JPH09118802A - Polymer alloy containing fluorine, its production and molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply obtain the subject alloy, useful as a sliding material requiring a low friction and a low wearing, and an electric insulating material having a high elasticity at a high temperature and also a high dimension stability by melting and mixing a grafted copolymer containing fluorine with a polymer not containing fluorine. SOLUTION: This polymer alloy containing fluorine is obtained by melting and mixing (A) a grafted copolymer containing fluorine obtained by grafting (ii) a compound capable of grafting and having a binding group capable of grafting with component (i) and a functional group imparting an adhesive property with (i) a polymer containing fluorine and hydrogen atom bonded to a carbon atom in its main chain and (B) a polymer not containing fluorine atom (suitably a polymer having amino group) in the presence of a radical generating agent at a radical generating temperature. Further, it is also preferable to contain (C) a polymer containing fluorine other than the component (A) and to use a ethylene tetrafluoroethylene based copolymer as the component (i).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluoropolymer alloy in which a fluoropolymer and a polymer containing no fluorine atom are uniformly dispersed and mixed.

[0002]

2. Description of the Related Art Fluorine-containing polymers are excellent in heat resistance, flame resistance, chemical resistance, weather resistance, non-adhesiveness, low friction properties, low dielectric properties, and heat resistance, as represented by tetrafluoroethylene polymers. It is used in a wide range of fields such as coating materials for flame-retardant wires, semiconductor cleaning line corrosion resistant piping materials, chemical plant corrosion resistant piping materials, agricultural greenhouse materials, release coating materials for kitchen appliances, and various sliding materials.

However, there is a problem that a good polymer alloy cannot be obtained because of poor compatibility with other polymer materials containing no fluorine atom. Therefore, in order to improve the compatibility between the fluoropolymer and the polyolefin, a method in which the polyolefin is modified with an alkyl acrylate (Japanese Patent Publication No. 4-73459) or a method in which the fluoropolymer contains a carbonyl group, a hydroxyl group or an epoxy group (JP-A-6
2-57448) has been carried out.

However, the former is effective for vinylidene fluoride-based polymers, vinyl fluoride-based polymers and the like in which the fluoropolymer has a high polarity, but tetrafluoroethylene-based polymers and chlorotrifluoroethylene-based polymers having a low polarity are used. The compatibility of the polymer with the fluoropolymer is not improved.

Also. As the latter, (1) a method of blending a fluorine-containing polymer with a non-fluorine-containing thermoplastic polymer containing a functional group, and (2) adding a polymerized unit based on a polymerizable monomer having a functional group to the fluorine-containing polymer. Method, (3) a method of reacting a reactive group present in the fluoropolymer with a compound containing a functional group or a compound which produces a functional group by the reaction, (4) oxidation, hydrolysis, heat of the fluoropolymer A method of denaturing by decomposition or the like can be mentioned.

However, regarding a fluoropolymer such as a tetrafluoroethylene-based polymer or a chlorotrifluoroethylene-based polymer, in the method (1), a fluorine-containing polymer and a non-fluorinated thermoplastic polymer containing a functional group are used in the same manner as the former. Not effective as it is not compatible with coalescence. The method (2) is not practical because the monomers used in the copolymerization reaction are extremely limited and are expensive. The method (3) cannot be adopted because the fluoropolymer usually does not have a reactive group. In the method (4), since the fluoropolymer is stable, a carboxyl group, a hydroxyl group, and an epoxy group cannot be formed by oxidation, hydrolysis, thermal decomposition, or the like.

On the other hand, a grafting compound having a fluorine-containing polymer containing a hydrogen atom bonded to a carbon atom of the main chain, a binding group capable of being grafted with the fluorine-containing polymer and a functional group imparting adhesiveness, is used. Using the grafted fluoropolymer formed by grafting as a molding material, a molded product, for example, a laminate by coextrusion molding, a film or a sheet is manufactured by a conventionally known molding method, and this film is laminated with another molded product. To produce a laminated body
-173230, JP-A-7-173446, JP-A-7-
173447) has been proposed.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to obtain a polymer alloy having excellent compatibility between a fluorine-containing polymer and a polymer containing no fluorine atom by a simple method.

[0009]

Means for Solving the Problems The present inventor can graft a fluoropolymer (d) having a hydrogen atom bonded to a carbon atom of the main chain as a compatibilizer with the fluoropolymer (d). The inventors have found that it is extremely effective to use a grafted fluoropolymer (a) obtained by grafting a grafting compound having a bonding group and a functional group that imparts adhesiveness, and achieved the present invention.

The above grafted fluoropolymer (a)
Is used as a compatibilizing agent, the compatibility between the fluorine-free polymer (c) and the fluorine-containing polymer (b) and the fluorine-free polymer (c) is improved. Therefore, the compatibility is improved, and a fluoropolymer alloy having uniform dispersion and a small dispersed particle diameter can be obtained.

That is, the present invention is the following invention relating to a fluoropolymer alloy, a method for producing the fluoropolymer alloy and a method for molding the fluoropolymer alloy.

The fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain has the fluorine-containing polymer (d), a bondable group capable of grafting, and a functional group imparting adhesiveness. A fluoropolymer alloy containing a grafted fluoropolymer (a) obtained by grafting a grafting compound and a polymer (c) containing no fluorine atom.

The above-mentioned fluoropolymer alloy further containing a fluoropolymer (b) other than the grafted fluoropolymer (a).

It has a fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a fluorine-containing polymer (d), a bondable group capable of grafting, and a functional group imparting adhesiveness. A method for producing a fluorine-containing polymer alloy, which comprises melt-mixing a grafting compound, a radical generator, and a polymer (c) containing no fluorine atom at a temperature at which radicals are generated.

It has a fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a bonding group capable of being grafted with the fluorine-containing polymer (d) and a functional group imparting adhesiveness. Grafting compound, radical generator, fluorine atom-free polymer (c), and fluoropolymer (b ') other than fluoropolymer (d)
A method for producing a fluorine-containing polymer alloy, which comprises melt-mixing at a temperature at which radicals are generated.

It has a fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a binding group capable of grafting with the fluorine-containing polymer (d), and a functional group imparting adhesiveness. A method for molding a fluorine-containing polymer alloy, which comprises melt-mixing and molding a grafting compound, a radical generator, and a polymer (c) containing no fluorine atom in a molding machine at a temperature at which radicals are generated.

It has a fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a binding group capable of grafting with the fluorine-containing polymer (d), and a functional group imparting adhesiveness. Grafting compound, radical generator, fluorine atom-free polymer (c), and fluoropolymer (b ') other than fluoropolymer (d)
A method for molding a fluorine-containing polymer alloy, which comprises melt-mixing and molding in a molding machine at a temperature at which radicals are generated.

The fluorine-containing polymer alloy is another polymer which is excellent in heat resistance, flame retardancy, chemical resistance, non-adhesiveness, low friction and low dielectric properties of the fluorine-containing polymer and which does not contain a fluorine atom. It also has various properties possessed by the material, and can be expected to reduce costs as a fluoropolymer. For example, sliding materials that require low friction and low wear,
It can be expected to find applications in the fields of heat resistant materials with high temperature and high elasticity and high dimensional accuracy, electrical insulating materials, and inexpensive fluoropolymer materials.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION As the fluoropolymer (b) used in the present invention, a homopolymer of a fluoroolefin such as tetrafluoroethylene or chlorotrifluoroethylene, or the fluoroolefin and hexafluoropropylene or perfluoro ( A copolymer with a fluorine-containing monomer such as alkyl vinyl ether), vinylidene fluoride, or vinyl fluoride can be used. Further, a copolymer of the above-mentioned fluoroolefin and an α-olefin containing no fluorine such as ethylene, propylene and butene can also be used.

Specific examples of the fluoropolymer (b) include:
Tetrafluoroethylene-based polymer, chlorotrifluoroethylene-based polymer, tetrafluoroethylene-hexafluoropropylene-based copolymer (hereinafter referred to as FEP),
Tetrafluoroethylene-perfluoro (alkyl vinyl ether) -based copolymer (hereinafter referred to as PFA), ethylene-tetrafluoroethylene-based copolymer (hereinafter referred to as ET
FE), an ethylene-chlorotrifluoroethylene-based copolymer, a tetrafluoroethylene-propylene-based copolymer, and the like, and FEP or PFA is particularly preferable.

Examples of the polymer (c) containing no fluorine atom are polyethylene, polypropylene, polystyrene, styrene resin, vinyl chloride resin, polymethylpentene, acrylic resin, urethane resin, silicone resin, polyvinyl alcohol, polyamide (nylon 12).
Etc.), polycarbonate (hereinafter referred to as PC), polybutylene terephthalate (hereinafter referred to as PBT), polyacetal, polyphenylene oxide, polyphenylene sulfide (hereinafter referred to as PPS), polysulfone, liquid crystal polyester (polyoxybenzoyl (hereinafter referred to as POB)
Etc.), polyamide imide (hereinafter referred to as PAI), polyimide, polyether imide (hereinafter referred to as PEI)
General purpose resins such as polyether sulfone (hereinafter referred to as PES), polyether ether ketone, and amorphous polyacrylate, and engineering plastics.

As the polymer (c), an amino group having a high reactivity with a functional group such as an epoxy group, a carboxyl group or a carboxylic acid anhydride residue contained in the grafted fluoropolymer (a) is used. Those having a terminal of (4) or in the molecule are particularly preferable.

The fluorine-containing polymer (d) before grafting used in the present invention is a type of fluorine-containing polymer in which a fluorine atom is bonded to a carbon atom of the main chain. In addition, it must also contain hydrogen atoms bonded to the carbon atoms of the main chain.

Such a fluorine-containing polymer (d) has a characteristic that the hydrogen atom bonded to the main chain is relatively unstable as compared with the fluorine atom and is easily extracted from the carbon atom by the action of a radical or the like. A grafting compound is bonded to the carbon atom from which the hydrogen atom has been extracted, and grafting occurs. In the present invention, since the grafted grafted compound has a functional group that imparts adhesiveness, the fluoropolymer is imparted with adhesiveness.

As the fluoropolymer (d) before grafting used in the present invention, a homopolymer or a copolymer of fluoroolefin is preferable. However, a fluoroolefin in which a hydrogen atom is not bonded to any of the two carbon atoms of the polymerizable unsaturated group such as tetrafluoroethylene or chlorotrifluoroethylene is any one of the two carbon atoms of the polymerizable unsaturated group. It is necessary to copolymerize with a monomer having one or more hydrogen atoms bonded thereto.

Examples of the fluoroolefin having a hydrogen atom bonded to the polymerizable unsaturated group include vinylidene fluoride and vinyl fluoride. These homopolymers can be used as the fluoropolymer (d) before grafting used in the present invention. Also, copolymers of these monomers with other monomers can be used. The other monomer may be various fluorine-containing monomers or monomers containing no fluorine atom.

As a monomer to be copolymerized with a fluoroolefin in which a hydrogen atom is not bonded to any of the two carbon atoms of the polymerizable unsaturated group, an olefin (that is,
Hydrocarbon-based olefins) are preferred, especially ethylene,
Alpha-olefins such as propylene and butene are preferred.

However, the present invention is not limited to this, and various types of vinyl olefins such as vinylidene fluoride, (perfluorobutyl) ethylene, and other fluoroolefins having a hydrogen atom bonded to an unsaturated group, vinyl ethers such as alkyl vinyl ethers and (fluoroalkyl) vinyl ethers, and the like can be used. Monomers can also be used. Further, together with these, a monomer in which a hydrogen atom is not bonded to a polymerizable unsaturated group such as hexafluoropropylene or perfluoro (alkyl vinyl ether) can be used together as the third monomer.

As the fluoropolymer (d) before grafting, ETFE, a tetrafluoroethylene-propylene copolymer and a vinylidene fluoride copolymer are preferable, and ETFE is particularly preferable.

When the preferred fluoropolymer (d) as described above is a copolymer and the comonomer is a monomer containing no fluorine atom, the fluoropolymer (d) is
The proportion of polymerized units obtained by polymerizing the fluorine-containing monomer therein is preferably 40 mol% or more based on all polymerized units. When the ratio of the polymerized units of the fluorinated monomer is lower than this, the compatibility with the fluorinated polymer (b) decreases and it is difficult to obtain a good polymer alloy.

By grafting a grafting compound onto the fluorine-containing polymer (d), a grafted fluorine-containing polymer (having a large adhesive force even to a material which has conventionally been insufficiently adhered or impossible to be adhered ( a) is obtained. The associative group in the grafting compound is a group that enables grafting to the fluoropolymer (d).

Examples of such a bonding group include, for example,
Examples include unsaturated or saturated hydrocarbon groups involved in radical association or addition, amino groups and phenolic hydroxyl groups involved in nucleophilic reactions. Further, it may be a group that easily generates a radical, for example, a peroxy group or an azo group. A preferred bonding group is a group having a carbon-carbon unsaturated bond (particularly an organic group having an α, β unsaturated double bond at the terminal),
A peroxy group and an amino group.

The functional group is a group capable of imparting adhesiveness to the fluoropolymer grafted with a reactive or polar group. Two or more such functional groups may be present in one molecule of the grafting compound. Further, two or more functional groups may be different from each other. Examples of such a functional group include a carboxyl group, a residue obtained by dehydration condensation of two carboxyl groups in one molecule (hereinafter referred to as a carboxylic acid anhydride residue), an epoxy group, a hydroxyl group, an isocyanate group, an ester group, Examples include an amide group, an aldehyde group, an amino group, a hydrolyzable silyl group, and a cyano group.

As the functional group, a carboxylic acid anhydride residue,
An epoxy group and a hydrolyzable silyl group are preferable, and a carboxylic acid anhydride residue is particularly preferable.

Examples of the grafting compound include a binding group selected from an organic group having an α, β unsaturated double bond at the terminal, a peroxy group, and an amino group as described above, a carboxylic acid anhydride residue, and an epoxy group. And a compound having one or more functional groups selected from hydrolyzable silyl groups. Among them, unsaturated polycarboxylic acid anhydrides, unsaturated carboxylic acids, epoxy group-containing unsaturated compounds, hydrolyzable silyl group-containing unsaturated compounds, epoxy group-containing peroxy compounds and the like are preferable.

Examples of unsaturated polycarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride. There are things. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, fumaric acid, itaconic acid, citraconic acid, crotonic acid, bicyclo [2.
2.1] Hept-2-ene-5,6-dicarboxylic acid and the like.

Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether.

The hydrolyzable silyl group-containing unsaturated compound includes one unsaturated group-containing organic group such as a vinyl group, an allyl group, a methacryloyloxyalkyl group and an acryloyloxyalkyl group and an alkoxy group or an acyl group. A compound in which 2-3 hydrolyzable groups are bonded to a silicon atom is preferable.
When one unsaturated group-containing organic group and two hydrolyzable groups are bonded to a silicon atom, the remaining groups are preferably lower alkyl groups such as methyl group.

Specific hydrolyzable silyl group-containing unsaturated compounds include, for example, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane,
Vinyl tris (β-methoxyethoxy) silane and the like.

Examples of the peroxy compound include diacyl peroxides, ketone peroxides, hydroperoxides, peroxy carbonates and the like, and compounds having the above functional groups. As the peroxy compound, a polymer type grafting compound described below can be used.

Examples of the graft compound other than the above are the following unsaturated compounds. Unsaturated compounds having a hydroxyl group such as allyl alcohol, N-methylol acrylamide, and N-methylol methacrylamide. Methyl acrylate, methyl methacrylate, dimethyl malate, diethyl fumarate, dimethyl itaconate, diethyl citracone, diethylene glycol bis (allyl carbonate) [(CH ₂ ═CHCH ₂ O
COOC ₂ H ₄ ) ₂ O] (hereinafter referred to as CR-39 monomer) and the like. Unsaturated acid amides such as acrylamide, N-methylacrylamide, N, N-dimethylmethacrylamide. Unsaturated amines such as allylamine, methylaminoethyl methacrylate, t-butylaminoethyl methacrylate and aminostyrene; Unsaturated compounds having a cyano group such as cyanoacrylate and cyanomethacrylate; Unsaturated aldehydes such as acrolein and crotonaldehyde.

As described above, as the grafting compound, in addition to the unsaturated group-containing compound, a compound having a saturated hydrocarbon group involved in radical association or addition, an amino group or a phenolic hydroxyl group involved in a nucleophilic reaction, etc. It may be a compound having Examples of this type of grafting compound include the following compounds.

Two or more of hexamethylenediamine, ethanolamine, diethanolamine, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane and the like. A compound having an amino group or a compound having an amino group and other functional groups.

The grafting compound may also be a polymer having a binding group such as a peroxy group or an amino group and a functional group imparting adhesiveness. Examples of such a polymer type grafting compound include a polymerizable unsaturated peroxide such as t-butylperoxymethacryloyloxyethyl carbonate, a carboxyl group, a carboxylic acid anhydride residue, an epoxy group, and a hydrolysis group. Examples thereof include a copolymer with a polymerizable unsaturated compound having a polymerizable silyl group and the like. A copolymer obtained by copolymerizing a polymerizable unsaturated amine and a polymerizable unsaturated compound having a functional group as described above can be used in the same manner.

The amount of the grafting compound used for grafting is preferably 0.01 to 100 parts by weight, and 0.1 to 2 parts by weight based on 100 parts by weight of the fluoropolymer (d).
0 parts by weight is more preferred. In the case of a polymer type grafting compound, a larger amount can be used, but it is preferable to set the upper limit to about 50 parts by weight. The more preferable amount of the grafting compound other than the polymer type is 0.5 to 10 parts by weight.

That is, the obtained grafted fluoropolymer (a) is one in which some hydrogen atoms bonded to the main chain of the fluoropolymer (d) are grafted with a grafting compound. If the amount of the grafting compound used is too small, the amount of the grafted fluoropolymer (a) formed in the fluoropolymer (d) will be small and the adhesion will be insufficient, and if it is too large, the excellent properties of the fluoropolymer (d) will be obtained. Is easily damaged.

As a method of grafting the grafting compound onto the fluoropolymer (d), a method of associating both of them in the presence of a radical generator is preferable. However, when a radical-generating grafting compound such as a compound having a peroxy group is used, it is not always necessary to use another radical-generating agent. The amount of the radical generator used is not particularly limited, and is 0.1 per 1 part by weight of the grafting compound.
-10 parts by weight is suitable.

It is speculated that the grafting is achieved by the following reaction mechanism. First, the radicals generated from the radical generator abstract hydrogen atoms from the fluoropolymer (d) to generate the fluoropolymer (d) radicals. Further, a radical generated from the radical generator is added to the grafting compound or a hydrogen atom is abstracted from the grafting compound to generate a radical. Grafting is achieved by the association of these two radicals. Grafting can also be achieved by directly adding the fluorine-containing polymer (d) radical to the unsaturated hydrocarbon group of the compound to be grafted. In addition, it is considered that grafting can occur by various reaction mechanisms.

The grafting reaction is preferably carried out by melt-mixing the fluorine-containing polymer (d), the grafting compound, and, if a radical generator is required, with a radical generator at a radical generation temperature. In some cases, a solvent is used to prepare a solution of the fluoropolymer (d),
The grafting reaction can also be carried out in this solution. The most preferable method is to carry out the grafting reaction while melt-kneading in an extruder or injection molding machine. The grafted grafted fluoropolymer (a) can be used as a molding material such as pellets.

The radical generator used in the grafting reaction preferably has a decomposition temperature in the range of 120 to 300 ° C. and a half-life of about 1 minute at the grafting reaction temperature. Specifically, the following can be exemplified.

Benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexyne-3,1,4-bis (t-butylperoxyisopropyl) Benzene, lauroyl peroxide, t-butyl peracetate, 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexyne-3,2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t
-Butyl perbenzoate, t-butyl perphenyl acetate and the like.

As the polymerizable unsaturated peroxide, the decomposition temperature of the peroxy group in the copolymer is in the range of 120 to 300 ° C., and the half-life under the grafting reaction temperature is 1 minute. Those before and after are preferable. As specific polymerizable unsaturated peroxides, for example, the following are preferable.

T-Butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1,1,3,3 3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropyl cumylperoxyacryloyloxyethyl carbonate and the like.

The fluorine-containing polymer alloy is a fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a grafting compound which is grafted with the fluorine-containing polymer (d), a radical generator, and fluorine. It is produced by melt mixing a composition having a polymer (c) containing no atom at a temperature at which radicals are generated.
Further, a fluoropolymer alloy can be produced by adding a fluoropolymer (b ') other than the fluoropolymer (d) to the above composition.

The fluoropolymer alloy can also be produced by adding the polymer (c) containing no fluorine atom to the grafted fluoropolymer (a), and further adding the fluoropolymer (b ').

In the production of the fluoropolymer alloy of the present invention, the amount of the polymer (c) is 30 to 300 parts by weight and the content of the fluoropolymer (b ') is 0.1 to 100 parts by weight of the fluoropolymer (d). 300 parts by weight are used.

The fluorinated polymer (b ') is a fluorinated polymer other than the fluorinated polymer (d), and is a concept that may include the grafted fluorinated polymer (a). Further, it may not be used in the production of the fluoropolymer alloy.

As the fluoropolymer (b ') used in the present invention, a homopolymer of a fluoroolefin such as tetrafluoroethylene or chlorotrifluoroethylene, the fluoroolefin and hexafluoropropylene, and perfluoro (alkyl vinyl ether). A copolymer with a fluorine-containing monomer containing no hydrogen atom such as Specific examples of the fluoropolymer (b ') include tetrafluoroethylene-based polymers, chlorotrifluoroethylene-based polymers, FEP, PFA and the like.

Further, the fluorine-containing polymer alloy is a composition having a fluorine-containing polymer (d), a grafting compound which is grafted with the fluorine-containing polymer (d), a radical generator, and a polymer (c) containing no fluorine atom. Alternatively, a composition obtained by adding a fluoropolymer (b ') other than the fluoropolymer (d) to this composition can be melt-mixed in a molding machine at a temperature at which radicals are generated, and molded.

The fluoropolymer alloy is a composition obtained by adding a polymer (c) containing no fluorine atom to the grafted fluoropolymer (a) and further a fluoropolymer (b ') in a molding machine. It can be molded by melt mixing.

The fluoropolymer alloy of the present invention contains the grafted fluoropolymer (a) and the polymer (c), and may or may not contain the fluoropolymer (b). When the fluoropolymer (b) is not contained, the blending ratio is preferably 10 to 90% by weight for the polymer (c) and 10 to 90% by weight for the grafted fluoropolymer (a). When the fluoropolymer (b) is contained, the blending ratio of the polymer (c) is 20 to 70% by weight, the grafted fluoropolymer (a) is 20 to 70% by weight, and the fluoropolymer (b) is 0. It is preferably from 1 to 60% by weight.

The fluoropolymer alloy of the present invention can be used as a molding material for producing various molded products. On this occasion,
Various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, or carbon can be added to the fluorine-containing polymer alloy within a range that does not impair its performance. In addition to the filler, pigments, ultraviolet absorbers, and other optional additives can be mixed depending on the application. These compounding agents can also be compounded in the grafting reaction system to carry out the grafting reaction in the presence of the compounding agent.

Using the fluorine-containing polymer alloy of the present invention as a molding material, a molded product can be obtained by a conventionally known molding method such as injection molding, extrusion molding, coextrusion molding, inflation molding, coating, and transfer molding using a mold. Can be manufactured.

[0064]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Examples 1 to 5 are synthetic examples of grafted ETFE. Examples 6 to 57 are examples of producing a fluoropolymer alloy. Examples 58 to 72 are examples of fluoropolymer alloy molding. Examples 58 to 62 are examples of tube molding with an outer diameter of 5 mm and a wall thickness of 0.5 mm using a tube die. Examples 63 to 67 have a film die thickness of 1
This is an example of film formation of 00 μm. Examples 68 to 72 are molding examples of wire coating having a thickness of 0.3 mm on a core wire having a diameter of 1 mm by a crosshead die for wire coating. Examples 73-85 are comparative examples.

Examples 1 to 5 1.1 parts by weight of the grafting compound and 0.1 part by weight of dicumyl peroxide as a radical generator were added to 100 parts by weight of ETFE as the fluoropolymer (d) in a twin-screw extruder. Is melt-kneaded by using a grafted ETFE which is a grafted fluoropolymer (a)
Pellets of (hereinafter referred to as ETFE (e)) were obtained. In Table 1, the ETFE used (manufactured by Asahi Glass, trade name AFLON LM
740A, AFLON COP C-88A) and its melting point (° C), grafting compound and extrusion temperature (° C).

[Examples 6 to 57] Fluorine-containing polymer (b),
Polymer (c) and ETFE (e) (shown by example number)
And its blending amount, the extrusion temperature (° C.) of the fluorine-containing polymer alloy by the twin-screw extruder, the dispersed particle diameter (μm) of the obtained fluorine-containing polymer alloy pellet observed by an electron microscope,
Tables 2 to 4 show the injection molding temperature (° C) and the tensile strength (kg / cm ² ) of the molded product in the above pellet molding. Parts of the compounding amount are parts by weight. In the fluoropolymer alloy pellet, a component having a volume ratio of 50% or less exists in a dispersed particle state, and the dispersed particle diameter is the average particle diameter (μm).

[Examples 58 to 72] 1.1 parts by weight of vinyltrimethoxysilane as a grafting compound was added to 100 parts by weight of the total amount of the fluorine-containing polymer (b '), the polymer (c) and the fluorine-containing polymer (d). 0.1 part by weight of dicumyl peroxide was melt-kneaded using a twin-screw extruder, and a die was attached to the tip of the twin-screw extruder to form a fluoropolymer alloy. Table 5 shows the fluorine-containing polymer (b '), the polymer (c), the fluorine-containing polymer (d) and their blending amounts, the extrusion molding temperature (° C), and the dispersed particle diameter (μm) of the obtained molded body by electron microscope observation.
Shown in Parts of the compounding amount are parts by weight. In the fluoropolymer alloy molded body, a component having a volume ratio of 50% or less exists in a dispersed particle state, and the dispersed particle diameter is the average particle diameter (μm).

[Examples 73 to 85] Fluorine-containing polymer (d), fluorine-containing polymer (b) and polymer (c)
And its blending amount, the extrusion temperature (° C.) of the fluoropolymer composition by a twin-screw extruder, the dispersed particle diameter (μm) of the obtained fluoropolymer composition pellets observed by an electron microscope,
Table 6 shows the injection molding temperature (° C.) and the tensile strength (kg / cm ² ) of the molded product in the above pellet molding. In addition,
In the fluoropolymer composition pellets, a component having a volume ratio of 50% or less exists in a dispersed particle state, and the dispersed particle diameter is the average particle diameter (μm).

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

[0075]

[Table 6]

[0076]

Industrial Applicability The fluoropolymer alloy of the present invention is a material having both the performance of a fluoropolymer and the performance of various non-fluorine-based polymers such as engineering plastics, and requires low friction and wear. It can be used in various fields as a sliding material and an electrical insulating material with high temperature, high elasticity and high dimensional accuracy.

Claims (10)

[Claims] 1. A fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a bonding group capable of being grafted with the fluorine-containing polymer (d), and a functional group imparting adhesiveness. A fluorine-containing polymer alloy containing a grafted fluorine-containing polymer (a) obtained by grafting a grafting compound having: and a polymer (c) containing no fluorine atom. 2. The fluoropolymer alloy according to claim 1, further comprising a fluoropolymer (b) other than the grafted fluoropolymer (a). 3. The fluoropolymer (b) comprises a homopolymer of a fluoroolefin selected from tetrafluoroethylene and chlorotrifluoroethylene, a copolymer of the fluoroolefin and perfluoro (alkyl vinyl ether), and the fluoro. The fluoropolymer alloy according to claim 2, which is one or more fluoropolymers selected from a copolymer of olefin and hexafluoropropylene. 4. The fluoropolymer alloy according to claim 1, wherein the fluoropolymer (d) is an ethylene-tetrafluoroethylene copolymer. 5. The fluorine-containing polymer alloy according to claim 1, wherein the polymer (c) containing no fluorine atom is a polymer having an amino group. 6. The binding group in the grafting compound is
At least one selected from an organic group having an α, β unsaturated double bond at the terminal, a peroxy group, and an amino group, and the functional group imparting the adhesiveness is a carboxyl group, a carboxylic acid anhydride residue, or an epoxy group. The fluorine-containing polymer alloy according to any one of claims 1 to 5, which is one or more selected from a group and a hydrolyzable silyl group. 7. A fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a bonding group capable of being grafted with the fluorine-containing polymer (d), and a functional group imparting adhesiveness. A method for producing a fluorine-containing polymer alloy, which comprises melt-mixing a grafting compound having a radical generator, a radical generator, and a polymer (c) containing no fluorine atom at a temperature at which radicals are generated. 8. A fluoropolymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a binding group capable of being grafted with the fluoropolymer (d) and a functional group imparting adhesiveness. -Containing grafting compound, radical generator, fluorine atom-free polymer (c), and fluorine-containing polymer (b ') other than fluorine-containing polymer (d)
A method for producing a fluorine-containing polymer alloy, which comprises melt-mixing at a temperature at which radicals are generated. 9. A fluorine-containing polymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a bonding group capable of being grafted with the fluorine-containing polymer (d) and a functional group imparting adhesiveness. Of a fluorine-containing polymer alloy, which comprises melt-mixing and molding a graft-forming compound having a radical, a radical generator, and a polymer (c) containing no fluorine atom in a molding machine at a temperature at which radicals are generated. Method. 10. A fluoropolymer (d) containing a hydrogen atom bonded to a carbon atom of the main chain, a binding group capable of being grafted with the fluoropolymer (d) and a functional group imparting adhesiveness. -Containing grafting compound, radical generator, fluorine atom-free polymer (c), and fluorine-containing polymer (b ') other than fluorine-containing polymer (d)
A method for molding a fluorine-containing polymer alloy, which comprises melt-mixing and molding in a molding machine at a temperature at which radicals are generated.