WO2011099414A1

WO2011099414A1 - Fluorine-containing copolymer

Info

Publication number: WO2011099414A1
Application number: PCT/JP2011/052254
Authority: WO
Inventors: 進吾榊原; 深川　亮一; 岳史関口; 剛志稲葉; 隆行平尾; 武司下野
Original assignee: ダイキン工業株式会社
Priority date: 2010-02-09
Filing date: 2011-02-03
Publication date: 2011-08-18

Abstract

Disclosed is a fluorine-containing copolymer having fuel crack resistance and fuel permeation resistance. In particular, the copolymer contains polymerization units derived from chlorotrifluoroethylene, polymerization units derived from tetrafluoroethylene, polymerization units derived from a monomer (A), and polymerization units derived from a monomer (B), wherein the total amount of the polymerization units derived from chlorotrifluoroethylene and the polymerization units derived from tetrafluoroethylene makes up 80.0-99.8 mol%, the polymerization units derived from the monomer (A) make up 19.0-0.1 mol%, and polymerization units derived from the monomer (B) make up 10.0-0.1 mol%. The monomers (A) are monomers of at least one kind selected from a group comprising fluoroolefins represented by formula (i) CX³X⁴ = CX¹(CF₂)_nX² (i) and perfluoro (alkyl vinyl ethers) represented by formula (ii) CF₂ = CF-ORf¹ (ii), and the monomers (B) are monomers of at least one kind selected from a group comprising fluoroolefins represented by formula (iii) CX³X⁴ = CX¹(CF₂)_mX² (iii) and perfluoro (alkyl vinyl ethers) represented by formula (iv) CF₂ = CF-ORf² (iv).

Description

Fluorine-containing copolymer

The present invention relates to a fluorine-containing copolymer.

Fluororesin is used for fuel transfer piping materials such as gasoline from the viewpoints of processability, rust prevention, weight reduction, economy, etc., and this fluororesin requires fuel crack resistance and fuel permeation resistance. It is done.

As a material having stress crack resistance, chemical resistance, and heat resistance, Patent Document 1 discloses a chlorotrifluoroethylene copolymer obtained by copolymerizing chlorotrifluoroethylene and tetrafluoroethylene with perfluoro (propyl vinyl ether) or the like. Polymers have been proposed.

International Publication No. 2005/100420 Pamphlet

However, in the conventional fluororesin, when stress is applied in a state where the fuel is in contact, there is a problem that cracks are easily generated and the fuel oozes through the cracks.

An object of the present invention is to provide a fluorine-containing copolymer having fuel crack resistance and fuel permeation resistance in view of the above situation.

The present invention includes a polymerized unit based on chlorotrifluoroethylene, a polymerized unit based on tetrafluoroethylene, a polymerized unit based on monomer (A), and a polymerized unit based on monomer (B). The total of the polymer units based on ethylene and the polymer units based on tetrafluoroethylene is 80.0 to 99.8 mol%, and the polymer units based on the monomer (A) is 19.0 to 0.1 mol%. The polymer unit based on the monomer (B) is 10.0 to 0.1 mol%, and the monomer (A) is represented by the general formula (i)
CX ³ X ⁴ = CX ¹ (CF ₂ ) _n X ² (i)
(Wherein X ¹ , X ³ and X ⁴ are the same or different and each represents a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents 1 or 2). And a general formula (ii)
CF ₂ = CF-ORf ¹ (ii)
(Wherein Rf ¹ represents a perfluoroalkyl group having 1 or 2 carbon atoms), and is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers). The monomer (B) has the general formula (iii)
CX ³ X ⁴ = CX ¹ (CF ₂ ) _m X ² (iii)
(Wherein X ¹ , X ³ and X ⁴ are the same or different and represent a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and m represents an integer of 3 to 10) .) And a general formula (iv)
CF ₂ = CF-ORf ² (iv)
(Wherein Rf ² represents a perfluoroalkyl group having 3 to 8 carbon atoms) and is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers). It is a characteristic fluorine-containing copolymer.

Since the fluorine-containing copolymer of the present invention has the above-described configuration, it has excellent fuel crack resistance and fuel permeation resistance. Moreover, when using for a laminated body, high adhesiveness with another material is shown.

The present invention is described in detail below.

The fluorine-containing copolymer of the present invention comprises polymerized units based on chlorotrifluoroethylene [CTFE units], polymerized units based on tetrafluoroethylene [TFE units], polymerized units based on monomer (A) [monomer ( A) units] and polymerized units [monomer (B) units] based on the monomer (B).

The fluorine-containing copolymer of the present invention contains specific monomer (A) units and monomer (B) units in specific amounts in addition to CTFE units and TFE units, and therefore has extremely high fuel crack resistance. . Moreover, since it contains a monomer (B) unit, the melting point can be lowered and the moldability is excellent.

The monomer (A) has the general formula (i)
CX ³ X ⁴ = CX ¹ (CF ₂ ) _n X ² (i)
(Wherein X ¹ , X ³ and X ⁴ are the same or different and represent a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and n is 1 or 2). And a general formula (ii)
CF ₂ = CF-ORf ¹ (ii)
(Wherein Rf ¹ represents a perfluoroalkyl group having 1 or 2 carbon atoms) is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers).

The monomer (A) has an important carbon number, and if n in the formula (i) exceeds 2, sufficient fuel crack resistance cannot be obtained. Similarly, if the carbon number of Rf ¹ in formula (ii) exceeds 2, sufficient fuel crack resistance cannot be obtained.

Examples of the fluoroolefin represented by the general formula (i) include 2,3,3,3-tetrafluoropropene [CH ₂ ═CFCF ₃ ], hexafluoropropylene and the like.

Examples of the perfluoro (alkyl vinyl ether) represented by the general formula (ii) include perfluoro (methyl vinyl ether) and perfluoro (ethyl vinyl ether).

The monomer (A) is particularly preferably hexafluoropropylene.

The monomer (B) has the general formula (iii)
CX ³ X ⁴ = CX ¹ (CF ₂ ) _m X ² (iii)
(Wherein X ¹ , X ³ and X ⁴ are the same or different and represent a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and m represents an integer of 3 to 10) .) And a general formula (iv)
CF ₂ = CF-ORf ² (iv)
(Wherein Rf ² represents a perfluoroalkyl group having 3 to 8 carbon atoms), and is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers).

X ^{2 in} formula (iii) is preferably a hydrogen atom or a fluorine atom.

The monomer (B) has an important carbon number, and if m in the formula (iii) is less than 3, sufficient mechanical strength cannot be obtained. Similarly, sufficient mechanical strength cannot be obtained when the number of carbon atoms in Rf ² in formula (iv) is less than 3.

Examples of the fluoroolefin represented by the general formula (iii) include perfluoro (1,1,5-trihydro-1-pentene) [CH ₂ ═CF (CF ₂ ) ₂ CF ₂ H], perfluorobutylethylene [ _{_{_{CH 2 = CH (CF 2)}}} 3 CF 3 ], perfluorohexylethylene _{_{_{[CH 2 = CH (CF 2)}}} 5 CF 3 ], perfluoro pentyl ethylene _{_{_{[CH 2 = CH (CF 2)}}} 4 CF 3 ] and the like is Can be mentioned.

Examples of the perfluoro (alkyl vinyl ether) represented by the general formula (iv) include perfluoro (propyl vinyl ether) and perfluoro (butyl vinyl ether).

The monomer (B) is particularly preferably perfluoro (propyl vinyl ether).

The fluorine-containing copolymer of the present invention has a total of 80.0 to 99.8 mol% of polymerized units based on chlorotrifluoroethylene and polymerized units based on tetrafluoroethylene, and is polymerized based on the monomer (A). The unit is 19.0 to 0.1 mol%, and the polymerized unit based on the monomer (B) is 10.0 to 0.1 mol% (100 mol% in total). The preferred lower limit of the total amount of polymer units based on chlorotrifluoroethylene and polymer units based on tetrafluoroethylene is 90.0 mol%, more preferably 92.5 mol%, and the preferred upper limit is It is 99.0 mol%, and it is more preferable that it is 98.0 mol%. The preferable lower limit of the polymerized units based on the monomer (A) is 0.5 mol%, more preferably 1.0 mol%, and the preferable upper limit is 9.5 mol%, and 4.0. More preferably, it is mol%. The preferable lower limit of the polymerized units based on the monomer (B) is 0.5 mol%, more preferably 1.0 mol%, and the preferable upper limit is 5 mol%, 3.5 mol%. It is more preferable that When there are too many monomer (A) units, it tends to be inferior in fuel permeation resistance, interlayer adhesion with other materials in a laminated tube, heat resistance, mechanical strength, productivity, etc., monomer (A) When the unit is too small, sufficient fuel crack resistance cannot be obtained. If the monomer (B) unit is too much, the fuel permeation resistance, interlayer adhesion with other materials in the laminated tube, heat resistance, mechanical strength, productivity, etc. tend to be inferior, and the monomer (B) When the unit is too small, sufficient fuel crack resistance cannot be obtained.

In the present specification, the content (mol%) of each polymerized unit is a polymerized unit based on chlorotrifluoroethylene, a polymerized unit based on tetrafluoroethylene, a polymerized unit based on monomer (A), and a monomer. It is content with respect to the sum total of the polymerization unit based on (B).

In the present invention, the ratio of each polymer unit in the copolymer is a value obtained by analysis such as ¹⁹ F-NMR. More specifically, it is a value obtained by appropriately combining NMR analysis, infrared spectrophotometer [IR], elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The fluorine-containing copolymer of the present invention has 1.0 to 50.0 mol% of polymerized units based on chlorotrifluoroethylene and 30.0 to 98.8 mol% of polymerized units based on tetrafluoroethylene. More preferably, the polymerized units based on chlorotrifluoroethylene are 5.0 to 25.0 mol%, and the polymerized units based on tetrafluoroethylene are more preferably 55.0 to 94.8 mol%.

The fluorine-containing copolymer of the present invention has a melt flow rate at 297 ° C. of preferably 1 to 70 g / 10 min, and more preferably 1 to 50 g / 10 min. If the melt flow rate is too large, the mechanical strength may be inferior and sufficient fuel crack resistance may not be obtained. If the melt flow rate is too small, molding may be difficult.

The melt flow rate is a value obtained by measuring the mass of the fluorine-containing copolymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm under a load of 297 ° C. and 5 kg using a melt indexer.

The fluorine-containing copolymer of the present invention preferably has a melting point [Tm] of 150 to 280 ° C. A more preferred lower limit is 160 ° C, a still more preferred lower limit is 170 ° C, a particularly preferred lower limit is 190 ° C, and a more preferred upper limit is 260 ° C.

The Tm is a temperature corresponding to a melting peak when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].

In the fluorinated copolymer of the present invention, the temperature [Tx] at which 1% by mass of the fluorinated copolymer of the present invention subjected to the heating test decomposes is preferably 370 ° C. or higher. A more preferred lower limit is 380 ° C., and a more preferred lower limit is 390 ° C. If the said thermal decomposition temperature [Tx] is in the said range, an upper limit can be made into 450 degreeC, for example.

The thermal decomposition temperature [Tx] is a temperature at which the mass of the fluorine-containing copolymer of the present invention subjected to the heating test is reduced by 1% by mass using a differential heat / thermogravimetry apparatus [TG-DTA]. It is a value obtained by doing.

In the fluorinated copolymer of the present invention, the difference [Tx−Tm] between the melting point [Tm] and the temperature [Tx] at which 1% by mass is decomposed is preferably 130 ° C. or more. If it is less than 130 ° C., the range in which molding is possible is too narrow, and the range of selection of molding conditions becomes small. Since the temperature range in which the fluorine-containing copolymer of the present invention can be molded is wide as described above, a high melting point polymer can be used as a counterpart material when coextrusion molding is performed.

The fluorine-containing copolymer can be obtained by a conventionally known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization or the like, but industrially, it is preferably obtained by suspension polymerization.

The fluorine-containing copolymer of the present invention preferably has an adhesive functional group. In the present specification, the above-mentioned “adhesive functional group” is a part of the molecular structure of a polymer contained in the fluorine-containing copolymer of the present invention and can be involved in adhesion to other materials. means. Examples of the adhesive functional group include a carbonyl group, a hydroxyl group, and an amino group.

In the present specification, the “carbonyl group” is a functional group having a carbon divalent group [—C (═O) —] composed of a carbon-oxygen double bond. The carbonyl group is not particularly limited, and examples thereof include a carbonate group, a halogenoformyl group, a formyl group, a carboxyl group, an ester bond [—C (═O) O—], and an acid anhydride bond [—C (═O) O. —C (═O) —], isocyanate group, amide group, imide group [—C (═O) —NH—C (═O) —], urethane bond [—NH—C (═O) O—], Carbamoyl group [NH ₂ —C (═O) —], carbamoyloxy group [NH ₂ —C (═O) O—], ureido group [NH ₂ —C (═O) —NH—], oxamoyl group [NH ₂ -C (= O) -C (= O)-] and the like in which a part of the chemical structure is -C (= O)-.

The amide group has the following general formula

(Wherein R ² represents a hydrogen atom or an organic group, and R ³ represents an organic group).

A hydrogen atom bonded to a nitrogen atom such as the amide group, imide group, urethane bond, carbamoyl group, carbamoyloxy group, ureido group, or oxamoyl group may be substituted with a hydrocarbon group such as an alkyl group.

The above-mentioned adhesive functional group is easy to introduce, and the coating film to be obtained has moderate heat resistance and good adhesion at a relatively low temperature, so that it has an amide group, a carbamoyl group, a hydroxyl group. A carboxyl group and a carbonate group are preferable, and a carbonate group is more preferable.

The carbonate group is a group having a bond generally represented by [—OC (═O) O—], and a —OC (═O) O—R group (wherein R represents an organic group). It is represented by Examples of the organic group represented by R in the above formula include an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having an ether bond, and preferably an alkyl group having 1 to 8 carbon atoms. And an alkyl group having 2 to 4 carbon atoms having an ether bond. Examples of the carbonate group include —OC (═O) O—CH ₃ , —OC (═O) O—C ₃ H ₇ , —OC (═O) O—C ₈ H ₁₇ , —OC (═O ) O—CH ₂ CH ₂ CH ₂ OCH ₂ CH _{3 and the} like.

When the fluorine-containing copolymer of the present invention has an adhesive functional group, it may consist of a polymer having an adhesive functional functional group at either the main chain end or the side chain. Or a polymer having both at the main chain terminal and at the side chain. In the case of having an adhesive functional group at the end of the main chain, it may be present at both ends of the main chain or only at one of the ends. The fluorine-containing copolymer of the present invention has an adhesive functional group at the end of the main chain because it does not significantly reduce mechanical properties and chemical resistance, or because it is advantageous in terms of productivity and cost. preferable.

Examples of the adhesive functional group at the end of the main chain include a carbonate group, —COF, —COOH, —COOCH ₃ , —CONH ₂ , or —CH ₂ OH. The adhesive functional group at the end of the main chain is usually formed at the end of the main chain by addition of a chain transfer agent or a polymerization initiator used during polymerization, and the structure of the chain transfer agent or polymerization initiator It is derived from.

When the fluorine-containing copolymer of the present invention is a polymer having an adhesive functional group at the end of the main chain and the adhesive functional functional group is a carbonate group, polymerization of peroxycarbonate is started. It can obtain by the method of superposing | polymerizing using as an agent. Use of the above method is preferable from the viewpoints of very easy introduction and control of introduction of carbonate groups, quality, such as economical efficiency, heat resistance, and chemical resistance.

As the peroxycarbonate, the following formula

(In the formula, R ⁴ and R ⁵ are the same or different and each represents a linear or branched monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a C 1 to 15 carbon atoms having an alkoxyl group at the terminal. Represents a linear or branched monovalent saturated hydrocarbon group, and R ⁶ represents a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms, or a carbon number having an alkoxyl group at the terminal. 1 to 15 linear or branched divalent saturated hydrocarbon groups) are preferred.

Among these peroxycarbonates, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di- 2-ethylhexyl peroxydicarbonate and the like are preferable.

When the fluorine-containing copolymer of the present invention is a polymer having an adhesive functional group at the end of the main chain, and the adhesive functional functional group is a polymer other than a carbonate group, As in the case of introduction, by using a peroxide such as peroxycarbonate, peroxydicarbonate, peroxyester, and peroxyalcohol as a polymerization initiator, an adhesive functional group derived from the peroxide is obtained. Can be introduced. In addition, “derived from peroxide” is directly introduced from the functional group contained in the peroxide or indirectly by converting the functional group introduced directly from the functional group contained in the peroxide. It means being introduced.

The amount of the above polymerization initiator such as peroxycarbonate and peroxyester varies depending on the type and composition of the target fluorine-containing copolymer, the molecular weight, the polymerization conditions, the type of initiator used, etc. The amount is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the coalescence, and the particularly preferable lower limit is 0.1 part by mass, and the particularly preferable upper limit is 1 part by mass.

The number of the adhesive functional functional groups may be appropriately selected depending on differences in the type, shape, purpose of use, application, required adhesive force, adhesion method, and the like of the counterpart material to be laminated.

In the case of melt molding at a molding temperature of less than 320 ° C., the number of functional functional groups for adhesion is preferably 3 to 800 per 1 × 10 ⁶ main chain carbon atoms. Adhesiveness may fall that it is less than 3 per 1 × 10 ⁶ main chain carbon atoms. A more preferred lower limit is 50, a still more preferred lower limit is 80, and a particularly preferred lower limit is 120. In the case of melt molding at a molding temperature of less than 320 ° C., the upper limit of the number of functional adhesive functional groups can be set to, for example, 500 from the viewpoint of productivity, provided that the number is within the above range.

The number of functional functional groups for adhesion is a thickness of 0.25 to 0.30 mm obtained by compression molding the powder of the fluorine-containing copolymer of the present invention at a molding temperature 50 ° C. higher than the melting point at a molding pressure of 5 MPa. The film sheet is analyzed by infrared absorption spectrum using an infrared spectrophotometer [IR], the type is determined by comparison with the infrared absorption spectrum of a known film, and the number calculated from the difference spectrum by the following formula is used. is there.
Number of terminal groups (per 1 × 10 ⁶ carbon atoms) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows the correction coefficients of the target end groups.

The correction coefficient in Table 1 is a value determined from the infrared absorption spectrum of the model compound in order to calculate the terminal group per 1 × 10 ⁶ main chain carbon atoms.

The fluorine-containing copolymer of the present invention is a fluororesin and not an elastomer.

The fluorine-containing copolymer of the present invention is a polymer unit based on chlorotrifluoroethylene, a polymer unit based on tetrafluoroethylene, a polymer unit based on the monomer (A) and a single amount within a range not to impair the purpose of the present invention. The polymer unit may have a polymer unit other than the polymer unit based on the body (B), and the content of the polymer unit is preferably 0.1 to 1.0 mol% of the total polymer units. Examples of the polymerized units include polymerized units based on unsaturated aliphatic polycarboxylic acids. The unsaturated aliphatic polycarboxylic acids are not particularly limited, and examples thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and the like, and acids such as maleic acid, itaconic acid, citraconic acid and the like. What can be an anhydride may be an acid anhydride.

However, the fluorine-containing copolymer of the present invention is based on a polymer unit based on chlorotrifluoroethylene, a polymer unit based on tetrafluoroethylene, a polymer unit based on monomer (A), and a monomer (B). It is also one of the preferable embodiments that it consists of only polymerized units.

Moreover, this invention relates to the laminated body which has the layer (C) which consists of a fluorine-containing copolymer of this invention, and the layer (K) which consists of a fluorine-free organic material. In the laminate of the present invention, the fluorine-containing copolymer of the present invention constituting the layer (C) improves interlayer adhesion, fuel permeability resistance, and fuel crack resistance.

The laminate of the present invention may further have a layer (J) made of a fluorine-containing ethylenic polymer (excluding the fluorine-containing copolymer of the present invention). The layer (J) made of the fluorine-containing ethylenic polymer includes a layer (P) made of a perhalo fluorine-containing ethylenic polymer other than the fluorine-containing copolymer of the present invention, and the fluorine-containing copolymer of the present invention. Examples include a layer (F) made of a non-perhalogenated fluorine-containing ethylenic polymer other than the coalescence.

When the laminate of the present invention has a layer (P) made of a perhalogenated fluorine-containing ethylenic polymer other than the fluorine-containing copolymer of the present invention, it is excellent in chemical resistance and heat resistance.

As the perhalogenated fluorine-containing ethylenic polymer, (III) at least a TFE unit and the following general formula (vi)
CF ₂ = CF-Rf ⁵ (vi)
(Wherein Rf ⁵ represents CF ₃ or ORf ⁶ , and Rf ⁶ represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Examples thereof include copolymers comprising body units. The perfluoromonomer unit may be one type or two or more types.

Examples of the perhalogenated fluorine-containing ethylenic polymer also include PCTFE.

Examples of the copolymer (III) include:
(III-I) a copolymer of 70 to 95 mol%, preferably 85 to 93 mol% of TFE units, 5 to 30 mol%, preferably 7 to 15 mol% of HFP units,
(III-II) TFE units 70 to 95 mol%, the following general formula (vii)
CF ₂ = CF-ORf ⁷ (vii)
(Wherein Rf ⁷ represents a perfluoroalkyl group having 1 to 5 carbon atoms), a total of 5 to 30 mol% of one or more PAVE units derived from PAVE represented by Polymer,
(III-III) 70 to 95 mol% of TFE units, 5 to 30 mol% of the total of HFP units and one or more PAVE units derived from PAVE represented by the above general formula (vii) Polymer,
Etc.

The PAVE unit may be one type or two or more types. It does not specifically limit as said copolymer (III), For example, it can use 1 type or in combination of 2 or more types.

When the laminate of the present invention has a layer (F) made of a non-perhalogenated fluorine-containing ethylenic polymer other than the fluorine-containing copolymer of the present invention, the laminate and the melt processability are excellent.

Examples of the non-perhalogenated fluorine-containing ethylenic polymer include (IV) a copolymer comprising at least a TFE unit and an Et unit.

Examples of the non-perhalogenated fluorine-containing ethylenic polymer include (V) a copolymer composed of at least a VdF unit.

Examples of the copolymer (IV) include a polymer comprising 20 mol% or more of TFE units. Examples of such a copolymer include 20 to 80 mol% of TFE units and 20 to 80 mol% of Et units. And a copolymer composed of 0 to 60 mol% of a unit derived from a monomer copolymerizable therewith.

Examples of the copolymerizable monomer include the following general formula (viii):
CX ⁹ X ¹⁰ = CX ⁷ (CF ₂ ) _n X ⁸ (viii)
(Wherein X ⁷ , X ⁹ and X ¹⁰ are the same or different and each represents a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10) A fluoroolefin represented by the following general formula (ix)
CF ₂ = CF-ORf ⁸ (ix)
(Wherein Rf ⁸ represents a perfluoroalkyl group having 1 to 5 carbon atoms), and one or more of these may be used.

As the copolymer (IV), among them, a fluoroolefin unit derived from the fluoroolefin represented by the general formula (viii) and / or a PAVE unit derived from PAVE represented by the general formula (ix) A copolymer comprising a total of 0 to 60 mol%, TFE units 20 to 80 mol%, and Et units 20 to 80 mol% is preferred.

Examples of such a copolymer include (IV-I) 30 to 70 mol% of TFE units, 20 to 55 mol% of Et units, and fluoroolefin units derived from the fluoroolefin represented by the above general formula (viii). A copolymer comprising ˜10 mol%,
(IV-II) A copolymer comprising 30 to 70 mol% of TFE units, 20 to 55 mol% of Et units, 1 to 30 mol% of HFP units, and 0 to 10 mol% of units derived from monomers copolymerizable therewith. Polymer,
(IV-III) a copolymer comprising 30 to 70 mol% of TFE units, 20 to 55 mol% of Et units, and 0 to 10 mol% of PAVE units derived from PAVE represented by the general formula (ix),
Etc.

The unit derived from the copolymerizable monomer constituting the copolymer (IV) is a fluoroolefin unit derived from the fluoroolefin represented by the general formula (viii) and / or the general formula (ix). The copolymer (IV) may or may not be contained, including the case where it is a PAVE unit derived from PAVE represented by:

Examples of the copolymer (V) include polymers composed of 10 mol% or more of VdF units. Examples of such copolymers include 15 to 100 mol% of VdF units and 0 to 85 mol% of TFE units. In addition, a copolymer comprising a total of 0 to 30 mol% of HFP units and / or trichlorofluoroethylene units is preferred.

Examples of the copolymer (V) include (VI) vinylidene fluoride homopolymer (sometimes referred to as polyvinylidene fluoride [PVdF] in this specification),
(V-II) a copolymer comprising 30 to 99 mol% of VdF units and 1 to 70 mol% of TFE units,
(V-III) a copolymer comprising 10 to 90 mol% of VdF units, 0 to 90 mol% of TFE units, and 0 to 30 mol% of trichlorofluoroethylene units,
(V-IV) a copolymer comprising 10 to 90 mol% of VdF units, 0 to 90 mol% of TFE units, and 0 to 30 mol% of HFP units,
Etc.

The copolymer (V-IV) is preferably a copolymer comprising 15 to 84 mol% of VdF units, 15 to 84 mol% of TFE units, and 0 to 30 mol% of HFP units.

Of the polymer units constituting the copolymers (III) to (V), any of the copolymer units that may be 0 mol% in various copolymers may be contained in the copolymer. It does not have to be included.

The fluorine-containing ethylenic polymer constituting the layer (J) preferably has an MFR of 0.1 to 70 (g / 10 minutes). When the MFR is within the above range, the fuel permeation resistance and the fuel crack resistance are excellent. The more preferable lower limit of the MFR is 1 (g / 10 minutes), and the more preferable upper limit is 50 (g / 10 minutes).

As said fluorine-containing ethylenic polymer, it can use in combination of 2 or more type. When two or more types are used in combination, by selecting and combining fluorine-containing ethylenic polymers having good compatibility with each other, mixing by melting can form a layer without a clear boundary, and delamination does not occur ,preferable. The mixing ratio or the layer thickness ratio can be adjusted so that the layer as a whole has a preferable fuel permeability coefficient and a preferable melting point.

The layer (J) made of the above-mentioned fluorine-containing ethylenic polymer, when two or more of the above-mentioned fluorine-containing ethylenic polymers are used, is laminated by feeding them into a co-extruder without previously mixing each type of polymer to be used. Even if it does not introduce the above-mentioned adhesion functional functional group by making the body or stacking the layers prepared separately and heat melting, it shall be excellent in each interlayer adhesion by compatibility Can do.

The layer (J) composed of the above-mentioned fluorine-containing ethylenic polymer is formed when two or more of the above-mentioned fluorine-containing ethylenic polymers are used, or after the polymer alloy is adjusted by mixing each type of polymer used in advance. It may be what you did.

The fluorine-containing ethylenic polymer may have the above-described adhesive functional group at the main chain terminal or may be present at the side chain.

The ratio of the polymerized units in the fluorine-containing ethylenic polymer is a value obtained by appropriately combining ¹⁹ F-NMR analysis, infrared spectrophotometer [IR], elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. .

The melting point of the fluorine-containing ethylenic polymer is preferably 130 to 280 ° C., and more preferably 150 to 280 ° C. from the viewpoint of facilitating coextrusion molding.

The fluorine-containing ethylenic polymer constituting the layer other than the layer having a wetted surface may be a polymer constituting either a resin or an elastomer, but preferably constitutes a resin.

The fluorine-containing ethylenic polymer can be obtained by a conventionally known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization or the like, but industrially, it is preferably obtained by suspension polymerization.

In the laminate of the present invention, the fluorine-containing copolymer and the fluorine-containing ethylenic polymer of the present invention constituting each layer may be a mixture of a conductive filler. By adding a conductive filler, accumulation of static electricity caused by friction between the fuel and the laminate of the present invention is prevented, and a fire or explosion that may occur due to electrostatic discharge, or a crack in the laminate of the present invention. It is possible to prevent perforation and fuel leakage caused thereby.

The conductive filler is not particularly limited, and examples thereof include conductive simple powders or conductive single fibers such as metals and carbons; powders of conductive compounds such as zinc oxide; surface conductive powders.

The conductive simple powder or conductive simple fiber is not particularly limited, and examples thereof include metal powder such as copper and nickel; metal fiber such as iron and stainless steel; carbon black, carbon fiber, and Japanese Patent Laid-Open No. 3-174018. Examples thereof include carbon fibrils, carbon nanotubes, and carbon nanohorns.

The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide. The method for conducting the conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating. Among the conductive fillers described above, carbon black is preferably used because it is advantageous from the viewpoint of economy.

When the conductive filler is blended with the polymer constituting each of the layers, it is preferable to prepare pellets in advance by melt-kneading.

The pellet heating conditions after melt-kneading at the time of pellet preparation are generally performed at a temperature not lower than the glass transition point of the polymer constituting each layer and lower than the melting point of the polymer constituting each layer. It is preferably performed at 200 ° C. for 1 to 48 hours. By preparing pellets in advance, it is possible to uniformly disperse the conductive filler in the polymer in the resulting layer, and to impart conductivity uniformly.

The blending amount of the conductive filler is appropriately determined based on the kind of polymer, the conductive performance required for the laminate, the molding conditions, and the like, but it is 1 to 30 parts by mass with respect to 100 parts by mass of the polymer. Is preferred. A more preferred lower limit is 5 parts by mass, and a more preferred upper limit is 20 parts by mass.

The surface resistance value of the polymer blended with the conductive filler is preferably 1 × 10 ⁰ to 1 × 10 ⁹ Ω · cm. A more preferred lower limit is 1 × 10 ² Ω · cm, and a more preferred upper limit is 1 × 10 ⁸ Ω · cm.

In the present specification, the above-mentioned “surface resistance value of a polymer containing a conductive filler” refers to a pellet obtained by melting and kneading the conductive filler and polymer into a melt indexer, This is a value obtained by measuring the surface resistance value of an extruded strand obtained by heating at 200 to 400 ° C. in a kusa and extruding it using a battery-type insulation resistance meter.

The fluorine-containing copolymer and fluorine-containing ethylenic polymer of the present invention constituting each layer are, for example, a stabilizer such as a heat stabilizer and a reinforcing agent, in addition to the above conductive filler, within a range that does not impair the object of the present invention. In addition, various additives such as a filler, an ultraviolet absorber, and a pigment may be added. The polymer layer can be improved in properties such as thermal stability, surface hardness, abrasion resistance, chargeability, and weather resistance by such an additive.

The laminate of the present invention has a layer (K) made of a fluorine-free organic material.

The fluorine-free organic material is an organic material that does not contain a fluorine atom. The fluorine-free organic material is preferably a resin that can be coextruded with a layer made of a fluorine-containing ethylenic polymer.

The fluorine-free organic material is preferably a resin made of a polymer having a high degree of crystallinity, and is a resin made of a polymer having a high degree of crystallinity and having a polar functional group and a large intermolecular force. Is more preferable.

The polar functional group is a functional group having polarity and capable of participating in adhesion between a layer made of a fluorine-free organic material and an adjacent layer. The polar functional group may be the same functional group as the adhesive functional functional group described above as the fluorine-containing copolymer of the present invention, but may be a different functional group.

The polar functional group is not particularly limited and includes, for example, those described above as the adhesive functional group, cyano group, sulfide group, and the like. Among them, carbonyloxy group, cyano group, sulfide group, hydroxyl group are included. Preferably, a hydroxyl group is more preferable.

Examples of the fluorine-free organic materials include polyamide resins, polyolefin resins, vinyl chloride resins, polyurethane resins, polyester resins, polyaramid resins, polyimide resins, polyamideimide resins, polyphenylene oxide resins, polyacetal resins, polycarbonate resins, acrylic resins. Resin, styrene resin, acrylonitrile / butadiene / styrene resin [ABS], cellulose resin, polyetheretherketone resin [PEEK], polysulfone resin, polyethersulfone resin [PES], polyetherimide resin, etc. Resin (hereinafter referred to as “structural member resin”), an ethylene / vinyl alcohol copolymer resin, polyphenylene sulfide resin, Butylene naphthalate resins, polybutylene terephthalate resins, polyphthalamide [PPA] high penetration resistance over performance for fuel or gas such as a resin (hereinafter. To permeation resistance resin) and the like.

The fluorine-free organic material is preferably at least one selected from the group consisting of polyamide resins and polyolefin resins.

The layered product of the present invention has excellent mechanical strength when it has the layer (A) made of the structural member resin, and it has resistance to permeation to the fuel when it has the layer (E) made of the permeation-resistant resin. It will be excellent.

The polyamide-based resin is composed of a polymer having an amide bond [—NH—C (═O) —] as a repeating unit in the molecule.

As the polyamide resin, a so-called nylon resin composed of a polymer in which an amide bond in a molecule is bonded to an aliphatic structure or an alicyclic structure, or a polymer in which an amide bond in a molecule is bonded to an aromatic structure Any of so-called aramid resins may be used.

The nylon resin is not particularly limited. For example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 46, metaxylylenediamine / adipic acid What consists of polymers, such as a copolymer, is mentioned, You may use combining 2 or more types from these.

The aramid resin is not particularly limited, and examples thereof include polyparaphenylene terephthalamide and polymetaphenylene isophthalamide.

The polyamide-based resin may be composed of a polymer in which a structure having no amide bond as a repeating unit is block-copolymerized or graft-copolymerized in a part of the molecule. Examples of such polyamide resins include nylon elastomers such as nylon 6 / polyester copolymers, nylon 6 / polyether copolymers, nylon 12 / polyester copolymers, and nylon 12 / polyether copolymers. And the like. These polyamide-based elastomers are obtained by block copolymerization of nylon oligomers and polyester oligomers via ester bonds, or by block copolymerization of nylon oligomers and polyether oligomers via ether bonds. It is obtained. Examples of the polyester oligomer include polycaprolactone and polyethylene adipate, and examples of the polyether oligomer include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the polyamide elastomer, nylon 6 / polytetramethylene glycol copolymer and nylon 12 / polytetramethylene glycol copolymer are preferable.

As the polyamide-based resin, sufficient mechanical strength can be obtained even if the layer made of the polyamide-based resin is thin. Among them, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 6 / polyester copolymer, nylon 6 / polyether copolymer, nylon 12 / polyester copolymer, nylon 12 / polyether copolymer, and the like are preferable. Two or more kinds may be used in combination.

The polyolefin resin is a resin having a polymer unit derived from a vinyl group-containing monomer having no fluorine atom. Although it does not specifically limit as said vinyl-group containing monomer which does not have a fluorine atom, What has the polar functional group mentioned above is preferable in the use for which interlayer adhesiveness is calculated | required.

The polyolefin-based resin is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene, and high-density polyolefin, modified polyolefins obtained by modifying the polyolefin with maleic anhydride, epoxy-modified polyolefins, amine-modified polyolefins, and the like. .

The fluorine-free organic material is formed by adding various additives such as a stabilizer such as a heat stabilizer, a reinforcing agent, a filler, an ultraviolet absorber, and a pigment, as long as the object of the present invention is not impaired. It may be. The fluorine-free organic material can be improved in properties such as thermal stability, surface hardness, abrasion resistance, charging property, weather resistance and the like by such additives.

The amine value of the polyamide resin is preferably 10 to 80 (equivalent / 10 ⁶ g). When the amine value is within the above range, the interlayer adhesion can be excellent even when co-extrusion is performed at a relatively low temperature. If the amine value is less than 10 (equivalent / 10 ⁶ g), the interlayer adhesion may be insufficient. If it exceeds 80 (equivalent / 10 ⁶ g), the resulting laminate is insufficient in mechanical strength, tends to be colored during storage, and has poor handling properties. A preferred lower limit is 15 (equivalent / 10 ⁶ g), a preferred upper limit is 60 (equivalent / 10 ⁶ g), and a more preferred upper limit is 50 (equivalent / 10 ⁶ g).

In the present specification, the amine value is a value obtained by dissolving 1 g of a polyamide-based resin in 50 ml of m-cresol and titrating with 1/10 N p-toluenesulfonic acid aqueous solution and using thymol blue as an indicator. Unless otherwise specified, it means the amine value of the polyamide-based resin before lamination. Of the number of amino groups in the polyamide-based resin before lamination, a part is considered to be consumed for adhesion to the adjacent layer, but the number is very small with respect to the entire layer. The amine value of the polyamide-based resin before the process and the amine value of the laminate of the present invention are substantially the same.

The laminate of the present invention may have an adhesive layer (S), and when having an adhesive layer (S), the adhesion between the layers is improved.

Examples of the adhesive layer (S) include adhesive functional group-containing TFE / Et / HFP copolymer, functional group-modified polyethylene, and high amine value nylon, but depending on the physical properties of the two layers to be bonded. You can choose as appropriate.

Of the layers in the laminate of the present invention, at least one layer preferably has a fuel permeability coefficient of 0.5 g · mm / m ² / day or less. At least one of the layer (C) made of the fluorine-containing copolymer of the present invention and the layer (J) made of the fluorine-containing ethylenic polymer has a fuel permeability coefficient of 0.4 g · mm / m ² / day or less. Those are preferred.

In this specification, the fuel permeability coefficient is obtained from a resin to be measured in a fuel permeability coefficient measuring cup charged with an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene and ethanol are mixed at a volume ratio of 45:45:10. It is a value calculated from the change in mass measured at 60 ° C.

The laminate of the present invention preferably has a fuel permeation rate of 2.5 g / m ² / day or less.

The laminated body of the present invention has a high fuel permeation resistance because the fuel permeation rate is within the above-mentioned range. If the fuel permeation rate is within the above range, the lower limit can be set to 0.1 g / m ² / day, for example. A more preferable upper limit of the fuel permeation rate is 2.0 g / m ² / day, and a further preferable upper limit is 1.0 g / m ² / day.

In the present specification, the fuel permeation rate is a fuel permeation mass per unit area per day, and an isooctane / toluene / ethanol mixed solvent [CE10] obtained by mixing isooctane, toluene and ethanol in a volume ratio of 45:45:10. Is a value obtained by measuring the permeation amount at 60 ° C. according to SAE J 1737.

The layer (J) made of the fluorine-containing ethylenic polymer constituting the laminate of the present invention may be a single layer made of one type of fluorine-containing ethylenic polymer, or one or two or more types of containing layers. It may have a multilayer structure of two or more layers made of a fluoroethylenic polymer. For example, two layers of a layer (P) and a layer (F) may be used. Examples of the laminate of the present invention include a laminate of 2 to 5 layers.

As a preferable laminated structure of the laminated body having a two-layer structure, layer (C) / layer (P), layer (P) / layer (C), layer (C) / layer (A), etc. in order from the liquid contact side. Is mentioned.

Among these, the layered structure of layer (C) / layer (P) and layer (P) / layer (C) is suitable as a chemical solution tube used in the semiconductor manufacturing field, and layer (C) / layer (A) This laminated structure is suitable as a fuel tube, and can also be used as a brake hose by attaching a metal blade.

As a preferable laminated structure of the laminate having a three-layer structure, layer (P) / layer (C) / layer (A), layer (C) / layer (E) / layer (A), layer (P) / layer (C) / layer (P), layer (C) / layer (A) / layer (C) and the like.

Of these, the layered structure of layer (P) / layer (C) / layer (A) and layer (C) / layer (E) / layer (A) is suitable as a fuel tube or a chemical tube that requires chemical resistance. It is. The layer (P) / layer (C) / layer (P) layered structure is excellent in solvent resistance and is suitable as an inner tube of an in-tank tube or underground tube. Layer (C) / layer (A) / layer The laminated structure (C) is suitable as a fuel tube or a chemical solution tube because it can prevent water absorption of the non-fluororesin and improve the environmental resistance.

As a preferable laminated structure of the laminate having a four-layer structure, layer (P) / layer (E) / layer (C) / layer (A), layer (P) / layer (S) / layer (C) / layer (A), layer (P) / layer (C) / layer (S) / layer (A), layer (P) / layer (C) / layer (E) / layer (A), layer (P) / layer (C) / layer (A) / layer (C), layer (C) / layer (E) / layer (S) / layer (A), layer (C) / layer (S) / layer (E) / layer (A), layer (C) / layer (E) / layer (C) / layer (A), layer (C) / layer (E) / layer (A) / layer (C) and the like.

These laminates having a four-layer structure are suitable as a fuel tube or a chemical solution tube.

As a preferable laminated structure of the laminate having a five-layer structure, layer (C) / layer (S) / layer (E) / layer (S) / layer (A), layer (P) / layer (C) / layer (A) / layer (C) / layer (P), layer (P) / layer (C) / layer (E) / layer (S) / layer (A), layer (P) / layer (C) / layer (E) / layer (C) / layer (A), layer (P) / layer (C) / layer (E) / layer (A) / layer (C) and the like.

Among these, the laminated structure of layer (C) / layer (S) / layer (E) / layer (S) / layer (A) is suitable as a fuel tube or a chemical liquid tube, and layer (P) / layer (C ) / Layer (A) / layer (C) / layer (P) is suitable as an inner tube of an underground tube, layer (P) / layer (C) / layer (E) / layer (S) / Layer (A), Layer (P) / Layer (C) / Layer (E) / Layer (C) / Layer (A) and Layer (P) / Layer (C) / Layer (E) / Layer (A) The layered structure of / layer (C) is suitable as a chemical solution tube and a fuel tube because it has high chemical resistance and high permeation resistance.

The layer (P), the layer (C), the layer (A), the layer (E) and the layer (S) may each be a single layer or have a multilayer structure of two or more layers. Also good. For example, when the layer (P) has a multilayer structure of two or more layers, a layer comprising a fluorine-containing ethylenic polymer blended with the above-mentioned conductive filler, and a fluorine-containing ethylenic polymer composition not containing the conductive filler And a layer composed of:

As a laminated body of this invention, other layers other than the said layer (P), layer (C), layer (A), layer (E), and layer (S) may also be included. The other layer is not particularly limited, and examples thereof include a protective layer, a colored layer, a marking layer, a dielectric layer for preventing static electricity, and the like in the laminate, and the protective layer, the dielectric layer, etc. In view of the function, the outermost layer in the laminate is preferable.

The laminate of the present invention is a laminate having a layer (C) made of the fluorine-containing copolymer of the present invention and a layer (K) made of a fluorine-free organic material.

In the above laminated body, each of the layer (C) and the layer (K) may be a single layer or may have a multilayer structure of two or more layers. When the layer (K) has a multilayer structure, for example, the layer (A) and the layer (E) may be stacked.

The laminated body of this invention has a layer (C) and a layer (K), and also may have another layer. Examples of the other layer include a layer made of an elastomer and the like, which protects the laminated body from vibrations and impacts and imparts flexibility. Examples of the elastomer include thermoplastic elastomers. For example, at least one selected from the group consisting of polyamide elastomers, polyurethane elastomers, polyester elastomers, polyolefin elastomers, styrene / butadiene elastomers, and vinyl chloride elastomers is selected. Can do.

The laminate of the present invention also comprises a layer (C) comprising the fluorine-containing copolymer of the present invention, a layer (K) comprising a fluorine-free organic material, and a layer (J) further comprising a fluorine-containing ethylenic polymer. It is preferable that the laminate has

The laminate of the present invention may have a layer (D) made of a fluorine-free organic material (Q) between the layer (C) and the layer (J).

The fluorine-free organic material (Q) in the layer (D) may be the same type as or different from the fluorine-free organic material in the layer (K), but the same type. Is preferable, and a polyamide-based resin is more preferable. By providing the layer (D), multilayer coextrusion molding can be easily applied, the line speed can be increased, and the moldability can be improved. Even when the layer (J) is a non-perfluoro fluororesin such as the above-mentioned copolymer (IV), multilayer coextrusion molding is easy and the line speed can be increased.

Examples of the laminate of the present invention include a laminate in which a layer (J), a layer (C), and a layer (K) are laminated in this order, a layer (J), a layer (C), a layer (K), and a layer. (J) Laminate in which layers are laminated in this order, Layer (J), Layer (D), Layer (C) and Laminate in which layers (K) are laminated in this order, (J), Layer (C) , Layer (K), layer (C) and layer (J) are laminated in this order, layer (J), layer (D), layer (C), layer (K) and layer (J). Examples include a laminated body laminated in this order.

The layer (J), the layer (C), the layer (K), and the layer (D) may each be a single layer or may have a multilayer structure of two or more layers.

When the layer (J) has a multilayer structure of two or more layers, the layer (J) includes, for example, a layer made of a fluorine-containing ethylenic polymer blended with the above-described conductive filler, and a fluorine-containing layer that does not contain a conductive filler. And a layer made of an ethylenic polymer.

When the laminate of the present invention has a layer (D) made of a fluorine-free organic material (Q) between the layer (C) and the layer (J), the layer (D) C) and the layer (J) are preferably in contact with each other, and the layer (C) is preferably in contact with the layer (K).

In the laminate of the present invention, the boundary between the layers in contact with each other is not necessarily clear, and the layer structure has a concentration gradient that penetrates from the surface where the molecular chains of the polymers constituting each layer are in contact with each other. May be.

In the laminate of the present invention, the layer (C) is preferably in contact with the layer (J) and the layer (K). When the fluorine-containing copolymer of the present invention in the layer (C) has the above-mentioned adhesive functional group, the adhesion with the layer (J) and the layer (K) can be made excellent. Further, when the layer (J) and the layer (C) are in contact with each other, the compatibility between the fluorine-containing copolymer of the present invention and the fluorine-containing ethylenic polymer can be obtained without introducing the adhesive functional group. Although it can have sufficient adhesiveness, it is preferable that the fluorine-containing copolymer of the present invention in the layer (C) has an adhesive functional functional group in terms of improving the adhesiveness. When the fluorine-containing copolymer of the present invention having a functional group is used, the fluorine-containing ethylenic polymer in the layer (J) exhibits sufficient interlayer adhesion even if it does not contain an adhesive functional functional group. be able to.

As a method for forming a laminate of the present invention, for example, (1) the layers constituting the laminate are co-extruded in a molten state so that the layers are thermally fused (melt-bonded) to form a multilayer structure in one step. The method (coextrusion molding) which forms is mentioned.

In addition to the above (1), (2) a method of laminating each layer separately produced by an extruder and laminating the layers by heat fusion, (3) producing in advance A method of forming a laminate by extruding a molten resin on the surface of the layer by means of an extruder, and (4) a polymer constituting the layer adjacent to the layer is statically formed on the surface of the layer prepared in advance. Examples of the method include forming a layer by heating and melting the polymer used for coating by heating the obtained coated product as a whole or from the coated side after electrocoating.

When the laminate of the present invention is a tube or a hose, for example, as a method corresponding to the above (2), (2a) each cylindrical layer is separately formed by an extruder, and the inner layer is formed on the layer. As a method of coating the contacting layer with a heat shrinkable tube, a method corresponding to the above (3), (3a) First, an inner layer is formed by an inner layer extruder, and this layer is formed on the outer peripheral surface by an outer layer extruder. As a method corresponding to (4) above, (4a) a polymer constituting the inner layer is electrostatically coated on the inner side of the layer in contact with the layer, and then the resulting coated product is heated. A method of heating and melting the polymer constituting the inner layer by inserting a rod-shaped heating device inside the cylindrical coated article and heating from the inside by putting it in an oven and heating it as a whole , Etc.

As long as each layer constituting the laminate of the present invention can be coextruded, it is generally formed by coextrusion molding (1). Examples of the coextrusion molding include conventionally known multilayer co-extrusion manufacturing methods such as a multi-manifold method and a feed block method.

In the molding methods (2) and (3), after forming each layer, the contact surface of each layer with another layer may be surface-treated for the purpose of improving interlayer adhesion. Examples of such surface treatment include etching treatment such as sodium etching treatment; corona treatment; plasma treatment such as low temperature plasma treatment.

As the molding method, a method of performing surface treatment in the above methods (1) and (2) and (3) is preferable, and the method (1) is most preferable.

As a method for forming a laminate of the present invention, a forming method in which a plurality of materials are divided into multiple stages and laminated by rotational molding is also possible. In that case, the melting point of the outer layer material does not necessarily need to be higher than the melting point of the inner layer material, and the melting point of the inner layer material may be higher by 100 ° C. or more than the melting point of the outer layer material. In that case, it is preferable to have a heating part inside.

The laminate of the present invention can have various shapes such as a film shape, a sheet shape, a tube shape, a hose shape, a bottle shape, and a tank shape. The film shape, sheet shape, tube shape, and hose shape may be a corrugated shape, a corrugated shape, a convoluted shape, or the like.

When the laminate of the present invention is a tube or a hose, by having a region where a plurality of such folds are arranged in an annular shape, one side of the annular shape is compressed in that region, and the other side is outward Since it can stretch, it can be easily bent at any angle without stress fatigue or delamination.

The method for forming the corrugated region is not limited, but it can be easily formed by first forming a straight tube and then performing molding or the like to obtain a predetermined corrugated shape.

The laminated body of this invention can be used for the following uses.

Films, sheets; food films, food sheets, chemical films, chemical sheets, diaphragm pump diaphragms and various packing tubes, hoses; fuel tubes such as automotive fuel tubes or automotive fuel hoses, or fuel Hose, solvent tube or solvent hose, paint tube or paint hose (including printer use), automotive radiator hose, air conditioner hose, brake hose, wire covering material, food and beverage tube or food and beverage hose, gasoline Underground buried tubes or hoses for stands, submarine oil field tubes or hoses (including injection tubes and crude oil transfer tubes), bottles, containers, tanks; fuel tanks such as automobile radiator tanks, gasoline tanks, solvent tanks, paints tank Chemical containers such as semiconductor chemical containers, food and beverage tanks, etc .; various automotive seals such as carburetor flange gaskets, fuel pump O-rings, hydraulic equipment seals, gears, medical tubes ( Including catheter), cable duct, etc.

The laminate of the present invention can be suitably used for applications that come into contact with flammable liquids such as tubes, hoses, tanks, etc., and in this case, it is preferable that the portion in contact with the liquid is the layer (C), When a layer (J) exists, it is preferable that it is a layer (J). Since the portion in contact with the liquid is usually an inner layer, when the layer (J) is an inner layer, the layer (C) is an intermediate layer and the layer (K) is an outer layer. In the present specification, the “inner layer”, “intermediate layer”, and “outer layer” are any of the layer (J) and the layer (K) in the shape with the concept of the inside / outside of tubes, hoses, tanks, etc. Represents only the inner side, the outer side, or between the two, and the laminate is a surface of the surface of the layer (C) opposite to the contact surface with the layer (J). Above and / or between the layer (J) and the layer (C) and / or between the layer (C) and the layer (K) and / or among the surfaces of the layer (K) It may have another layer on the surface opposite to the contact surface with (C).

In this specification, the “intermediate layer” is a concept indicating a layer between the inner layer and the outer layer.

When the laminate of the present invention is in contact with a flammable liquid such as gasoline, the flammable liquid is liable to accumulate and static charges are likely to accumulate. However, in order to avoid igniting by this static charge, the layer in contact with the liquid is electrically conductive. It is preferable to contain a functional filler.

When the portion in contact with the liquid in the laminate of the present invention is a layer (J), the layer (J) may be a layer made of a fluorine-containing ethylenic polymer in which the innermost layer is blended with a conductive filler, A multilayer structure having the innermost layer and a layer made of a fluorine-containing ethylenic polymer not containing a conductive filler outside the innermost layer may be used. The latter innermost layer may be in contact with the layer made of the fluorine-containing ethylenic polymer composition not containing the conductive filler. Moreover, the laminated body of this invention can improve chemical-solution resistance further by making an innermost layer and an outermost layer into a layer (J).

The above laminate as a fuel tube is also one aspect of the present invention.

As described above, since the laminate of the present invention has excellent fuel permeation resistance and fuel crack resistance, it can be suitably used as a laminate for a fuel tube used for a fuel tube.

The preferred layer structure of the laminate of the present invention is not particularly limited, but is particularly suitable as a fuel tube, for example,
Layer 1: Layer made of the fluorine-containing copolymer of the present invention having an adhesive functional functional group Layer 2: Laminated body made of a layer made of polyamide resin;
Layer 1: Layer made of the fluorine-containing copolymer of the present invention having an adhesive functional functional group Layer 2: Layer made of the fluorine-containing copolymer of the present invention having an adhesive functional functional group Layer 3: Made of a polyamide-based resin A laminate comprising layers;
Layer 1: Layer made of fluorine-containing copolymer of the present invention having an adhesive functional group Layer 2: Resin layer made of ethylene / vinyl alcohol copolymer Layer 3: Layer layer made of modified polyolefin resin 4: High-density polyolefin A laminate comprising a resin layer;
Etc.

As a laminate and a preferred layer structure of the present invention,
Layer 1: Layer made of fluorine-containing ethylenic polymer (may be blended with conductive filler) Layer 2: Layer made of fluorine-containing copolymer of the present invention Layer 3: Layer made of polyamide resin And the laminated body
Layer 1: Layer made of copolymer (III) (may be blended with conductive filler) Layer 2: Layer made of fluorine-containing copolymer of the present invention having an adhesive functional group 3: The laminated body which consists of a layer which consists of polyamide-type resin is mentioned.

As a preferred layer structure of the laminate of the present invention,
Layer 1: Layer made of fluorine-containing ethylenic polymer (may be blended with conductive filler) Layer 2: Layer made of polyamide resin Layer 3: Layer layer made of the fluorine-containing copolymer of the present invention 4: A laminate composed of a layer made of polyamide-based resin can be mentioned, among others,
Layer 1: Layer made of copolymer (IV) (may be blended with conductive filler) Layer 2: Layer made of polyamide-based resin Layer 3: Fluorine-containing fluorine-containing material having an adhesive functional group Layer layer 4 made of copolymer: A laminate made of a layer made of polyamide resin is preferred,
Layer 1: Layer made of copolymer (IV-II) (may be blended with conductive filler) Layer 2: Layer made of polyamide resin Layer 3: Adhesive functional functional group Layer layer 4 made of fluorine-containing copolymer: A laminate made of a layer made of polyamide-based resin may be mentioned.

Each layer of the tube for fuel tubes mentioned above is laminated | stacked in order of the number of layers, Preferably the layer 1 is an innermost layer.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples.

Example 1
51.5 kg of demineralized pure water was placed in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 30.5 kg of octafluorocyclobutane, 10.2 kg of hexafluoropropylene [HFP], 0.9 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2. 8 kg was injected. The temperature was adjusted to 35 ° C. and stirring was started. Polymerization was initiated by adding 0.37 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate [NPP] and 0.30 kg of methanol [MeOH] as polymerization initiators. During the polymerization, a mixed monomer prepared in the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.78 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 18.3 kg of a fluorine-containing copolymer of granular powder. Next, melt kneading was performed at a cylinder temperature of 290 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet-like fluorine-containing copolymer was heated at 205 ° C. for 8 hours.

Example 2
Initial monomer and initiator charge amounts were 10.2 kg of hexafluoropropylene [HFP], 0.9 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2 Polymerization was carried out in the same manner as in Example 1 except that 0.26 kg of a 50 mass% methanol solution of NPP was changed to 0.28 kg to obtain 18.3 kg of a fluorine-containing copolymer in the form of granular powder. Moreover, the same melt kneading and heating as in Example 1 were performed to obtain pellets.

Example 3
Initial monomer and initiator charge amounts were 10.2 kg of hexafluoropropylene [HFP], 0.6 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2 Polymerization was carried out in the same manner as in Example 1 except that 0.48 kg of a 50 mass% methanol solution of NPP was changed to 0.48 kg to obtain 18.3 kg of a fluorine-containing copolymer in the form of granular powder. Moreover, the same melt kneading and heating as in Example 1 were performed to obtain pellets.

Example 4
Initial monomer and initiator charge amounts were 10.2 kg of hexafluoropropylene [HFP], 0.6 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2 Polymerization was carried out in the same manner as in Example 1 except that 0.87 kg of a 50 wt% methanol solution of NPP was changed to 0.37 kg to obtain 18.3 kg of a fluorine-containing copolymer in the form of granular powder. Moreover, the same melt kneading and heating as in Example 1 were performed to obtain pellets.

Example 5
Initial monomer and initiator charge amounts were 10.2 kg of hexafluoropropylene [HFP], 0.9 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2 Polymerization was carried out in the same manner as in Example 1 except that 0.47 kg of a 50 mass% methanol solution of NPP was changed to 0.47 kg to obtain 18.3 kg of a fluorine-containing copolymer as granular powder. Moreover, the same melt kneading and heating as in Example 1 were performed to obtain pellets.

Example 6
Initial monomer and initiator charge amounts were 10.2 kg of hexafluoropropylene [HFP], 3.5 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], perfluoro (propyl vinyl ether) [PPVE] 2 Polymerization was carried out in the same manner as in Example 1 except that 8.7 kg, 0.25 kg of a 50 mass% methanol solution of NPP, and the pressure in the tank was 0.88 MPa, to obtain 18.3 kg of a fluorine-containing copolymer of granular powder. It was. Next, melt kneading was performed at a cylinder temperature of 250 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet-like fluorine-containing copolymer was heated at 170 ° C. for 8 hours.

Comparative Example 1
51.5 kg of demineralized pure water was placed in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 40.6 kg of octafluorocyclobutane, 1.3 kg of chlorotrifluoroethylene [CTFE], 4.5 kg of tetrafluoroethylene [TFE], and 2.8 kg of perfluoro (propyl vinyl ether) [PPVE] were injected. 0.084 kg of n-propyl alcohol [PrOH] was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. To this, 0.44 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate [NPP] and 0.30 kg of methanol [MeOH] were added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 18.3 kg of a fluorine-containing copolymer of granular powder. Next, melt kneading was performed at a cylinder temperature of 290 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet-like fluorine-containing copolymer was heated at 205 ° C. for 8 hours.

Comparative Example 2
Initial monomer and chain transfer agent amount, initiator charge amount: chlorotrifluoroethylene [CTFE] 1.3 kg, tetrafluoroethylene [TFE] 4.5 kg, perfluoro (propyl vinyl ether) [PPVE] 2.8 kg, [PrOH Polymerization was carried out in the same manner as in Comparative Example 1 except that 0 kg and a 50 wt% methanol solution of NPP was changed to 0.33 kg to obtain 18.3 kg of a fluorine-containing copolymer in the form of granular powder. Moreover, the same melt kneading and heating as in Comparative Example 1 were performed to obtain pellets.

Comparative Example 3
51.5 kg of demineralized pure water was placed in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and then the nitrogen gas was removed in vacuum. Next, 40.6 kg of octafluorocyclobutane, 2.0 kg of chlorotrifluoroethylene [CTFE], 6.6 kg of tetrafluoroethylene [TFE], and 0.06 kg of (perfluorohexyl) ethylene [PFHE] were injected. The temperature was adjusted to 35 ° C. and stirring was started. To this, 0.72 kg of a 50 mass% methanol solution of di-n-propyl peroxydicarbonate [NPP] and 0.30 kg of methanol [MeOH] were added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while additionally charging so that the pressure in the tank is maintained at 0.84 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 18.3 kg of a fluorine-containing copolymer of granular powder. Next, melt kneading was performed at a cylinder temperature of 290 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet-like fluorine-containing copolymer was heated at 205 ° C. for 8 hours.

Comparative Example 4
Without using octafluorocyclobutane and perfluoro (propyl vinyl ether) [PPVE], chlorotrifluoroethylene [CTFE] 1.7 kg, tetrafluoroethylene [TFE] 8.9 kg, hexafluoropropylene [HFP] 88.0 kg Otherwise, polymerization was carried out in the same manner as in Comparative Example 1 to obtain 11.2 kg of a granular powdery fluorinated copolymer. Next, melt kneading was performed at a cylinder temperature of 270 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet-like fluorine-containing copolymer was heated at 185 ° C. for 8 hours.

About the copolymer obtained by the Example and the comparative example, physical property evaluation was performed with the following method. The results are shown in Table 2.

(1) Measurement of the number of carbonate groups A white powder of a copolymer or a cut piece of a melt-extruded pellet was compression molded at room temperature to prepare a film having a thickness of 50 to 200 μm. According to infrared absorption spectrum analysis of this film, a peak derived from a carbonyl group of a carbonate group [—OC (═O) O—] appears at an absorption wavelength of 1817 cm ⁻¹ [ν (C═O)]. = O) and the absorbance peak was measured to calculate the main chain number of tens per ⁶ carbon atoms, the copolymer according to the following formula.
Number of end groups (per 1 × 10 ⁶ carbon atoms) = (l × K) / t
l: Absorbance K: Correction coefficient (-OC (= O) OR: 1426)
t: Film thickness (mm)

The infrared absorption spectrum analysis was scanned 40 times using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by Perkin Elmer). The obtained IR spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of the peak at 1817 cm ⁻¹ was measured. The film thickness was measured using a micrometer.

(2) Measurement of copolymer composition The copolymer composition was determined by ¹⁹ F-NMR and elemental analysis of chlorine.

(3) Measurement of melting point (Tm) Using a Seiko differential scanning calorimeter [DSC], record the melting peak when the temperature was raised at a rate of 10 ° C / min, and set the temperature corresponding to the maximum value to the melting point (Tm). It was.

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

Next, the evaluation test of the fluorine-containing copolymer obtained in the Example and the comparative example was done.
(A) Measurement of single-layer fuel permeability coefficient The pellets of the copolymer used for each layer of the tube-shaped laminate were placed in a 120 mm diameter mold and set in a press machine heated to 300 ° C., about 2 It was melt-pressed at a pressure of .9 MPa to obtain a sheet having a thickness of 0.15 mm. Put the obtained sheet into a SUS316 transmission coefficient measuring cup made of SUS316 with an inner diameter of 40 mmφ and a height of 20 mm with 18 ml of CE10 (fuel obtained by mixing 10% by volume of ethanol in a 50:50 volume ratio of isooctane and toluene) The mass change at 60 ° C. was measured up to 1000 hours. Table 3 shows the results of calculating the fuel permeability coefficient (g · mm / m ² / day) from the change in mass per hour, the surface area of the sheet in the wetted part, and the thickness of the sheet.

(B) Single-layer crack generation test after immersion in fuel The pellets of the copolymer used for each layer of the tube-shaped laminate are placed in a 120 mm diameter mold and set in a press machine heated to 300 ° C., The sheet was melt-pressed at a pressure of about 2.9 MPa to obtain a sheet having a thickness of 0.12 mm. A test piece was punched with a JISK6301 No. 1 dumbbell, and immediately after being immersed in CE10 for 1 week, it was stretched at 20 mm / min to observe the occurrence of cracks on the sheet surface. Table 3 shows the results of the maximum elongation without cracks.

Using an extruding device (manufactured by Plastic Engineering Laboratory Co., Ltd.) of two types and two layers equipped with a multi-manifold, the outer layer is polyamide 12 (trade name: Vestamid X7297, manufactured by Degussa Huls AG), and the inner layer is an example and Two types of two-layered tubes having an outer diameter of 8 mm and an inner diameter of 6 mm were formed by supplying them to two extruders so as to be the respective fluorinated copolymers of Comparative Examples. About the obtained multilayer tube, the moldability and interlayer adhesive strength were measured with the following method. The evaluation results are shown in Table 3.

(C) Confirmation of formability Multi-layer tube forming was performed at a line speed of 8 m / min. Table 3 shows the state of occurrence of melt fracture on the inner surface and outer surface of the obtained tube. Table 3 shows x if it occurred very much, Δ if it occurred slightly, and ○ if it did not.

(D) Measurement of adhesive strength A test piece with a width of 1 cm was cut from a tube-shaped laminate, and a 180 ° peel test was performed at a speed of 25 mm / min using a Tensilon universal testing machine, and the maximum in the elongation-tensile strength graph. The 5-point average was determined as the initial adhesive strength (N / cm). Table 3 shows the interlayer adhesion. It was found that the fluorine-containing copolymer of Comparative Example 4 could not provide sufficient adhesive strength.

The fluorine-containing copolymer of the present invention can be suitably used for, for example, an automobile fuel tube that requires high fuel permeation resistance and fuel crack resistance.

Claims

Polymerized units based on chlorotrifluoroethylene, polymerized units based on tetrafluoroethylene, polymerized units based on monomer (A), and polymerized units based on monomer (B),
The total number of polymerized units based on chlorotrifluoroethylene and polymerized units based on tetrafluoroethylene is 80.0 to 99.8 mol%,
The polymerized units based on the monomer (A) are 19.0 to 0.1 mol%,
The polymerized units based on the monomer (B) are 10.0 to 0.1 mol%,
The monomer (A) has the general formula (i)
CX 3 X 4 = CX 1 (CF 2 ) n X 2 (i)
(Wherein X 1 , X 3 and X 4 are the same or different and each represents a hydrogen atom or a fluorine atom, X 2 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents 1 or 2). And a general formula (ii)
CF 2 = CF-ORf 1 (ii)
(Wherein Rf 1 represents a perfluoroalkyl group having 1 or 2 carbon atoms) is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers) represented by:
The monomer (B) has the general formula (iii)
CX 3 X 4 = CX 1 (CF 2 ) m X 2 (iii)
(Wherein X 1 , X 3 and X 4 are the same or different and each represents a hydrogen atom or a fluorine atom, X 2 represents a hydrogen atom, a fluorine atom or a chlorine atom, and m represents an integer of 3 to 10) .) And a general formula (iv)
CF 2 = CF-ORf 2 (iv)
(Wherein Rf 2 represents a perfluoroalkyl group having 3 to 8 carbon atoms) and is at least one monomer selected from the group consisting of perfluoro (alkyl vinyl ethers). A characteristic fluorine-containing copolymer.
1.0 to 50.0 mol% of polymerized units based on chlorotrifluoroethylene,
The fluorine-containing copolymer according to claim 1, wherein the polymerized units based on tetrafluoroethylene are 30.0 to 98.8 mol%.
The fluorine-containing copolymer according to claim 1 or 2, wherein the monomer (A) is hexafluoropropylene.
The fluorine-containing copolymer according to claim 1, 2 or 3, wherein the monomer (B) is perfluoro (propyl vinyl ether).
The fluorine-containing copolymer according to claim 1, wherein the melt flow rate at 297 ° C is 1 to 70 g / 10 min.
6. The fluorine-containing copolymer according to claim 1, wherein the melt flow rate at 297 ° C. is 1 to 50 g / 10 min.
A laminate comprising the layer (C) made of the fluorine-containing copolymer according to claim 1, and the layer (K) made of a fluorine-free organic material.
A layer (C) comprising the fluorine-containing copolymer according to claim 1, 2, 3, 4, 5 or 6, a layer (K) comprising a fluorine-free organic material, and a fluorine-containing ethylenic polymer (provided that And a layer (J) composed of a layer (J) excluding the fluorine-containing copolymer, wherein the layer (J), the layer (C) and the layer (K) are laminated in this order. A featured laminate.
The laminate according to claim 7 or 8, wherein the fluorine-free organic material is at least one selected from the group consisting of polyamide resins and polyolefin resins.
The laminate according to claim 7, 8 or 9, which is a fuel tube.