JP2006328195A - Resin composition and fuel container comprising the same - Google Patents

Abstract

The present invention provides a resin composition comprising (A) a fluoropolymer, and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less, and the resin composition. A molded article and a fuel container are provided.
A resin composition comprising (A) a fluoropolymer, and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less.
[Selection figure] None

Description

The present invention includes (A) a fluoropolymer, and (B) a resin composition comprising a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less, and a molding comprising the resin composition. Products and fuel containers.

  Fluororesin is excellent in properties such as slidability, heat resistance, chemical resistance, weather resistance, and electrical properties, and is used in a wide range of fields such as automobiles, industrial machinery, OA equipment, and electrical and electronic equipment. On the other hand, a fluororesin generally has a problem that its mechanical strength is insufficient or it is expensive in price. In order to impart mechanical strength to fluororesin and to reduce cost, it is known to combine fluororesin and non-fluorine thermoplastic resin. Generally, fluororesin and non-fluorine thermoplastic resin are used. Has a poor affinity, and simply melting and kneading the two causes poor dispersion and causes problems such as delamination and strength reduction.

In order to solve this problem, a resin composition comprising a fluorine-containing ethylenic polymer having a reactive functional group at the main chain and / or side chain terminal and a non-fluorine polymer having a bond-forming site, is reactive. A resin composition in which a functional group and a bond-forming site are bonded is disclosed (for example, see Patent Document 1). In the resin composition obtained by such a technique, the reactive functional group of the fluorine-containing ethylenic polymer and the bond-forming site of the non-fluorine polymer are chemically bonded. It can be solved. However, in the examples of Patent Document 1, only a non-fluorine thermoplastic resin having a fuel permeability exceeding 5 g · mm / m ² · day is used, and the obtained resin composition still has a fuel barrier property. There was a problem that it was enough.

JP 2003-176394 A

The present invention includes (A) a fluoropolymer, and (B) a resin composition comprising a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less, and a molding comprising the resin composition. Products and fuel containers.

That is, the present invention relates to a resin composition comprising (A) a fluoropolymer, and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less.

  The fluorinated polymer (A) is preferably a polymer having a reactive functional group at the main chain end and / or side chain end.

  The reactive functional group is preferably a carboxyl group, an anhydrous carboxyl group, a carbonyldioxy group, a haloformyl group, a hydroxyl group, an epoxy group and / or an amino group.

  The non-fluorinated thermoplastic resin (B) is preferably at least one selected from the group consisting of a metaxylenediamine / adipic acid copolymer, an ethylene / vinyl alcohol copolymer, a polyphenylene sulfide, and a liquid crystal polymer.

  It is preferable that melting | fusing point of a fluoropolymer (A) is 120-270 degreeC.

  The fluorinated polymer (A) is preferably a copolymer containing a tetrafluoroethylene unit and an ethylene unit.

The fluoropolymer (A) has a tetrafluoroethylene unit and the general formula (1):
CF ₂ = CF-R _f ¹ (1)
(In the formula, R _f ¹ is —CF ₃ and / or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)
It is preferable that it is a copolymer containing the perfluoroethylenically unsaturated compound unit shown by these.

  It is preferable that the fluoropolymer (A) and the non-fluorine thermoplastic resin (B) are bonded. It is preferable that either the fluoropolymer (A) or the non-fluorine thermoplastic resin (B) forms a dispersed phase and has a particle size of 5 μm or less.

  The present invention also relates to an injection molded product made of the resin composition and a fuel container made of the injection molded product.

The present invention provides a fuel permeability by using a resin composition comprising (A) a fluoropolymer and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less. It is possible to provide an injection molded article and a fuel container which are excellent in heat resistance, impact resistance and strength.

The present invention relates to a resin composition comprising (A) a fluoropolymer, and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less.

  The fluorine-containing polymer (A) is not particularly limited, but has a reactive functional group at the main chain end and / or side chain end from the viewpoint of forming a bond with the non-fluorine thermoplastic resin (B). It is preferable that it is a polymer which has.

  Examples of the reactive functional group include a carboxyl group, an anhydrous carboxyl group, a carbonyldioxy group, a haloformyl group, a hydroxyl group, an isocyanate group, an alkoxycarbonyl group, an epoxy group, and / or an amino group.

The carbonyldioxy group is a group having a structure represented by -O-C (= O) -O-. For example, the general formula (2):
—O—C (═O) —O—R ¹ (2)
And a group represented by the formula (wherein R ¹ is an alkyl group having 1 to 20 carbon atoms or a group 17 element which may contain an etheric oxygen atom). Examples of the group represented by the general formula (2) include —O—C (═O) —OCH ₃ , —O—C (═O) —OC ₃ H ₇ , —O—C (═O) —OC ₈ H. ₁₇ , —O—C (═O) —OCH ₂ CH ₂ CH ₂ OCH ₂ CH _{3 and the} like.

The haloformyl group is a group having a structure represented by —C (═O) —X ¹ , and examples of X ¹ include a fluorine atom and a chlorine atom.

  Among these, from the viewpoint of heat resistance and mechanical properties, a carbonyl group-containing group such as a carboxyl group, an anhydrous carboxyl group, a carbonyldioxy group, a haloformyl group, an isocyanate group, and an alkoxycarbonyl group is preferable. More preferred are functional groups containing a carbonyldioxy group and haloformyl group.

  As a method for introducing the reactive functional group into the main chain terminal and / or the side chain terminal of the fluoropolymer (A), the reactive site or the reactive site is converted during the polymerization of the fluoropolymer (A). Examples thereof include a method of copolymerizing a monomer having a possible site, and a method using a polymerization initiator having a site that can be converted to the reactive site or the reactive site. The fluorine-containing polymer is preferable because it does not significantly reduce heat resistance, mechanical properties, and chemical resistance, or is advantageous in terms of productivity and cost.

  Moreover, as a method of introducing a haloformyl group into the fluoropolymer (A), for example, the fluoropolymer (A) having a carbonyldioxy group or an ester group at the terminal is heated and thermally decomposed (decarboxylated). Can be obtained. The heating temperature varies depending on the type of the carbonyldioxy group or ester group and the type of the fluoropolymer (A), but the polymer itself is 200 ° C or higher, preferably 220 ° C or higher, particularly preferably 230 ° C or higher. The upper limit of the heating temperature is preferably not more than the thermal decomposition temperature of the portion other than the carbonyldioxy group or ester group of the fluoropolymer (A), specifically 400 ° C. or less, More preferably, it is 350 degrees C or less.

The number of reactive functional groups in the fluoropolymer (A) may be appropriately selected depending on the type of the non-fluorine thermoplastic resin (B) used, but the number of main chain carbons of the fluoropolymer (A). The number per 1 × 10 ⁶ is preferably 3 to 1000, more preferably 3 to 500, and still more preferably 10 to 300. When the number of reactive functional groups is less than 3 per 1 × 10 ⁶ main chain carbon atoms of the fluoropolymer (A), there is a tendency that the non-fluorine thermoplastic resin (B) does not sufficiently react.

  The structure of the main chain and / or the side chain of the fluoropolymer (A) in the present invention is not particularly limited, and may be a fluororesin composed of at least one fluoroethylenic polymer (a). Preferably, the fluorine-containing ethylenic polymer (a) has only to have a structural unit derived from at least one fluorine-containing ethylenic monomer.

Examples of the fluorine-containing ethylenic monomer (a) include tetrafluoroethylene, general formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ and / or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). Perfluoroolefins such as compounds, chlorotrifluoroethylene, trifluoroethylene, hexafluoroisobutene, vinylidene fluoride, vinyl fluoride, general formula (3):
CH ₂ = CX ² (CF ₂ ) _n X ³ (3)
(Wherein X ² is a hydrogen atom or a fluorine atom, X ³ is a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10). Can do.

  The fluorine-containing ethylenic polymer (a) may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Non-fluorine ethylenic monomers other than olefins and perfluoroolefins can be mentioned. Examples of the non-fluorine ethylenic monomer include ethylene, propylene, and alkyl vinyl ethers. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

Among these, the fluorine-containing ethylenic polymer (a) is excellent in the heat resistance, impact resistance and strength of the obtained thermoplastic polymer composition and easy to process.
(A-1) An ethylene-tetrafluoroethylene copolymer (ETFE) comprising tetrafluoroethylene and ethylene
(A-2) Tetrafluoroethylene and general formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ and / or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). Tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) or tetrafluoroethylene-hexafluoropropylene-perfluoro (alkyl vinyl ether) copolymer Compound (a-3) tetrafluoroethylene, ethylene and general formula (1):
CF ₂ = CF-R _f ¹ (1)
(Wherein R _f ¹ is —CF ₃ and / or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). Ethylene-tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (Et-TFE-PAVE copolymer) or ethylene-tetrafluoroethylene-hexafluoropropylene copolymer (EFEP) comprising a compound
(A-4) Polyvinylidene fluoride (PVDF)
It is preferable that it is either. Next, preferred fluorine-containing ethylenic polymers (a-1) to (a-4) will be described.

(A-1) ETFE
In the case of ETFE, in addition to the above-described effects, it is preferable in terms of low fuel permeability and flexibility. The content molar ratio of the tetrafluoroethylene unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 62:38 to 90:10, and particularly preferably 63:37 to 80:20. Further, the third component may be contained, and the type of the third component is not limited as long as it is copolymerizable with tetrafluoroethylene and ethylene. As the third component, the following general formulas (4) to (7) are usually:
CX ⁴ ₂ = CX ⁴ R _f ³ (4),
CX ⁴ ₂ = CFR _f ³ (5),
CX ⁴ ₂ = CFOR _f ³ (6),
CX ⁴ ₂ = C (R _f ³ ) ₂ (7)
(Wherein X ⁴ is a hydrogen atom or a fluorine atom, and R _f ³ is a fluoroalkyl group)
Among these, a fluorine-containing vinyl monomer represented by the general formula (4) is more preferable, and a monomer having 1 to 8 carbon atoms in R _f ³ is particularly preferable.

Specific examples of the fluorine-containing vinyl monomer represented by the general formulas (4) to (7) include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,7- Trihydroperfluoroheptene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1,2,2,3,3,4,4,5 , 5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluorobutene-1, 3,3,3-trifluoro-2-trifluoromethylpropene-1, 2,3,3,4,4,5,5- heptafluoro-1-pentene _{(CH 2 = CFCF 2 CF 2} CF 2 H) and the like.

  The content of the third component is preferably from 0.1 to 10 mol%, more preferably from 0.1 to 5 mol%, particularly preferably from 0.2 to 4 mol%, based on the fluorine-containing ethylenic polymer (a). preferable.

(A-2) PFA or FEP
In the case of PFA or FEP, heat resistance is particularly excellent in the above-described effects, and it is preferable in that low fuel permeability is exhibited in addition to the above-described effects. More preferably, the fluorine-containing ethylenic polymer (a) is composed of 90 to 99 mol% of tetrafluoroethylene units and 1 to 10 mol% of perfluoroethylenically unsaturated compound units represented by the general formula (1). In addition, the fluorine-containing ethylenic polymer (a) composed of tetrafluoroethylene and the perfluoroethylenically unsaturated compound represented by the general formula (1) may contain a third component. As long as it is copolymerizable with tetrafluoroethylene and the perfluoroethylenically unsaturated compound represented by the formula (1), the kind thereof is not limited.

(A-3) Et-TFE-PAVE copolymer, EFEP
Et-TFE-PAVE copolymer and EFEP are preferable in terms of low fuel permeability and flexibility in addition to the above-described effects. Fluorine-containing ethylenic polymer comprising 19 to 90 mol% tetrafluoroethylene units, 9 to 80 mol% ethylene units, and 1 to 72 mol% perfluoroethylenically unsaturated compound units represented by the general formula (1) ( a), more preferably 20 to 70 mol% of tetrafluoroethylene units, 20 to 60 mol% of ethylene units, and 1 to 1 of perfluoroethylenically unsaturated compound units represented by the general formula (1). This is a fluorine-containing ethylenic polymer (a) comprising 60 mol%.

Further, the fluorine-containing ethylenic polymer (a) composed of tetrafluoroethylene, ethylene and the perfluoroethylenically unsaturated compound represented by the general formula (1) may contain an additional component, and as an additional component Includes 2,3,3,4,4,5,5-heptafluoro-1-pentene (CH ₂ ═CFCF ₂ CF ₂ CF ₂ H) and the like.

  It is preferable that content of an additional component is 0.1-3 mol% with respect to a fluorine-containing ethylenic polymer (a).

(A-4) PVDF
In the case of PVDF, in addition to the above-described effects, it is preferable in terms of flexibility and excellent mechanical properties.

  Moreover, it is preferable that it is 120-270 degreeC, as for melting | fusing point of a fluoropolymer (A), it is more preferable that it is 120-230 degreeC, and it is further more preferable that it is 120-210 degreeC. If the melting point is less than 120 ° C., the heat resistance of the resulting resin composition tends to decrease, and if it exceeds 270 ° C., during the melt-kneading of the fluoropolymer (A) and the non-fluorinated thermoplastic resin (B). The temperature needs to exceed 270 ° C., and the non-fluorinated thermoplastic resin (B) may be thermally deteriorated.

As the polymerization method for the fluoropolymer (A), suspension polymerization in an aqueous medium using a fluorine-based solvent industrially and using peroxycarbonate or the like as a polymerization initiator is preferable, but other polymerization methods are also available. For example, solution polymerization, emulsion polymerization, bulk polymerization and the like can also be employed. In suspension polymerization, a fluorinated solvent may be used in addition to water. Examples of the fluorine-based solvent used for suspension polymerization include hydrochlorofluoroalkanes (for example, CH ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CCl ₂ H, CF ₂ ClCF ₂ CFHCl), chlorofluoroalkanes (for example, , CF ₂ ClCFClCF ₂ CF ₃ , CF ₃ CFClCFClCF ₃ ), perfluoroalkanes (for example, perfluorocyclobutane, CF ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ) can be used, and perfluoroalkanes are particularly preferred. The amount of the fluorine solvent used is preferably 10 to 100% by weight with respect to water from the viewpoint of suspendability and economy.

  The polymerization temperature is not particularly limited, and is preferably 0 to 100 ° C. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, and the polymerization temperature, but it is usually preferably 0 to 9.8 MPaG.

  In order to adjust the molecular weight, conventional chain transfer agents such as hydrocarbons such as isopentane, n-pentane, n-hexane and cyclohexane; alcohols such as methanol and ethanol; carbon tetrachloride, chloroform, methylene chloride and methyl chloride Halogenated hydrocarbons such as can be used.

The non-fluorine thermoplastic resin (B) used in the present invention is not particularly limited as long as the fuel permeability is 5 g · mm / m ² · day or less, but the reactivity of the fluoropolymer (A) is not limited. Those having a site capable of reacting with a functional group are preferred.

  Examples of the site capable of reacting include a hydroxyl group, a carboxyl group, an amino group, and an epoxy group.

The fuel permeability is 5 g · mm / m ² · day or less, preferably 3 g · mm / m ² · day or less, and more preferably 1 g · mm / m ² · day or less. When the fuel permeability exceeds 5 g · mm / m ² · day, the fuel barrier property becomes insufficient when the resin composition of the present invention is used as a fuel peripheral part, which is not preferable. Note that the lower the fuel permeability, the better the permeation preventing ability of the fuel, and conversely, if the fuel permeability is large, the fuel is likely to permeate, so that it is not suitable as a molded product such as a fuel container.

The fuel permeability was 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, fuel permeability 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.

Non-fluorinated thermoplastic resins (B) having a fuel permeability of 5 g · mm / m ² · day or less include metaxylenediamine / adipic acid copolymer, ethylene / vinyl alcohol copolymer, polyphenylene sulfide, liquid crystal polymer, etc. It is preferable to use one or more of these from the viewpoint that the fuel barrier property of the resin composition of the present invention is excellent.

  The ethylene / vinyl alcohol copolymer is preferably a copolymer composed of 10 to 60 mol% ethylene and 90 to 40 mol% vinyl alcohol, from 20 to 50 mol% ethylene and 80 to 50 mol% vinyl alcohol. More preferably, it is a copolymer. 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.

  Examples of the liquid crystal polymer include liquid crystal polyesters such as paraoxybenzoic acid (POB) / polyethylene terephthalate (PET) copolymer, hydroxynaphthoic acid (HNA) / POB copolymer, and biphenol / benzoic acid / POB copolymer.

  The resin composition of the present invention can be obtained by mixing the fluororesin (A) and the non-fluorine thermoplastic resin (B) under melting conditions. Moreover, it is preferable that the fluorine-containing polymer (A) and the non-fluorine thermoplastic resin (B) are bonded to each other from the viewpoint that phase separation hardly occurs or the strength is improved. Here, bonding means that a covalent bond, an ionic bond and / or a hydrogen bond is formed between the fluoropolymer (A) and the non-fluorine thermoplastic resin (B). The covalent bond refers to, for example, a chemical bond formed by a reaction between the reactive functional group of the fluoropolymer (A) and the non-fluorine thermoplastic resin (B).

  The term “mixing” refers to mixing using a commonly used Banbury mixer, pressure kneader, extruder or the like. Among these, an extruder is preferable and a twin screw extruder is particularly preferable in that the reaction between the fluoropolymer (A) and the non-fluorine thermoplastic resin (B) is efficiently promoted. In this case, since the fluorine-containing polymer (A) and the non-fluorine thermoplastic resin (B) are more uniformly mixed, even in a molding method that applies a high share such as injection molding, such as correlation peeling. Problems are less likely to occur, which is preferable.

  The melting condition means a temperature at which the fluoropolymer (A) and the non-fluorinated thermoplastic resin (B) are melted. The melting temperature varies depending on the glass transition temperature and / or melting point of the fluoropolymer (A) and the non-fluorinated thermoplastic resin (B), respectively, but is preferably 120 to 400 ° C, and preferably 150 to 350 ° C. It is more preferable. When the temperature is less than 120 ° C., the dispersion between the fluoropolymer (A) and the non-fluorine thermoplastic resin (B) tends to become coarse, and when the temperature exceeds 400 ° C., the non-fluorine thermoplastic resin ( B) tends to thermally degrade.

  In the resin composition of the present invention, when the weight ratio of the fluoropolymer (A) is large with respect to the total of the fluoropolymer (A) and the non-fluorine thermoplastic resin (B), the fluoropolymer (A) forms a continuous phase, and the non-fluorine thermoplastic resin (B) easily forms a dispersed phase. On the other hand, when the weight ratio of the non-fluorine thermoplastic resin (B) is large relative to the total of the fluoropolymer (A) and the non-fluorine thermoplastic resin (B), the non-fluorine thermoplastic resin (B) A continuous phase is formed, and the fluoropolymer (A) can easily form a dispersed phase.

In the resin composition of the present invention, in order to have excellent fuel barrier properties,
(I) When the fluoropolymer (A) forms a continuous phase and the non-fluorinated thermoplastic resin (B) forms a dispersed phase,
(B) When the non-fluorinated thermoplastic resin (B) forms a continuous phase and the fluoropolymer (A) forms a dispersed phase,
In any case, the particle diameter of the dispersed phase is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less.

  The structure in which the non-fluorine thermoplastic resin (B) forms a continuous phase and the fluorine-containing polymer (A) forms a dispersed phase having a particle diameter of 5 μm or less includes the non-fluorine thermoplastic resin (B). A case where the fluoropolymer (A) does not form a multiphase morphological structure may also be included.

  The particle size of the fluoropolymer (A) as a dispersed phase is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. When the particle diameter exceeds 5 μm, the strength of the resulting resin composition tends to decrease.

  Further, the resin composition of the present invention is a part of a structure in which the non-fluorine thermoplastic resin (B) which is a preferred form forms a continuous phase and the fluoropolymer (A) forms a dispersed phase. A co-continuous structure of the fluoropolymer (A) and the non-fluorine thermoplastic resin (B) may be included.

  The resin composition of the present invention comprises 0.1 to 90% by weight of the fluoropolymer (A) and 10 to 99.9% by weight of the non-fluorinated thermoplastic resin (B). 1) to 80% by weight, non-fluorinated thermoplastic resin (B) 20 to 99% by weight, fluorinated polymer (A) 5 to 50% by weight, non-fluorinated thermoplastic resin (B) 50 to 95 More preferably, it is% by weight. When the fluoropolymer (A) is less than 0.1% by weight, impact resistance and the like tend to be insufficient when the resin composition of the present invention is used as a molded product. The resin composition price tends to be high.

  The melt flow rate (MFR) of the resin composition of the present invention is preferably 0.5 to 150 g / 10 minutes and more preferably 1 to 100 g / 10 minutes in the temperature range of 200 to 300 ° C. When the MFR is less than 0.5 g / 10 minutes or exceeds 150 g / 10 minutes, injection molding tends to be difficult.

The resin composition of the present invention preferably has a fuel permeability of 5 g · mm / m ² · day or less, preferably 3 g · mm / m ² · day or less, in consideration of use in fuel peripheral parts. More preferably, it is 1 g · mm / m ² · day or less. Here, the fuel permeability was measured by the cup method using CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel.

  In addition, the resin composition of the present invention includes other polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane, inorganic fillers such as calcium carbonate, talc, clay, titanium oxide, carbon black, and barium sulfate, pigments, Flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc. will not affect the effects of the present invention. It can be added in a range.

  The resin composition of the present invention can be molded using a general molding method or molding apparatus. As the molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding and the like can be adopted, and the resin composition of the present invention can be used depending on the purpose of use. Although it is molded into a molded body having an arbitrary shape, it is preferably molded by injection molding from the viewpoint of ease of production.

  Furthermore, the present invention relates to a molded article obtained by using the resin composition of the present invention, and the molded article includes a molded article of a sheet or a film, and the resin composition of the present invention. It includes a laminated structure having a layer made of a material and a layer made of another material. In the conventional molded product, it was necessary to separately provide a layer having excellent fuel permeability and a layer having excellent heat resistance, impact resistance, and strength, and to share the functions, but according to the resin composition of the present invention, It can also be expected to provide excellent fuel permeability and excellent heat resistance, impact resistance and strength in this layer.

  The resin composition of the present invention and a molded product comprising the composition are tubes, hoses: automobile fuel piping tubes or hoses, automobile radiator hoses, brake hoses, air conditioner hoses, electric wire coating materials, optical fiber coating materials, etc. , Sheets: Sliding members that require high chemical resistance such as diaphragms of diaphragm pumps and various packings, agricultural films, linings, weathering covers, tanks such as laminated steel plates used in the construction and home appliance fields, etc. : Used as various automobile products such as automobile radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, gasoline tanks, etc., but particularly suitable as fuel peripheral parts and fuel containers.

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

<Fluidity>
Using the pellets of the thermoplastic polymer composition produced in Examples and Comparative Examples, 230 ° C. (Examples 1 and 2 and Comparative Example 1) or 240 using a melt flow measuring device (manufactured by Yasuda Seiki Seisakusho) The melt flow rate (MFR) was measured under the conditions of ° C. (Examples 3 and 4 and Comparative Example 2) and a 5 kg load.

<Fuel permeability>
Using the pellets of the thermoplastic polymer composition produced in Examples and Comparative Examples, the pellets were heated at 210 ° C. (Comparative Example 1), 230 ° C. (Examples 1 and 2), and 270 ° C. (Examples). Compression molding was performed under the conditions of 3, 4 and Comparative Example 2), and 3 MPa to prepare a sheet-like test piece having a thickness of 0.5 mm. 18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) is placed in a SUS container (open area 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the 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 was determined by the following formula.

<Test piece preparation>
Using an injection molding machine, cylinder temperature 240 ° C. (Examples 1 and 2, Comparative Example 1), 265 ° C. (Examples 3 and 4 and Comparative Example 2) and mold temperature 90 ° C. (Examples 1, 2 and 2) Comparative Example 1), test piece for measurement (No. 5 test piece) for measuring tensile strength, tensile elastic modulus and elongation at break under conditions of 130 ° C. (Examples 3 and 4 and Comparative Example 2) And test specimens (dimensions: 64 mm × 12.7 mm × 3.2 mm) for measuring impact resistance were prepared.

<Izod strength measurement>
The notched Izod impact value at 23 ° C. was measured with an Izod impact tester (manufactured by Ueshima Seisakusho Co., Ltd.) using the test piece produced by the method described above.

<Measurement of tensile strength, tensile modulus and elongation at break>
Using the dumbbell-shaped test piece prepared by the above-described method, a tensile test is performed at a speed of 50 mm / min using a Tensilon universal testing machine (manufactured by A & D), and tensile strength, tensile modulus, elongation at break I asked for a degree.

<Fluoropolymer (A)>
Synthesis Example 1 Synthesis of fluorinated ethylenic polymer (A) 380 L of distilled water was charged into an autoclave and sufficiently substituted with nitrogen, and then 75 kg of 1-fluoro-1,1-dichloroethane and 155 kg of hexafluoropropylene (HFP) were synthesized. In addition, 0.5 kg of 2,3,3,4,4,5,5-heptafluoro-1-pentene [HF-Pe] was charged, and the system was maintained at 35 ° C. and a stirring speed of 200 rpm. Thereafter, tetrafluoroethylene (TFE) was injected to 0.7 MPa, and then ethylene (Et) was injected to 1.0 MPa. Then, 2.4 kg of di-n-propyl peroxydicarbonate was added to start polymerization. did. Since the system pressure decreases as the polymerization proceeds, a mixed gas of TFE: Et: HFP = 40.5: 44.5: 15.0 mol% is continuously supplied to keep the system pressure at 1.0 MPa. It was. Then, HF-Pe was continuously charged so that the total amount became 1.5 kg, and stirring was continued for 20 hours. Then, after releasing the pressure to return to atmospheric pressure, the reaction product was washed with water and dried to obtain 205 kg of a fluorine-containing ethylenic polymer (A) powder. As a result of analysis, the fluorine-containing ethylenic polymer (A) was TEF: Et: HFP: HF-Pe = 40.8: 44.8: 13.9: 0.5 mol%, and the melting point was 162. The reactive functional group contained 300 carbonyldioxy groups per 1 × 10 ⁶ main chain carbon atoms. The fuel permeability was less than 6.5 g · mm / m ² · day.

<Non-fluorine thermoplastic resin (B-1)>
A commercially available ethylene / vinyl alcohol copolymer (EVOH) (manufactured by Kuraray Co., Ltd., Eval F101, fuel permeability less than 0.4 g · mm / m ² · day) was used.

<Non-fluorine thermoplastic resin (B-2)>
A commercially available meta-xylenediamine / adipic acid copolymer (nylon MXD6) (manufactured by Mitsubishi Gas Chemical Co., Ltd., MX nylon S6001, fuel permeability less than 0.5 g · mm / m ² · day) was used.

Examples 1-4
The above-mentioned fluoropolymer (A) and non-fluorine thermoplastic resin (B-1) or (B-2) are supplied to the twin-screw extruder at the mixing ratio shown in Table 1, and the cylinder temperature is 220 ° C. (implemented) Examples 1 and 2 and Comparative Example 1), 250 ° C. (Examples 3 and 4 and Comparative Example 2) Melt-kneaded under the conditions of ° C. and screw rotation speed of 300 rpm, respectively, to produce thermoplastic polymer composition pellets. Table 1 shows the results of measurement of fuel permeability and Izod strength by the above-described method using the obtained pellets of the thermoplastic polymer composition. Moreover, the cross section of each pellet was observed by SEM. In Examples 1 to 4, it was confirmed that the fluororesin (A) was a dispersed phase and the non-fluorinated thermoplastic resin (B-1) or (B-2) was a continuous phase.

Comparative Examples 1 and 2
A test piece was prepared in the same manner as in Example 1 except that only the non-fluorine thermoplastic resin (B-1) or (B-2) was used without using the fluorine-containing resin. The evaluation results are shown in Table 1.

2 is an SEM observation image of the resin composition of Example 1. 3 is a SEM observation image of the resin composition of Example 2. 4 is a SEM observation image of the resin composition of Example 3. 4 is a SEM observation image of the resin composition of Example 4. 3 is a SEM observation image of the resin composition of Comparative Example 1. 3 is a SEM observation image of the resin composition of Comparative Example 2.

Claims (11)

A resin composition comprising (A) a fluoropolymer, and (B) a non-fluorine thermoplastic resin having a fuel permeability of 5 g · mm / m ² · day or less. The resin composition according to claim 1, wherein the fluorinated polymer (A) is a polymer having a reactive functional group at the main chain terminal and / or side chain terminal. The resin composition according to claim 2, wherein the reactive functional group is a carboxyl group, an anhydrous carboxyl group, a carbonyldioxy group, a haloformyl group, a hydroxyl group, an epoxy group and / or an amino group. The non-fluorine thermoplastic resin (B) is at least one selected from the group consisting of a metaxylenediamine / adipic acid copolymer, an ethylene / vinyl alcohol copolymer, a polyphenylene sulfide, and a liquid crystal polymer. The resin composition in any one. The resin composition according to any one of claims 1 to 4, wherein the melting point of the fluoropolymer (A) is 120 to 270 ° C. The resin composition according to any one of claims 1 to 5, wherein the fluoropolymer (A) is a copolymer containing a tetrafluoroethylene unit and an ethylene unit. The fluoropolymer (A) has a tetrafluoroethylene unit and the general formula (1):
CF ₂ = CF-R _f ¹ (1)
(In the formula, R _f ¹ is —CF ₃ and / or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms)
The resin composition according to claim 1, which is a copolymer containing a perfluoroethylenically unsaturated compound unit represented by: The resin composition according to any one of claims 1 to 7, wherein the fluoropolymer (A) and the non-fluorine thermoplastic resin (B) are bonded. The resin composition according to any one of claims 1 to 8, wherein either the fluoropolymer (A) or the non-fluorine thermoplastic resin (B) forms a dispersed phase and has a particle size of 5 µm or less. An injection-molded article comprising the resin composition according to any one of claims 1 to 9. A fuel container comprising the injection molded product according to claim 10.

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