JP2016215602A - Fluorine resin laminate and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine resin laminate having a layer of a fluorine resin and an adhesive layer, capable of strongly adhering a layer composed of other materials to the layer of the fluorine resin and having flexibility and heat resistance, a multilayer sheet and a multilayer tube obtained by using the fluorine resin laminate and a manufacturing method of the fluorine resin laminate.SOLUTION: There is provided a fluorine resin laminate having at least a layer (I) of a fluorine-containing polymer (i) having a carbonyl group-containing group and having the melting point of less than 230°C and a layer (II) of an epoxy group-containing non-fluorine thermoplastic polymer (ii) arranged in contact with the layer (I) and having tensile fracture elongation (%) measured according to ASTM-D638 of 100% or more and no melting point.SELECTED DRAWING: None

Description

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

  As represented by polytetrafluoroethylene, the fluororesin is excellent in properties such as heat resistance, flame retardancy, chemical resistance, weather resistance, non-adhesiveness, low friction, and low dielectric properties. Therefore, it is used in a wide range of fields such as chemical plant corrosion-resistant piping materials, agricultural greenhouse materials, release coating materials for kitchen appliances, coating materials for electronic devices, and coating materials for heat-resistant flame-retardant wires. In particular, an ethylene / tetrafluoroethylene copolymer (hereinafter, also referred to as “ETFE”) is excellent in the above-described characteristics and can be melt-molded, and thus has a wide variety of uses.

As described above, the fluororesin has excellent characteristics but is expensive, and in recent years, attempts have been made to form a laminate with other inexpensive general-purpose resin materials and the like.
However, since the fluororesin has low surface energy and low affinity with other materials, adhesion between the layers with other materials is insufficient. Therefore, when a sheet, a tube, or the like obtained from a laminate of a fluororesin and another material is bent, there is a problem that these layers are easily separated.

With respect to the above-described problem, Patent Document 1 has been studied to produce a laminate of a specific fluororesin and another material using an epoxy group-containing ethylene copolymer that is a thermoplastic resin as an intermediate primer layer. Yes. However, when this laminate is used at a high temperature, the shape of the laminate may collapse and peeling may occur between the layers.
Patent Document 2 proposes a laminate using a polyamide resin as an adhesive layer between a fluororesin layer and a polyurethane elastomer layer. However, the adhesion between the polyamide resin layer and the polyurethane elastomer layer is still insufficient. Moreover, the polyamide-based resin is inferior in flexibility and easily broken.

JP 2006-297843 A Japanese Patent No. 4832081

  The present invention includes a fluororesin laminate having a fluororesin layer and an adhesive layer, capable of firmly bonding a layer made of another material to the fluororesin layer, and having flexibility and heat resistance. It aims at providing the manufacturing method of the multilayer sheet | seat and multilayer tube which were obtained using the resin laminated body, and this fluororesin laminated body.

The present invention has the following configuration.
[1] A layer (I) of a fluoropolymer (i) having a carbonyl group-containing group and a melting point of less than 230 ° C., provided in contact with the layer (I), in accordance with ASTM-D638 A layer (II) of an epoxy group-containing non-fluorinated thermoplastic polymer (ii) having a measured tensile breaking elongation (%) of 100% or more and having no melting point, Fluororesin laminate.
[2] The fluororesin laminate of [1], wherein the epoxy group-containing non-fluorine thermoplastic polymer (ii) is an epoxidized product of a polystyrene-polybutadiene block copolymer.
[3] The fluoropolymer (i) is a copolymer having units based on perhalofluoroethylene having 3 or 4 fluorine atoms and units based on ethylene, and having a carbonyl group-containing group. The fluororesin laminate of [1] or [2].
[4] The fluorine-containing polymer (i) has at least one of a unit based on a monomer having a carbonyl group-containing group and a main chain end group having a carbonyl group-containing group, [1] to [3] Laminated body.
[5] The fluoropolymer (i) includes a unit (A) based on tetrafluoroethylene, a unit (B) based on ethylene, and a unit (C1) based on a non-fluorine monomer having an acid anhydride residue, And a unit (C) consisting of at least one of units (C2) based on a non-fluorine monomer having two or more carboxy groups, the unit (A), the unit (B), and the unit (C) The unit (A) is 25 to 79.99 mol%, the unit (B) is 20 to 74.99 mol%, and the unit (C) is 0.01 to 5 mol% The fluororesin laminate according to [4], which has a melting point of 100 to 220 ° C.
[6] The fluoropolymer (i) is a unit based on other monomers other than tetrafluoroethylene, ethylene, a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups. The fluororesin laminate according to [5], further comprising (D), wherein the molar ratio of the unit (A) to the unit (D) is from 70/30 to 99.9 / 0.1.
[7] The fluoropolymer (i) is a unit based on other monomers other than tetrafluoroethylene, ethylene, a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups. [5] or [6], further comprising (D), wherein the molar ratio of the unit (D) to the sum of the unit (A) and the unit (B) is from 1/99 to 20/80. Fluoropolymer laminate.
[8] The fluororesin laminate according to [6] or [7], wherein the unit (D) includes a unit (D1) based on hexafluoropropylene as the other monomer.
[9] The unit (D) further includes a unit (D2) based on CH ₂ ═CH (CF ₂ ) _Q1 F (where Q1 is an integer of 2 to 10) which is the other monomer. ] Fluororesin laminate.
[10] It further has a layer (III) made of a non-fluorine thermoplastic polymer (iii) having no epoxy group provided in contact with the side of the layer (II) where the layer (I) is not provided, The fluororesin laminate of [1] to [9].
[11] The fluororesin laminate according to [10], wherein the non-fluorine thermoplastic polymer (iii) is a polyurethane-based thermoplastic elastomer.
[12] A multilayer tube or multilayer sheet obtained from the fluororesin laminate of [1] to [11].
[13] A method for producing a fluororesin laminate according to [1] to [11], wherein at least the layer (I) and the layer are in a temperature range from the melting point of the fluoropolymer (i) to less than 400 ° C. The manufacturing method of a fluororesin laminated body which has a heat | fever lamination process which heat-seal | fuses (II) in 1 second or more and less than 60 minutes.

The fluororesin laminate of the present invention has a fluororesin layer and an adhesive layer, and a layer made of another material can be firmly adhered to the fluororesin layer via the adhesive layer, and is also flexible and heat resistant. It also has sex.
According to the method for producing a fluororesin laminate of the present invention, a fluororesin layer and an adhesive layer are provided, and a layer made of another material can be firmly adhered to the fluororesin layer via the adhesive layer, and A fluororesin laminate having flexibility can be produced.

The “unit” in the present specification means a unit based on the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction or a unit in which a part of the unit is converted into another structure by treating the polymer.
“Monomer” means a compound having a polymerizable unsaturated bond, that is, a polymerization-reactive carbon-carbon double bond.
“Main chain” refers to a portion having the maximum number of carbon atoms in a carbon chain formed by polymerization of monomers.

  The fluororesin laminate of the present invention has at least two layers of a layer (I) of a fluoropolymer (i) and a layer (II) of an epoxy group-containing non-fluorine thermoplastic polymer (ii). Here, the layer (II) acts as an adhesive layer for adhering the layer (I) to a layer (III) described later.

[Layer (I) of fluoropolymer (i)]
The fluoropolymer (i) constituting the layer (I) is a polymer having a carbonyl group-containing group and a melting point of less than 230 ° C.
If the melting point of the fluoropolymer (i) is less than the above upper limit value, in the thermal lamination step of thermally fusing at least the layer (I) and the layer (II) when producing the fluororesin laminate, for example, The die temperature of the extruder and the temperature of the press plate in the heating press can be set to a low temperature. Therefore, the fluorine-containing polymer (i) constituting the layer (I) and the epoxy group-containing non-fluorine thermoplastic polymer (ii) constituting the layer (II) are hardly thermally decomposed in the heat lamination step, and the fluorine-containing polymer. Foaming and the like of (i) and the epoxy group-containing non-fluorinated thermoplastic polymer (ii) can be suppressed. The melting point of the fluoropolymer (i) is preferably from 100 to 220 ° C, more preferably from 120 to 205 ° C, and even more preferably from 150 to 200 ° C. If the melting point is not more than the upper limit of the above range, the fluoropolymer (i) and the epoxy group-containing non-fluorinated thermoplastic polymer (ii) in the thermal lamination step described above are more difficult to be thermally decomposed and foaming and the like are further suppressed. it can. When the melting point is not less than the lower limit of the above range, it is easy to obtain a fluororesin laminate in which the layer (I) and the layer (II) are firmly bonded.
Fluoropolymer (i) may be used individually by 1 type, or may use 2 or more types together.

  In the present specification, the “melting point (° C.)” means a temperature at which a solid melts and liquefies in a resin having a crystal structure. Specifically, a sample is measured at a constant speed using a differential scanning calorimeter. The melting peak when the temperature is raised at is recorded and the temperature (° C.) corresponding to the maximum value is taken as the melting point.

As the fluoropolymer (i), the following polymers (a) to (d) are preferred.
(A) a copolymer having a carbonyl group-containing group, a unit based on perhalofluoroethylene having 3 or 4 fluorine atoms, and a unit based on ethylene,
(B) a polyvinylidene fluoride having a carbonyl group-containing group,
(C) polychlorotrifluoroethylene having a carbonyl group-containing group,
(D) A copolymer having a carbonyl group-containing group, a unit based on perhalofluoroethylene having 3 or 4 fluorine atoms, a unit based on hexafluoropropylene, and a unit based on vinylidene fluoride.
Among the above polymers (a) to (d), it is excellent in properties such as heat resistance, flame retardancy, chemical resistance, weather resistance, non-adhesiveness, low friction, low dielectric properties, and mechanical strength. From the viewpoint, the copolymer (a) is preferred. The copolymer (a) may contain units (D) based on other monomers, as will be described later.
Perhalofluoroethylene means a compound in which all of the hydrogen atoms of ethylene are substituted with halogen atoms, and at least one of the halogen atoms is a fluorine atom. Examples of the perhalofluoroethylene having 3 or 4 fluorine atoms include tetrafluoroethylene (hereinafter also referred to as “TFE”), chlorotrifluoroethylene, and the like, and TFE is preferable. Perhalofluoroethylene having 3 or 4 fluorine atoms may be used alone or in combination of two or more.

The carbonyl group-containing group is a group containing a carbonyl group (—C (═O) —) in the structure.
Examples of the carbonyl group-containing group include 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, an acid anhydride residue, and the like.
Examples of the hydrocarbon group in the group having a carbonyl group between carbon atoms of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms. In addition, carbon number of this alkylene group is carbon number in the state which does not contain a carbonyl group. The alkylene group may be linear or branched.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferred from the viewpoint of reactivity with other base materials. 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 may be linear or branched, and is preferably an alkoxy group having 1 to 8 carbon atoms, particularly preferably a methoxy group or an ethoxy group, from the viewpoint of reactivity with other substrates.

The carbonyl group-containing group can be introduced into the fluoropolymer (i) by the following methods (1) to (4).
(1) A method of using a monomer having a carbonyl group-containing group when producing the fluoropolymer (i) by a polymerization reaction. According to this method, a fluoropolymer (i) having a unit based on a monomer having a carbonyl group-containing group is obtained.
(2) A method of using at least one of a radical polymerization initiator having a carbonyl group-containing group and a chain transfer agent having a carbonyl group-containing group when producing the fluoropolymer (i) by a polymerization reaction. According to this method, a fluoropolymer (i) having a main chain terminal group having a carbonyl group-containing group is obtained.
(3) A method of generating a carbonyl group-containing group by heating a fluorine-containing polymer having a thermal decomposition site that generates a carbonyl group-containing group by thermal decomposition and partially thermally decomposing the fluorine-containing polymer.
(4) A method in which a monomer having a carbonyl group-containing group is graft-polymerized to a fluorine-containing polymer having no carbonyl group-containing group, and the carbonyl group-containing group is introduced into the fluorine-containing polymer.

  Especially, what has the unit based on the monomer which has a carbonyl group containing group obtained by the method of said (1) as a fluoropolymer (i) is preferable at the point which is excellent in thermal stability.

  As the fluoropolymer (i), a copolymer having a unit (A) based on TFE, a unit (B) based on ethylene, and a unit (C) is particularly preferable. The unit (C) is a unit based on a monomer having a carbonyl group-containing group, and is based on a unit (C1) based on a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups. It consists of at least one of the units (C2).

Examples of the non-fluorine monomer having an acid anhydride residue constituting the unit (C1) include itaconic anhydride (hereinafter also referred to as “IAH”), 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as “IAH”). And “NAH”), citraconic anhydride (hereinafter also referred to as “CAH”), and the like. The non-fluorine monomer having an acid anhydride residue may be used alone or in combination of two or more.
Examples of the non-fluorine monomer having two or more carboxy groups constituting the unit (C2) include itaconic acid (hereinafter also referred to as “IAC”), 5-norbornene-2,3-dicarboxylic acid (hereinafter referred to as “NAC”). And citraconic acid (hereinafter also referred to as “CAC”), and the like. The non-fluorine monomer having two or more carboxy groups may be used alone or in combination of two or more.

Conventionally, for example, a unit based on one or more selected from the group consisting of IAH, NAH and CAH (C1) or a unit based on one or more selected from the group consisting of IAC, NAC and CAC (C2), The fluorine-containing polymer (i) containing the unit (C) can be easily produced without using a special polymerization method which is necessary when maleic anhydride described in Kaihei 11-19312 is used. .
Of these, units based on IAH are preferred from the viewpoint of excellent polymerizability.

The content of each unit (A) to (C) in the fluoropolymer (i) is such that the unit (A) is based on the total molar amount of the unit (A), the unit (B) and the unit (C). It is preferably 25 to 79.99 mol%, the unit (B) is 20 to 74.99 mol%, the unit (C) is preferably 0.01 to 5 mol%, and the unit (A) is 50 to 50 mol%. More preferably, the unit (B) is 35 to 49.97 mol%, the unit (C) is 0.03 to 3 mol%, and the unit (A) is 50 to 59 mol%. It is most preferable that it is 0.995 mol%, a unit (B) is 40-49.95 mol%, and a unit (C) is 0.05-1 mol%.
If content of each unit (A)-(C) is in the said range, fluoropolymer (i) will be excellent in chemical resistance and heat resistance. In particular, when the content of the unit (C) is within the above range, in addition to the chemical resistance and heat resistance, the adhesion between the layer (I) and the layer (II) described later becomes higher.
Moreover, if content of each unit (A)-(C) is in the said range, it will be easy to control melting | fusing point of fluoropolymer (i) to 100-220 degreeC.

  The molar ratio ((A) / (B)) of the unit (A) to the unit (B) in the fluoropolymer (i) is preferably 25/75 to 80/20, more preferably 50/50 to 65/35. Preferably, 50/50 to 61/39 is more preferable, and 50/50 to 60/40 is most preferable. If it is below the upper limit, the mechanical strength of the fluoropolymer (i) is more excellent. If it is more than a lower limit, the heat resistance of fluoropolymer (i) will be more excellent. Within the above range, the mechanical strength and heat resistance of the fluoropolymer (i) are both excellent.

The fluoropolymer (i) preferably further has a unit (D) based on another monomer in addition to the units (A) to (C) from the viewpoint of easily controlling the melting point within the above range. When the content ratio of the unit (D) with respect to all the units constituting the fluoropolymer (i) is large, the melting point of the fluoropolymer (i) tends to be low.
The other monomer is a monomer other than TFE, ethylene, a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups, and is divided into a fluorine-containing monomer and a non-fluorine monomer.

Among the other monomers, 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 ( although, Q1 is 2-10 _{integer.), CH 2 = CF (} CF 2) Q2 H ( provided that, Q2 is Fluorine-containing olefins such as 2 to 10), and fluoro such as CF ₂ = CFOR ¹ (wherein R ¹ represents a C 1-10 fluoroalkyl group which may contain an etheric oxygen atom). alkyl vinyl ^{_{ether), CF 2 = CFOR 2 SO}} 2 X 1 ( provided that, ^{R 2} is 1 to 10 carbon atoms which may contain an etheric oxygen atom Represents 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 etheric fluoroalkylene group having 1 to 10 also carbon atoms include an 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 is preferably a C 1-6 fluoroalkyl group, and more preferably a C 1-4 fluoroalkyl group.
R ² and R ³ are preferably a C 1-6 fluoroalkylene group, and more preferably a C 1-4 fluoroalkylene group.
The fluoroalkyl group is particularly preferably a perfluoroalkyl group such as a CF ₃ group, a C ₂ F ₅ group, or a C ₃ F ₇ group, and the fluoroalkylene group is a CF ₂ group, a C ₂ F ₄ group, or a C ₃ F _6. A perfluoroalkylene group such as a group is particularly preferred.

_{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, the non-fluorine monomer is a non-fluorine monomer other than ethylene, a non-fluorine monomer having an acid anhydride residue, and a non-fluorine monomer having two or more carboxy groups. For example, methyl vinyl ether, ethyl vinyl ether, Examples include vinyl ethers such as butyl vinyl ether, 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 viewpoints of thermal stability and processability of the fluoropolymer (i).
A non-fluorine monomer may be used individually by 1 type, or may use 2 or more types together.

The unit (D) is preferably a unit based on a fluorinated monomer from the viewpoint of heat resistance of the fluorinated polymer (i).
The fluoropolymer (i) preferably has at least a unit (D1) based on HFP as the unit (D). When the fluoropolymer (i) contains the unit (D1), the melting point of the fluoropolymer (i) can be easily controlled within the above range without reducing the heat resistance of the fluoropolymer (i). .
In addition to the unit (D1) as the unit (D), the fluoropolymer (i) has the above-mentioned VDF, CF ₂ = CFOR ¹ , CH ₂ = CH (CF ₂ ) _Q1 F, and CH ₂ = CF (CF ₂ ) more preferably contains the units based on one monomer selected from the group consisting of _Q2 H, and more preferably has a unit (D2) based on inter alia _{CH 2 = CH (CF 2)} Q1 F. When the fluoropolymer (i) contains the unit (D2) together with the unit (D1) as the unit (D), the melting point of the fluoropolymer (i) can be easily controlled within the above range, and The coalescence (i) is excellent in stress crack resistance, moldability and productivity.

The molar ratio of unit (A) to unit (D) ((A) / (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 it is below an upper limit, melting | fusing point of a fluoropolymer (i) falls and it becomes easy to control this melting | fusing point in the said range. If it is more than the lower limit, the chemical resistance and heat resistance of the fluoropolymer (i) are more excellent.
Further, the molar ratio ((D) / ((A) + (B))) of the unit (D) to the sum of the unit (A) and the unit (B) is 1/99 to 20/80. Preferably, 2/98 to 15/85 is more preferable, and 4/96 to 12/88 is most preferable. If it is below the upper limit, the chemical resistance and heat resistance of the fluoropolymer (i) are more excellent. If it is more than a lower limit, melting | fusing point of fluoropolymer (i) will fall and it will become easy to control this melting | fusing point to the said range.

As described above, when the fluorinated polymer (i) contains the unit (D), if the content ratio of the unit (D) with respect to all the units constituting the fluorinated polymer (i) is large, The melting point of the coalescence (i) tends to be low.
6-15 mol% is preferable and, as for the content rate of the unit (D1) with respect to all the units which comprise a fluoropolymer (i), 7-12 mol% is more preferable. If it is below an upper limit, the melting point of the fluoropolymer (i) does not become too high, and the moldability is excellent. If it is more than the lower limit, the polymerization reaction during the production of the fluoropolymer (i) proceeds without problems, and the productivity is excellent, and the heat resistance and moldability of the fluoropolymer (i) are more excellent. Within the above range, the productivity, heat resistance and moldability of the fluoropolymer (i) are excellent.

  When the fluoropolymer (i) includes the unit (D1) and the unit (D2) as the unit (D), the molar ratio of the unit (D1) to the unit (D2) ((D1) / (D2)) is 75 / 25 to 97/3 is preferable, 80/20 to 96/4 is more preferable, and 85/15 to 95/5 is most preferable. If it is below an upper limit, the stress crack resistance and moldability of the fluoropolymer (i) are more excellent. If it is more than a lower limit, it will become easy to control melting | fusing point of a fluoropolymer (i) by the said range.

  When the fluoropolymer (i) contains a unit (P) based on propylene as the unit (D), the content ratio of the unit (P) to all the units constituting the fluoropolymer (i) is 6 to 20 mol% is preferable and 7-15 mol% is more preferable. If it is below the upper limit, the melting point of the fluoropolymer (i) does not become too high and is excellent in moldability, and if it is at least the lower limit, the polymerization reaction of the fluoropolymer (i) proceeds without problems, While being excellent in productivity, the heat resistance of a fluoropolymer (i) and a moldability are more excellent.

Examples of the fluorinated polymer (i) include copolymers comprising the following units (1) to (5). Among these, the following (5) copolymers are preferred.
(1) Unit (A) / Unit (B) / Unit (C);
(2) Unit (A) / Unit (B) / Unit (C) / Unit (D1);
(3) Unit (A) / Unit (B) / Unit (C) / Propylene-based unit;
(4) Unit (A) / Unit (B) / Unit (C) / Unit (D2) / Propylene-based unit;
(5) Unit (A) / Unit (B) / Unit (C) / Unit (D1) / Unit (D2).

When the fluorocopolymer (i) is produced by a polymerization reaction, the polymerization method is not particularly limited. For example, a known radical polymerization initiator and a chain transfer agent as described in Patent Document 1 are known. A polymerization method is mentioned.
As a radical polymerization initiator, the temperature at which the half-life is 10 hours is preferably 0 to 100 ° C, and more preferably 20 to 90 ° C. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert- butyl peroxypivalate, tert- butylperoxy isobutyrate, peroxy esters such as tert- butylperoxy _{acetate, 2} (where _{(Z (CF 2) r COO} ), Z is a hydrogen atom, a fluorine atom or a chlorine atom, r is an integer of 1 to 10.) Inorganic peroxides such as fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

  When an initiator having a carbonyl group-containing group is used as the radical polymerization initiator, the carbonyl group-containing group can be introduced as the main chain end group of the fluoropolymer (i). Examples of such radical polymerization initiators include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2. -Ethylhexyl peroxydicarbonate and the like.

Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed.
When a chain transfer agent having a carbonyl group-containing group is used as the chain transfer agent, the carbonyl group-containing group can be introduced as the main chain terminal group of the fluoropolymer (i). Examples of such chain transfer agents include acetic acid, acetic anhydride, methyl acetate and the like.
When a chain transfer agent is used, the melt flow rate (MFR) of the fluoropolymer (i) and the capacity flow rate described later can be controlled.

Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Suspension polymerization, and emulsion polymerization using an aqueous medium and an emulsifier. Preferably, it is solution polymerization.
The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.

The concentration of the non-fluorine monomer constituting the unit (C1) and the unit (C2) during the polymerization is preferably 0.01 to 5 mol% with respect to the total of all monomers, preferably 0.1 to 3 mol%. It is more preferable to set it as 0.1-1 mol%. When the concentration of the non-fluorine monomer is within the above range, the polymerization rate is good, and when the concentration is too high, the polymerization rate tends to decrease.
During the polymerization, as the non-fluorine monomer is consumed in the polymerization, it is preferable to supply the consumed amount into the polymerization tank continuously or intermittently and maintain the concentration of the non-fluorine monomer within the above range.

The fluoropolymer (i) has a temperature at which the capacity flow rate (hereinafter also referred to as “Q value”) is 0.1 to 1000 mm ³ / sec at a temperature 20 to 50 ° C. higher than the melting point. 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 polymer. 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 fluoropolymer (i), 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.

  In addition to the fluoropolymer (i), the layer (I) is composed of components other than the fluoropolymer (i) such as a filler (for example, carbon black, carbon fiber, glass fiber, carbon nanotube, etc.) ( In I), it may be contained in a range of less than 50% by mass. The content of components other than the fluoropolymer (i) in the layer (I) is preferably less than 20% by mass, and more preferably less than 15% by mass.

[Layer (II) of Epoxy Group-Containing Non-Fluorine Thermoplastic Polymer (ii)]
The layer (II) is provided in contact with the layer (I) and functions as an adhesive layer for bonding the layer (I) and a layer (III) described later.
The epoxy group-containing non-fluorine thermoplastic polymer (ii) constituting the layer (II) is a thermoplastic polymer having an epoxy group and having no fluorine atom. Further, it is a so-called elastomer having a tensile elongation at break (%) measured in accordance with ASTM-D638 of 100% or more and having no melting point because it has no crystal structure. The epoxy group is a functional group that reacts with the carbonyl group-containing group of the fluoropolymer (i) constituting the layer (I). Since the epoxy group-containing non-fluorinated thermoplastic polymer (ii) constituting the layer (II) has a tensile elongation at break of the above lower limit or more, the layer (II) is excellent in flexibility, and the layer (II) In the fluororesin laminate having, cracks are unlikely to occur. In addition, since the epoxy group-containing non-fluorinated thermoplastic polymer (ii) constituting the layer (II) has an epoxy group, it adheres firmly to the layer (I) and the layer (III) described later. In addition, since the epoxy group-containing non-fluorine thermoplastic polymer (ii) does not exhibit a melting point and does not have a crystal structure, the layer (I ) And the sheet forming the layer (II) are considered to have a small shrinkage rate upon cooling after being heated and laminated. This is not only because the layer (II) of the epoxy group-containing non-fluorinated thermoplastic polymer (ii) adheres well to the layer (I) but also to the layer (III) described later. It is thought that it is one factor of adhesion to the surface. Moreover, since the epoxy group-containing non-fluorinated thermoplastic polymer (ii) does not have a crystal structure, it is excellent in heat resistance. Therefore, even when the fluororesin laminate having the layer (II) of the epoxy group-containing non-fluorine thermoplastic polymer (ii) is used at a high temperature and bent, it is difficult to cause delamination between layers. The epoxy group-containing non-fluorine thermoplastic polymer (ii) may be used alone or in combination of two or more.
Since the epoxy group-containing non-fluorine thermoplastic polymer (ii) does not have a melting point, it does not show a melting peak when heated at a constant rate using a differential scanning calorimeter.

  From the point that the tensile elongation at break (%) of the epoxy group-containing non-fluorinated thermoplastic polymer (ii) is excellent in flexibility and hardly cracked, and a fluororesin laminate excellent in heat resistance is easily obtained. 150% or more is preferable, 300% or more is more preferable, and 700% or more is most preferable. The upper limit of the tensile elongation at break (%) is not particularly limited, but is preferably 1500% or less, more preferably 1200% or less, and most preferably 1000% or less from the viewpoint of strength.

The epoxy group-containing non-fluorine thermoplastic polymer (ii) can be produced by a known method, for example, by a method of oxidizing and epoxidizing the non-fluorine thermoplastic polymer.
Specifically, using a percarboxylic acid obtained by reacting hydrogen peroxide with a lower carboxylic acid such as formic acid or acetic acid as an epoxidizing agent, the epoxidizing agent and a non-fluorine thermoplastic polymer are reacted. The method of performing an epoxidation reaction is mentioned. The reaction is performed in the presence or absence of a solvent.
Other methods include epoxidizing non-fluorine thermoplastic polymers with hydrogen peroxide in the presence of catalysts and solvents such as osmium salts, tungstic acid, etc., and solid non-fluorine thermoplastic polymers as organic Examples include a method of epoxidizing by dispersing or suspending in a solvent and using a peroxide as an epoxidizing agent.

The non-fluorine thermoplastic polymer to be epoxidized is preferably a solid having a double bond in the molecule. The non-fluorine thermoplastic polymer may be a polymer of one kind of monomer or a copolymer of two or more kinds of monomers. Moreover, the non-fluorine thermoplastic polymer needs to exhibit a solid at normal temperature (23 ° C.). To exhibit a solid at normal temperature means to exhibit a solid such as a powder or a granule at normal temperature, and does not indicate a liquid or paste at normal temperature.
Examples of the polymer of one kind of monomer include polybutadiene, polyisoprene rubber, polybutylene, dicyclopentadiene resin and cyclopentadiene resin which are polymers of alicyclic diene monomers.
Random copolymers and blocks of two or more non-fluorine monomers selected from vinyl aromatic hydrocarbon monomers, diene monomers, olefins, and other monomers as copolymers of two or more monomers A copolymer is mentioned.

Specific examples of the vinyl aromatic hydrocarbon monomer include styrene, alkyl-substituted styrene (α-methylstyrene, etc.), alkoxy-substituted styrene, vinyl naphthalene, alkyl-substituted vinyl naphthalene, divinylbenzene, vinyl toluene and the like. A vinyl aromatic hydrocarbon monomer may be used individually by 1 type, or may use 2 or more types together.
Specific examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1 , 3-butadiene and the like; dicyclopentadiene, cyclopentadiene, ethylidene norbornene and the like having an alicyclic skeleton. A diene monomer may be used individually by 1 type, or may use 2 or more types together.
Specific examples of olefins include ethylene and propylene. Olefin may be used alone or in combination of two or more.
Examples of other monomers include acrylonitrile. Other monomers may be used alone or in combination of two or more.

In the case of a random copolymer, an ethylene-propylene-diene-terpolymer is preferred.
In the case of a block copolymer, for example, a polystyrene-polybutadiene block copolymer, a polystyrene-polybutadiene-polystyrene block copolymer, a polystyrene-polyisoprene-polystyrene block copolymer, a polyacrylonitrile-polybutadiene block copolymer, etc. Among them, a polystyrene-polybutadiene block copolymer is preferable because it is excellent in elasticity.
That is, the epoxy group-containing non-fluorine thermoplastic polymer (ii) is preferably an epoxidized product of a polystyrene-polybutadiene block copolymer.

  The structure of the block copolymer molecule itself may be any structure such as linear, branched, and radial. The average molecular weight of the block copolymer is not particularly limited, but is preferably such that it does not dissolve in low molecular weight organic solvents.

There are no particular restrictions on the end groups of the non-fluorine thermoplastic polymer that is the subject of epoxidation.
The form of the non-fluorinated thermoplastic polymer in the epoxidation may be in the form of pellets, but in order to efficiently perform the epoxidation reaction and achieve a high epoxidation rate, the pellets are crushed to reduce the surface area. It is preferable to make the powder large and small in particle size. Examples of the pulverization method include a pulverization method using a normal pulverizer and a pulverization method using a freeze pulverization method.

  The organic solvent used for the epoxidation reaction varies depending on the type of non-fluorine thermoplastic polymer to be epoxidized and the reaction conditions for epoxidation, but linear and branched carbonization such as hexane and octane. Hydrogens; alkyl-substituted derivatives of the hydrocarbons; alicyclic hydrocarbons such as cyclohexane and cycloheptane; alkyl-substituted derivatives of the alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, naphthalene, toluene, and xylene Alkyl substituted aromatic hydrocarbons of the aromatic hydrocarbons; aliphatic carboxylic acid esters such as methyl acetate and ethyl acetate; halogenated hydrocarbons such as chloroform; Among these, from the viewpoint of the solubility of the non-fluorine thermoplastic polymer to be epoxidized and the ease of recovery of the organic solvent after the reaction, it is selected from the group consisting of cyclohexane, ethyl acetate, chloroform, toluene, xylene, and hexane. One or more are preferred.

The amount of epoxidizing agent to be used is not particularly limited, and the reactivity of the epoxidizing agent to be used, the desired degree of epoxidation, the type of non-fluorinated thermoplastic polymer to be epoxidized and the unsaturation An appropriate amount can be arbitrarily used depending on conditions such as the amount of binding. The epoxy equivalent of the finally obtained epoxy group-containing non-fluorine thermoplastic polymer (ii) is preferably 120 to 3000, preferably 300 to 2 in terms of the reactivity of the epoxy group-containing non-fluorine thermoplastic polymer (ii). , 500 is more preferable, and 800 to 1,500 is particularly preferable. Therefore, it is preferable to select the amount of the epoxidizing agent so that the epoxy equivalent is in the above range. If an epoxy equivalent is more than the lower limit of the said range, an epoxy group containing non-fluorine thermoplastic polymer (ii) will be excellent in the reactivity of an epoxy group. When the epoxy equivalent is not more than the upper limit of the above range, the degree of epoxidation is moderate and the reactivity is excellent.
Here, the epoxy equivalent is calculated by the formula: epoxy equivalent = 1,600 / {oxirane oxygen concentration (% by mass) in epoxy group-containing non-fluorine thermoplastic polymer (ii)}, and epoxy groups per mol of oxirane oxygen. The mass (g) of the containing non-fluorine thermoplastic polymer (ii) is shown. The oxirane oxygen concentration is determined by titration using an acetic acid solution of hydrogen bromide.

  Commercially available products may be used as the epoxy group-containing non-fluorinated thermoplastic polymer (ii) having a tensile elongation at break within the above range and having no melting point.

[Layer (III) of non-fluorine thermoplastic polymer (iii) having no epoxy group]
The layer (III) is provided in contact with the layer (II) and adheres to the layer (I) through the layer (II).
The non-fluorine thermoplastic polymer (iii) having no epoxy group constituting the layer (III) (hereinafter also simply referred to as “non-fluorine thermoplastic polymer (iii)”) does not have an epoxy group and a fluorine atom. It is a thermoplastic polymer. The non-fluorine thermoplastic polymer (iii) constituting the layer (III) can be appropriately selected depending on the use of the fluororesin laminate, but polyester (polyethylene terephthalate, polybutylene) is excellent in flexibility and workability. Resins such as terephthalate, polyethylene naphthalate, etc.), polyarylate, polyvinyl butyral, polyvinyl alcohol, polyvinyl acetate, ethylene vinyl acetate copolymer, ethylene ionomer;
Styrenic thermoplastic elastomer, PVC thermoplastic elastomer, olefin thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester thermoplastic elastomer, nitrile thermoplastic elastomer, polyamide thermoplastic elastomer, chlorinated polyethylene, 1,2- And elastomers such as polybutadiene-based thermoplastic elastomers. A non-fluorine thermoplastic polymer (iii) may be used individually by 1 type, or may use 2 or more types together.

  The non-fluorine thermoplastic polymer (iii) having no epoxy group is one selected from the group consisting of an amide group, an amine group, a carbonyl group, an acid anhydride group, a carboxy group, a hydroxy group, a carbonate group, and an isocyanate group. It preferably has the above functional group. Since the functional group reacts with the epoxy group of the epoxy group-containing non-fluorine thermoplastic polymer (ii) constituting the layer (II), the layer (III) is firmly bonded to the layer (II).

The non-fluorine thermoplastic polymer (iii) having the functional group and having no epoxy group is, for example, a method of copolymerizing a monomer containing the functional group at the time of polymerization of the non-fluorine thermoplastic polymer (iii), A method using at least one of a polymerization initiator containing the functional group and a chain transfer agent during the polymerization of the fluorothermoplastic polymer (iii), heat-treating the non-fluorine thermoplastic polymer (iii) to oxidatively decompose the functional group, It can be manufactured by a method of generating.
Among the non-fluorine thermoplastic polymers (iii) having the functional group and having no epoxy group, as the resin, since the functional group can be easily introduced, polyethylene having the functional group (medium density polyethylene, low density Density polyethylene, etc.), polypropylene having the functional group, polybutene having the functional group, polybutadiene having the functional group, and the like.
Among the non-fluorine thermoplastic polymers (iii) having the functional group and having no epoxy group, the elastomer is a polyurethane-based thermoplastic elastomer having the functional group because of its excellent heat resistance, strength and flexibility. Of these, polyether polyurethane thermoplastic elastomers, polyester polyurethane thermoplastic elastomers, and polycarbonate polyurethane thermoplastic elastomers are more preferable, and polyether polyurethane thermoplastic elastomers are particularly preferable. Elastomers are preferred because they do not have a crystal structure and therefore do not have a melting point, and therefore are excellent in heat resistance. Moreover, it is thought that a shrinkage rate is small at the time of cooling after heating and laminating with the sheet | seat which forms layer (I) and the sheet | seat which forms layer (II) in the below-mentioned thermal lamination process. This is considered to be one of the factors that the layer (III) of the non-fluorine thermoplastic polymer (iii) made of an elastomer easily adheres well to the layer (II).

  The tensile elongation at break (%) of the non-fluorine thermoplastic polymer (iii) having no epoxy group is excellent in flexibility, hardly cracks, and easily obtains a fluororesin laminate excellent in heat resistance. 100% or more, more preferably 150% or more, particularly preferably 300% or more, and most preferably 450% or more. The upper limit of the tensile elongation at break (%) is not particularly limited, but is preferably 1500% or less, more preferably 1200% or less, and most preferably 1000% or less from the viewpoint of strength.

  In addition to the non-fluorine thermoplastic polymer (iii) having no epoxy group, the layer (III) comprises a non-fluorine thermoplastic polymer such as a filler, stabilizer, lubricant, plasticizer, colorant and polymer modifier ( Components other than iii) may be included in the layer (III) in a range of less than 50% by mass. The content of components other than the non-fluorine thermoplastic polymer (iii) in the layer (III) is preferably less than 30% by mass, and more preferably less than 20% by mass.

[Fluoropolymer laminate]
Although there is no restriction | limiting in particular in the thickness of each layer in a fluororesin laminated body, For example, it is preferable that layer (I) is 3-2000 micrometers, and layer (II) and layer (III) are 50-100,000 micrometers, respectively. One or more other layers may be further provided on the side of the layer (III) where the layer (II) is not provided. The total thickness of one or more other layers thus provided is preferably 75 to 100,000 μm.
There is no restriction | limiting in particular in the total thickness of a fluororesin laminated body, Although the thickness of each layer should just be in the said range, For example, 100-100000 micrometers is preferable.

The shape of the fluororesin laminate may be a sheet shape, a three-dimensional shape obtained by three-dimensionally forming a sheet, a tube shape, or the like, and the shape is not limited. Among these, a sheet shape (multilayer sheet) and a tube shape (multilayer tube) are preferable in that the peel strength between layers can be maintained and the shape retention of the fluororesin laminate is excellent.
Depending on the use of the multilayer tube, the layer (I) may be positioned on the inner peripheral side or the outer peripheral side, but the multilayer tube is, for example, a drug solution tube or a food transport tube It is preferable that the layer (I) is located on the inner peripheral side.
When the multilayer tube is a chemical solution tube and the layer (I) is located on the inner peripheral side, the chemical resistance to a strongly alkaline or acidic chemical solution is based on the fluoropolymer (i) contained in the layer (I). Excellent.
When the multilayer tube is a food transport tube, if the layer (I) is located on the inner peripheral side, fruit juice or pasty food as food based on the fluoropolymer (i) contained in the layer (I) Excellent resistance to bacteria when transporting etc. Moreover, it is excellent also in the tolerance with respect to the cleaning agent which wash | cleans a foodstuff conveyance tube.

[Method for producing fluororesin laminate]
The fluororesin laminate of the present invention has a multilayer extrusion molding (coextrusion molding), an extrusion laminate molding, a multilayer laminate molding using a heating roll and a heating press, a multilayer injection molding, and a multilayer blow molding because of the ease of molding and productivity. It can manufacture suitably by the method which has the heat | fever lamination process using etc. By the thermal lamination step, at least the layer (I) and the layer (II) may be laminated, and in addition, the layer (III) and other layers may be laminated.

The temperature in the heat lamination step is preferably not less than the melting point of the fluoropolymer (i) and less than 400 ° C.
For example, when a fluororesin laminate is produced by performing a thermal lamination process by multilayer extrusion using a plurality of extruders, the die temperature of the extruder is not less than 400 ° C. above the melting point of the fluoropolymer (i). preferable. The temperature is more preferably 170 to 320 ° C, further preferably 200 to 280 ° C. If the die temperature is equal to or higher than the lower limit value, the fluoropolymer (i) is sufficiently softened and excellent in workability and adhesiveness. If the die temperature is equal to or lower than the upper limit value, the layer (I) is formed in the thermal lamination step. The fluoropolymer (i) and the epoxy group-containing non-fluorinated thermoplastic polymer (ii) constituting the layer (II) can be prevented from being decomposed, foamed, etc., and excellent in adhesiveness.

When the thermal lamination process is performed by a hot press, it is preferable to perform a preliminary melting process and a pressurizing process after the preliminary melting process as the thermal lamination process. In the preliminary melting step, at least the sheet for forming the layer (I) and the sheet for forming the layer (II) are overlapped, and the pressure (pressing pressure) at a temperature not lower than the melting point of the fluoropolymer (i) and lower than 400 ° C. It is the process of hold | maintaining without adding. Specifically, for example, a mold provided with a press plate used for a heating press is controlled to a temperature not lower than the melting point and lower than 400 ° C., and a sheet for forming the layer (I) and the layer (II) are formed in the mold. At least the sheet to be stacked is held. This makes each sheet into a molten state. After the preliminary melting step, a pressurizing step is performed by applying pressure (pressing pressure) to the mold and heating and pressing at a temperature not lower than the melting point of the fluoropolymer (i) and lower than 400 ° C.
As described above, the temperature of the press plate (temperature in the thermal lamination step) is preferably not less than the melting point of the fluoropolymer (i) and less than 400 ° C, more preferably 160 to 320 ° C, further preferably 170 to 280 ° C, and more preferably 180 to Most preferred is 260 ° C. If the temperature of the press plate is not less than the above lower limit value, the surface smoothness of the fluororesin laminate and the thin moldability of the fluororesin laminate are excellent, and if it is not more than the above upper limit value, the layer (I) in the thermal lamination step Decomposition, foaming, etc. of the fluorine-containing polymer (i) constituting the layer (II) and the epoxy group-containing non-fluorine thermoplastic polymer (ii) constituting the layer (II) can be suppressed, and the adhesiveness is excellent.

The heating and holding time in the thermal lamination step is preferably 1 second or more and less than 60 minutes as the sum of the preliminary melting step and the pressurizing step after the preliminary melting step. If it is 1 second or more, the adhesive force between each layer is more stable, and if it is less than 60 minutes, it is excellent in productivity.
The pressing time in the pressing step is preferably 0.1 seconds to 30 minutes or less. If it is 0.1 second or more, the adhesive force between each layer is more stable, and if it is 30 minutes or less, the productivity is excellent.
The press pressure in the pressurizing step is preferably 0.1 MPa to 50 MPa. If it is 0.1 MPa or more, the adhesive force between each layer is more stable, and if it is 50 MPa or less, it is excellent in productivity.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to this.
<Production Example 1>
The fluoropolymer (i-1) used for the layer (I) was produced as follows.
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, and 1.31 kg of CH ₂ = CH (CF ₂ ) ₄ F were charged, the temperature in the polymerization tank was raised to 66 ° C., and TFE was added. 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 fluoropolymer (i-1) was put into an 860 L granulation tank charged with 300 kg of water, heated to 105 ° C. with stirring, and distilled while removing the solvent. Grained. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 33.2 kg of a dry granulated product of the fluoropolymer (i-1).

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

Further, the Q value of the fluoropolymer (i-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 fluoropolymer (i-1) was 7.2 mm ³ / sec.

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

<Epoxy group-containing non-fluorine thermoplastic polymer (ii)>
As the epoxy group-containing non-fluorinated thermoplastic polymer (ii), “Epofriend (registered trademark) AT501” (hereinafter referred to as “EF”) manufactured by Daicel Corporation, which is an epoxidized product of a polystyrene-polybutadiene block copolymer. )It was used. The tensile breaking elongation (%) measured in accordance with ASTM-D638 of the EF is 830%, and the epoxy equivalent is 1067.
The EF was heated to 240 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (DSC-7020, manufactured by SII Corporation), but no melting peak was observed, and the EF had a melting point. I did not.

<Non-fluorine thermoplastic polymer having no epoxy group (iii)>
As the non-fluorine thermoplastic polymer (iii) having no epoxy group, “Elastollan (registered trademark) 1180AD” (hereinafter also referred to as “TPU”) manufactured by BASF Japan, which is an ether polyurethane thermoplastic elastomer. used.
TPU: A reaction product of a polyol having a hydroxyl group at the terminal and a bifunctional or higher functional isocyanate, and has a functional group such as an amide group, a urea group, a urethane group, or a hydroxy group in the molecular chain. The functional group can be confirmed by analysis using a Fourier transform infrared spectrophotometer (FT-IR), a nuclear magnetic resonance apparatus (NMR), or the like. The tensile elongation at break (%) measured in accordance with ASTM-D638 is 550%.
The TPU was heated up to 240 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (SII Corporation, DSC-7020), but no melting peak was observed, and the TPU had a melting point. I did not.

<Other materials>
The following materials were used for the comparative examples.
“Fluon (registered trademark) ETF LM730AP” (hereinafter, also referred to as “LM730”) manufactured by Asahi Glass Co., Ltd .: ethylene-tetrafluoroethylene copolymer (having no carbonyl group-containing group), melting point 224 ° C.
“Bond First (registered trademark) E” (hereinafter also referred to as “BF-E”) manufactured by Sumitomo Chemical Co., Ltd .: Special ethylene copolymer thermoplastic resin (ethylene-glycidyl methacrylate copolymer), melting point 103 ° C., ASTM-D638 The tensile elongation at break (%) measured according to the standard is 700%.
“Bond First (registered trademark) BF-VC40” manufactured by Sumitomo Chemical Co., Ltd. (hereinafter also referred to as “BF-VC40”): Special copolyester thermoplastic resin having no epoxy group, melting point 95 ° C., ASTM-D638 The tensile elongation at break (%) measured in accordance with JIS is 650%.
“Bond First (registered trademark) BF-2B” (hereinafter also referred to as “BF-2B”) manufactured by Sumitomo Chemical Co., Ltd .: Special ethylene copolymer thermoplastic resin (ethylene-glycidyl methacrylate-vinyl acetate copolymer), melting point 95 The tensile breaking elongation (%) measured in accordance with ASTM-D638 is 750%.

<Preparation of sheets constituting each layer>
Each press sheet was created under the following conditions using a tester industry press molding machine.
“Preparation of Press Sheet for Layer (I) Using Fluoropolymer (i-1) and LM730”
A 13 × 13 × 0.03 t (cm) press sheet was produced under the conditions of pre-melting time: 5 min, pressing time: 2 min, pressing pressure: 5 MPa, molding temperature: 240 ° C.
“Preparation of press sheet for layer (II) using EF”
A 13 × 13 × 0.05 t (cm) press sheet was produced under the conditions of pre-melting time: 5 min, pressing time: 2 min, pressing pressure: 5 MPa, molding temperature: 220 ° C.
"Production of press sheet for layer (III) using TPU"
A 13 × 13 × 0.03 t (cm) press sheet was produced under the conditions of pre-melting time: 2 min, pressing time: 2 min, pressing pressure: 5 MPa, molding temperature: 220 ° C.
“Preparation of Press Sheet for Layer (II) Using BF-E, BF-VC40, and BF-2B”
A 13 × 13 × 0.05 t (cm) press sheet was produced under the conditions of pre-melting time: 5 min, pressing time: 2 min, pressing pressure: 10 MPa, molding temperature: 180 ° C.

<Example 1, Comparative Examples 1-4>
As shown in Table 1, as the layers (I) to (III), each of the press sheets manufactured by the above-described method is used, and each sheet is thermally laminated at a temperature shown in Table 1 by a press molding machine manufactured by Tester Sangyo Co., Ltd. The thermal lamination process (pre-melting process and pressurizing process) was performed.
The conditions other than the temperature were a heating and holding time in the preliminary melting step: 2 min, a holding time in the pressurizing step (press time): 2 min, and a press pressure in the pressurizing step: 5 MPa.
The thickness of each layer was 0.03 cm for layer (I), 0.05 cm for layer (II), and 0.03 cm for layer (III).
About the obtained fluororesin laminated body, the peeling strength was measured by the following peeling tests. A bending test was also performed. The results are shown in Table 1.

<Evaluation>
(Peel test)
About the fluororesin laminated body, the peeling adhesive strength test method was performed according to JISK6854-2: 1999, and the peeling strength between each layer was measured.

(Bending test)
From the fluororesin laminate, a sheet sample having the same dimensions as the above peel test was cut out, and the test was performed by bending the sample into two by hand. After the sample was folded in half on one side, the operation of folding the sample in two along the same fold line was counted as one time, and the folding operation was repeated 30 times continuously. The presence or absence of delamination or cracks between layers was visually confirmed.

As shown in Table 1, the layer (I) of the fluoropolymer (i) having a carbonyl group-containing group and the epoxy-containing non-fluorine thermoplastic polymer (ii) having a high tensile elongation at break and no melting point The layer (II) of the fluororesin laminate of Example 1 in which the layer (II) was laminated by a thermal lamination step of not less than the melting point of the fluoropolymer (i) and less than 400 ° C. showed high adhesion between the layers and was flexible It was excellent in properties, and no delamination or cracks were observed in the bending test.
On the other hand, in Comparative Example 1 using a fluoropolymer having no carbonyl group-containing group in the layer (I), the adhesive strength between the layer (I) and the layer (II) is weak, and the peel strength cannot be measured stably. It was. In the bending test, the sample layer (I) and the layer (II) were separated.
Further, in the comparative examples 2 and 4 using the epoxy group-containing non-fluorinated thermoplastic polymer having a melting point, although the layer (II) has a high tensile elongation at break, the layer (I) has a carbonyl group-containing group. The layers (I) and (II) adhered well. However, the adhesive strength between the layer (II) and the layer (III) was weak, and the peel strength could not be measured stably. In the bending test, the sample layer (II) and the layer (III) were separated. This is because the epoxy group-containing non-fluorinated thermoplastic polymer forming the layer (II) exhibits a melting point and has a crystal structure, and therefore has a large shrinkage ratio upon cooling after the thermal lamination step, The layer (II) is considered to adhere to the layer (I) having a carbonyl group-containing group but hardly adhere to the layer (III).
In addition, in Comparative Example 3 in which the layer (II) has a large tensile elongation at break but does not have an epoxy group and uses a polyester polymer having a melting point, although the detailed reason is not clear, the layer (II) and Although it adhered well to layer (III), the adhesive strength between layer (I) and layer (II) was weak, and the peel strength could not be measured stably.

  In the fluororesin laminate of the present invention, a layer made of another material is firmly bonded to the fluororesin layer and also has flexibility. Moreover, it is excellent in weather resistance, electrical insulation, acid / alkali resistance, flame retardancy, and gas permeability. Therefore, for example, laminated printed wiring boards, wiring / piping cover ducts (protection pipes), aircraft parts, vehicle parts, protection of outdoor parts of building members called exteriors, building parts such as outer wall protection and inner layer walls, electrical parts, etc. Industrial hose for transportation of oils, chemicals, paints, fruit juices, pasty foods, etc., hose for fuel transportation of gasoline, light oil, alcohol, etc., hot water supply hose, chemical tank, fuel tank, packaging, agriculture It can be used for industrial films such as houses, release films for producing cast films, semiconductor green sheets, release films such as release films for producing IC chips, food films, wire coatings, core materials for rubber processing, and the like.

Claims (13)

A layer (I) of a fluoropolymer (i) having a carbonyl group-containing group and a melting point of less than 230 ° C .;
Epoxy group-containing non-fluorinated thermoplastic polymer which is provided in contact with the layer (I) and has a tensile elongation at break (%) of 100% or more measured according to ASTM-D638 and has no melting point. Layer (II) of (ii);
A fluororesin laminate having at least   The fluororesin laminate according to claim 1, wherein the epoxy group-containing non-fluorinated thermoplastic polymer (ii) is an epoxidized product of a polystyrene-polybutadiene block copolymer.   The fluoropolymer (i) is a copolymer having a unit based on perhalofluoroethylene having 3 or 4 fluorine atoms and a unit based on ethylene, and having a carbonyl group-containing group. The fluororesin laminate according to claim 1 or 2.   The said fluoropolymer (i) has at least one of the main chain terminal group which has a unit based on the monomer which has a carbonyl group-containing group, and a carbonyl group-containing group. Fluororesin laminate. The fluoropolymer (i) includes a unit (A) based on tetrafluoroethylene, a unit (B) based on ethylene, a unit (C1) based on a non-fluorine monomer having an acid anhydride residue, and two A unit (C) comprising at least one of units (C2) based on a non-fluorine monomer having a carboxy group, and a total mole of the unit (A), the unit (B) and the unit (C). The unit (A) is 25 to 79.99 mol%, the unit (B) is 20 to 74.99 mol%, and the unit (C) is 0.01 to 5 mol% based on the amount,
The fluororesin laminated body of Claim 4 whose melting | fusing point is 100-220 degreeC. The fluoropolymer (i) is a unit (D) based on another monomer other than tetrafluoroethylene, ethylene, a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups. Further containing
The fluororesin laminate according to claim 5, wherein the molar ratio of the unit (A) to the unit (D) is 70/30 to 99.9 / 0.1. The fluoropolymer (i) is a unit (D) based on another monomer other than tetrafluoroethylene, ethylene, a non-fluorine monomer having an acid anhydride residue and a non-fluorine monomer having two or more carboxy groups. Further containing
The fluororesin laminate according to claim 5 or 6, wherein the molar ratio of the unit (D) to the sum of the unit (A) and the unit (B) is from 1/99 to 20/80.   The fluororesin laminate according to claim 6 or 7, wherein the unit (D) includes a unit (D1) based on hexafluoropropylene as the other monomer. The unit (D), said a other monomers _{CH 2 = CH (CF 2)} Q1 F ( although, Q1 is an integer. 2-10) further comprises units (D2) based on, according to claim 8 Fluoropolymer laminate.   The layer (III) made of a non-fluorine thermoplastic polymer (iii) having no epoxy group provided in contact with the side of the layer (II) where the layer (I) is not provided is further provided. The fluororesin laminated body as described in any one of -9.   The fluororesin laminate according to claim 10, wherein the non-fluorine thermoplastic polymer (iii) is a polyurethane-based thermoplastic elastomer.   The multilayer tube or multilayer sheet obtained from the fluororesin laminated body as described in any one of Claims 1-11. It is a manufacturing method of the fluororesin laminated body as described in any one of Claims 1-11,
A thermal lamination step of thermally fusing at least the layer (I) and the layer (II) in a range of 1 second to less than 60 minutes in a temperature range of the melting point of the fluoropolymer (i) to less than 400 ° C. A method for producing a fluororesin laminate.