JP2016049764A - Fluororesin laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluororesin laminate which is excellent in adhesiveness between a layer composed mainly of a fluorine-containing copolymer and a layer composed mainly of a non-fluororesin and has suppressed foaming of a laminate caused by heat applied during molding.SOLUTION: There is provided a fluororesin laminate which is obtained by laminating a layer (I) mainly composed of a fluorine-containing copolymer (1) having a melting point of 220°C or less and a layer mainly composed of a thermoplastic non-fluoroelastomer or a thermoplastic non-fluororesin (2) having a melting point of 260°C or less.SELECTED DRAWING: None

Description

  The present invention relates to a fluororesin laminate and a method for producing the same.

As represented by tetrafluoroethylene polymer, the fluorine-containing resin is excellent in properties such as heat resistance, flame retardancy, chemical resistance, weather resistance, non-adhesiveness, low friction and low dielectric properties. Therefore, fluorine-containing resins are widely used for chemical plant corrosion-resistant piping materials, agricultural greenhouse materials, release coating materials for kitchen appliances, electronic devices, and coating materials for heat-resistant and flame-retardant wires.
Among these, an ethylene / tetrafluoroethylene copolymer (hereinafter, also referred to as “ETFE”) is particularly useful because it has particularly excellent characteristics and can be melt-molded.

Fluorine-containing resins have lower mechanical strength than other resins, and require raw material costs. Therefore, the fluorine-containing resin is a laminate in which non-fluororesin is laminated with inexpensive and high mechanical strength compared to the fluorine-containing resin for the purpose of increasing the mechanical strength while enjoying the characteristics and obtaining an inexpensive molded product. Sometimes it is said.
However, in general, the fluorine-containing resin has poor adhesion to such a non-fluorine resin. In particular, since a fluororesin has poor adhesion to a non-fluorinated resin having a low molding temperature zone, a laminate of the fluororesin and the non-fluorinated resin is difficult to use.

In recent years, a fluororesin laminate having improved adhesion between a fluororesin and a non-fluororesin has been developed.
For example, Patent Document 1 discloses that a fluorine-containing copolymer is provided by providing an epoxy group-containing ethylene copolymer layer between a specific fluorine-containing copolymer layer and a polyolefin resin layer. A fluororesin laminate in which the adhesion between the layer and the layer made of polyolefin resin or the like is improved is disclosed.

JP 2006-297843 A

However, the melting point of the fluorine-containing copolymer used in the examples of Patent Document 1 is as high as 240 ° C., and the set temperature of the die is as high as 320 ° C. In such a case, if the residence time in the die becomes long, the thermal decomposition of the resin component tends to proceed, so that foaming is likely to occur in the obtained fluororesin laminate, and the molding process range becomes narrow.
Therefore, the present invention is excellent in adhesiveness between a layer containing a fluorine-containing copolymer as a main component and a layer containing a non-fluorine resin as a main component, and foaming of the laminate due to heat applied during molding processing is possible. It aims at providing the fluororesin laminated body reduced.

The present invention has the following aspects [1] to [9].
[1] Mainly comprises a layer (I) mainly composed of a fluorinated copolymer (1) having a melting point of 220 ° C. or lower, and a thermoplastic non-fluorine elastomer or a thermoplastic non-fluorine resin (2) having a melting point of 260 ° C. or lower. A fluororesin laminate obtained by laminating a layer (II) as a component. [2] A layer (III) mainly composed of an epoxy group-containing ethylene copolymer (3) having a melting point of 240 ° C. or lower between the layer (I) and the layer (II), or a melting point A layer (IV) mainly composed of a polyamide-based elastomer or resin (4) having a temperature of 240 ° C. or lower, and the component of the layer (III) or the layer (IV) is combined with the component of the layer (II). Different fluororesin laminates according to [1]. [3] The fluorine-containing copolymer (1) comprises a structural unit (A) based on tetrafluoroethylene, a structural unit (B) based on ethylene, itaconic acid, itaconic anhydride, 5-norbornene-2,3. -A structural unit (C) based on one or more selected from the group consisting of dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, citraconic acid and citraconic anhydride, [1] or [2 ] The fluororesin laminated body of description.

[4] The structural unit (A) is 25 to 79.99 mol% based on the total molar amount of the structural unit (A), the structural unit (B), and the structural unit (C), The structural unit (B) is 20 to 74.99 mol%, the structural unit (C) is 0.01 to 5 mol%, and the melting point of the fluorinated copolymer (1) is 100 to 220 ° C. The fluororesin laminate according to [3], wherein the fluorine-containing copolymer (1) has a melting point of 100 to 220 ° C. [5] The structural unit (D) based on the monomer (d) other than the structural unit (A), the structural unit (B), and the structural unit (C). Or a molar ratio (A / D ratio) between the structural unit (A) and the structural unit (D) of 70/30 to 99.9 / 0.1, [3] or [4] ] The fluororesin laminated body of description. [6] The fluorine-containing copolymer (1) is a structural unit (D) based on another monomer (d) other than the structural unit (A), the structural unit (B), and the structural unit (C). And the fluorine-containing copolymer (1) contains, as the structural unit (D), a structural unit (D1) based on hexafluoropropylene, according to any one of [3] to [5]. Fluoropolymer laminate. [7] The fluorine-containing copolymer (1) is further a structural unit based on CH ₂ ═CH (CF ₂ ) _Q1 F (where Q1 is an integer of 2 to 10) as the structural unit (D). The fluororesin laminate according to [6], containing (D2). [8] The fluororesin laminate according to any one of [1] to [7], wherein the peel strength between adjacent layers is 5 N / cm or more in the peel adhesion strength test method based on JIS K 6854-2: 1999 body. [9] The method according to any one of [1] to [8], further including a heat lamination step by multilayer extrusion using a plurality of extruders, wherein a die temperature of the extruder in the heat lamination step is 170 to 280 ° C. The manufacturing method of the fluororesin laminated body of description.

  According to the present invention, the adhesiveness between the layer containing a fluorine-containing copolymer as a main component and the layer containing a non-fluorine resin as a main component is excellent, and foaming due to heat applied during molding processing is reduced. In addition, a fluororesin laminate can be provided.

In this specification, “main component” means containing 50% by mass or more of the target component.
“Monomer” means a compound having a polymerizable unsaturated bond, that is, a polymerization-reactive carbon-carbon double bond. “Fluorine monomer” means a monomer having a fluorine atom in the molecule. “Non-fluorine monomer” means a monomer other than a fluorine monomer.
“Structural unit” means a unit based on a monomer formed by polymerization of the monomer. The structural 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 treating the polymer.
The “fluorinated polymer” is a polymer composed only of structural units based on one kind of fluorine monomer. The “fluorinated copolymer” is a copolymer containing two or more structural units, at least one of which is a structural unit based on a fluorine monomer.
“Fluorine resin” is a resin containing a fluorine-containing copolymer. The “non-fluororesin” is a resin that does not include a fluorine-containing copolymer and includes a copolymer other than the fluorine-containing copolymer.

[Fluoropolymer laminate]
The fluororesin laminate of the present invention has a layer (I) (hereinafter, also simply referred to as “layer (I)”) mainly composed of a fluorinated copolymer (1) having a melting point of 220 ° C. or lower, and thermoplasticity. A layer (II) mainly composed of a non-fluorine elastomer or a thermoplastic non-fluorine resin (2) having a melting point of 260 ° C. or less (hereinafter also simply referred to as “layer (II)”) is laminated.
The fluororesin laminate is a layer mainly composed of an epoxy group-containing ethylene copolymer (3) having a melting point of 240 ° C. or lower between the layer (I) and the layer (II). (III) (hereinafter also simply referred to as “layer (III)”), or a layer (IV) (hereinafter simply referred to as “layer (IV)” having a polyamide-based elastomer or resin (4) having a melting point of 240 ° C. or lower. ) ”) Is preferably laminated.

The shape of the fluororesin laminate is not particularly limited, and may be a sheet shape, a three-dimensional shape obtained by three-dimensionally forming a sheet, or a tube shape.
The total thickness of the fluororesin laminate is not particularly limited. For example, 100-100,000 micrometers is preferable.
The thickness of each layer in the fluororesin laminate is not particularly limited. The layer (I) is preferably 3 to 2000 μm, the layer (II) is preferably 50 to 100,000 μm, and the layer (III) or the layer (IV) is preferably 2 to 1500 μm.
The ratio of the thickness of each layer to the total thickness of the fluororesin laminate is not particularly limited. The layer (I) is preferably 0.003 to 98%, the layer (II) is preferably 1.4 to 99.99% with respect to the total thickness of the fluororesin laminate, and the layers (III) and (IV) ) Is preferably 0.002 to 97%.
Hereinafter, the materials of the layers (I) to (IV) will be described in detail.

(Layer (I))
In the fluororesin laminate, the layer (I) is laminated. Layer (I) has a fluorine-containing copolymer (1) as a main component.
The fluorine-containing copolymer (1) is a fluorine-containing copolymer having a melting point of 220 ° C. or lower. Examples of the fluorine-containing copolymer include ETFE, EFEP (ethylene-hexafluoropropylene-tetrafluoroethylene copolymer), ECTFE (ethylene-chlorotrifluoroethylene copolymer), and THV (tetrafluoroethylene-hexafluoropropylene). -Vinylidene fluoride copolymer) and the like.
The fluorine-containing copolymer (1) has a melting point of 220 ° C. or less because it has excellent properties such as heat resistance, flame retardancy, chemical resistance, weather resistance, non-adhesiveness, low friction and low dielectric properties. ETFE is preferred. Among ETFE, a structural unit (A) based on tetrafluoroethylene (hereinafter referred to as “TFE”) (hereinafter also simply referred to as “structural unit (A)”) and a structural unit based on ethylene (B ) (Hereinafter also simply referred to as “structural unit (B)”) and a structural unit (C) based on a non-fluorine monomer having an acid anhydride residue or two or more carboxy groups (hereinafter simply referred to as “structural unit”). A copolymer containing (C) ".") Is preferred.
A fluorine-containing copolymer (1) may be used individually by 1 type, or may use 2 or more types together.

The structural unit (C) is a structural unit based on a non-fluorine monomer having an acid anhydride residue or two or more carboxy groups. Among them, itaconic acid (hereinafter referred to as “IAC”), itaconic anhydride (hereinafter referred to as “IAH”), 5-norbornene-2,3-dicarboxylic acid (hereinafter referred to as “NAC”), and 5-norbornene. 1 selected from the group consisting of -2,3-dicarboxylic anhydride (hereinafter referred to as "NAH"), citraconic acid (hereinafter referred to as "CAC") and citraconic anhydride (hereinafter referred to as "CAH"). Structural units based on species or more are preferred. If it is a structural unit based on one or more selected from the group consisting of IAC, IAH, NAC, NAH, CAC and CAH, it is necessary when conventional maleic anhydride described in, for example, JP-A-11-19312 is used. The fluorine-containing copolymer containing the structural unit (C) can be easily produced without using such a special polymerization method.
Among these, a structural unit based on IAH is preferable from the viewpoint of excellent polymerizability.

Content of each structural unit (A)-(C) in a fluorine-containing copolymer (1) is with respect to the total molar amount of a structural unit (A), a structural unit (B), and a structural unit (C). It is preferable that the structural unit (A) is 25 to 79.99 mol%, the structural unit (B) is 20 to 74.99 mol%, and the structural unit (C) is 0.01 to 5 mol%. The structural unit (A) is 50 to 64.97 mol%, the structural unit (B) is 35 to 49.97 mol%, and the structural unit (C) is 0.03 to 3 mol%. More preferably, the structural unit (A) is 50 to 59.95 mol%, the structural unit (B) is 40 to 49.95 mol%, and the structural unit (C) is 0.05 to 1 mol%. Most preferred.
If content of each structural unit (A)-(C) is in the said range, a fluorine-containing copolymer (1) will be excellent in chemical resistance and heat resistance. In particular, when the content of the structural unit (C) is within the above range, in addition to the chemical resistance and heat resistance, the adhesion between the layer (I) and other layers becomes higher.

The melting point of the fluorinated copolymer (1) is 220 ° C. or less.
100-220 degreeC is preferable, as for melting | fusing point of a fluorine-containing copolymer (1), 120-205 degreeC is more preferable, and 150-200 degreeC is further more preferable. If the melting point of the fluorinated copolymer (1) is not more than the above upper limit, for example, when producing a fluororesin laminate, the die temperature of the extruder in the thermal lamination step can be set to a low temperature. Therefore, foaming of the resin component is reduced by suppressing thermal decomposition of the fluorine-containing copolymer (1) or the thermoplastic resin (2). Furthermore, a fluororesin laminate in which layer (I) and other layers are firmly bonded is obtained.

The fluorine-containing copolymer (1) has a structural unit (D) based on another monomer (d) (below) in addition to the structural units (A) to (C) because the melting point can be easily controlled within the above range. Further, it is preferable to further contain a “structural unit (D)”. The other monomer (d) is a monomer other than TFE, ethylene, and an acid anhydride residue or a non-fluorine monomer having two or more carboxy groups. The other monomer (d) is classified into a fluorine-containing monomer and a non-fluorine monomer.
The structural unit (D) may be contained singly or in combination of two or more.

Among the other monomers (d), the fluorine-containing monomer is a fluorine-containing monomer other than TFE. For example, vinyl fluoride, vinylidene fluoride (hereinafter also referred to as “VdF”), trifluoroethylene, hexafluoropropylene ( Hereinafter, also referred to as “HFP”), chlorotrifluoroethylene, CH ₂ ═CH (CF ₂ ) _Q1 F (where Q1 is an integer of 2 to 10), CH ₂ ═CF (CF ₂ ) _Q2 H (wherein , Q2 is an integer of 2 to 10.) Fluorine-containing olefin, such as CF ₂ = CFOR ¹ (where R ¹ represents a C 1-10 fluoroalkyl group which may contain an etheric oxygen atom), etc. fluoro (alkyl vinyl _{ether) ^{of, CF 2 = CFOR 2 SO 2}} X 1 ( provided that, ^{R 2} is carbon atoms which may contain an etheric oxygen atom 1-1 Represents a fluoroalkylene group, ^{X 1} is a halogen atom or a hydroxyl ^{_{group.), CF 2 = CFOR 3}} CO 2 X 2 ( provided that, ^{R 3} is fluoroalkylene having 1 to 10 carbon atoms which may contain an etheric oxygen atom X ² represents a hydrogen atom or an alkyl group having 3 or less carbon atoms.), CF ₂ ═CF (CF ₂ ) _P OCF═CF ₂ (wherein P represents 1 or 2), and perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like. The fluorine-containing monomer may be linear or branched. Moreover, a fluorine-containing monomer may be used individually by 1 type, or may use 2 or more types together.
R ^{1 to} R ³ are each preferably a C 1-10 fluoroalkyl group.
The number of carbon atoms of the fluoroalkyl group in R ¹ to R ³ is 1 to 6 preferably 1 to 4 is more preferred. As the fluoroalkyl group, a perfluoroalkyl group such as CF ₃ group, C ₂ F ₅ group, C ₃ F ₇ group and the like is particularly preferable.

_{Q 2 of} CH ₂ ═CH (CF ₂ ) _Q1 F is preferably an integer of 2 to 6 in terms of polymerizability and continuous operation.
Specific examples of CF ₂ = CFO ¹ include CF ₂ = CFOCF ₃ , CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F and the like can be mentioned, and CF ₂ = CFOCF ₂ CF ₂ CF ₃ is preferable.
Specific examples of _{CH 2 = CF (CF 2)} Q2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H , and the like.

Among the other monomers (d), the non-fluorine monomer is a non-fluorine monomer other than ethylene and an acid anhydride residue or a non-fluorine monomer having two or more carboxy groups, such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether. And vinyl ethers such as tert-butyl vinyl ether, methoxyethyl vinyl ether and ethoxyethyl vinyl ether; and α-olefins such as propylene, butene and isobutene. Of these, propylene is preferred from the viewpoint of thermal stability and processability.
A non-fluorine monomer may be contained individually by 1 type, and may be contained in combination of 2 or more type.

From the viewpoint of heat resistance of the fluorinated copolymer (1), the structural unit (D) is preferably a structural unit based on a fluorinated monomer among the other monomers (d).
The fluorinated copolymer (1) preferably contains at least a structural unit (D1) based on HFP (hereinafter also simply referred to as “structural unit (D1)”) as the structural unit (D). When the fluorine-containing copolymer (1) contains the structural unit (D1), the melting point of the fluorine-containing copolymer (1) is within the above range without reducing the heat resistance of the fluorine-containing copolymer (1). It becomes easy to control.
In addition to the structural unit (D1) as the structural unit (D), the fluorinated copolymer (1) includes VdF, CF ₂ = CFOR ¹ , CH ₂ = CH (CF ₂ ) _Q1 F, and CH ₂ = CF. It is preferable to further contain one selected from the group consisting of (CF ₂ ) _{Q 2} H, and more preferably to further contain CH ₂ ═CH (CF ₂ ) _{Q 1} F. In addition to the structural unit (D1), the fluorine-containing copolymer (1) is a structural unit (D), VdF, CF ₂ = CFOR ¹ , CH ₂ = CH (CF ₂ ) _Q1 F, and CH ₂ = CF (CF ₂ ) one of the further contains selected from the group consisting of _{Q2 H,} fluorine-containing copolymer a melting point of (1) with easily controlled in the above range, the stress crack resistance of the fluorocopolymer (1), Excellent formability and productivity.

Examples of the fluorinated copolymer (1) include copolymers comprising the following structural units (1) to (5), and among them, the copolymer of the following (5) is preferable.
(1) Structural unit (A) / Structural unit (B) / Structural unit (C);
(2) Structural unit (A) / Structural unit (B) / Structural unit (C) / Structural unit (D1);
(3) Structural unit (A) / Structural unit (B) / Structural unit (C) / Structural unit based on propylene;
(4) Structural unit (A) / Structural unit (B) / Structural unit (C) / Structural unit (D2) / Structural unit based on propylene;
(5) Structural unit (A) / Structural unit (B) / Structural unit (C) / Structural unit (D1) / Structural unit (D2).

  The melting point of the fluorinated copolymer (1) can be adjusted, for example, by the content of the structural unit (D), and the content ratio of the structural unit (D) to all the structural units constituting the fluorinated copolymer (1). When there is much, melting | fusing point of a fluorine-containing copolymer (1) will become low.

  The molar ratio (A / D ratio) between the structural unit (A) and the structural unit (D) is preferably 70/30 to 99.9 / 0.1, more preferably 75/25 to 98/2. 80/20 to 95/5 is most preferable. If A / D ratio is below the said upper limit, melting | fusing point of a fluorine-containing copolymer (1) will fall, and it will become easy to control this melting | fusing point to the said range. If A / D ratio is more than the said lower limit, it will be excellent by the chemical resistance and heat resistance of a fluorine-containing copolymer (1).

  When the fluorine-containing copolymer (1) contains the structural unit (D1), all the structural units other than the structural unit (D1) and the structural unit (D1) constituting the fluorine-containing copolymer (1) The molar ratio (M1 / D1 ratio) to (M1) is preferably 85/15 to 94/6, more preferably 90/10 to 93/7. If M1 / D1 ratio is below the said upper limit, melting | fusing point of a fluorine-containing copolymer (1) will not become high too much, and it is excellent in a moldability. If the M1 / D1 ratio is equal to or higher than the lower limit, the polymerization reaction during the production of the fluorinated copolymer (1) proceeds without problems and is excellent in productivity, and the heat resistance of the fluorinated copolymer (1). More formability. When the M1 / D1 ratio is within the above range, the productivity, heat resistance and moldability of the fluorinated copolymer (1) are excellent.

  In the case where the fluorinated copolymer (1) includes the structural unit (D1) and the structural unit (D2) as the structural unit (D), the molar ratio (D1 / D2) of the structural unit (D1) to the structural unit (D2) The ratio is preferably 75/25 to 97/3, more preferably 80/20 to 96/4, and most preferably 85/15 to 95/5. When the D1 / D2 ratio is not more than the above upper limit, the stress-resistant crack resistance and moldability of the fluorine-containing copolymer (1) are more excellent. If D1 / D2 ratio is more than the said lower limit, it will become easy to control melting | fusing point of a fluorine-containing copolymer (1) by the said range.

  When the fluorinated copolymer (1) contains a structural unit based on propylene (hereinafter, also referred to as “structural unit (P)”) as the structural unit (D), the structural unit (P) and the fluorinated copolymer The molar ratio (M2 / P ratio) to all the structural units (M2) other than the structural unit (P) constituting the copolymer (1) is preferably 80/20 to 94/6, and 85/15 to 93. / 7 is more preferable. If the M2 / P ratio is not more than the above upper limit value, the melting point of the fluorine-containing copolymer (1) will not be too high and the moldability will be excellent, and if the M2 / P ratio is not less than the above lower limit value, The polymerization reaction of the polymer (1) proceeds without problems, and the productivity is excellent, and the heat resistance and moldability of the fluorine-containing copolymer (1) are more excellent.

The fluorine-containing copolymer (1) has a temperature at which an amount flow rate (hereinafter also referred to as “Q value”) at a temperature 20 to 50 ° C. higher than the melting point is 0.1 to 1000 mm ³ / sec. It is more preferable that a temperature of 0.1 to 500 mm ³ / second is present, more preferably a temperature of 0.1 to 200 mm ³ / second is present, and 0.2 to 100 mm ³ / second is more preferable. Most preferably, there is a temperature at which The Q value is a measure of the molecular weight of the copolymer. A larger Q value indicates a smaller molecular weight, and a smaller Q value indicates a larger molecular weight.
If Q value is more than the said lower limit, it will be excellent in the moldability of a fluorine-containing copolymer (1), and if Q value is below the said upper limit, a fluororesin laminated body will have sufficient intensity | strength.
In addition, Q value in this specification is the value measured on the conditions of 20-50 degreeC temperature higher than melting | fusing point, and load 68.6N. Specifically, in the Koka flow tester, the speed (mm ³ / sec) of the resin flowing out from a nozzle having a diameter of 2.1 mm and a length of 8 mm in 10 minutes.

The layer (I) may further contain components other than the fluorinated copolymer (1), such as carbon black, carbon fiber, glass fiber, and carbon nanotube.
Content of components other than a fluorine-containing copolymer (1) is less than 50 mass% in layer (I), less than 20 mass% is preferable, and less than 15 mass% is more preferable.

The production method of the fluorinated copolymer (1) is not particularly limited, and for example, TFE, ethylene, a non-fluorine monomer having an acid anhydride residue or two or more carboxy groups, and other as necessary. The monomer (d), propylene, and the like are charged into a polymerization reactor, and a commonly used radical polymerization initiator is added for copolymerization. For example, it may be produced according to the polymerization method described in Patent Document 1.
Specifically, known bulk polymerization; solution polymerization using an organic solvent such as fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated chlorohydrocarbon, alcohol, hydrocarbon; an aqueous medium and an appropriate organic solvent as required Suspension polymerization using an aqueous medium; emulsion polymerization using an aqueous medium and an emulsifier, and the like, and solution polymerization is preferred. The polymerization can be carried out by a batch operation or continuous operation using a single tank or multi-tank type stirring polymerization apparatus, tube polymerization apparatus, and the like.

(Layer (II))
In the fluororesin laminate, the layer (II) is laminated. Layer (II) is mainly composed of a thermoplastic non-fluorine elastomer or a thermoplastic non-fluorine resin (2) having a melting point of 260 ° C. or lower.

  Examples of the thermoplastic non-fluorine elastomer include styrene / butadiene elastomers, polyolefin elastomers, polyester elastomers, polyurethane elastomers, polyvinyl chloride elastomers, polyamide elastomers, and fluorine elastomers.

The thermoplastic non-fluorine resin is not particularly limited as long as it has a melting point of 260 ° C. or lower.
Thermoplastic non-fluorine resins include polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene, ultra low density polyethylene), polypropylene, polybutene, polybutadiene, ABS resin, polystyrene, methacrylic resin, norbornene resin, polyvinyl chloride, Polyester such as polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyamino bismaleimide, polysulfone, polyphenylene sulfide, polyethersulfone, polythioethersulfone, polyethernitrile, polyphenylene ether, or Mixing them with carbon black, various elastomer components, glass fibers, carbon fibers, etc. Thing, and the like. Furthermore, those obtained by modifying these resins by copolymerizing a small amount of monomers having an acid anhydride group, an epoxy group or an amino group are also included. Examples thereof include maleic anhydride-modified polyolefins, and specific examples include maleic anhydride-modified propylene and maleic anhydride-modified polyethylene.
From the viewpoint of better adhesion to the layer (I), “thermoplastic non-fluorinated elastomer or thermoplastic non-fluorinated resin (2) having a melting point of 260 ° C. or lower” is polyamide 6, polyamide 11, polyamide 12, polyamide 12 An elastomer, a polyamide-based elastomer or a polyethylene grafted with a polyamide-based resin is preferred.

The layer (II) further comprises a thermoplastic non-fluorine elastomer having a melting point of 260 ° C. or lower, such as a stabilizer, a lubricant, a plasticizer, a filler, a polymer modifier such as a coloring material or an elastomer (2). It may contain other components.
The content of components other than the thermoplastic non-fluorine elastomer or the thermoplastic non-fluorine resin (2) having a melting point of 260 ° C. or less is less than 50% by mass in the layer (III), preferably less than 30% by mass, and 20% by mass. Less than is more preferable.

(Layer (III))
In the fluororesin laminate, the layer (III) is preferably laminated between the layer (I) and the layer (II). Layer (III) has as its main component an epoxy group-containing ethylene copolymer (3) having a melting point of 240 ° C. or lower (hereinafter also simply referred to as “epoxy group-containing ethylene copolymer (3)”). However, in the fluororesin laminate, the component of the layer (III) is different from the component of the layer (II).
Layer (III) acts as an adhesive layer between layers (I) and (II).

As the epoxy group-containing ethylene copolymer (3), a structural unit (E) based on ethylene (hereinafter also simply referred to as “structural unit (E)”) and a structural unit (F) based on an epoxy group-containing monomer ( Hereinafter referred to simply as “structural unit (F)”); a structural unit (G) based on structural unit (E), structural unit (F) and other monomer (g) (hereinafter simply referred to as “structural unit (F)”). A copolymer comprising “a structural unit (G)”), and the like.
A structural unit (F) may be contained individually by 1 type, and may be contained in combination of 2 or more type. Moreover, the structural unit (G) may be contained singly or in combination of two or more.
The epoxy group-containing ethylene copolymer (3) may be used alone or in combination of two or more.

  Examples of the epoxy group-containing monomer include unsaturated glycidyl ethers (for example, allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.) and unsaturated glycidyl esters (for example, glycidyl acrylate, glycidyl methacrylate, etc.). ), And the like. Among these, glycidyl methacrylate is preferable from the viewpoint of further improving the adhesiveness.

  Examples of the other monomer (g) include ethylenically unsaturated esters, α-olefins other than ethylene, and styrenes. Examples of the ethylenically unsaturated esters include acrylic acid esters (for example, methyl acrylate, Ethyl acrylate, etc.), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, etc.), and fatty acid vinyl esters such as vinyl acetate. Styrenes include those copolymerized with butadiene in addition to styrene homopolymers. Of these, ethylenically unsaturated esters are preferred.

As the epoxy group-containing ethylene copolymer (3), a copolymer containing the structural unit (E) and a unit (F1) based on glycidyl methacrylate is preferable.
Specific examples of the copolymer include an ethylene-glycidyl methacrylate copolymer. When the copolymer is used, the adhesion between the layer (III) and the layer (I) and the layer (II) is more excellent.
Further, a copolymer composed of the structural unit (E), the structural unit (F1) based on glycidyl methacrylate, and the structural unit (G1) based on the ethylenically unsaturated ester is also preferable in terms of moldability and mechanical strength. preferable. Specific examples of the copolymer include ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, and ethylene-ethyl acrylate-glycidyl methacrylate copolymer. . Among these, ethylene-methyl acrylate-glycidyl methacrylate copolymer and ethylene-ethyl acrylate-glycidyl methacrylate copolymer are preferable in terms of adhesiveness.

  The epoxy group-containing ethylene copolymer (3) is composed of polyethylene terephthalate and polybutylene terephthalate because the adhesion and adhesion between the layer (III) and the layers (I) and (II) become better. Polyester such as polyethylene naphthalate, Polyester such as polycarbonate polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, Polycarbonate, Maleic anhydride modified polyolefin, Itaconic anhydride modified polyolefin, Polyvinyl chloride, Polyvinylidene chloride, Thermoplastic polyurethane, etc. preferable.

55-99.9 mol% is preferable and, as for content of the structural unit (E) which occupies in all the structural units which comprise an epoxy-group-containing ethylene-type copolymer (3), 70-94 mol% is more preferable. If the repeating unit (E) based on ethylene is at least the lower limit value, the heat resistance and toughness of the layer (III) are more excellent.
0.1-15 mol% is preferable and, as for content of the structural unit (F) which occupies in all the structural units which comprise an epoxy-group-containing ethylene-type copolymer (3), 1-10 mol% is more preferable. If content of a structural unit (F) is more than the said lower limit, layer (II) will be excellent in adhesiveness with another layer.

  When the epoxy group-containing ethylene copolymer (3) has the structural unit (G), the structural unit (G) occupies in all the structural units constituting the epoxy group-containing ethylene copolymer (3). The content is preferably 1 to 30 mol%, more preferably 10 to 30 mol%.

  There are no particular limitations on the method for producing the epoxy group-containing ethylene copolymer (3). For example, ethylene, an epoxy group-containing monomer, and other monomers used as necessary under a pressure of 50 to 250 MPa. (G) may be charged into a polymerization reactor, and radical polymerization may be performed at 120 to 300 ° C. in the presence of a suitable radical generator. Examples of the polymerization method include known bulk polymerization, solution polymerization, suspension polymerization and the like. The polymerization can be carried out by a batch operation or continuous operation using a single tank or multi-tank type stirring polymerization apparatus, tube polymerization apparatus, and the like.

  A commercially available epoxy group-containing ethylene copolymer can also be used. Commercially available products include “Bondfast E (trade name, manufactured by Sumitomo Chemical Co., Ltd.)” which is an ethylene-glycidyl methacrylate copolymer, and “Bondfast 7M (product) which is an ethylene-methyl acrylate-glycidyl methacrylate copolymer. Name, manufactured by Sumitomo Chemical Co., Ltd.).

The layer (III) may further contain components other than the epoxy group-containing ethylene copolymer (3).
Examples of the components other than the epoxy group-containing ethylene copolymer (3) to be included in the layer (III) include, for example, rubbers, thermoplastic elastomers, ethylene copolymers other than the epoxy group-containing ethylene copolymer (3), and the like. And various additives such as heat stabilizers, lubricants and pigments.
An ethylene copolymer other than the epoxy group-containing ethylene copolymer (3) is an ethylene-ethylenically unsaturated ester copolymer in that it has excellent compatibility with the epoxy group-containing ethylene copolymer (3). Is preferred. Examples of the thermoplastic elastomer include olefinic TPO (thermoplastic polyolefin elastomer) in terms of excellent compatibility with the epoxy group-containing ethylene copolymer.
The content of components other than the epoxy group-containing ethylene copolymer (3) is less than 50% by mass in the layer (III), preferably less than 30% by mass, and more preferably less than 20% by mass.

(Layer (IV))
In the fluororesin laminate, the layer (IV) is preferably laminated between the layer (I) and the layer (II). The layer (IV) contains a polyamide-based elastomer or resin (4) having a melting point of 240 ° C. or lower (hereinafter also simply referred to as “polyamide (4)”) as a main component. However, in the fluororesin laminate, the component of the layer (IV) is different from the component of the layer (II).
The layer (IV) acts as an adhesive layer between the layer (I) and the layer (II), like the layer (III).

Examples of the polyamide (4) include nylon (polyamide 12) elastomer, polyamide grafted polyolefin, polyamide 11, polyamide 12, polyamide 6, polyamide 610, polyamide 612, and the like.
Polyamide (4) may be used individually by 1 type, or may use 2 or more types together.

The layer (IV) may further contain components other than the polyamide (4) such as a flame retardant and a plasticizer.
Content of components other than polyamide (4) is less than 50 mass% in layer (IV), less than 30 mass% is preferable, and less than 20 mass% is more preferable.

(Peeling strength between adjacent layers)
In the peel adhesion strength test method based on JIS K 6854-2: 1999, the fluororesin laminate preferably has a peel strength between all adjacent layers of preferably 5 N / cm or more, and preferably 10 N / cm or more. More preferably, it is most preferable that peeling is impossible.
The fluororesin laminate used in the peel adhesion strength test method may be obtained by multilayer extrusion molding (coextrusion molding) or may be obtained by press molding.

(Other aspects)
In the fluororesin laminate, one or more layers (V) other than the layers (I) to (IV) (hereinafter also simply referred to as “layer (V)”) are adjacent to the layer (II). You may laminate. The number of other layers (V) is not particularly limited. As such a fluororesin laminate formed by laminating other layers (V), for example, a fluororesin laminate in which the layers (I) (III), (II), and (V) are laminated in this order. A fluororesin laminate in which layer layers (I) (IV), layer (II) and layer (V) are laminated in this order; a fluororesin laminate in which layer layers (I) (II) and layer (V) are laminated in this order Body; and the like.
The resin as the main component of the other layer (V) is not particularly limited, and examples thereof include polyethylene (high density polyethylene, medium density polyethylene, low density polyethylene, ultra low density polyethylene, etc.), polypropylene, polybutene, polybutadiene, ABS. Resin, thermoplastic polyurethane, polystyrene, methacrylic resin, norbornene resin, polyvinylidene chloride, polyvinyl chloride, polybutylene terephthalate, polyethylene naphthalate, polyester, polycarbonate, polyamide, polyimide, thermoplastic polyimide, polyamino bismaleimide, polysulfone, poly Phenylene sulfide, polyetheretherketone, polyetherimide, polyetherketone, polyethersulfone, polythioethersulfone, polyethernitrile, polyphenylene Niren'eteru, thermosetting epoxy resins, urethane resins, urea resins, phenol resins, melamine resins, guanamine resins, furan resins, alone or as a mixture or diallyl phthalate resin.

(Method for producing fluororesin laminate)
The production method of the fluororesin laminate of the present invention includes multilayer extrusion molding (coextrusion molding), extrusion lamination molding, heating roll, multilayer lamination molding using a heating press, multilayer injection from the viewpoint of ease of molding and productivity. It has a heat lamination process by molding, multilayer blow molding or the like. At least the above-mentioned layer (I) and layer (II) are laminated by the thermal lamination step.
When manufacturing a fluororesin laminated body by the heat | fever lamination process by the multilayer extrusion molding using a some extruder, 170-280 degreeC is preferable for the die temperature of this extruder, and 200-280 degreeC is more preferable. If the die temperature is equal to or higher than the lower limit value, the processability is excellent. On the other hand, if the die temperature is equal to or lower than the upper limit value, the adhesion to other materials is excellent.

In the method for producing a fluororesin laminate of the present invention, in addition to the layer (I) and the layer (II), the layer (III), the layer (IV) or the layer (V) may be thermally laminated.
Examples of the thermal lamination method include a method using a one-step thermal lamination process in which all layers are thermally laminated at once, and a method using two or more thermal lamination processes in which each layer is thermally laminated in order.
As a specific method of the one-step thermal lamination process, for example, the layer (I), the layer (III) or the layer (IV), and the layer (II) are heated by multilayer extrusion molding or multilayer laminate molding. Lamination and obtaining a fluororesin laminate; layer (I), layer (II) and layer (V) are thermally laminated to obtain a fluororesin laminate; layer (I) and layer (III) ) Or layer (IV), layer (II), and layer (V) are thermally laminated to obtain a fluororesin laminate.
As a specific method of the two-stage or more thermal lamination process, for example, the first thermal lamination process in which the layer (I) and the layer (III) or the layer (IV) are thermally laminated is performed to obtain a laminate. Next, a second thermal lamination step of heat-pressing the layer (II) is performed on the layer (III) or layer (IV) side of the laminate obtained in the first thermal lamination step, and the fluororesin lamination is performed. A method of obtaining a body; a third thermal lamination step of heating and pressing another layer (V) on the layer (II) side of the fluororesin laminate obtained in the second thermal lamination step; And a method of obtaining a resin laminate.
The thermal lamination process is preferably a one-stage thermal lamination process from the viewpoint of cost and handling properties. Of the one-stage heat lamination process, a heat lamination process by multilayer extrusion using a plurality of extruders is more preferable.

  In particular, the temperature of the die in the step of thermally laminating the layer (II) and a layer other than the layer (II) is preferably 180 to 280 ° C. When the temperature is equal to or higher than the lower limit, the layer (II) and the layer other than the layer (II) can be more sufficiently bonded. If the upper limit or less, thermal decomposition of the epoxy group-containing ethylene copolymer (3) that is the main component of the layer (III) or the polyamide (4) that is the main component of the layer (IV) is suppressed, The adhesion between the layers becomes more sufficient. For example, a laminate is obtained by performing a first thermal lamination process in which the layer (I) and the layer (III) or the layer (IV) are thermally laminated, and then the lamination obtained in the first thermal lamination process. In the case of performing a method of obtaining a fluororesin laminate by performing a second thermal lamination step in which the layer (II) is heated and pressed on the layer (III) or layer (IV) side of the body, the second thermal lamination step Is preferably performed within the above temperature range.

The heating and holding time in each thermal lamination step is preferably 0.1 second to 1 hour. If it is 0.1 second or more, the adhesive force between each layer will be more stable, and if it is 1 hour or less, it will be excellent in productivity.
The pressing pressure is preferably 0.1 MPa to 50 MPa. If it is 1 MPa, the adhesive force between each layer will be more stable, and if it is 50 MPa or less, it will be excellent in productivity.
The pressing time is preferably within 1 second to 30 minutes. If it is 1 second or more, the adhesive force between each layer will be more stable, and if it is within 30 minutes, it will be excellent in productivity.
The thermal lamination step may be performed in the air, in an inert gas, or under reduced pressure. For example, when the layer (III) is thermally laminated, it may be performed in an inert gas or under reduced pressure from the viewpoint of suppressing thermal decomposition of the epoxy group-containing ethylene copolymer that is the main component of the layer (III). preferable.

(Function and effect)
According to the present invention, the adhesiveness between the layer containing a fluorine-containing copolymer as a main component and the layer containing a non-fluorine resin as a main component is excellent, and foaming due to heat applied during molding processing is reduced. In addition, a fluororesin laminate is obtained.

  In the present invention, a fluorine-containing copolymer having a low melting point is used as the main component of the layer (I), and a thermoplastic non-fluorine elastomer or a thermoplastic non-fluorine resin having a low melting point is used as the main component of the layer (II). It is done. When a thermoplastic non-fluorine elastomer is used as the main component of the layer (II), the shrinkage rate is small, so even if the layers (I) and (II) are laminated at a low temperature, both layers have good adhesion. Become. Moreover, when a thermoplastic non-fluorine resin having a low melting point is used as the main component of the layer (II), both layers can be fused at a lower temperature to improve the adhesion between the two layers. In any case, since the layer (I) and the layer (II) can be laminated at a lower temperature, the thermal decomposition of the resin component of each layer and the accompanying foaming are suppressed, and the produced fluororesin laminate is Its surface smoothness is excellent.

  In the present invention, the layer (III) mainly composed of an epoxy group-containing ethylene copolymer (3) having a melting point of 240 ° C. or lower between the layer (I) and the layer (II), or a melting point of 240 When the layer (IV) whose main component is a polyamide-based elastomer or resin (4) having a temperature of ℃ or less is laminated, the adhesion between the layer (I) and the layer (III) or the layer (IV) is remarkably excellent. . This is because the layer (I) and the layer (III) or the layer (IV) can be laminated at a lower temperature as well as the adhesion between the layer (I) and the layer (II) described above. Moreover, since layer (I) and layer (III) or layer (IV) can be laminated | stacked at lower temperature, the thermal decomposition of the resin component of each layer and the foaming accompanying it are suppressed.

In particular, when a fluorine-containing copolymer that is a main component of the layer (I) is one containing a structural unit (C) based on a non-fluorine monomer having an acid anhydride residue or two or more carboxy groups In this case, the adhesive strength between the layer (I) and other layers is further improved.
As this mechanism, the improvement in the adhesive strength between the layer (I) and the layer (II) is due to the fact that the acid anhydride residue of the structural unit (C) in the fluorinated copolymer that is the main component of the layer (I) or An amine group, a hydroxyl group, an epoxy group, an oxazoline group, an isocyanate group, an isocyanurate group in a thermoplastic non-fluorinated elastomer whose carboxy group is the main component of the layer (II) or a thermoplastic non-fluorinated resin having a melting point of 260 ° C. or less, It is presumed that this is caused by reacting with and binding to a functional group such as a urea group.
Moreover, the improvement of the adhesive strength between the layer (I) and the layer (III) is due to the fact that the epoxy group in the epoxy group-containing ethylene copolymer having a melting point of 240 ° C. or less, which is the main component of the layer (III), is due to an acid or the like. Ring opening and the group generated by ring opening of the epoxy group reacts with the acid anhydride residue or carboxy group of the structural unit (C) in the fluorinated copolymer which is the main component of the layer (I), Presumed to be due to the combination.
Moreover, the improvement of the adhesive strength between the layer (I) and the layer (IV) is achieved by the fact that the acid anhydride residue or carboxy group of the structural unit (C) in the fluorine-containing copolymer that is the main component of the layer (I) is added. , By reacting with an amide bond or an amino group at the end of the polymer in a polyamide elastomer or resin whose melting point is 240 ° C. or lower, which is the main component of layer (IV), to form a chemical bond such as an amide bond or an imide bond It is estimated to be.

The fluororesin laminate of the present invention is preferably used for the following uses. Moreover, the use example mentioned later is not limited to the fluororesin laminated body of this invention, The layer which has a fluorine-containing copolymer (1) as a main component, and resin or metals other than a fluorine-containing copolymer (1) It is also preferred as a use for a laminate.
For example, it can be used in various fields such as various parts such as electronic parts, aircraft parts, and vehicle parts, and can be used as a film, a sheet, a tube, a hose, a tank, a seal, and the like.
Examples of the film and sheets include a single layer or a multilayer film used in at least a part thereof in the following applications. Interlayer insulation film for electronic boards, steel sheet laminating film used for building materials and solvents, steel making for solution storage, etc., battery packaging such as lithium ion battery by laminating metal foil such as aluminum as soft moisture proof packaging, polyethylene, polypropylene, ethylene・ Medical or chemical liquid packaging materials laminated with vinyl acetate copolymers, industrial films such as agricultural houses and membrane structures, single-layer or multilayer release films for cast film production, wiring board and IC chip manufacturing Release films for food, food packaging or wrapping films, diaphragms for diaphragm pumps and various packings that require high chemical resistance, belt conveyors, insulation coating films for electric wires, and the like.
As tubes and hoses, refuel such as paint line tubes or paint line hoses, chemical solution tubes or chemical solution hoses, agricultural chemical tubes or agricultural chemical hoses, beverage tubes or beverage hoses, hydraulic tubes or hydraulic hoses, gas stations, etc. Underground buried tube used for station, automotive fuel piping tube or automotive fuel piping hose, filler neck hose, automotive radiator hose, brake hose, air conditioner hose, electric cable, fuel cell hose, for electrical parts, fruit juice, Examples include industrial hoses for transporting pasty foods, ink tubes, chemical tubes, pneumatic tubes or hoses, fuel transport hoses for gasoline, light oil, alcohol, and hot water supply hoses.
Tanks include automobile radiator tanks, chemical tanks, chemical liquid bags, multi-layer bottles for chemical storage containers, fuel tanks, chemical liquid containers and abrasives that are highly corrosive and corrosive to acids and alkalis such as chemical liquids for semiconductors, etc. And a container for urea water in a system for reducing NOX by spraying urea water on diesel engine exhaust gas.
Seals include LIB aluminum laminate seal layers, various automotive seals such as fuel pump O-rings, chemical related seals such as chemical pumps and flow meter seals, various mechanical related seals such as hydraulic equipment seals, Etc.
In addition, laminated printed wiring boards, multilayer monofilaments, wiring / pipe cover ducts (protection pipes), protection of outdoor parts of building parts called exteriors, building parts such as outer wall protection and inner layer walls, rubber hose mandrel core materials, light guides Examples include ropes, belts for food machinery, belts for food conveyance, carburetor flange gaskets, gears, and the like.
Especially, it is preferable that the fluororesin laminated body of this invention is used as a hose or a tube as a multilayer molded article.

  In addition, about the manufacture of the composite material by laminate shaping | molding of a fluorine-containing copolymer (1) and a metal plate or metal foil, the shaping | molding method by extrusion lamination is preferable, and aluminum, stainless steel, copper etc. are mention | raise | lifted as a metal plate. For example, as for the extrusion laminate molding conditions with aluminum, the extruder temperature during processing is 180 ° C. or higher and lower than 400 ° C., preferably 190 ° C. or higher and lower than 300 ° C. The nip roll temperature is 100 ° C or higher, preferably 200 ° C or higher and lower than 400 ° C. The line speed is preferably 50 m / min or less and particularly preferably 10 m / min or less. Moreover, the thickness of the preferable fluorine-containing copolymer and metal plate or metal foil in extrusion lamination is not particularly limited as long as it is 1 mm or less.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to this.

[Production Example 1]
Hereafter, the manufacturing method of the fluorine-containing copolymer (henceforth "fluorine-containing copolymer (1-1)") used for layer (I) of Examples 1-10 is demonstrated.
First, a polymerization tank equipped with a stirrer having an internal volume of 430 L was degassed, and 237.2 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (Asahi Glass) 49.5 kg of AK225cb (hereinafter referred to as “AK225cb”), 122 kg of HFP, 1.31 kg of CH ₂ = CH (CF ₂ ) ₄ F were charged, and the temperature inside the polymerization tank was raised to 66 ° C. The pressure was increased to 1.5 MPa / G with a mixed gas of ethylene and ethylene (TFE / ethylene = 89/11 (molar ratio)). As a polymerization initiator, 2.5 L of a 2 mass% 1-hydrotridecafluorohexane solution of tert-butylperoxypivalate was charged to initiate polymerization.
During the polymerization, a monomer mixed gas of TFE and ethylene (TFE / ethylene = 54/46 (molar ratio)) was continuously charged so that the pressure was constant. Further, CH ₂ ═CH (CF ₂ ) ₄ F in an amount corresponding to 1 mol% and IAH in an amount corresponding to 0.4 mol% are continuously added to the total number of moles of TFE and ethylene charged during the polymerization. Prepared.
9.3 hours after the start of polymerization, when 29 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

  The obtained slurry-like fluorine-containing copolymer (1-1) was put into an 860 L granulation tank charged with 300 kg of water, and heated to 105 ° C. with stirring to distill off the solvent. Granulated. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 33.2 kg of a dry granulated product of the fluorinated copolymer (1-1).

From the results of melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis of the fluorinated copolymer (1-1), the content ratio of each structural unit in the fluorinated copolymer (1-1) was determined. . As a result, the fluorinated copolymer (1-1) is composed of a structural unit based on TFE / a structural unit based on HFP / a structural unit based on CH ₂ ═CH (CF ₂ ) ₄ F / a structural unit based on IAH / ethylene. The ratio of the constituent units based on it was 46.2 / 9.4 / 1.0 / 0.4 / 43.0 (molar ratio).

Further, the Q value of the fluorinated copolymer (1-1) was measured under the conditions of a measurement temperature of 220 ° C. and a load of 68.6 N using a flow tester manufactured by Shimadzu Corporation. As a result, the Q value of the fluorinated copolymer (1-1) was 7.2 mm ³ / sec.

  Also, using a differential scanning calorimeter (DSC-7020, manufactured by SII Corporation), the melting peak when the temperature of the fluorine-containing copolymer (1-1) was raised at a rate of 10 ° C./min was recorded, and the maximum The temperature (° C.) corresponding to the value was taken as the melting point. As a result, the melting point of the fluorinated copolymer (1-1) was 170 ° C.

[Reference Example] Physical property evaluation of fluorine-containing copolymer (1-1) The amount of hydrogen fluoride gas generated when the fluorine-containing copolymer (1-1) was heated to the melting point or higher was evaluated. In addition, temperature measured the temperature (210 degreeC) 40 degreeC higher than melting | fusing point supposing the processing temperature of a fluorine-containing copolymer (1-1). Similarly, the measurement was also performed at a temperature 60 ° C. higher (230 ° C.) and a temperature 80 ° C. higher (250 ° C.). Moreover, it measured also about the commercially available fluororesin ("Kynar720" (PVdF), melting | fusing point 170 degreeC by the Arkema company) whose melting | fusing point is the same as fluorine-containing copolymer (1-1) on the same measurement conditions. The measurement results are shown in Table 1. From the measurement results, it was found that the fluorine-containing copolymer (1-1) was less likely to generate hydrogen fluoride gas due to thermal melting, similar to a commercially available fluorine-containing resin (Kynar 720 (PVdF)).
(Measuring method)
Heat each resin in a corrosion-resistant container under the conditions of adjusting the heating temperature and residence time, absorb the generated hydrogen fluoride gas with the absorbing solution, and ionize the fluorine ions contained in this solution Quantitative analysis was performed by chromatographic analysis. The value in the table is the amount of fluorine ions, the unit is mass%, and “<0.01” represents less than 0.01 mass%.
Sample amount: 1g
Carrier gas: Air
Gas flow rate: 500ml / min
Absorbent: Pure water 30 ml × 2 stations Equipment: Ion chromatograph analyzer ICS-3000 type, manufactured by Dionex

[Material of Layer (II) of Examples 1 to 10]
The following materials were used as the thermoplastic non-fluorine elastomer used as the material for the layer (II) in Examples 1 to 10 or the thermoplastic non-fluorine resin having a melting point of 260 ° C. or lower. Polyethylene terephthalate (hereinafter referred to as “PET”): Teijin Tetron (registered trademark) film G2C (manufactured by Teijin DuPont), film thickness 50 μm, melting point 258 ° C. Polycarbonate (hereinafter referred to as “PC”): Iupilon (registered trademark) H-3000 (Mitsubishi Engineering Plastics Co., Ltd.), melting point 250 ° C. Linear low density polyethylene 1 (hereinafter referred to as “LLDPE”): Neozex (registered trademark) 2015M (manufactured by Prime Polymer Co., Ltd.), melting point 122 ° C. Ether polyol thermoplastic polyurethane (hereinafter referred to as “TPU-1”): Elastollan (registered trademark) 1180AD (manufactured by BASF Japan), no melting point. Ester polyol-based thermoplastic polyurethane 2 (hereinafter referred to as “TPU-2”): Elastollan (registered trademark) C80A10 (manufactured by BASF Japan), no melting point. Polyamide 12 (hereinafter referred to as “PA12”): UBESTA (registered trademark) 3030JI6L (manufactured by Ube Industries), melting point 175 ° C.
Of these, PET has already been molded and used as it is as a press sheet.

[Materials of Layer (III) or Layer (IV) of Examples 1 to 6, 8 to 10]
The epoxy group-containing ethylene copolymer or polyamide elastomer or resin used as the material of the layer (III) or layer (IV) of Examples 1 to 6, 8 to 10 was as follows. (Epoxy group-containing ethylene copolymer having a melting point of 240 ° C. or lower)
As the epoxy group-containing ethylene copolymer having a melting point of 240 ° C. or lower, the following was used. Epoxy group-containing ethylene copolymer 1 (hereinafter referred to as “BF-E”): Bondfast (registered trademark) -E (manufactured by Sumitomo Chemical Co., Ltd.), a structural unit based on glycidyl methacrylate / a structural unit based on ethylene Contains, melting point 103 ° C. Epoxy group-containing ethylene copolymer 2 (hereinafter referred to as “BF-7M”): Bondfast (registered trademark) -7M (manufactured by Sumitomo Chemical Co., Ltd.), constitutional unit based on glycidyl methacrylate / configuration based on methyl acrylate Contains unit, melting point 52 ° C. Epoxy group-containing ethylene copolymer 3 (hereinafter referred to as “BF-2B”): Bondfast (registered trademark) -2B (manufactured by Sumitomo Chemical Co., Ltd.), a structural unit based on glycidyl methacrylate / a structural unit based on vinyl acetate Mp 95 ° C.

(Polyamide elastomer or resin having a melting point of 240 ° C. or lower)
The following polyamide-based elastomer or resin having a melting point of 240 ° C. or lower was used. Nylon (polyamide 12) elastomer (hereinafter referred to as “PAE”): UBESTA (registered trademark) XPA 9055THV (manufactured by Ube Industries), melting point 142 ° C.

[Production Example 2]
Hereinafter, the manufacturing method of the press sheet used in Examples 1-7 is explained.
The following materials were press-molded using a press molding machine manufactured by Tester Sangyo Co., Ltd. to obtain each press sheet having a sheet size of 8 cm × 8 cm × 500 μm. The press molding was performed for each of the following materials under the following molding temperature, pre-melting time 12 minutes, compression time 4 minutes, and press pressure 10 MPa.
In addition, since PET was already shape | molded, press molding was not performed.
(Press sheet for layer (I))
Fluorine-containing copolymer (1-1): Molding temperature 240 ° C
(Press sheet for layer (III))
・ BF-E: Molding temperature 180 ° C
-BF-7M: Molding temperature 180 ° C
・ BF-2B: Molding temperature 180 ° C
・ PAE: Molding temperature 200 ℃
(Press sheet for layer (II))
・ PC: Molding temperature 280 ℃
・ LLDPE: Molding temperature 200 ℃
-TPU-1, TPU-2: Molding temperature 220 ° C
PA12: Molding temperature 250 ° C

[Examples 1-7]
Using a press molding machine manufactured by Tester Sangyo Co., Ltd., the fluororesin laminates of Examples 1 to 7 were manufactured with a press premelting time and a compression time of 2 minutes each.
In Examples 1 to 6, the layer (III) or layer (IV) press sheet shown in Table 2 and the layer (II) press sheet were laminated in this order on the layer (I) press sheet. A sheet-like fluororesin laminate was produced.
In Example 7, a sheet-like fluororesin laminate was produced by laminating the layer (II) press sheet shown in Table 2 on the layer (I) press sheet.
No foaming was observed on the surface of any of the fluorine-containing laminates of Examples 1 to 7.

About the fluororesin laminated body manufactured in Examples 1-7, the peel adhesion strength test method was done according to JISK6854-2: 1999. For the fluororesin laminates of Examples 1 to 6, the peel strength between layer (I) and layer (III) or layer (IV), and layer (III) or layer (IV) and layer (II) The peel strength between was measured. In Example 7, the peel strength between the layer (I) and the layer (II) was measured.
Table 2 shows the combinations of the press sheets of Examples 1 to 7 and the peel strength between the respective layers.

As a result, in each of the fluororesin laminates of Examples 1 to 7, the respective layers were sufficiently bonded. In particular, the layer (I) and the layer (III) in the fluororesin laminates of Examples 1 to 6 provided with the layer (III) were not peelable. Also in Example 7, the layer (I) and the layer (III) had a sufficient peel strength.
Moreover, it had sufficient peeling strength between the layer (II) and layer (III) in the fluororesin laminated body of Examples 1-6.

[Example 8]
Using a three-layer tube forming die, the layer (I) (inner layer) is the fluorine-containing copolymer (1-1), the layer (III) or the layer (IV) (intermediate layer) is PAE, and the layer (II) ( Multi-layer extrusion molding was performed so that the outer layer was TPU-1. As the extruder for the inner layer, one having a diameter of 40 mm was used, and the die temperature after joining the resins forming the three layers was 220 ° C. As the extruder for the inner layer, one having a diameter of 40 mm was used, and the cylinder temperature was set to 210 to 250 ° C. As the extruder for layer (III) or layer (IV), an extruder having a diameter of 30 mm was used, and the cylinder temperature was set to 190 to 210 ° C. An outer layer extruder having a diameter of 50 mm was used, and the cylinder temperature was set to 190 to 210 ° C. The discharge amount of each extruder and the take-up speed of the tube were adjusted so that the final tube shape was 6 mm inside diameter, 8 mm outside diameter, and the wall thickness was 0.1 mm inner layer, 0.1 mm intermediate layer, and 0.8 mm outer layer. As a result, the take-up speed was 6 m / min. The tube discharged from the die passed through the vacuum sizing part, and then cooled in a water tank to fix the final shape.

As described above, the layer (I) of the fluorocopolymer (1-1), the layer (IV) of the polyamide-based elastomer or resin, and the layer (II) of the thermoplastic non-fluororesin are laminated in order from the inner layer. A fluororesin laminate was obtained.
In addition, the outer diameter of this fluororesin laminated body was measured with the infrared outer diameter measuring device after cooling. The inner diameter and the thickness of each layer were calculated from an image obtained by enlarging the cut surface of the molded tube 20 times with an optical microscope.

After cutting this three-layer tube into a length of 75 mm, a rectangular sample having a length of 75 mm in the longitudinal direction and a side length of 10 mm perpendicular to the longitudinal direction was obtained. Then, the laminated interface between the sample layer (IV) and the layer (II) was peeled by about 10 mm in the longitudinal direction by hand to obtain a test piece. At that time, the layer (I) and the layer (IV) could not be separated by hand.
A peel adhesion strength test was performed between the layer (IV) and the layer (II) of the test piece. Specifically, the peel strength (adhesive strength) was calculated by dividing the load when peeled off at 30 mm / min with a tensile tester by the test piece width.

[Example 9]
Multi-layer extrusion molding is performed so that layer (I) (inner layer) is a fluorinated copolymer (1-1), layer (III) (intermediate layer) is BF-7M, and layer (II) (outer layer) is LLDPE. It was. At this time, the die temperature after joining the resins forming the three layers was 220 ° C. As the extruder for the inner layer, one having a diameter of 40 mm was used, and the cylinder temperature was set to 210 to 250 ° C. An intermediate layer extruder having a diameter of 30 mm was used, and the cylinder temperature was set to 170 to 190 ° C. An outer layer extruder having a diameter of 50 mm was used, and the cylinder temperature was set to 190 to 220 ° C. The discharge amount of each extruder and the take-up speed of the tube were adjusted so that the final tube shape was 6 mm inside diameter, 8 mm outside diameter, and the wall thickness was 0.1 mm inner layer, 0.1 mm intermediate layer, and 0.8 mm outer layer. Thereby, the take-up speed was set to 2 m / min. The tube discharged from the die passed through the vacuum sizing part, and then cooled in a water tank to fix the final shape.

By the above, the layer (I) of the fluorine-containing copolymer (1-1), the layer (III) of the epoxy group-containing ethylene-based copolymer, and the layer (II) of the thermoplastic non-fluorine resin are separated from the inner layer. A fluororesin laminate laminated in order was obtained.
A test piece was obtained in the same manner as in Example 8. At that time, the layer (I) and the layer (II) could not be separated by hand. A peel adhesion strength test was performed between the layer (IV) and the layer (II) of the test piece.

[Example 10]
Multi-layer extrusion molding is performed so that layer (I) (inner layer) is the above-mentioned fluorinated copolymer (1-1), layer (III) (intermediate layer) is BF-E, and layer (II) (outer layer) is LLDPE. went. At this time, the temperature in the heat lamination step of each layer and the cylinder temperature of each extruder were the same as in Example 9. The discharge amount of each extruder and the take-up speed of the tube were adjusted so that the final tube shape was 6 mm inside diameter, 8 mm outside diameter, and the wall thickness was 0.1 mm inner layer, 0.1 mm intermediate layer, and 0.8 mm outer layer. Thereby, the take-up speed was set to 2 m / min. The tube discharged from the die passed through the vacuum sizing part, and then cooled in a water tank to fix the final shape.

As described above, the layer (I) mainly composed of the fluorine-containing copolymer (1-1), the layer (III) mainly composed of the epoxy group-containing ethylene copolymer, and the thermoplastic non-fluorine resin are mainly used. A fluororesin laminate in which the component layer (II) was laminated in order from the inner layer was obtained.
Using the fluororesin laminate, a test piece adjustment method and a peel adhesion strength test were conducted in the same manner as in Example 8. At that time, layer (I) and layer (III) could not be separated by hand.
Table 3 shows the combination of materials of each layer of Examples 8 to 10 and the peel strength between each layer.

  As a result, in each of the fluororesin laminates of Examples 8 to 10, the respective layers were sufficiently bonded. In particular, separation between layer (I) and layer (III) or layer (IV) was impossible. Moreover, it had sufficient peeling strength between layer (II) and layer (III) or layer (IV).

Examples of the use of the fluororesin laminate of the present invention or a laminate of four or more layers combined with other layers include, for example, a laminated printed circuit board, a wiring / pipe cover duct (protection tube), an aircraft part, and a vehicle part Protecting outdoor parts of building parts called exteriors, building parts such as outer wall protection and inner layer walls, electrical parts, industrial hoses for transporting oils, chemicals, paints, fruit juices, pasty foods, etc., gasoline , Fuel oil hoses for gas oil, alcohol, etc., hot water supply hoses, chemical tanks, fuel tanks, packaging, industrial films for agricultural houses, release films for cast film manufacture, semiconductor green sheets, release molds for IC chip manufacture A release film such as a film, a food film, a wire coating, a core material for rubber processing, and the like are conceivable.
The fluororesin laminate of the present invention is excellent in weather resistance, electrical insulation, acid / alkali resistance, flame retardancy, and gas permeability.

Claims (9)

  The main component is a layer (I) mainly composed of a fluorine-containing copolymer (1) having a melting point of 220 ° C. or lower, and a thermoplastic non-fluorine elastomer or a thermoplastic non-fluorine resin (2) having a melting point of 260 ° C. or lower. A fluororesin laminate obtained by laminating layer (II). Between the layer (I) and the layer (II), a layer (III) mainly composed of an epoxy group-containing ethylene copolymer (3) having a melting point of 240 ° C. or lower, or a melting point of 240 ° C. Layer (IV) mainly composed of the following polyamide elastomer or resin (4) is laminated,
The fluororesin laminate according to claim 1, wherein the component of the layer (III) or the layer (IV) is different from the component of the layer (II).   The fluorine-containing copolymer (1) comprises a structural unit (A) based on tetrafluoroethylene, a structural unit (B) based on ethylene, itaconic acid, itaconic anhydride, and 5-norbornene-2,3-dicarboxylic acid. And a constituent unit (C) based on one or more selected from the group consisting of 5-norbornene-2,3-dicarboxylic anhydride, citraconic acid and citraconic anhydride. Resin laminate. The structural unit (A) is 25 to 79.99 mol% with respect to the total molar amount of the structural unit (A), the structural unit (B), and the structural unit (C), and the structural unit ( B) is 20 to 74.99 mol%, the structural unit (C) is 0.01 to 5 mol%,
The fluororesin laminate according to claim 3, wherein the fluorine-containing copolymer (1) has a melting point of 100 to 220 ° C. The fluorine-containing copolymer (1) further contains a structural unit (D) based on another monomer (d) other than the structural unit (A), the structural unit (B), and the structural unit (C). And
The fluororesin laminate according to claim 3 or 4, wherein a molar ratio (A / D ratio) between the structural unit (A) and the structural unit (D) is 70/30 to 99.9 / 0.1. body. The fluorine-containing copolymer (1) further contains a structural unit (D) based on another monomer (d) other than the structural unit (A), the structural unit (B), and the structural unit (C). And
The fluororesin laminate according to any one of claims 3 to 5, wherein the fluorine-containing copolymer (1) contains a structural unit (D1) based on hexafluoropropylene as the structural unit (D). . The fluorine-containing copolymer (1) further comprises, as the structural unit (D), a structural unit (D2) based on CH ₂ ═CH (CF ₂ ) _Q1 F (where Q1 is an integer of 2 to 10). The fluororesin laminate according to claim 6, comprising:   The fluororesin laminate according to any one of claims 1 to 7, wherein the peel strength between adjacent layers is 5 N / cm or more in the peel adhesion strength test method based on JIS K 6854-2: 1999. Having a thermal lamination process by multilayer extrusion using multiple extruders;
The manufacturing method of the fluororesin laminated body as described in any one of Claims 1-8 whose die temperature of the said extruder in the said thermal lamination process is 170-280 degreeC.