JP2010179611A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having resistances to heat, chemicals and solvents, low chemical permeability and firm adhesiveness between a fluorine resin layer and a thermoplastic resin layer. <P>SOLUTION: The laminate includes a fluorine resin layer (a) made of a fluorine resin composition comprising a fully halogenated fluorine resin having at least one of carbonyl, olefinic and amino groups at ends of the principal and side chains of the polymer and a polyfunctional compound and a thermoplastic resin layer (b) made of a fluorine-free thermoplastic resin having a polar functional group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a laminate.

Conventionally, due to the recent increase in environmental awareness, the development of laws to prevent fuel volatilization has progressed. Especially in the automobile industry, there is a significant tendency to suppress fuel volatilization, especially in the United States, and there is a great need for materials with excellent fuel barrier properties. It is becoming.

An example of a material having excellent fuel barrier properties is a fluororesin. However, fluororesin has inherently low adhesive strength, and it is difficult to directly bond fluororesin and other materials (base materials). Even if there is a certain level of adhesive strength, the adhesive strength tends to vary depending on the type of substrate, and the reliability of adhesiveness is often insufficient.

As a method of bonding fluororesin and other materials: A method of physically roughing the surface of the substrate by sandblasting, etc.,
2. A method of surface treatment of fluororesin such as sodium etching, plasma treatment, photochemical treatment,
3. A method of bonding using an adhesive,
Etc. are mainly considered.

However, the above processes 1 and 2 require a processing step, and the process is complicated and the productivity is poor. Moreover, the kind and shape of a base material are limited. In the first place, the adhesive strength is insufficient, and problems (coloring and scratches) on the appearance of the obtained laminate are likely to occur.

Various studies on the adhesive of the above 3 have been conducted. General hydrocarbon adhesives have inadequate adhesion and inadequate heat resistance, and can withstand the adhesive conditions of fluoropolymers that generally require molding and processing at high temperatures. It causes peeling and coloring due to decomposition. Since the laminate using this adhesive also has insufficient heat resistance, chemical resistance and water resistance of the adhesive layer, the adhesive force cannot be maintained due to temperature change or environmental change, and lacks reliability.

On the other hand, studies on adhesion using an adhesive or an adhesive composition using a fluororesin having a functional group have been conducted. For example, a fluororesin obtained by graft polymerization of a hydrocarbon monomer having a carboxyl group, carboxylic anhydride residue, epoxy group or hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane on the fluororesin Fluorine-containing copolymers obtained by copolymerization of tetrafluoroethylene and chlorotrifluoroethylene with reports on adhesives (for example, Patent Documents 1 to 6) and hydrocarbon monomers containing a functional group such as hydroxyl alkyl vinyl ether And a report of using an adhesive composition of an ethylene / tetrafluoroethylene polymer (hereinafter also referred to as ETFE) cured with vinyl chloride and a corona discharge treatment by curing an adhesive composition with an isocyanate curing agent (for example, Patent Document 7) ) Has been made. These adhesives or adhesive compositions using a fluorine-containing polymer obtained by graft polymerization or copolymerization of a hydrocarbon-based functional group monomer have insufficient heat resistance and are processed at a high temperature with a fluororesin. During use, decomposition, foaming, etc. occur, reducing the adhesive strength, peeling off, or coloring. In the adhesive composition described in Patent Document 7, the fluororesin requires corona discharge treatment.

Moreover, what used the fluorine-containing polymer which has a functional group which copolymerized the perfluoro vinyl ether compound containing a carboxylic acid or its derivative with the fluorine-containing monomer for the adhesive agent or adhesive composition is reported. Patent Document 8 describes a laminate using a fluororesin having a functional group introduced by copolymerizing perfluorovinyl ether having a carboxylic acid group or a derivative thereof with tetrafluoroethylene or the like. This is a laminate of the above fluoropolymer having a carboxylic acid group or the like on a metal or other substrate through an adhesive resin such as an epoxy resin or a urethane resin, and directly adheres to a metal, glass or other resin. However, there are problems in heat resistance, chemical resistance, and solvent resistance of epoxy resin and urethane resin during use.

Patent Document 9 describes a resin composition comprising a fluorine-containing polymer having a reactive functional group at the main chain terminal or side chain terminal and a non-fluorine thermoplastic resin such as an ethylene / vinyl alcohol copolymer. A laminate of a fluoropolymer and a non-fluorine thermoplastic resin is not described.

Patent Document 10 describes a laminate including a layer made of a chlorotrifluoroethylene copolymer and a layer made of a fluorine-free organic material, but further improvement in the adhesion between the layers is required.

JP-A-7-18035 Japanese Patent Application Laid-Open No. 7-259592 Japanese Patent Laid-Open No. 7-25594 JP 7-173230 A JP-A-7-173446 JP-A-7-173447 Japanese Unexamined Patent Publication No. 7-228848 US Pat. No. 4,916,020 JP 2006-328195 A International Publication No. 2005/108051 Pamphlet

The present invention provides a laminate having heat resistance, chemical resistance, solvent resistance, and low chemical permeability, in which a fluororesin layer and a thermoplastic resin layer are firmly bonded.

The present invention includes a fully halogenated fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer and a polyfunctional compound. A laminate comprising: a fluororesin layer (a) formed from a fluororesin composition; and a thermoplastic resin layer (b) formed from a fluorine-free thermoplastic resin having a polar functional group. .

Furthermore, the polyfunctional compound is preferably an aromatic asymmetric polyfunctional compound.

Furthermore, the fluororesin is preferably at least one selected from the group consisting of a copolymer composed of tetrafluoroethylene and hexafluoropropylene and a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene.

Furthermore, the fluorine-free thermoplastic resin is preferably at least one selected from the group consisting of polyethylene terephthalate, modified polyolefin resin, and ethylene / vinyl alcohol copolymer.

The present invention also relates to a molded article formed from the laminate.

The present invention also relates to a method for manufacturing the laminate.

The present invention is described in detail below.

The laminate of the present invention is a fully halogenated fluororesin and polyfunctional compound having at least one selected from the group consisting of a carbonyl group, an olefin group, and an amino group at the main chain end or side chain end of the polymer And a thermoplastic resin layer (b) formed from a fluorine-free thermoplastic resin having a polar functional group. .

Since the layered product of the present invention is formed from a fluororesin composition containing a fluororesin in which the layer (a) is completely halogenated, it is excellent in chemical resistance, solvent resistance and chemical low permeability. Fully halogenated fluororesin is a material that is extremely difficult to bond to other materials among fluororesins, so the conventional technology provides chemical resistance, solvent resistance, low chemical permeability and adhesion. A compatible laminate could not be obtained. However, in the present invention, in addition to using a resin having a reactive functional group as the fluororesin and the fluorine-free thermoplastic resin, respectively, the fluororesin layer (a) is obtained from the fluororesin composition containing a polyfunctional compound. By forming the film, it was possible to obtain a laminate having excellent properties of a completely halogenated fluororesin and at the same time having a very high adhesion between layers.

The fluororesin layer (a) is composed of a fully halogenated fluororesin having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer. It forms from the fluororesin composition containing a functional compound.

In the fluororesin composition, the fluororesin and the polyfunctional compound may be present alone without bonding with each molecule, or may be bonded to each other by the reaction of each functional group. It may exist, and what existed independently and what combined may be mixed.

The polyfunctional compound is a compound having two or more functional groups of the same or different types in one molecule. The polyfunctional compound not only has a high affinity with the thermoplastic resin, but also reacts with the functional group of the fluororesin, and thus greatly contributes to an improvement in adhesiveness.

The functional group is preferably at least one selected from the group consisting of a carbonyl group, a carboxyl group, a haloformyl group, an amide group, an olefin group, an amino group, an isocyanate group, a hydroxy group, and an epoxy group.

Specific examples of the polyfunctional compound include
Hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, 4,4′-diaminodiphenyl ether [4,4′-DPE], 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane [BAPP], p-phenylenediamine, m-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N′-dimethyl- 1,4-phenylenediamine, 4,4′-methylenedianiline, dianilinoethane, 4,4′-methylene-bis (3-nitroaniline), 4,4′-methylene-bis (2-chloroaniline), diaminopyridine , Melamine, 4-aminophenol, 3,4'-diaminodiphenyl ether [3,4'-DPE], 2,4,4′-triaminodiphenyl ether [TADE], 2,3′-diaminodiphenyl ether [2,3′-DPE], 2,5-bis (4-aminophenoxy) -biphenyl [P-TPE-Q] 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene [TMBAB], 4,4′-diamino-2- (trifluoromethyl) diphenyl ether [TFDPE], and other amine compounds,
Triallyl cyanurate, triallyl isocyanurate [TAIC], trimethallyl isocyanurate, TAIC prepolymer, triacryl formal, triallyl trimellitate, N, N′-n-phenylenebismaleimide, dipropargyl terephthalate, diallyl phthalate , Tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5-triazine- 2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N ', N'-tetraa Rutetraphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, tri Olefin compounds such as allyl phosphite,
Epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin,
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1, 7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2- Bis (4-hydroxyphenyl) butane [bisphenol B], 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl Sulfone, 4,4'-dihydroxy Hydroxy compounds such as sidiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A, etc. It is done.

The polyfunctional compound is N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-DPE, BAPP, bisphenol AF, 3,4′-DPE, TADE, 2,3′-DPE, P -It is preferable that it is at least 1 sort (s) selected from the group which consists of TPE-Q, TMBAB, and TFDPE.

These polyfunctional compounds may be used alone or in any combination with polyfunctional compounds having other structures.

The polyfunctional compound is more preferably an aromatic asymmetric polyfunctional compound because a fluororesin composition having a relatively large MFR can be obtained and foaming during high temperature molding can be avoided. When the symmetric polyfunctional compound is used, the MFR is reduced to less than 0.2 or the moldability at the time of melt molding is extremely lowered. However, by using the aromatic asymmetric polyfunctional compound, You can avoid the disadvantages.

The aromatic asymmetric polyfunctional compound is an organic compound having at least one aromatic ring in one molecule and having two or more reactive functional groups of the same or different types. A compound having an unsymmetrical structure. Even if the reactive functional groups possessed by the compounds having an asymmetric structure are of the same type, the reactivity differs from each other due to the difference in the bonding position in the molecule. N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-DPE, BAPP, bisphenol AF and the like are compounds having an aromatic ring and having two or more amino groups or hydroxyl groups. The symmetric polyfunctional compound is not included in the aromatic asymmetric polyfunctional compound.

Examples of the aromatic asymmetric polyfunctional compound include 3,4′-diaminodiphenyl ether [3,4′-DPE], 2,4,4′-triaminodiphenyl ether [TADE], 2,3′-diaminodiphenyl ether [ 2,3′-DPE], 2,5-bis (4-aminophenoxy) -biphenyl [P-TPE-Q], the following chemical formula

2,2-bis (3,4'-hydroxyphenyl) perfluoropropane represented by the following general formulas (1) to (3)

(In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group, and when having a plurality of R ^{1 s} , they may be the same or different.)
And a diamine compound represented by the following general formula (4):

(In the formula, each R ² is the same or different and represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, and at least one of the four R ² is fluoroalkyl. Group.)
It is preferable that it is at least 1 sort (s) selected from the group which consists of diamine compound represented by these.

Examples of the diamine compound represented by the general formulas (1) to (3) include 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene [TMBAB] and the like. Examples of the diamine compound represented by (4) include 4,4′-diamino-2- (trifluoromethyl) diphenyl ether [TFDPE].

The aromatic asymmetric polyfunctional compound preferably has a fluorine atom bonded to a carbon atom, more preferably has a fluoroalkyl group or a fluorophenyl group, from the viewpoint of excellent affinity with a fluororesin. , 2-bis (3,4'-hydroxyphenyl) perfluoropropane and at least one selected from the group consisting of diamine compounds represented by the general formulas (1) to (4) are more preferable. Particularly preferred is at least one selected from the group consisting of TMBAB and TFDPE. When the aromatic asymmetric polyfunctional compound is a compound having a fluorine atom, the amount of the polyfunctional compound used can be reduced without impairing the adhesive force with the thermoplastic resin.

The said polyfunctional compound is 0.05-10.0 mass parts with respect to 100 mass parts of fluororesins, and it is preferable that it is 0.06-5.0 mass parts. If the blending amount of the polyfunctional compound is too small, there is a tendency that sufficient adhesive strength cannot be obtained when laminated with a thermoplastic resin, and if it is too large, the dispersibility in the fluororesin is deteriorated and the mechanical properties of the molded product are lowered. Or foaming tends to occur during molding.

The fluororesin has at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer, and is completely halogenated.

The fluororesin has at least one functional group selected from the group consisting of a carbonyl group, an olefin group, and an amino group at the main chain end or side chain end of the polymer. When the fluororesin has these functional groups, adhesion with the thermoplastic resin is improved.

A carbonyl group is a functional group having —C (═O) —.

Specifically, for example,
Carbonate group [—O—C (═O) —OR ³ (wherein R ³ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) ],
A haloformyl group [—C (═O) X ¹ , X ¹ is a halogen atom],
Formyl group [—C (═O) H],
Formula: —R ⁴ —C (═O) —R ⁵ (wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent group having 1 to 20 carbon atoms. An organic group of
Formula: —O—C (═O) —R ⁶ (wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) A group represented by
Carboxyl group [—C (═O) OH],
An alkoxycarbonyl group [—C (═O) OR ⁷ (wherein R ⁷ is a monovalent organic group having 1 to 20 carbon atoms)],
Carbamoyl group [—C (═O) NR ⁸ R ⁹ (wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) )],
Acid anhydride bond [—C (═O) —O—C (═O) —],
An isocyanate group [—N═C═O],
Etc.

Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ⁴ include a methylene group, —CF ₂ — group, —C ₆ H ₄ — group, and specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group. Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like. Specific examples of R ⁸ and R ⁹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

Among these carbonyl groups, at least one selected from the group consisting of a carboxyl group, a haloformyl group, an alkoxycarbonyl group, and a carbonate group from the viewpoint of ease of introduction into a fluororesin and reactivity with other materials. And at least one selected from the group consisting of —COOH, —OC (═O) OCH ₂ CH ₂ CH ₃ , —COF, and —OC (═O) OCH (CH ₃ ) _2. More preferably.

An olefin group is a functional group having a carbon-carbon double bond. As the olefin group, the following formula:
-CR ¹⁰ = CR ¹¹ R ¹²
(Wherein R ¹⁰ , R ¹¹ and R ¹² may be the same or different and are a hydrogen atom, a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms). functional group can be mentioned _{that, -CF = CF 2, -CH =} CF 2, it is preferably at least one -CF = CHF, selected from the group consisting of -CF = CH ₂ and -CH = CH ₂ .

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. As an amino group, the following formula:
-NR ¹³ R ¹⁴
(Wherein, R ¹³ and R ¹⁴ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). , —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , and —NH (C ₆ H ₅ ) It is preferably at least one selected from the group consisting of

The number of terminal groups of the fluororesin can be measured by the methods described in JP-B-37-3127 and WO99 / 45044. For example, when an infrared absorption spectrum analysis of a fluororesin film sheet is performed using an infrared spectrophotometer and the number of functional groups is measured from an absorption band having a frequency specific to the functional group, for example, the —COF terminal is 1884 cm ^{− 1} absorption bands, -COOH ends are absorption bands of 1813 cm ^-1 and 1775 cm ^-1 , -COOCH ₃ ends are absorption bands of 1795 cm ^-1 , -CONH ₂ ends are absorption bands of 3438 cm ^-1 , -CH ₂ OH ends are The absorption band at 3648 cm ^−1, the —CF═CF ₂ end can be calculated from the absorption band at 1790 cm ⁻¹ .

The method for introducing the functional group into the fluororesin is not particularly limited. For example, a method of copolymerizing a monomer having the functional group at the time of fluororesin polymerization, the functional group or a functional group that can be converted to the functional group. A method of polymerizing using a polymerization initiator having a polymer, a method of introducing the above functional group into a fluororesin by a polymer reaction, a method of thermally decomposing a polymer main chain in the presence of oxygen, a strong shear force such as a twin screw extruder And a method for converting the terminal of the fluororesin using a device capable of adding.

The number of functional groups of the fluororesin is preferably 20 to 5000 per 1 million carbon atoms constituting the fluororesin, more preferably 30 to 4000, and 40 to 3000. Further preferred. If the number is less than 20, the adhesive strength with the thermoplastic resin tends to decrease, and if it exceeds 5000, foaming tends to occur in the molded product.

The fluororesin having the functional group used in the present invention is not only composed of molecules having the functional group at one end, both ends or side chains of the main chain in one polymer, It may be a mixture of a molecule having the functional group at one end, both ends or side chains of the main chain, and a molecule not containing the functional group.

The fluororesin is a completely halogenated fluororesin (perhalopolymer). Here, the completely halogenated fluororesin means that the element bonded to the carbon atom constituting the polymer main chain skeleton does not contain hydrogen and is a halogen such as fluorine or chlorine, or a fluoroalkyl group or a fluoroalkoxy group. Means.

The fully halogenated fluororesin is a monomer unit derived from at least one monomer selected from the group consisting of tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, and chlorotrifluoroethylene. It is preferably a polymer composed of 97 to 100 mol% and 0 to 3 mol% of monomer units derived from monomers other than the monomers.

Since the fluororesin is excellent in chemical resistance, solvent resistance and low chemical liquid permeability, it is a copolymer [FEP] composed of tetrafluoroethylene [TFE] and hexafluoropropylene [HFP], TFE and perfluoro (alkyl). Vinyl ether) [PAVE] copolymer [PFA] and at least one selected from the group consisting of chlorotrifluoroethylene [CTFE] and tetrafluoroethylene [TFE] copolymer [CTFE / TFE copolymer]. Preferably it is a seed. It is at least one selected from the group consisting of FEP and CTFE / TFE copolymers because it has a relatively low melting point and facilitates co-extrusion with a fluorine-free thermoplastic resin having a polar functional group. It is more preferable.

The CTFE / TFE copolymer is preferably a copolymer comprising 2 to 98 mol% of CTFE units and 98 to 2 mol% of TFE units, and includes 5 to 90 mol% of CTFE units and 95 to 10 of TFE units. More preferably, it is a copolymer consisting of mol%. If the CTFE unit is less than 2 mol%, the chemical permeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

As the CTFE / TFE copolymer, in addition to the CTFE unit and the TFE unit, FEP or CF ₂ = CF-OR _f ¹ (wherein R _f ¹ represents a perfluoroalkyl group having 1 to 5 carbon atoms). It is also preferable to have a monomer unit derived from perfluoro (alkyl vinyl ether) [PAVE] represented by the formula, and more preferable to have a PAVE unit.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the CTFE / TFE copolymer, a total of 90 to 99.9 mol% of CTFE units and TFE units and a copolymer weight of 0.1 to 10 mol% of monomer units other than CTFE units and TFE units are used. More preferably, it is a coalescence. If the monomer unit other than the CTFE unit and the TFE unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be poor, and if it exceeds 10 mol%, the chemical solution has low permeability and heat resistance. Tend to be inferior in performance, mechanical properties and productivity.

Although it does not specifically limit as said FEP, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of HFP units, 80-97 mol% of TFE units, and 3-20 HFP units. More preferably, it is a copolymer consisting of mol%. If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

FEP may be a copolymer composed of TFE, HFP, and a monomer copolymerizable with TFE and HFP, and the monomer is preferably PAVE. As the monomer, perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—OR _f ⁴ (wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). , CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, fluorine represents an atom or a chlorine atom, n represents a vinyl monomer represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is 1 to carbon atoms 5 represents a perfluoroalkyl group, and the like. Among them, PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

FEP has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and 90 to 99.9 mol% of TFE units and HFP units in total. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

PFA is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as PFA, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of PAVE units, 80-97 mol% of TFE units, and 3-20 mol% of PAVE units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE, and even more preferably PMVE.

PFA may be a copolymer composed of TFE, PAVE, and a monomer copolymerizable with TFE and PAVE, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. As the monomer, HFP, CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 2 to 10), and CF ₂ = CF—OCH ₂ —Rf ⁵ (wherein Rf ⁵ represents a perfluoroalkyl group having 1 to ⁵ carbon atoms.) And the like.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of TFE unit and PAVE unit is 90 to 99.9 mol%. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

The FEP, PFA, and CTFE / TFE copolymer may contain a third component in the range of 0.1 to 10 mol%, and the third component is an essential monomer constituting each copolymer. The kind is not limited as long as it can be copolymerized with the polymer.

The melting point of the fluororesin is preferably 150 to 340 ° C, more preferably 150 to 330 ° C, and further preferably 170 to 320 ° C. When the melting point of the fluororesin is less than 150 ° C., the heat resistance tends to decrease. When the melting point exceeds 340 ° C., the functional group is thermally deteriorated under the melting conditions of the fluororesin, and the adhesiveness to the thermoplastic resin Tends to be insufficient.

The fluororesin preferably has a fuel permeability coefficient of 10 (g · mm) / (m ² · day) or less when formed into a sheet, and is 5 (g · mm) / (m ² · day) or less. More preferably, it is more preferably 3 (g · mm) / (m ² · day) or less, and particularly preferably 1 (g · mm) / (m ² · day) or less. The lower limit value of the fuel permeability coefficient is not particularly limited, and the lower the value, the better. When the fuel permeation coefficient exceeds 10 (g · mm) / (m ² · day), the fuel permeation resistance is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product. Economically unfavorable. Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability. On the other hand, when the fuel permeation coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

The fuel permeability coefficient is measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method defined in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. Put 18 mL, and set the sheet-like test piece in the container open part and seal it to make a test body. The test specimen is placed in a thermostatic device (60 ° C.), the weight of the test specimen is measured, and when the weight loss per unit time becomes constant, the fuel permeability is obtained by the following formula.

Although it does not specifically limit as a manufacturing method of the said fluororesin, The method as described in Unexamined-Japanese-Patent No. 2005-298702, international publication 2005/100420 pamphlet, etc. can be mention | raise | lifted.

The fluororesin composition may further contain fluororubber, but when used in applications where high chemical resistance and low chemical liquid permeability are required and flexibility is not required, fluoropolymer is included. Preferably not. Examples of the fluororubber include perfluorofluororubber, non-perfluorofluororubber, fluorine-containing thermoplastic elastomer, and the like, which may be crosslinked or uncrosslinked. When fluororubber is included, flexibility can be imparted.

The fluororesin composition includes other polymers such as polyethylene, polypropylene, polyamide, polyester, polyurethane, inorganic fillers such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate, pigments, flame retardants , Lubricants, light stabilizers, weathering stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc., in a range that does not affect the effects of the present invention You may contain.

The melt flow rate (MFR) of the fluororesin composition is preferably 0.2 to 50 g / 10 minutes, and more preferably 1 to 25 g / 10 minutes. If the MFR is less than 0.2 g / 10 min, the fluidity tends to deteriorate and the moldability tends to decrease. Here, MFR shows the value at the time of implementing on the conditions of 297 degreeC and 5000 g load using the Toyo Seiki Seisakusho make melt flow rate measuring device.

The method for producing the fluororesin composition is not particularly limited, but a method in which a fluororesin and a polyfunctional compound are melt-kneaded at a temperature equal to or higher than the melting point of the fluororesin using a Banbury mixer, a pressure kneader, an extruder, Examples thereof include a method of co-coagulating by adding a polyfunctional compound to an aqueous dispersion containing a resin.

The thermoplastic resin layer (b) is formed from a fluorine-free thermoplastic resin having a polar functional group. The polar functional group has reactivity or affinity with the functional group in the fluororesin composition forming the layer (a). Therefore, the layered product of the present invention has the layer (a) and the layer (b) firmly bonded.

The polar functional group includes a hydroxyl group (hydroxyl group), a silanol group, a carboxyl group, an ester group, a carbonate group, a haloformyl group (—C (═O) X ¹ , X ¹ is a halogen atom), a formyl group (—C (= O) H), at least one selected from the group consisting of amino groups, amide groups, imide groups, mercapto groups, thiolate groups, thiol groups, sulfonic acid groups, oxazolyl groups, epoxy groups, and glycidyl groups. Is preferred. The carboxyl group and sulfonic acid group may be acid type or salt type.

The fluorine-free thermoplastic resin is preferably at least one selected from the group consisting of polyethylene terephthalate, modified polyolefin resin, and ethylene / vinyl alcohol copolymer.

The modified polyolefin resin preferably has at least one functional group selected from the group consisting of a carbonyl group, an amino group, an oxazolyl group, a glycidyl group, an epoxy group, a hydroxyl group, and a silanol group. These functional groups may be located at either the main chain end or the side chain, or may be located at both the main chain end and the side chain, or only at either one end. Also good.

A hydrogen atom bonded to a nitrogen atom such as a carbonyl group or an amino group may be substituted with a hydrocarbon group such as an alkyl group.

The functional group may be introduced by copolymerizing an unsaturated monomer having the functional group, or introduced by polymerizing an olefin using a chain transfer agent or a polymerization initiator having the functional group. May be. Alternatively, an unsaturated monomer having a functional group may be graft-polymerized by melt-mixing an unsaturated monomer having a functional group and a polyolefin resin in the presence of a radical generator.

Examples of the modified polyolefin resin include propylene homopolymer, propylene-ethylene block copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, and ultra high density polyethylene, maleic acid modified, epoxy modified, glycidyl modified, amine (NH ₂ ) modified and the like.

The modified polyolefin resin is preferably a polyolefin resin having a carboxyl group or an acid anhydride group introduced therein. Further, the unsaturated monomer includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, aconitic acid and anhydrides thereof. At least one selected from the above is preferable, and maleic anhydride is particularly preferable.

The ethylene / vinyl alcohol copolymer is preferably a copolymer composed of 10 to 60 mol% ethylene and 90 to 40 mol% vinyl alcohol, 20 to 50 mol% ethylene, and 80 to 50 mol% vinyl alcohol. More preferably, it is a copolymer comprising Further, it may contain a third component, and the third component is an α-olefin such as propylene, isobutylene, 4-methylpentene-1, 1-hexene, 1-octene; vinyl acetate, vinyl propionate , Vinyl esters of versatic acid, vinyl esters of pivalic acid, vinyl esters of valeric acid, vinyl esters of capric acid, vinyl esters of benzoic acid; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride Or a derivative thereof (eg, salt, ester, nitrile, amide, anhydride, etc.); vinylsilane compound such as vinyltrimethoxysilane; unsaturated sulfonic acid or salt thereof; N-methylpyrrolidone; Of ethylene and vinyl alcohol Relative to the amount is preferably 10 mol% or less.

The manufacturing method of the laminated body of this invention is also one of this invention.

The laminate of the present invention can be produced by laminating a sheet-like fluororesin and a sheet-like non-fluorine-containing thermoplastic resin, setting them in a mold, and heat-pressing them. In addition, a laminate composed of an inner layer and an outer layer is obtained by simultaneously extruding two layers of a fluororesin composition and a fluorine-free thermoplastic resin with an extruder, or extruding an outer layer onto an inner layer with two extruders. It can also be manufactured by extruding and integrating the body with an extruder.

The structure of the laminate is not particularly limited. For example, a two-layer structure composed of a fluororesin layer (a) and a thermoplastic resin layer (b), or between two identical or different thermoplastic resin layers (b). For example, a three-layer structure in which a fluororesin layer (a) is inserted can be used. It is also possible to further laminate an arbitrary material on the laminate of the present invention.

In order to further improve the adhesion between the fluororesin layer (a) and the thermoplastic resin layer (b), the fluororesin may be subjected to a surface treatment as necessary. The type of the surface treatment is not particularly limited as long as it is a treatment method that enables adhesion. For example, discharge treatment such as plasma discharge treatment or corona discharge treatment, wet metal sodium / naphthalene liquid treatment Etc. A primer treatment is also suitable as the surface treatment. Primer treatment can be performed according to a conventional method. When the primer treatment is performed, the surface of the fluororesin that has not been surface-treated can be treated, but the surface of the fluororesin that has been previously subjected to plasma discharge treatment, corona discharge treatment, metal sodium / naphthalene liquid treatment, etc. is further primed Processing is more effective.

A molded article formed from the laminate of the present invention is also one aspect of the present invention.

The laminate of the present invention is a laminate having high adhesion strength between layers, heat resistance, chemical resistance, solvent resistance, and low chemical permeability, and is useful as a multilayer fuel tube (hose) or multilayer fuel tank. . In particular, it is useful as a multilayer fuel tube or multilayer fuel tank for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices. For example, fuel tubes (hoses) such as automobile filler hoses, evaporation hoses, and breather hoses; fuels for automobile fuel tanks, motorcycle fuel tanks, small generator fuel tanks, lawn mower fuel tanks, etc. A tank is raised.

In addition, the laminated body is further used as an engine body of an automobile engine, a main motion system, a valve system, a lubricant / cooling system, a fuel system, an intake / exhaust system; a drive system transmission system; a chassis steering system; Brake system: Gaskets and non-contact types that require heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance, such as basic electrical parts of control equipment, control system electrical parts, equipment electrical parts, etc. Sealing materials such as contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.) are included.

Applications other than those for automobiles are not particularly limited, for example, oil-resistant, chemical-resistant, heat-resistant, steam- or weather-resistant packings, O-rings, and other sealing materials in transportation such as ships and airplanes; Packing, O-rings, sealing materials for food plants, and similar packings, O-rings, sealing materials for food plant equipment (including household products); similar packings, O-rings, sealing materials for nuclear plant equipment; The same packing, O-ring, sealing material and the like can be mentioned.

Moreover, the following uses are also suitable.
Films, sheets; food films, food sheets, chemical films, chemical sheets, diaphragm pump diaphragms and various packings, semiconductor films, semiconductor sheets, semiconductor diaphragm pump diaphragms and various packings, and the like.
Tubes, hoses; solvent tubes or solvent hoses, paint tubes or paint hoses (including printer applications), air conditioner hoses, brake hoses, food and beverage tubes or food and beverage hoses, semiconductor tubes or semiconductor hoses, Underground tube or hose for gas station, subsea oil field tube or hose (including injection tube and crude oil transfer tube), etc.
Bottles, containers, tanks; chemical tanks such as solvent tanks, paint tanks, semiconductor chemical tanks, food and beverage tanks, etc.
Others: Cable covering materials such as cables and wires, jacket materials, various mechanical seals such as seals for hydraulic equipment, gears, medical tubes (including catheters), cable ducts, etc.

The molded article of the present invention can be suitably used for the various applications described above, and is particularly suitable as a peripheral component for fuel or semiconductor chemicals. The molded product of the present invention is particularly useful as a tank, a sealing material, packing, a roller, a tube or a hose.

Since the laminate of the present invention has a fluororesin layer formed from the fluororesin composition and a thermoplastic resin layer having a polar functional group, the interlaminar adhesive strength is extremely high, and excellent chemical solution low permeability is exhibited. . In addition, since the molded article using the laminate of the present invention is formed by laminating an expensive fluororesin layer with an inexpensive thermoplastic resin layer, it is more economically advantageous than a molded article composed only of a fluororesin. It is.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Preparation of sheet-shaped test piece (fluororesin layer)>
Various fluororesin compositions are set in a mold, held at 260 to 300 ° C. for 15 to 30 minutes with a heat press machine, and after the fluororesin composition is melted, a 3 MPa load is applied for 1 minute and compression molding is performed. Then, a sheet-like test piece having a predetermined thickness was produced.

<Preparation of sheet specimen (thermoplastic resin layer)>
Various thermoplastic resins are set in a mold, held at 130 to 300 ° C. for 15 to 30 minutes by a heat press machine, and after the fluororesin composition is melted, it is compression molded by applying a load of 3 MPa for 1 minute. A sheet-like test piece having a predetermined thickness was prepared.

<Production of laminate>
A sheet-shaped test piece of a fluororesin composition having a thickness of 0.5 mm and a sheet-shaped test piece of a fluorine-free thermoplastic resin having a thickness of 0.5 mm were produced by the above-described method (only polyethylene terephthalate was originally a film of 188 μm). These sheet-shaped test pieces were stacked and set in a mold heated to 100 to 240 ° C. (below the melting point of the fluorine-free thermoplastic resin), and a heat press machine applied a 3 MPa load at 100 to 240 ° C. for 1 minute. Then, a fluororesin layer-thermoplastic resin layer laminate was produced.

<Adhesion evaluation test>
The obtained laminate was cut into strips each having a width of 1.0 cm and a width of 10 cm to produce a test piece for adhesion test, and an autograph (AGS-J 5kN, manufactured by Shimadzu Corporation) was used for this test piece. Then, in accordance with the method described in JIS-K-6256 (crosslinking rubber adhesion test method), a peel test was performed at 25 ° C. at a tensile rate of 50 mm / min, and the following criteria were evaluated.

(Adhesion evaluation)
A: The fluororesin layer / thermoplastic resin layer interface did not peel, and the fluororesin layer or the thermoplastic resin layer broke down.
○: Peeled at the fluororesin layer / thermoplastic resin layer interface, but was sufficiently adhered and difficult to peel.
Δ: Peeled relatively easily at the fluororesin layer / thermoplastic resin layer interface, but adhesion was observed.
X: The fluororesin layer and the thermoplastic resin layer did not show adhesiveness at all.

<Functional group analysis by infrared absorption spectrum>
A sheet having a thickness of 0.15 to 0.30 mm was prepared by the above method, and an infrared absorption spectrum was analyzed using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by PerkinElmer). The obtained infrared absorption spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of a predetermined peak was measured. The film thickness was measured using a micrometer. Moreover, the difference spectrum with the base resin which does not have a functional group was also used as needed.

<Measurement of composition of fluororesin copolymer>
The copolymer composition of the fluororesin was determined from ¹⁹ F-NMR, fluorine elemental analysis and IR.

<Measurement of fuel permeability coefficient>
A sheet-like test piece having a thickness of 0.5 mm was produced by the above method. 18 mL of CE10 (toluene / isooctane / ethanol = 45/45/10 vol%), which is a simulated fuel, is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the above sheet A test specimen is prepared by setting a cylindrical test piece in the container opening and sealing it. The test specimen was placed in a thermostatic device (60 ° C.), the weight of the test specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following formula.

<Measurement of tensile modulus>
A sheet-shaped test piece having a thickness of 2 mm is prepared by the above method, and a dumbbell-shaped test piece having a width of 3.18 mm and a distance between marked lines of 7.6 mm is punched out using an ASTM V type dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. and a tensile speed of 50 mm / min according to ASTM D638 using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation). It was.

<Measurement of melting point of fluororesin>
Using a Seiko differential scanning calorimeter [DSC], the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

<Measurement of melt flow rate (MFR)>
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a load of 5 kg at 297 ° C. It was measured.

<Confirmation of foaming>
The polymer was allowed to flow out of the nozzle of the melt indexer in the same manner as in the above MFR measurement except that the measurement temperature was 330 ° C., and the foamed state of the obtained polymer strand was observed using a 10 × loupe.
○: Foaming was observed.
X: No foaming was observed.

<Production example>
In the examples and comparative examples, the following materials were used.

(Fluorine resin layer)
Fluororesin (a-1): FEP having a —COOH group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 6.9 g / 10 min. The number of —COOH groups is 480 (per 1 million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-2): FEP having —OC (═O) OCH ₂ CH ₂ CH ₃ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.8 / 7.6 / 0.6 (molar ratio). 261 ° C. The MFR at 297 ° C. is 8.0 g / 10 min. _{-OC (= O) OCH 2 CH} 2 CH 3 radix 410 pieces (carbon atoms per million). Tensile modulus is 460 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ₂ · day).

Fluororesin (a-3): FEP having —CF═CF ₂ group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 14.8 g / 10 min. -CF = CF _{2 The} number of groups is 380 (per 1 million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-4): FEP having —CF ₃ group and —CF ₂ H group. The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 7.8 g / 10 min. -COOH _{group, -OC (= O) OCH 2} CH 2 CH 3 group, -OC (= O) OCH ( CH 3) 2 group, -COF groups, -CF = CF ₂ group, are both -NH ₂ group Less than 20 (per million carbon atoms). The tensile modulus is 450 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

Fluororesin (a-5): CTFE-TFE copolymer having —OC (═O) OCH ₂ CH ₂ CH ₃ group. The monomer composition is CTFE / TFE / perfluoro (propyl vinyl ether) = 77/21/2 (molar ratio). Mp 245 ° C. The MFR at 297 ° C. is 29.5 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 160 (per 1 million carbon atoms). Tensile modulus is 440 MPa. The fuel permeability coefficient is 0.3 (g · mm) / (m ² · day).

(Thermoplastic resin layer)

Fluorine-free thermoplastic resin (b-1): Polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300, thickness 188 μm, melting point 250 ° C.).

Fluorine-free thermoplastic resin (b-2): ethylene / vinyl alcohol copolymer (EVOH) (manufactured by Kuraray Co., Ltd., Eval F101, melting point 183 ° C.). The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluorine-free thermoplastic resin (b-3): Epoxy-modified polyethylene (LOTADER AX8840 manufactured by ARKEMA, melting point 105 ° C.).

Example 1
After 80 g of fluororesin (a-1) was melted in a lab plast mill (produced by Toyo Seiki Seisakusho Co., Ltd.) having an internal volume of 80 ml heated to 280 ° C., 3,4′-DPE (Wakayama Seika Co., Ltd.) )) 0.64 g was added and melt-kneaded for 10 minutes to obtain a fluororesin composition. From the infrared absorption spectrum, since an absorption band of 1744 cm ⁻¹ that was not observed in the fluororesin (a-1) was observed, at least a part of the fluororesin (a-1) and 3,4′-DPE was observed. It was suggested that is bound by an amide bond.

The tensile elasticity modulus, fuel permeability coefficient, and MFR of the obtained fluororesin composition were measured to evaluate the presence or absence of foaming. The results are shown in Table 1.

Using the fluororesin composition and the fluorine-free thermoplastic resin (b-1 to 3), a laminate was produced according to the above method. The adhesion of this laminate was evaluated by the above method. The results are shown in Table 1.

Examples 2-9, Comparative Example 1
A fluororesin composition was obtained in the same manner as in Example 1 except that the fluororesin and polyfunctional compound shown in Table 1 were used. MFR of the obtained fluororesin composition was measured and the presence or absence of foaming was evaluated. Moreover, the laminated body was created like Example 1 and adhesiveness was evaluated. The results are shown in Table 1.

The laminate of the present invention can be suitably used for molded products such as fuel tubes, fuel hoses, fuel tanks, chemical liquid tanks and the like.

Claims (7)

A fluororesin composition comprising a fully halogenated fluororesin and a polyfunctional compound having at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer A fluororesin layer (a) formed from
A thermoplastic resin layer (b) formed from a fluorine-free thermoplastic resin having a polar functional group;
The laminated body characterized by including. The laminate according to claim 1, wherein the polyfunctional compound is an aromatic asymmetric polyfunctional compound. The laminate according to claim 1 or 2, wherein the fluororesin is at least one selected from the group consisting of a copolymer composed of tetrafluoroethylene and hexafluoropropylene and a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene. body. The laminate according to claim 1, 2 or 3, wherein the fluorine-free thermoplastic resin is at least one selected from the group consisting of polyethylene terephthalate, modified polyolefin resin, and ethylene / vinyl alcohol copolymer. The molded article formed from the laminated body of Claim 1, 2, 3 or 4. The molded article according to claim 5, which is a fuel tube, a fuel hose, a fuel tank, or a chemical tank. The manufacturing method of the laminated body of Claim 1, 2, 3 or 4.