Thermoplastic resin composition Number:7,087,679 from the United States Patent and Trademark Office (PTO) owispatent

Title: Thermoplastic resin composition

Abstract: A thermoplastic resin composition comprising a blend obtainable by blending 0.1 to 99% by weight of (a) a fluorine-containing polymer having a number-average molecular weight of 2000 to 1000000 and having hydroxy group or epoxy group at least at one of end portions of a main chain and side chain of the polymer, and 1 to 99.9% by weight of (b) a heat resisting thermoplastic resin having a crystalline melting point or glass transition temperature of not less than 150.degree. C. The present invention can provide a composition comprising various heat resisting thermoplastic resins and a fluorine-containing polymer having a functional group which is capable of developing an affinity with said resins and forming a uniform dispersion.

Patent Number: 7,087,679 Issued on 08/08/2006 to Shimizu,   et al.

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Inventors:	Shimizu; Tetsuo (Settsu, JP), Yamamoto; Yoshihisa (Settsu, JP), Yamaguchi; Seitaro (Settsu, JP), Tsuda; Nobuhiko (Settsu, JP), Yamane; Noriyasu (Settsu, JP), Yamato; Takafumi (Settsu, JP), Kumegawa; Masahiro (Settsu, JP), Araki; Takayuki (Settsu, JP)
Assignee:	Daikin Industries, Ltd. (Osaka, JP)
Appl. No.:	10/334,066
Filed:	December 31, 2002

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Related U.S. Patent Documents

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	Application Number	Filing Date	Patent Number	Issue Date
	09540759	Mar., 2000	6552127
	09186427	Nov., 1998	6054537
	08838063	Apr., 1997	5869574
	08284548		5750626
	PCT/JP93/01784	Dec., 1993

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Foreign Application Priority Data

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Dec 10, 1992 [JP]			353104/1992
Jun 04, 1993 [JP]			160329/1993

Current U.S. Class:	525/151 ; 525/133; 525/150; 525/153; 525/166; 525/179; 525/189
Current International Class:	C08L 27/02 (20060101); C08L 67/02 (20060101); C08L 69/00 (20060101); C08L 71/00 (20060101); C08L 79/00 (20060101)
Field of Search:	525/166,179,150,189,151,153,133

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References Cited [Referenced By]

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U.S. Patent Documents

	4925381		May 1990		Aoki et al.
	6552127		April 2003		Shimizu et al.

Foreign Patent Documents

	275186		Jul., 1988		EP
	63-081159		Apr., 1986		JP
	62-057448		Mar., 1987		JP
	63-264672		Nov., 1988		JP
	3-215548		Sep., 1991		JP
	3-263464		Nov., 1991		JP
	63-172749		Feb., 1997		JP

Primary Examiner: Robertson; Jeffrey B.
Attorney, Agent or Firm: Posz Law Group, PLC Varndell, Jr.; R. Eugene

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Parent Case Text

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CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of Ser. No. 09/540,759 filed Mar. 31, 2000, now U.S. Pat. No. 6,552,127, which is a divisional application of Ser. No. 09/186,427 filed Nov. 5, 1998, now U.S. Pat. No. 6,054,537, which is a divisional application of Ser. No. 08/838,063 filed Apr. 17, 1997, now U.S. Pat. No. 5,869,574, which is a divisional application of Ser. No. 08/284,548 filed Aug. 9, 1994, now U.S. Pat. No. 5,750,626, which is a U.S. national phase application of International Application No. PCT/JP93/01784 filed Dec. 8, 1993.

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Claims

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What is claimed is:

1. A method for mixing a heat resistive thermoplastic resin (b), which has a crystalline melting point or glass transition temperature of not less than 150.degree. C., a fluorine-containing polymer (a) having a functional group and a number-average molecular weight of 2,000 to 1,000,000 and a fluorine-containing polymer other than the fluorine-containing polymer (a) and having no functional group by blending the thermoplastic resin (b), the fluorine-containing polymer (a) having the functional group and the fluorine-containing polymer other than the fluorine-containing polymer (a) at least at a temperature not less than a crystalline melting point or glass transition temperature of the thermoplastic resin (b); said fluorine-containing polymer (a) having the functional group is at least one selected from fluorine-containing polymers having functional groups, in which a concentration of the functional group at a main chain end portion and side chain portion is 2 to 2000 .mu.mol/g per the total weight of the fluorine-containing polymer, and represented by the formula (1): A.sup.1-(X)--(Y)-A.sup.2 (1) wherein X is a structural unit of the formula --(CH.sub.2CX.sup.1X.sup.2)-- (wherein X.sup.1 and X.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, --(CH.sub.2).sub.p--(O).sub.q--R--B.sup.1 (R is a dihydric hydrocarbon group having carbon atoms of 1 to 20 or dihydric fluorine-substituted organic group having carbon atoms of 1 to 20, B.sup.1 is hydrogen atom, fluorine atom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1), --OCO--R--B.sup.1 (R and B.sup.1 are the same as above) or --COO--R--B.sup.1 (R and B.sup.1 are the same as above)); Y is a structural unit of the formula --(CF.sub.2CY.sup.1Y.sup.2)-- (wherein Y.sup.1 and Y.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, chlorine atom, --(CF.sub.2).sub.r--(O).sub.s--(R.sub.f).sub.t--(CH.sub.2).sub.u--B.sup.2 (R.sub.f is a dihydric fluorine-substituted organic group having carbon atoms of 1 to 14, B.sup.2 is hydrogen atom, halogen atom, hydroxy group, epoxy group or glycidyloxy group, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is an integer of 1 to 3) or S(CF.sub.2).sub.v--B.sup.3 (B.sup.3 is hydrogen atom, fluorine atom or chlorine atom, and v is an integer of 1 to 10)); both A.sup.1 and A.sup.2 are end portions of a main chain; provided that each of X and Y may comprise two or more structural units; Y may not be present when X has the structural unit derived from CH.sub.2.dbd.CHF, CH.sub.2.dbd.CF.sub.2 or fluoroalkyl-.alpha.-substituted acrylate (substituent is hydrogen atom, fluorine atom or methyl); X may not be present when Y has the structural unit derived from CH.sub.2.dbd.CF.sub.2 or CH.sub.2.dbd.CHCl; at least one of A.sup.1 and A.sup.2 contains hydroxy group, epoxy group or glycidyl group when both of X and Y do not contain hydroxy group, epoxy group or glycidyl group.

2. A method of mixing a heat resistive thermoplastic resin (b), which has a crystalline melting point or glass transition temperature of not less than 150.degree. C., with a fluorine-containing polymer (a) having a functional group and a number-average molecular weight of 2,000 to 1,000,000, by blending the thermoplastic resin (b) and the fluorine-containing polymer (a) having the functional group at least at a temperature not less than a crystalline melting point or glass transition temperature of the thermoplastic resin (b); said fluorine-containing polymer (a) having the functional group is at least one selected from fluorine-containing polymers having functional groups, in which a concentration of the functional group at a main chain end portion and side chain portion is 2 to 2000 .mu.mol/g per the total weight of the fluorine-containing polymer, and represented by the formula (1): A.sup.1-(X)--(Y)-A.sup.2 (1) wherein X is a structural unit of the formula --(CH.sub.2CX.sup.1X.sup.2)-- (wherein X.sup.1 and X.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, --(CH.sub.2).sub.p--(O).sub.q--R--B.sup.1 (R is a dihydric hydrocarbon group having carbon atoms of 1 to 20 or dihydric fluorine-substituted organic group having carbon atoms of 1 to 20, B.sup.1 is hydrogen atom, fluorine atom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1), --OCO--R--B.sup.1 (R and B.sup.1 are the same as above) or --COO--R--B.sup.1 (R and B.sup.1 are the same as above)); Y is a structural unit of the formula --(CF.sub.2CY.sup.1Y.sup.2)-- (wherein Y.sup.1 and Y.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, chlorine atom, --(CF.sub.2).sub.r--(O).sub.s--(R.sub.f).sub.t--(CH.sub.2).sub.u--B.sup.2 (R.sub.f is a dihydric fluorine-substituted organic group having carbon atoms of 1 to 14, B.sup.2 is hydrogen atom, halogen atom, hydroxy group, epoxy group or glycidyloxy group, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is an integer of 1 to 3) or S(CF.sub.2).sub.v--B.sup.3 (B.sup.3 is hydrogen atom, fluorine atom or chlorine atom, and v is an integer of 1 to 10)); both A.sup.1 and A.sup.2 are end portions of a main chain; provided that each of X and Y may comprise two or more structural units; Y may not be present when X has the structural unit derived from CH.sub.2.dbd.CHF, CH.sub.2.dbd.CF.sub.2 or fluoroalkyl-.alpha.-substituted acrylate (substituent is hydrogen atom, fluorine atom or methyl); X may not be present when Y has the structural unit derived from CH.sub.2.dbd.CF.sub.2 or CH.sub.2.dbd.CHCl; at least one of A.sup.1 and A.sup.2 contains hydroxy group, epoxy group or glycidyl group when both of X and Y do not contain hydroxy group, epoxy group or glycidyl group; wherein the heat resistive thermoplastic resin (b) is at least one member selected from the group consisting of aromatic polyesters, polyamide imides, polyarylene sulfides, polyketones, polyether nitriles, polycarbonates, polyalylates, polyphenylene ethers, polysulfones, polyether sulfones, polyether imides, polyimides, polyamides and polyesteramides.

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Description

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TECHNICAL FIELD

The present invention relates to a thermoplastic resin composition which comprises a specific fluorine-containing polymer having a functional group and a thermoplastic resin having a crystalline melting point or glass transition temperature of not less than 150.degree. C., and has improved mechanical and chemical properties.

BACKGROUND ARTS

Heat resisting crystalline thermoplastic resins (having a crystalline melting point of not less than 150.degree. C.) such as polyacetals, polyamides, aromatic polyesters, polyarylene-sulfides, polyketones, polyether ketones, polyamide imides and polyether nitrites are excellent in mechanical properties and moreover moldability, and therefore are used for functional parts for automobiles, industrial machineries, office automation equipments, and electrical and electronic equipments. Meanwhile there is a market demand for higher chemical resistance, sliding properties and the like, and particularly impact resistance is desired to be enhanced because those resins are generally brittle. Also, heat resisting amorphous thermoplastic resins (having a glass transition temperature of hot less than 150.degree. C.) such as polycarbonates, polyphenylene ethers, polyalylates, polysulphones, polyether sulphones, and polyetherimides are widely used for making the best use of transparency, dimensional stability, impact resistance, and the like, but generally there are problems with chemical resistance, solvent resistance and moldability.

Fluorine-containing resins such as polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene/hexafluoropropylene copolymer (FEP), polyvinylidene fluoride (PVDF) and ethylene/tetrafluoroethylene copolymer (ETFE) are excellent in thermal resistance, chemical resistance, solvent resistance, weather resistance, sliding properties, pliability, electrical properties and the like, and are widely used for automobiles, industrial machineries, office automation equipments, electrical and electronic equipments, and the like. However, there are many cases where those resins are inferior in mechanical properties and physical thermal resistance as represented by a deflection temperature under load, as compared with heat resisting crystalline thermoplastic resins, and the uses thereof are within the limited range because the dimensional stability is inferior as compared with heat resisting amorphous thermoplastic resins.

Attempts have been actively made to obtain novel materials by combining a fluorine-containing polymer (including resinous and elastomeric form) with the aforementioned heat resisting thermoplastic resins having no fluorine to modify such resins to eliminate disadvantages of the resins, and on the contrary by combining mainly a resinous fluorine-containing polymer with the heat resisting thermoplastic resin having no fluorine to moldify such polymers.

First, as an example for simply melting and blending by the use of a kneading machine, JP-A-202344/1982 discloses that a fluorine-containing elastomer commercially available is added to improve impact resistance, crack resistance and strength against thermal shock without impairing properties of polyarylene sulfides such as thermal resistance, chemical resistance, and the like. Also, JP-A-165647/1989 and JP-A-110156/1990 disclose that a polymer the, that is to say, a liquid crystal polymer (aromatic polyester or the like) forming an anisotropic melt is added to decrease a coefficient of linear expansion without impairing weather resistance and anti-soil property of a fluorine-containing polymer such as a PVDF and further to improve mechanical properties and moldability. As examples of a blend of a liquid crystal polymer and a PTFE, there are JP-B-5693/1992 and JP-A-230756/1988. JP-A-7850/1975 discloses that it is effective to blend the PVDF for improving water absorption and hygroscopicity of polyamides.

Furthermore, JP-A-23448/1985 discloses an example that a property of release from a mold is improved by blending a fluorine-containing polymer with an aromatic polysulphone composition of which shrinkage from mold dimensions has been decreased by blending fibrous reinforcements such as glass fiber and wollastonite and inorganic fillers such as talc and glass beads.

Also, attempts have been widely and generally made to improve sliding properties of various synthetic resins by blending a PTFE powder.

However, since a surface energy of a fluorine-containing polymer is small, there is a problem that such a polymer is generally short of an affinity with other materials. Therefore, when the fluorine-containing polymer and other materials are melted and blended, there occurs a phase separation. Interfacial adhesion thereof is nearly nothing substantially, and an interfacial adhesive failure occurs easily, the fluorine-containing polymer is difficult to be dispersed in other materials during blending, and an aggregation occurs. Thus it is difficult to display an effect of blending that polymer.

In order to eliminate such drawbacks and to enhance an affinity between different polymers, it is often conducted to add so-called compatibilizing agents as the third component. JP-A-218446/1987 discloses a composition prepared by blending a thermoplastic fluorine-containing elastomer to improve impact resistance of polyarylene sulfides without impairing flowability thereof, and that patent publication describes that it is more effective to add a fluoroaliphatic group-containing polymer to improve an affinity of the polymer. Also, JP-A-62853/1988 discloses a method to add, as a compatibilizing agent, a graft polymer comprising a vinyl polymer having epoxy group and a methyl methacrylate polymer or an acrylonitrile/styrene copolymer when blending polyarylene sulfides and thermoplastic resins containing a PVDF.

Also, claim 2 of the mentioned JP-A-165647/1986, JP-A-197551/1986 and JP-A-263144/1986 disclose that it is more effective to add an acrylic polymer, polyvinyl acetate and polyvinyl methyl ketone, respectively than a simple blending, in blending a PVDF and a polymer forming an anisotropic melt.

JP-A-11109/1989 discloses an example of using, as a compatibilizing agent for blending polyamides and PVDF, a block polymer comprising any one of N-vinylpyrrolidone or methyl(meta)acrylate and any one of unsaturated ethylenic monomer, polycondensated monomer or lactam.

Also, JP-A-98650/1986 and JP-A-110550/1986 disclose that when blending a polyphenylene ether and a fluorine-containing polymer like a PVDF, a copolymer comprising polystyrene and an acrylic polymer is used as a compatibilizing agent, taking advantage of an excellent compatibility of polyphenylene ether with polystyrene and PVDF with acrylic polymer.

However, in JP-A-218446/1987, an effect of an improvement in affinity property is insufficient. It may be because a fluoroaliphatic group in an compatibilizing agent is of low polymerization having carbon atoms of not less than 20. All the other publications substantially describes the examples of using compatibilizing agents having no fluorine, which are synthesized, making use of an excellent affinity between a PVDF and a carbonyl group-containing polymer such as acrylic polymer, and the fluorine-containing polymer is limited to the PVDF. In the method to improve an affinity by the use of such a compatibilizing agent, there is a problem that physical properties of the molded articles deteriorate because chemical resistance and thermal resistance of the compatibilizing agents themselves are inferior to that of a main component, i.e. the polymer.

Also, attempts have been made to improve dispersibility of a composition comprising a fluorine-containing polymer and a thermoplastic resin, by a so-called dynamic vulcanization. JP-A-185042/1991 discloses that, when blending a crosslinkable fluorine-containing elastomer and a thermoplastic polymer having a crystalline melting point or glass transition temperature of not less than 150.degree. C., the dispersibility is enhanced and a thermoplastic elastomer can be obtained by vulcanizing the fluorine-containing elastomer during melting and blending. JP-A-172352/1991 also discloses that a fine dispersion of a fluorine-containing rubber is achieved by improving impact resistance of a polyphenylene sulfide by the use of a fluorine-containing elastomer by utilizing the dynamic vulcanization method.

Though those dynamic vulcanization methods are economically advantageous since the vulcanization of the fluorine-containing elastomer is carried out during melting and blending with other materials, there is a problem that impurities resulting from vulcanizing agents and other additives, which are used in the usual vulcanization methods, remain in a composition, and properties such as chemical resistance of a molded article deteriorate.

On the other hand, there are reports on a composition using a fluorine-containing polymer having a reactive functional group. JP-A-105062/1988, JP-A-254155/1988 and JP-A-264672/1988 disclose examples of blending a matrix polymer and, for instance, a fluoropolyether in which a functional group is introduced at the end thereof, a polymer containing a functional group and a polyfluoroalkyl group having carbon atoms of 2 to 20 and a fluorine-containing elastomer having a functional group. However, any of those examples is a manner to form, a network structure by dispersing the polymer having two kinds of functional groups in the matrix polymer and causing an inter-reaction therebetween and to physically bond that network structure to the matrix polymer, but not a manner to directly utilize a chemical affinity and reactivity with the matrix polymer.

Thus a combination of functional groups of not less than two kinds reacting with each other is necessary without fail, and also it is necessary to provide the conditions for forming the network structure by those functional groups. Also, a fluoropolyether is usually obtained as an oily substance and is expensive, and an effect of addition thereof is only limited to an improvement of lubricity of the matrix polymer. Furthermore exemplified is only such a polyfluoroalkyl group-containing polymer of a low molecular weight which is difficult to be prescribed as a polymer.

As mentioned hereinabove, when blending a fluorine-containing polymer and a thermoplastic resin, it is difficult to obtain a blend having stable characteristics because the fluorine-containing polymer is generally short of an affinity, and physical properties of the molded article obtained using that polymer are deteriorated. In order to improve the affinity, various studies have been made in relation to additives, but the present status is such that a composition comprising a fluorine-containing polymer and a thermoplastic resin, which do not deteriorate thermal resistance, chemical resistance and the like of the composition, has not yet been obtained.

The object of the present invention is to provide a composition comprising various heat resisting thermoplastic resins and fluorine-containing polymers having a functional group, which have a good affinity with the resins and are capable of forming uniform dispersing conditions.

DISCLOSURE OF THE INVENTION

The thermoplastic resin composition of the present invention comprises a blend obtainable by blending (a) 0.1 to 99% (% by weight, hereinafter the same) of a fluorine-containing polymer having a functional group and (b) 1 to 99.9% of a heat resisting thermoplastic resin having a crystalline melting point or glass transition temperature of not less than 150.degree. C.; said fluorine-containing polymer (a) having the functional group is at least one selected from fluorine-containing polymers having functional groups, in which a concentration of the functional groups at the end portion of a main chain and the side chain portion is 2 to 2000 .mu.mol/g per the total weight of the fluorine-containing polymer, represented by the formula [I], A.sup.1XYA.sup.2 [I] wherein X is a structural unit of the formula CH.sub.2CX.sup.1X.sup.2 (wherein X.sup.1 and X.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, CH.sub.2.sub.pO.sub.qR--B.sup.1 (R is a dihydric hydrocarbon group having carbon atoms of 1 to 20 or dihydric fluorine-substituted organic group having carbon atoms of 1 to 20, B.sup.1 is hydrogen atom, fluorine atom, hydroxy group or epoxy group, p is 0 or 1 and q is 0 or 1), --OCO--R--B.sup.1 (R and B.sup.1 are the same as above) or --COO--R--B.sup.1 (R and B.sup.1 are the same as above)); Y is a structural unit of the formula CF.sub.2CY.sup.1Y.sup.2 (wherein Y.sup.1 and Y.sup.2 are the same or different, and each is hydrogen atom, fluorine atom, chlorine atom, CF.sub.2.sub.rO.sub.sR.sub.f.sub.tCH.sub.2.sub.uB.sup.2 (R.sub.f is a dihydric fluorine-substituted organic group having carbon atoms of 1 to 14, B.sup.2 is hydrogen atom, halogen atom, hydroxy group, epoxy group or glycidyloxy group, r is 0 or 1, s is 0 or 1, t is 0 or 1, and u is an integer of 1 to 3) or CF.sub.2.sub.vB.sup.3 (B.sup.3 is hydrogen atom, fluorine atom or chlorine atom, v is an integer of 1 to 10)); both A.sup.1 and A.sup.2 are end portions of a main chain; provided that each of X and Y may comprise two or more structural units; Y may not be present when X has the structural unit derived from CH.sub.2.dbd.CHF, CH.sub.2.dbd.CF.sub.2 or fluoroalkyl-.alpha.-substituted acrylate (substituent is hydrogen atom, fluorine atom or methyl); X may not be present when Y has the structural unit derived from CF.sub.2.dbd.CF.sub.2 or CF.sub.2.dbd.CFCl; at least one of A.sup.1 and A.sup.2 contains hydroxy group, epoxy group or glycidyl group when both of X and Y do not contain hydroxy group, epoxy group or glycidyl group.

BRIEF EXPLANATION OF THE DRAWINGS

FIG. 1 is a microscopic photograph of a cut surface of the molded article obtained in Example 2.

FIG. 2 is a microscopic photograph of a cut surface of the molded article obtained in Example 3.

FIG. 3 is a microscopic photograph of a cut surface of the molded article obtained in Comparative Example 1.

FIG. 4 is a microscopic photograph of a cut surface of the molded article obtained in Comparative Example 2.

FIG. 5 is a stress-strain curve of the molded article obtained in Examples 6 to 8 and Comparative Examples 3 and 4.

FIG. 6 is a microscopic photograph of a cut surface of the molded article obtained in Example 12.

FIG. 7 is a microscopic photograph of a cut surface of the molded article obtained in Comparative Example 9.

PREFERRED EMBODIMENTS OF THE INVENTION

Though a prior resin composition of a heat resisting thermoplastic resin and a fluorine-containing polymer could provide a uniform molded article only by a special method, according to the present invention, there can be provided a composition capable of easily making a uniform molded article by introducing a specific functional group into a fluorine-containing polymer.

The fluorine-containing polymer having a functional group is represented by the formula (I), and is characterized in that the polymer has hydroxy group or epoxy group (inclusive of a glycidyl group) at least at one of end portions of a main chain and end portions of side chains if present, and the fluorine-containing polymer (I) or a precursor polymer before introducing a functional group to obtain (I) is prepared by a radical polymerization. The details are mentioned hereinbelow.

The fluorine-containing polymer having a functional group of the present invention has basic structural units of X represented by CH.sub.2--CX.sup.1X.sup.2 and Y represented by CF.sub.2--CY.sup.1Y.sup.2.

As monomers producing the structural unit X, there are employed, for instance, olefins such as ethylene, propylene, 1-butane and isobutylene; for instance, fluoroalkenes such as CH.sub.2.dbd.CHF, CH.sub.2.dbd.CF.sub.2, CH.sub.2.dbd.C(CF.sub.3).sub.2 and CH.sub.2.dbd.CZ(CF.sub.2)wZ (z is hydrogen atom or fluorine atom and w is an integer of 1 to 8. For instance, CH.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.2CF.sub.3, CH.sub.2.dbd.CHCF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.3, CH.sub.2.dbd.CFCF.sub.3, CH.sub.2.dbd.CFCF.sub.2CF.sub.3, CH.sub.2.dbd.CFCF.sub.2CF.sub.2CF.sub.2H and CH.sub.2.dbd.CFCF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2H); alkylvinylethers, for instance, CH.sub.2.dbd.CHOCH.sub.2CH.sub.3, CH.sub.2.dbd.CHOCH.sub.2CH.sub.2CH.sub.2CH.sub.3 and

##STR00001## fluoroalkyl vinylethers, for instance, CH.sub.2.dbd.CHOCH.sub.2CF.sub.2CF.sub.2H, CH.sub.2.dbd.CHOCH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2H and CH.sub.2.dbd.CHOCH.sub.2CH.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2C- F.sub.3; hydroxyalkyl vinylethers, for instance, CH.sub.2.dbd.CHOCH.sub.2CH.sub.2 CH.sub.2CH.sub.2OH; fluoroalkyl allylethers, for instance, CH.sub.2.dbd.CHCH.sub.2OCH.sub.2CH.sub.2CF.sub.2CF.sub.3; hydroxyalkyl allylethers, for instance, CH.sub.2.dbd.CHCH.sub.2OCH.sub.2CH.sub.2OH; alkyl or allylvinyl esters, for instance, CH.sub.2.dbd.CHOCOCH.sub.3, CH.sub.2.dbd.CHOCOC(CH.sub.3).sub.3 and

##STR00002## alkyl-.alpha.-substituted acrylates, of which substituent is hydrogen atom, fluorine atom or methyl, for instance, CH.sub.2.dbd.CHCOOCH.sub.3, CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.3 and CH.sub.2.dbd.CFCOOCH.sub.3; fluoroalkyl-.alpha.-substituted acrylates, of which substituent is hydrogen atom, fluorine atom or methyl, for instance, CH.sub.2.dbd.CHCOOCH.sub.2CF.sub.2CF.sub.2CF.sub.3, CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF.sub.2CF.sub.3, CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF.sub.2CF.sub.2H and CH.sub.2.dbd.CFCOOCH.sub.2CF.sub.2CF.sub.3; hydroxy(fluoro)alkyl-.alpha.-substituted acrylates, of which substituent is hydrogen atom, fluorine atom or methyl, for instance, CH.sub.2.dbd.CHCOOCH.sub.2CH.sub.2OH, CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CH.sub.2OH and CH.sub.2.dbd.C(CH.sub.3)COOCH.sub.2CF.sub.2CF.sub.2CH.sub.2OH; CH.sub.2.dbd.CHCH.sub.2C(CF.sub.3).sub.2OH; CH.sub.2.dbd.CHCH.sub.2OH;

##STR00003##

##STR00004##

As monomers producing the structural unit Y, there are employed, for instance, fluoroalkenes such as CF.sub.2.dbd.CFH, CF.sub.2.dbd.CF.sub.2, CF.sub.2.dbd.CFC1, CF.sub.2.dbd.CZ(CF.sub.2).sub.wZ (Z and w are the same as those mentioned hereinbefore, for instance, CF.sub.2.dbd.CHCF.sub.3, CF.sub.2.dbd.CFCF.sub.3, CF.sub.2.dbd.CFCF.sub.2CF.sub.3 and CF.sub.2.dbd.CFCF.sub.2CF.sub.2H); formulae, for instance, CF.sub.2.dbd.CFCH.sub.2CH.sub.2OH, CF.sub.2.dbd.CFCF.sub.2CH.sub.2OH, CF.sub.2.dbd.CFCF.sub.2CF.sub.2CH.sub.2CH.sub.2OH and

##STR00005## a compound represented by CF.sub.2.dbd.CF--R.sub.fCH.sub.2.sub.xB.sup.2 (R.sub.f and B.sub.2 are the same as mentioned hereinabove, and x is an integer of 1 to 3); perfluoro(alkylvinyl ether), for instance, CF.sub.2.dbd.CFOCF.sub.3, CF.sub.2.dbd.CFO(CF.sub.2CF(CF.sub.3)O).sub.yCF.sub.2CF.sub.2CF.sub.3 (y is an integer of 1 to 3), and CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CF.sub.2CF.sub.3; formulae, for instance, CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CH.sub.2OH, CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CF.sub.2CH.sub.2OH, CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2CF.sub.2CH.sub.2OH, CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CH.sub.2Br, CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CH.sub.2OCF.sub.2CF.sub.2CH.sub.2F, CF.sub.2.dbd.CFOCF.sub.2CF.sub.2CH.sub.2I and CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2CH.sub.2I: a compound represented by CF.sub.2.dbd.CF--O--R.sub.fCH.sub.2.sub.zB.sup.2 (R.sub.f and B.sup.2 are the same as mentioned hereinabove, and z is an integer of 1 to 3); perfluoro(alkylallylether), for instance, CF.sub.2.dbd.CFCF.sub.2OCF.sub.2CF.sub.2CF.sub.3.

The structural units X and Y each may comprise two kinds or more of structural units, Y may not be present, when X has the structural unit derived from CH.sub.2.dbd.CHF, CH.sub.2.dbd.CF.sub.2 or fluoroalkyl-.alpha.-substituted acrylates (A substituent is hydrogen atom, fluorine atom or methyl). X may not be present, when Y has the structural unit derived from CF.sub.2.dbd.CF.sub.2 or CF.sub.2.dbd.CFC1.

A.sup.1 and A.sup.2 representing the end portions of a main chain-X--Y-- are cut pieces of an initiator or a chain transfer agent, for instance, --OCOR.sup.1, --OR.sup.1, --R.sup.1, COOH, hydrogen atom, halogen atom (R.sup.1 is an alkyl group or fluoroalkyl group having carbon atoms of 1 to 10), but not limited to those. When any of structural units X and Y does not include a structural unit having hydroxy group, epoxy group or glycidyl group, at least one of A.sup.1 and A.sup.2 must include hydroxy group, epoxy group or glycidyl group.

A basic component of a fluorine-containing polymer (a) having a functional group has the structure represented by the formula (I), and is formed by a radical polymerization. As is explicit from the formula (I), the polymer does not have an ether bond at a portion of the main chain. A fluorine-containing polymer having an ether bond at the bonded portion of the main chain, for instance, a perfluoroxy alkylene unit is also disclosed in JP-B-42446/1991 besides the JP-A-105062/1988, JP-A-254155/1988 and JP-A-264672/1988. That fluoropolyether is usually made by an ion polymerization, and is expensive. Furthermore, the fluoropolyether of a high molecular weight is difficult to be obtained. The fluoropolyether becomes in the form of grease or oil at room temperature or at a high temperature, and it is difficult to form a uniform blend of fluoropolyether alone with a thermoplastic resin, which results in deterioration of physical properties of the obtained blend. Also, it is difficult to introduce a side chain into the fluoropolyether.

A functional group (hydroxy group or epoxy group (Glycidyl group is also included therein hereinafter the same)) in the fluorine-containing polymer represented by the formula (I) can be made also by using the mentioned functional group-containing monomer, and also can be introduced, for example, by the method mentioned below.

For instance, there is a method (method with an initiator) to polymerize a basic component by the use of an initiator for the radical polymerization, which has a functional group to be introduced. When using, for instance, a hydroperoxide as an initiator, hydroxy group can be introduced at the end of the main chain.

Also, a functional group can be introduced by the use of a specific chain transfer agents (method with a chain transfer agent). Hydroxy group is introduced at the end of the main chain when, for instance, methanol and mercaptoethanol are used as a chain transfer agent.

Also, another preferable method is the one (polymer reaction method) to introduce a functional group at the end or side chain of a polymer by a polymer reaction after polymerization. The polymer reaction method includes a polymerization using a radical polymerization initiator, which can easily convert a cut piece of the initiator at the end of the polymer into an intended functional group after polymerization and, in the same manner, a polymerization using a chain transfer agent and comonomer, which can easily convert the ends of a main chain and side chain of the polymer into an intended functional group after polymerization.

As a polymer reaction method, there is an example, for instance, to convert, into an intended functional group, iodine at the end of a polymer polymerized by using, as a chain transfer agent, an iodinated compound containing an iodine, such as a fluorine-containing elastomer and a thermoplastic fluorine-containing elastomer. Concretely, suitable is a fluorine-containing elastomer disclosed in JP-A-40543/1977, which is mainly comprises a copolymer comprising a VDF and at least one kind of the other fluorine-containing monomers which are copolymerizable with the VDF, wherein 0.001 to 10% by weight, preferably 0.01 to 5% by weight of iodine is bonded at the end of a polymer chain, and a thermoplastic fluorine-containing elastomer disclosed in JP-B-4728/1982, which has at least one block of fluorine-containing resin as a hard segment and at least one block of fluorine-containing elastomer as a soft segment, wherein the thermoplastic fluorine-containing elastomer is a linear, branched or radial block copolymer having a weight ratio of fluorine-containing resin to fluorine-containing elastomer of 5:95 to 60:40. An iodine of a fluorine-containing polymer, of which end is iodinated, has much reactivity and can be converted to a functional group such as epoxy group, hydroxy group, carboxyl group, amino group- and isocyanate group by the known organic chemical method. The end of the polymer becomes an epoxy group after addition of an allylalcohol and then dehydroiodination by an alkali, or becomes hydroxy group by adding ethylene and further reacting with dimethyl sulfoxide.

Also, as disclosed in JP-A-12734/1987, a side chain type fluorine-containing polymer having a functional group can be made by letting a halogen be contained in the side chain by copolymerizing 0.05 to 20% by mole of a halogen-containing monomer among those represented by the formula of CF.sub.2.dbd.CFOCF.sub.2CFR.sup.2O.sub.aCF.sub.2CF.sub.2CH.sub.2O.sub.bCF- .sub.2CF.sub.2--CH.sub.2--R.sup.3 (wherein R.sup.2 is F or CF.sub.3, a is an integer of 0 to 2, b is an integer of 0 to 2 and R.sup.3 is a halogen atom), in which R.sup.3 is selected from Cl, Br and I, and 80 to 99.95% by mole of a monomer producing a structural unit X and a structural unit Y if necessary, and then by converting to a functional group in the same manner as the example of the iodine terminated fluorine-containing polymer.

As a method to introduce a functional group by using a polymer reaction, there can be adopted, for instance, as shown in Polym. Mater. Sci Eng., 49,518 (1983), such a method as to add a nucleophilic functional group into a double bond produced by dehydrofluorinating a fluorine-containing elastomer having vinyliden fluoride with a base. However, that method has a drawback that the functional group is difficult to be quantitatively introduced.

It is naturally possible to further convert the fluorine-containing polymer having a functional group which is introduced by each of the mentioned methods, to the polymer having the desired functional group by applying the usual organic chemical technique to the polymer reaction. For instance, the iodine at the end and/or side chain of the fluorine-containing polymer can also be converted to glycidyloxy group by converting the iodine of the polymer to hydroxy group and further reacting with an epichlorohydrin.

Also, it is possible to combine the functional group introducing methods such as the method with an initiator, method with a chain transfer agent, copolymerization method and polymer reaction method. The reaction for introducing a functional group can also be carried out in a melting and kneading equipment such as an extruder, and not limited to in a polymerization reactor for a general use.

In the formula (I), such a polymer as containing CH.sub.2 unit in a main chain in combination of X and Y as mentioned below is preferable because a wide range of temperature for kneading with a thermoplastic resin can be selected and a compatibility with the thermoplastic resin is relatively excellent among fluorine-containing polymers.

That is to say, one (referred to as Polymer P.sup.1) is a polymer using CH.sub.2.dbd.CF.sub.2 (vinylidene fluoride: VDF) as at least one component of X in the formula (I) (others are the same as those of the formula (I)), and another one (referred to as Polymer P.sup.2) is a copolymer containing at least one of hydrocarbon olefins as X (VDF is not contained) and at least one of CF.sub.2.dbd.CF.sub.2 (tetrafluoroethylene: TFE), CF.sub.2.dbd.CFC1 (chlorotrifluoroethylene: CTFE) or CF.sub.2.dbd.CFCF.sub.3 (hexafluoropropene: HFP) as Y (others are the same as those of the formula (I)). Any of those polymers has hydroxy group or epoxy group at least at one of the main chain and the end of the side chain thereof.

Among those polymers having CH.sub.2 unit at the main chain, further preferable is the one which is excellent in a thermal stability (thermal resistance), when kneaded with a thermoplastic resin. The main chain and the end of the side chain, which have a functional group, are usually inferior to the other parts in thermal resistance, and it is unavoidable even if there is a thermal decomposition to a certain extent on kneading as far as an effect thereof can be recognized. However, at least main portions of the main chain and the side chain of the aforesaid fluorine-containing polymer having a functional group should have thermal resistance of 170.degree. C. at lowest, preferably not less than 250.degree. C. The thermal resistance depends mainly on a kind and ratio of components of the monomers to be used. In the Polymer P.sup.1 and Polymer P.sup.2, when a hydrocarbon olefin is used as X, it is recommendable to lower a ratio of the hydrocarbon olefins such as alkylvinyl ether and alkylvinyl ester excluding CH.sub.2.dbd.CH.sub.2, CH.sub.2.dbd.CHCH.sub.3 and CH.sub.2.dbd.C(CH.sub.3).sub.2 in the polymer to not more than 20% by mole. This is because those may be thermally the most unstable portions, among the monomers producing the fluorine-containing polymer having a functional group of the present invention.

The thermal resistance of the present invention means a temperature at the time of weight decrease by 1% in a measurement (raising at a rate of 10.degree. C./minute) of a thermobalance in a nitrogen gas stream.

Among the Polymer P.sup.1 and Polymer P.sup.2, there are employed below particularly preferable fluorine-containing polymers having a functional group in order to further give the features such as oil resistance and chemical resistance, which are inherent to fluorine-containing polymers, to the composition, even if the thermal resistance is enough as mentioned hereinabove.

That is to say, the Polymer P.sup.1 essentially comprises a polyvinylidene fluoride (PVDF) and VDF, and is obtained by copolymerization with at least one selected from, for instance, TFE, CTFE, perfluoro(alkylvinyl ether), perfluoro(alkylallyl ether), CH.sub.2.dbd.C(CF.sub.3).sub.2, CF.sub.2.dbd.CZ(CF.sub.2).sub.wZ (Z and w are the same as mentioned hereinabove), CH.sub.2.dbd.CZ(CF.sub.2).sub.wZ (Z and w are the same as mentioned hereinabove), CF.sub.2.dbd.CFR.sub.f(CH.sub.2).sub.x--B.sub.2 and fluorine-containing olefins such as fluoroalkene represented by CF.sub.2.dbd.CFOR.sub.f(CH.sub.2).sub.z--B.sup.2 (R.sub.f, B.sup.2, x and z are the same as mentioned hereinabove), and occasionally furthermore with at least one hydrocarbon olefin selected from CH.sub.2.dbd.CH.sub.2, CH.sub.2.dbd.CHCH.sub.3 and CH.sub.2.dbd.C(CH.sub.3).sub.2, wherein at least one end of the main chain and the side chains of the polymer has hydroxy group or epoxy group.

The Polymer P.sup.2 is a polymer containing at least one hydrocarbon olefin selected from CH.sub.2.dbd.CH.sub.2, CH.sub.2.dbd.CHCH.sub.3 and CH.sub.2.dbd.C(CH.sub.3).sub.2, at least one of TFE, CTFE, and CF.sub.2.dbd.CFCF.sub.3 (hexafluoropropene: HFP), and occasionally, further at least one fluorine-containing olefin selected from, for instance, perfluoro(alkylvinyl ether), perfluoro(alkylallyl ether), CH.sub.2.dbd.C(CF.sub.3).sub.2, CF.sub.2.dbd.CZ(CF.sub.2).sub.wZ (Z and w are the same as mentioned hereinabove), CH.sub.2.dbd.CZ(CF.sub.2).sub.wZ (Z and w are the same as mentioned hereinabove), fluoroalkylvinylether, CF.sub.2.dbd.CFR.sub.f(CH.sub.2).sub.x--B.sup.2 and fluoroalkene represented by CF.sub.2.dbd.CFOR.sub.f(CH.sub.2).sub.z--B.sup.2 (R.sub.f, B.sup.2, x and z are the same as mentioned hereinabove), wherein at least one end of the main chain and the side chains of the polymer has hydroxy group or epoxy group.

A molecular weight of the fluorine-containing polymer having a functional group of the present invention is the same level as those of a usual fluorine-containing resin and fluorine-containing elastomer except a PTFE which is said to have a high molecular weight of usually not less than millions, and is 2000 to 1000000 in a number-average molecular weight. When the molecular weight is too low, thermal resistance and chemical resistance are impaired, and therefore, it is necessary to decrease a content of a fluorine-containing polymer having a functional group in the composition When the molecular weight is too high, moldability is impaired. Preferable number-average molecular weight differs depending on a kind of a thermoplastic resin and a purpose of the composition, but is about 10000 to 500000. A concentration of functional groups in the fluorine-containing polymer of the present invention may be a minimum necessary for improving a dispersion condition when blending with the thermoplastic resin. When the functional group is only at the end of a molecule, the concentration of the functional group is too low and the effect is insufficient unless the fluorine-containing polymer is of relatively low molecular weight. In case where a functional group is introduced at the side chain with a functional group-containing comonomer or by a high polymer reaction, the concentration of the functional group can be relatively freely selected irrespective of a molecular weight. However, an excessive concentration of the functional group is not desirable by the reason of a restriction in the production and in view of properties such as thermal resistance and chemical resistance of the composition. The concentration of the functional groups both at the ends and in side chains of the molecule can be 2 to 2000 .mu.mol/g, particularly preferably 2 to 1000.mu.mol/g per the total weight of the fluorine-containing polymer.

The fluorine-containing polymer (a) having a functional group of the present invention may be in either resinous or elastomeric form depending on a kind of a monomer to be used and a ratio of components thereof. The resin is discriminated from the elastomer in a point that the latter has a glass transition temperature lower than room temperature, and either one can be selected depending on the purpose of a blend. The elastomeric fluorine-containing polymer having a functional group is used for the purposes to improve impact resistance of the thermoplastic resin and to obtain a blend in the elastomeric form.

In the present invention, the fluorine-containing polymer (a) having a functional group is blended with a thermoplastic resin (b) of a crystalline melting point or a glass transition temperature of not less than 150.degree. C. As the thermoplastic resin (b), there are, for example, polyacetals, polyamides, polycarbonates, polyphenylene ethers, aromatic polyesters, aromatic polyesteramides, aromatic azomethines, polyarylene sulfides, polysulfones, polyether sulfones, polyketones, polyether ketones, polyetherimides, polyamide imides, polymethyl pentenes and polyether nitrites. Among those, preferable for the present invention are thermoplastic resins which have a high thermal resistance, and do not deteriorate thermal resistance of a composition after mixed with the fluorine-containing polymer (a) having a functional group, or thermoplastic resins, for which usual impact modifiers and chemical resistance modifiers cannot be used because thermal resistance is deteriorated thereby. Examples of such resins are aromatic polyesters, polyamides, polyamide imides, polyarylene sulfides, polyketones, polyether nitriles, polycarbonates, polyphenylene ethers, polysulfones, polyetherimides and polyimides.

Further, particularly preferable are, for example, polyarylene sulfides, of which impact resistance is generally desired to be improved without impairing thermal resistance and chemical resistance, and polyamides which are desired to improve solvent resistance, particularly gasohol resistance for the use as materials for auto parts and aromatic polyesters which are expected to enhance moldability and mechanical properties of the fluorine-containing polymer, being added thereto. Among those, particularly preferable are liquid crystal polyesters forming an anisotropic melt, which can be expected to enhance, to a large extent, mechanical properties, moldability, dimensional stability and deflection temperature under load by enhancing a compatibility with the fluorine-containing polymer, because those polyesters have high modulus of elasticity and are excellent in moldability and dimensional stability.

Also, when considering reactivity of the fluorine-containing polymer (a) having a functional group of the present invention and a thermoplastic resin (b), since polyphenylene sulfides contain mercapto group, polyamides contain carboxyl group and amino group, and aromatic polyesters contain hydroxy group, carboxyl group and ester group, there is a high possibility of those resins' reacting with hydroxy group or epoxy group (also inclusive of glycidyl group) in the fluorine-containing polymer having a functional group of the present invention. From this point of view, too, those resins are preferable.

The functional group of the fluorine-containing polymer of the present invention are epoxy group (including glycidyl group) and hydroxy group. The reactivity of those functional groups is high with an ester bond of a main chain and hydroxy group and carboxyl group at the end when the heat resisting thermoplastic resin (b) is an aromatic polyester, with an amide bond of main chain and carboxyl group and amino group at the end when the resin is a polyamide (PA), and with mercapto group at the end when the resin is a polyarylene sulfide. That is to say, it can be thought that those highly reactive functional groups are introduced in the fluorine-containing polymer, and partly react with the main chain or the end of the thermoplastic resin to improve a compatibility of the polymer or that the introduction of the functional group enhances a polarity of the fluorine-containing polymer, which improves an interface affinity with the thermoplastic resin and a dispersibility without particularly causing a chemical reaction. Also, it can be considered that a part of the thermoplastic resin causes a chemical reaction with the fluorine-containing polymer and the reaction products act as a compatibilizing agent.

Therefore, in the composition of the present invention, a blend of the fluorine-containing polymer (a) having the functional group and the thermoplastic resin (b) is presumed to be present in the form of (1) a mere mixture of the fluorine-containing polymer (a) having the functional group and the thermoplastic resin (b), (2) a reaction product between the fluorine-containing polymer (a) having the functional group and the thermoplastic resin (b) or (3) a mixture of (1) and (2). Thus, though a mechanism of the blend is not clear, it does not limit the present invention.

It is not excluded from the present invention that the thermoplastic resin (b) is modified by a normal method in order to enhance an affinity or reactivity with the fluorine-containing polymer having a functional group of the present invention.

The resin composition of the present invention can also contain polymer components other than the thermoplastic resin (b) and the fluorine-containing polymer (a) having a functional group.

Preferable components are fluorine-containing polymers which have neither hydroxy group nor epoxy group at the main chain and the end of the side chain in the formula (I). Particularly preferable are (1) a perfluoro fluorine-containing resin or elastomer such as PTFE (including a copolymer having less than 1% by weight of fluorine-containing olefin copolymerable with TFE), TFE/perfluoro(alkylvinyl ether) copolymer (so-called PFA), TFE/HFP copolymer (so-called FEP) and TFE/perfluoro(alkylvinyl ether)/HFP terpolymer; (2) a resinous copolymer, in which a mole ratio of an ethylene to a TFE and/or CTFE, which are known as a so-called ETFE and ECTFE, is 2:3 to 3:2 and the third fluorine-containing monomer copolymerable therewith is contained in an amount of 0 to 15% by mole per a total amount of the ethylene and the TFE and/or CTFE monomer, or an elastomeric copolymer having about 40 to 90% by mole of ethylene, about 0.1 to 20% by mole of TFE and/or CTFE and about 10 to 60% by mole of the third fluorine-containing monomer. As the third fluorine-containing monomer, there is used at least one of those represented by CH.sub.2.dbd.CZ(CF.sub.2).sub.wZ, CF.sub.2.dbd.CZ(CF.sub.2).sub.wZ, CF.sub.2.dbd.CFO(CF.sub.2).sub.wZ (Z and w are the same as mentioned hereinabove) and CH.sub.2.dbd.C(CF.sub.3).sub.2; (3) a PVDF and a VDF copolymer (a resinous or elastomeric copolymer of the VDF and at least one fluorine-containing olefin selected from TFE, CTFE, HFP, CH.sub.2.dbd.C(CF.sub.3).sub.2, (CF.sub.3).sub.2C.dbd.O, and the like), wherein VDF/HFP copolymer, VDF/CTFE copolymer and VDF/TFE/HFP or CTFE terpolymer usually become an elastomer in the range of about 20 to 80% by mole of VDF, less than about 40% by mole of TFE, about 10 to 60% by mole of HFP and about 15 to 40% by mole of CTFE; and (4) other fluorine-containing resins or elastomers such as chlorotrifluoroethylene (PCTFE) and poly(fluoroalkyl-.alpha.-substituted acrylate) (a substituent is hydrogen atom, a methyl, fluorine atom or chlorine atom).

That is to say, in the compositions having three components of the aforesaid fluorine-containing polymer (a) having a functional group, the thermoplastic resin (b) and the fluorine-containing polymer having no functional group, it can be thought that a mixture of a part of the thermoplastic resin (b) in the composition and the fluorine-containing polymer (a) having a functional group functions as a compatibilizing agent and enhances a dispersibility, and a mechanical property, chemical resistance, and the like, which cannot be obtained in case of a simple blend of a fluorine-containing polymer having no functional group and a thermoplastic resin (b), can be enhanced.

Therefore, in those compositions, it is preferable that the fluorine-containing polymer (a) having a functional group and the fluorine-containing polymer having no functional group are highly compatible with each other.

For example, when mixing the perfluoro fluorine-containing resin or elastomer of (1) above and the polymer of (2) above, such as a ETFE and ECTFE, with the thermoplastic resin, it is the most preferable to mix a fluorine-containing polymer having a functional group, which has the functional group at the end or the side chain and has a structure similar to those of fluorine-containing polymers to be mixed therewith.

Also, when mixing the PVdF or the VdF copolymer of (3) above with the thermoplastic resin, it is the most preferable to mix the fluorine-containing polymer having a functional group, which is selected from PVdF and VdF copolymers and has the functional group at the end or the side chain thereof.

It is necessary to blend the thermoplastic resin (b) and the fluorine-containing polymer (a) having a functional group or to blend those and a fluorine-containing polymer having no functional group under melting and fluidizing conditions at least at not less than a crystalline melting point or a glass transition temperature of the thermoplastic resin. It is desirable that the fluorine-containing polymer having a functional group is also under melting conditions during blending, but a non-melting property may be maintained because of a high melting viscosity or a crosslinking property.

The resin composition of the present invention has the functional group at the end of the main chain and/or the side chain, and is obtained by mixing a fluorine-containing polymer (a) having a molecular weight of 2000 to 1000000 and a thermoplastic resin (b) having a crystalline melting point or glass transition temperature of not less than 150.degree. C. The polymer (a) is 0.1 to 99% by weight, and the resin (b) is 1 to 99.9% by weight.

When (a) is 0.1 to 40% by weight and (b) is 60 to 99.9% by weight, such properties as an impact resistance, sliding property, chemical resistance and moldability can be improved by a fluorine-containing polymer, though those properties are drawbacks for many of thermoplastic resins. Also, when (a) is 40 to 99% by weight and (b) is 1 to 60% by weight, a strength, deflection temperature under load, moldability and dimensional stability of the fluorine-containing polymer can be improved by the thermoplastic resin. When, in a weight ratio to the resin composition, (a) is less than 0.1% by weight and (b) is less than 1% by weight, the effect of that improvement becomes unsatisfactory.

A content, in the composition, of a fluorine-containing polymer having a functional group and a kind thereof differ depending on a kind, position, concentration, basic component and molecular weight of the functional group, and therefore, cannot be determined unequivocally but is selected depending on a kind of thermoplastic resin to be blended in the mentioned range and a purpose of blending.

The preferable resin composition of the present invention is the composition comprising a fluorine-containing polymer having hydroxy group or epoxy group at the end of main chain or the side chain and a polyarylene sulfide, polyamide, aromatic polyester or polycarbonate.

A polyarylene sulfide is excellent in thermal resistance, chemical resistance, and mechanical properties, but inferior in impact resistance.

There can be obtained a composition, of which impact resistance is improved by mixing a fluorine-containing elastomer particularly having a number-average molecular weight of 2000 to 200000, among fluorine-containing polymers (a) having a functional group.

As a functional group of the fluorine-containing elastomer having a functional group, there are employed hydroxy group and epoxy group (including glycidyl group). Either of those groups enhances a dispersibility and impact resistance.

A preferable concentration of the functional group differs depending on a kind and mixing ratio of a fluorine-containing elastomer and a polyarylene sulfide, and 2 to 2000 .mu.mol/g, particularly 2 to 1000 .mu.mol/g is sufficiently effective per a total amount of the fluorine-containing elastomer.

As the aforesaid fluorine-containing elastomers having a functional group, there can be used those, in which the functional groups are introduced at the respective ends or side chains thereof, such as vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidenefluoride-tetrafluoroethylene-chlorotrifluoroethylene copolymer, propylenetetrafluoroethylene copolymer, tetrafluoroethyleneperfluoroalkyl vinyl ether copolymer, tetrafluoroethylenevinylidene fluoride-propylene copolymer, ethylene-tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-hexafluoropropylene copolymer, perfluoroalkyl acrylate elastomer, tetrafluoroethylene-alkylvinylether copolymer, and tetrafluoroethylene-alkylvinylester copolymer. Among those, particularly preferable are vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer and propylene-tetrafluoroethylene copolymer, in which hydroxy group or epoxy group (including glycidyl group) is introduced respectively.

The fluorine-containing elastomer having a functional group and the polyarylene sulfide can be used in the range of 0.1 to 40% by weight and 60 to 99.9% by weight, respectively, particularly preferably 5 to 30% by weight and 70 to 90% by weight, respectively.

When the fluorine-containing elastomer having a functional group is less than 5% by weight, impact resistance cannot be improved sufficiently, and contrarily when exceeding 30% by weight, mechanical strength decreases remarkably.

Perfluoro fluorine-containing resins (PTFE, FEP, PFA, and the like), ETFE, ECTFE, PVdF and VDF copolymer resins are excellent in thermal resistance, chemical resistance, weather resistance, electrical properties, and the like, but there are many cases where those resins are inferior to the heat resisting crystalline thermoplastic resin (b) in mechanical properties and physical thermal resistance as represented by a deflection temperature under load.

The mechanical property and deflection temperature under load, which fluorine-containing resins themselves have, can be improved, instead of using the aforesaid fluorine-containing resins, by blending an aromatic polyester or polycarbonate with the fluorine-containing resin having a functional group of the present invention, which is introduced at the end or the side chain thereof, or by using, as a compatibilizing agent, the fluorine-containing polymer having a functional group of the present invention, for the mentioned blend of the fluorine-containing resin and the aromatic polyester or polycarbonate.

When blending with the aromatic polyester or polycarbonate, the both of hydroxy group and epoxy group (including glycidyl group) of the present invention can be used as the functional group of the fluorine-containing polymer having the functional group. It is more preferable to use the fluorine-containing polymer having hydroxy group at the end or side chain thereof, which is considered to easily cause an transesterification with an ester bond or carbonate bond in the main chain of the aromatic polyester or polycarbonate.

A preferable concentration of the functional group differs depending on the kind of the fluorine-containing polymer and the kind and ratio of the aromatic polyester or polycarbonate, and 2 to 2000 .mu.mol/g, particularly 2 to 1000 .mu.mol/g is sufficiently effective per a total weight of the fluorine-containing polymer having a functional group.

When blending two components of the fluorine-containing resin having a functional group and the aromatic polyester or polycarbonate, various fluorine-containing resins having a functional group can be selected, and those having hydroxy group at the end or side chain thereof, such as PTFE, FEP, PFA, ETFE, ECTFE, PVdF, and VDF-TFE copolymer are preferable. Mechanical properties and deflection temperature under load, which each of the corresponding fluorine-containing resins themselves has, can be improved.

In case of a blend composition by blending the fluorine-containing polymer having a functional group of the present invention as a compatibilizing agent with a blend of the fluorine-containing resin and the aromatic polyester or polycarbonate, various combinations can be used. Most preferable are those such as a composition obtainable by blending a mixture of perfluoro fluorine-containing resin (PTFE, FEP, PFA, and the like) and aromatic polyester or polycarbonate,