20 Molded object 30 Mold 32 Upper mold 34 Lower mold

Claims (8)

A laminate,
a thermoplastic elastomer layer;
a polymer layer containing a fluorine-containing polymer ;
a prepreg layer including a fiber sheet and a resin matrix;
has
The thermoplastic elastomer layer and the polymer layer are laminated so as to be in contact with each other,
The prepreg layer is laminated so as to be in contact with the surface of the thermoplastic elastomer layer on the side opposite to the side in contact with the polymer layer,
an adhesive functional group is present on the surface of the polymer layer in contact with the thermoplastic elastomer layer ;
A laminate, wherein the resin matrix includes a thermosetting resin . The laminate according to claim 1 , wherein the resin matrix includes an uncured thermosetting resin . The laminate according to claim 1 or 2 , wherein the polymer layer is a film containing a fluoropolymer. The laminate according to any one of claims 1 to 3 , wherein the polymer layer is a film containing a fluoropolymer, the surface of which is in contact with the thermoplastic elastomer layer subjected to corona treatment. According to any one of claims 1 to 4 , the adhesive functional group is at least one selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group. The described laminate. The thermoplastic elastomer layer is a styrene-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a nitrile-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, The laminate according to any one of claims 1 to 5 , comprising at least one member selected from the group consisting of chlorinated polyethylene and 1,2-polybutadiene thermoplastic elastomer. The laminate according to any one of claims 1 to 6 , wherein the fluoropolymer has a melting point of 100 to 325°C. The laminate according to any one of claims 1 to 7 , wherein the fluoropolymer has an oxygen index of 27 or more according to JIS K 7201-2:2007.

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