CN1954029A - Thermoplastic polymer composition - Google Patents

Abstract

This invention provides a composition of thermoplastic polymers that is soft, possesses excellent heat and chemical resistance, and exhibits excellent processability. The thermoplastic polymer composition comprises a fluorinated resin (A) and a non-fluorinated crosslinked rubber (B), wherein the fluorinated resin (A) contains a fluorinated vinyl polymer (a), and in the non-fluorinated crosslinked rubber (B), at least a portion of at least one rubber (b) is crosslinked.

Description

Composition of thermoplastic polymers

technical field

The present invention relates to a thermoplastic polymer composition containing a specific fluorine-containing resin and a specific crosslinked rubber, and also to molded articles, sheets, films, laminated structures, and electric wires made of the thermoplastic polymer composition crust.

Background technique

Cross-linked rubber is widely used in automotive parts, home appliance parts, wire sheaths, and medical products because of its excellent heat resistance, chemical resistance, and flexibility. However, when cross-linked rubber is used to make molded products, complex processes are generally required, such as: (1) the process of mixing and processing uncross-linked rubber with cross-linking agent, acid neutralizer and filler, (2) ) A molding process using an extruder or an injection molding machine, (3) a cross-linking process using a press or an oven, etc., so that it takes a long time to obtain a molded product. In addition, because cross-linked rubber cannot be melted after cross-linking, it also has disadvantages such as inability to perform subsequent processing such as fusion, or even recycling.

In order to solve the above-mentioned problems, so-called dynamic cross-linking technology has been developed, in which thermoplastic resins such as polypropylene-based resins, uncross-linked cross-linkable rubber, and cross-linking agents are melt-kneaded in an extruder, and simultaneously to cross-link.

As a dynamically crosslinked rubber (TPV), for example, a rubber having a structure in which crosslinked ethylene-propylene-diene rubber (EPDM) is dispersed in a polypropylene-based resin (see For example: JP-A-06-287368, JP-A-06-256571 and JP-11-228750), some of which have already been put into practical use.

However, the above-mentioned TPV formed of polypropylene-based resin and cross-linked EPDM has no heat resistance above the melting point of the polypropylene-based resin because its matrix is polypropylene-based resin, and its chemical resistance is relatively poor. Difference.

In order to develop TPV excellent in heat resistance and chemical resistance, for example, polyester resin or 4-methyl-1-pentene resin is used as a matrix, and cross-linked rubber is dispersed in the structure, and the obtained rubber has been It is known (for example: JP-A-10-212392 and JP-A-11-269330), but compared with TPVs formed of polypropylene-based resins and cross-linked EPDM, these TPVs are less heat-resistant and Chemical resistance, although improved somewhat, is still not enough, and there are also problems such as softness and poor mechanical properties.

In addition, research has been carried out on TPVs that use fluorine-containing resin as a matrix in the structure and disperse cross-linked fluororubber as cross-linked rubber (refer to for example: Japanese Patent Application Publication No. 61-57641, Japanese Patent Application Publication No. 05-140401 and Japanese Patent Application Kaiping Bulletin No. 06-228397). This TPV has excellent heat resistance and chemical resistance due to the base fluororesin, but it lacks cold resistance, has poor physical properties such as flexibility and compression set, and its molding processability is not sufficient.

Contents of the invention

An object of the present invention is to provide a thermoplastic polymer composition having both excellent heat resistance and chemical resistance, which is flexible and excellent in molding processability.

That is, the present invention relates to a thermoplastic polymer composition that is a thermoplastic polymer composition containing a fluorine-containing resin (A) and a fluorine-free crosslinked rubber (B), and the fluorine-containing resin (A) Containing a fluorine-containing vinyl polymer (a), at least a part of at least one type of rubber (b) is cross-linked in the fluorine-free cross-linked rubber (B).

The melting point of the fluorine-containing vinyl polymer (a) is preferably 120°C to 310°C.

Preferably, the rubber (b) is at least one rubber selected from olefin-based rubber, acrylic rubber, nitrile rubber, silicon-based rubber, polyurethane-based rubber, and epichlorohydrin-based rubber.

The crosslinked rubber (B) is preferably a rubber obtained by subjecting the rubber (b) to a dynamic crosslinking treatment in the presence of the fluorine-containing resin (A) and the crosslinking agent (C).

It is preferable to have a structure in which the fluorine-containing resin (A) forms a continuous phase, and the crosslinked rubber (B) forms a dispersed phase.

The fluorine-containing resin (A) is preferably a copolymer of tetrafluoroethylene and ethylene.

Preferably, the fluorine-containing resin (A) is a copolymer of tetrafluoroethylene and a perfluoroethylenically unsaturated compound represented by the following general formula (1);

CF ₂ =CF-R _f ¹ (1)

In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.

The melting point of the copolymer of tetrafluoroethylene and the perfluoroethylene compound represented by the above general formula (1) is preferably 120°C to 245°C.

Preferably, the fluorine-containing resin (A) contains 19mol% to 90mol% of tetrafluoroethylene units, 9mol% to 80mol% of ethylene units and 1mol% to 72mol% of perfluoroethylenically unsaturated compound units represented by the following general formula (1);

CF ₂ =CF-R _f ¹ (1)

In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.

The fluorine-containing resin (A) is preferably polyvinylidene fluoride.

Preferably rubber (b) is selected from the group consisting of ethylene-propylene-diene rubber, ethylene-propylene rubber, butyl rubber, halobutyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, dimethyl At least one rubber selected from the group consisting of silicone rubber, vinyl methyl silicone rubber, and styrene-diene-styrene block copolymer.

Preferably, the crosslinking agent (C) is at least one selected from the group consisting of organic peroxides, amino compounds, hydroxyl compounds, phenol resin compounds, sulfur-containing compounds, bismaleimide compounds, and quinoid compounds. compound of.

Preferably, the rubber (b) is a difunctional or higher compound having at least one cross-linkable functional group in its molecule, and the cross-linking agent (C) is capable of reacting with the above-mentioned functional group.

Preferably, the thermoplastic polymer composition further contains a flame retardant.

In addition, the present invention relates to a molded article, a sheet, a film, an electric wire sheath, and a LAN cable provided with the above-mentioned thermoplastic polymer composition.

In addition, the present invention relates to a laminated structure having a layer formed from the thermoplastic polymer composition.

Detailed ways

The present invention relates to a thermoplastic polymer composition, which is a thermoplastic polymer composition containing a fluorine-containing resin (A) and a fluorine-free crosslinked rubber (B), and the fluorine-containing resin (A) contains fluorine-containing vinyl In the type polymer (a), at least a part of at least one rubber (b) is cross-linked in the fluorine-free cross-linked rubber (B).

The melting point of the fluorine-containing resin (A) is preferably 120°C to 310°C, more preferably 150°C to 290°C, even more preferably 170°C to 250°C. If the melting point of the fluorine-containing resin (A) is lower than 120° C., the resulting thermoplastic polymer composition tends to have lower heat resistance; In the case of dynamic crosslinking of the rubber (b), it is necessary to set the melting temperature above the melting point of the fluororesin (A), and if the melting point of the fluororesin (A) exceeds 310°C, during the above-mentioned crosslinking, Rubber (b) has a tendency to heat age.

The fluorine-containing resin (A) is not particularly limited as long as it is a polymer containing at least one fluorine-containing vinyl polymer (a). The ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) can be exemplified as follows: tetrafluoroethylene, perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by the general formula (1), chlorotrifluoro Ethylene, trifluoroethylene, hexafluoroisobutylene, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene, and fluoroolefins such as the following general formula (2), etc.

CF ₂ =CF-R _f ¹ (1)

(In formula (1), R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group with 1 to 5 carbon atoms);

CH ₂ =CX ¹ (CF ₂ ) _n X ² (2)

(In formula (2), ^X1 represents a hydrogen atom or a fluorine atom, ^X2 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10).

In addition, examples of the ethylenically unsaturated compound constituting the fluorine-containing ethylenic polymer (a) include fluorine-free ethylenically unsaturated compounds other than the above-mentioned fluoroolefins and perfluoroolefins. Examples of the fluorine-free ethylenically unsaturated compound include ethylene, propylene, and alkyl vinyl ethers. Here, the term "alkyl vinyl ether" refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

From the viewpoint of excellent heat resistance and oil resistance of the resulting thermoplastic polymer composition and ease of molding process, among these examples, the fluorine-containing ethylenic polymer (a) composed of tetrafluoroethylene and ethylene is preferably used, More preferably, a fluorine-containing ethylenic polymer (a) containing 20 mol% to 80 mol% of tetrafluoroethylene units and 80 mol% to 20 mol% of ethylene units is used. In addition, the fluorine-containing ethylenic polymer (a) formed from tetrafluoroethylene and ethylene may contain a third component. As the third component, 2,3,3,4,4,5,5-7 Fluoro-1-pentene (CH ₂ =CFCF ₂ CF ₂ CF ₂ H) and the like.

Preferably, the content of the third component is 0.1 mol% to 3 mol% of the fluorine-containing vinyl polymer (a).

In addition, from the viewpoint of excellent heat resistance, oil resistance and flame retardancy of the resulting thermoplastic polymer composition, and ease of molding and processing, it is preferable that the fluorine-containing vinyl polymer (a) is composed of tetrafluoroethylene and the following Formed by the perfluoroethylenic unsaturated compound represented by general formula (1);

CF ₂ =CF-R _f ¹ (1)

In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.

Specific examples include the following combinations: tetrafluoroethylene/hexafluoropropylene, tetrafluoroethylene/CF ₂ =CF-OR _f ² , tetrafluoropropylene/hexafluoropropylene/CF ₂ =CF-OR _f ² and the like. Examples of CF ₂ =CF-OR _f ² include perfluoro(alkyl vinyl ether) such as perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(propyl vinyl ether), and the like.

In addition, the fluorine-containing ethylenic polymer (a) composed of tetrafluoroethylene and the perfluoroethylenic unsaturated compound represented by the general formula (1) may contain another third component.

From the viewpoint that the molding process of the obtained thermoplastic polymer composition becomes easy, in the case of such a copolymer formed of tetrafluoroethylene and the perfluoroethylenically unsaturated compound represented by the above-mentioned general formula (1), , particularly preferably a melting point of 120°C to 245°C, which can be set by adjusting the copolymerization ratio of tetrafluoroethylene and the perfluoroethylene compound represented by the above general formula (1).

In addition, from the viewpoint of excellent heat resistance and oil resistance of the resulting thermoplastic polymer composition and ease of molding and processing, it is preferable that the fluorine-containing vinyl polymer (a) is composed of tetrafluoroethylene, ethylene and the following general formula (1) Formed from perfluoroethylenically unsaturated compounds;

CF ₂ =CF-R _f ¹ (1)

(In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)

More preferably, the fluorine-containing ethylenic polymer (a) contains 19mol% to 90mol% of tetrafluoroethylene units, 9mol% to 80mol% of ethylene units, and 1mol% to 72mol% of perfluoroethylene represented by general formula (1). Saturated compound unit; more preferably fluorine-containing ethylenic polymer (a) contains 20mol%～70mol% tetrafluoroethylene unit, 20mol%～60mol% ethylene unit, and 1mol%～60mol% all Fluoroethylene type unsaturated compound unit.

In addition, the fluorine-containing ethylenic polymer (a) formed of tetrafluoroethylene, ethylene, and a perfluoroethylenically unsaturated compound represented by the general formula (1) may contain additional components, and examples of the additional components include 2, 3 , 3,4,4,5,5-heptafluoro-1-pentene (CH ₂ =CFCF ₂ CF ₂ CF ₂ H), etc.

The content of the additional component is preferably 0.1 mol% to 3 mol% of the fluorine-containing vinyl polymer (a).

Furthermore, the fluorine-containing vinyl polymer (a) is preferably polyvinylidene fluoride from the viewpoint of excellent heat resistance and oil resistance of the resulting thermoplastic polymer composition and ease of processing and molding.

In the fluorine-free cross-linked rubber (B), at least one rubber (b) is at least partially cross-linked, and the cross-linked rubber does not contain fluorine atoms. In addition, it is preferable that it is a fluorine-free non-silicone rubber. Here, in the fluorine-free non-silicon cross-linked rubber, at least a part of at least one rubber (b) is cross-linked, and the cross-linked rubber does not contain fluorine atoms, and does not contain silicone formed of silicon and oxygen atoms skeleton.

The rubber (b) is not particularly limited, for example, in the case of at least one rubber selected from the group consisting of olefin-based rubber, acrylic rubber, nitrile rubber, silicone-based rubber, urethane-based rubber, and epichlorohydrin-based rubber, It is preferable at the point that the obtained thermoplastic polymer composition can be excellent in heat resistance and oil resistance.

Examples of the olefin-based rubber include diene-based rubber, butyl-based rubber, ethylene-based rubber, and the like.

Examples of diene rubber include natural rubber, isoprene rubber, butadiene rubber, neoprene rubber, styrene-butadiene rubber, and styrene-diene-styrene block copolymers. -Diene rubber, etc. Here, the styrene-diene rubber also includes hydrogenated or acid-modified products thereof.

Examples of the butyl-based rubber include butyl rubber, halogenated butyl rubber such as chlorobutyl rubber, or bromobutyl rubber, and the like.

Ethylene-based rubbers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), polyvinyl chloride, and chlorosulfonated polyethylene rubber.

Acrylic rubber includes acrylic rubber, ethylene acrylic rubber, and the like. Examples of the nitrile rubber include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, and the like. Examples of the silicone rubber include simethicone rubber, vinylmethyl silicone rubber, phenylmethyl silicone rubber, phenylvinylmethyl silicone rubber, fluorosilicone rubber and the like. Examples of the urethane-based rubber include polyester urethane rubber, polyether urethane rubber, and the like.

From the standpoint of superior heat resistance and oil resistance of the resulting thermoplastic polymer composition, among these rubbers, at least one selected from the group consisting of ethylene-propylene-diene rubber, ethylene-propylene-diene rubber, and Propylene rubber, butyl rubber, halobutyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, simethicone rubber, vinyl methyl silicone rubber, and styrene-butadiene-benzene Ethylene block copolymer.

It is necessary for at least a part of the crosslinked rubber (B) to be crosslinked.

The amount of the rubber (b) to be added is preferably 10 to 1000 parts by weight, more preferably 50 to 900 parts by weight, and still more preferably 100 to 800 parts by weight, based on 100 parts by weight of the fluororesin (A). share.

If the rubber (b) is less than 10 parts by weight, the flexibility of the obtained thermoplastic polymer composition tends to decrease. If the amount of the rubber (b) exceeds 1000 parts, the moldability of the obtained thermoplastic polymer composition tends to decrease.

The composition of the thermoplastic polymer of the present invention can be obtained by a production method in which a previously crosslinked fluorine-free cross-linked rubber (B) is melt-kneaded into a fluorine-containing resin (A) and compounded , or in the presence of the fluorine-containing resin (A) and the crosslinking agent (C), the rubber (b) is subjected to dynamic crosslinking treatment under molten conditions, thereby performing a composite production method.

The dynamic cross-linking treatment referred to here means that the rubber (b) is dynamically cross-linked while being melt-kneaded using a Banbury mixer, a pressure kneader, an extruder, or the like. Among these machines, extruders such as twin-screw extruders are preferable because of the feature that extruders such as twin-screw extruders can apply high shearing force. Through the dynamic crosslinking treatment, the phase structure of the fluororesin (A) and the crosslinked rubber (B) and the dispersion of the rubber (b) can be controlled.

As the crosslinking agent (C), it is preferably at least A kind of compound.

Examples of organic peroxides include 2,5-dimethyl-2,5-bis-(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis-( Dialkyl peroxides such as t-butyl peroxide) hexane and dicumene peroxide; hydrogen peroxides such as diisopropylbenzene hydroperoxide and cumene hydroperoxide.

In addition, examples of amino compounds include 6-aminohexyl carbamate (H ₂ N-CO ₂ (CH ₂ ) ₆ NH ₂ ), 1,4-butanediamine, 1,4-diaminocyclohexyl alkanes etc.

In addition, if necessary, a crosslinking auxiliary agent may be used together with the crosslinking agent (C).

The crosslinking agent (C) can be appropriately selected according to the kind of rubber (b) used for crosslinking, the conditions of melt kneading, and the like.

In addition, the rubber (b) preferably has at least one crosslinkable functional group in the molecule. In this case, it is preferable to use a bifunctional or higher compound capable of reacting with the crosslinkable functional group as the crosslinking agent (C).

Examples of the crosslinkable functional group that the rubber (b) may have include hydroxyl group, epoxy group, amino group, carboxyl group, dehydrated carboxyl group, chlorine, bromine, and the like.

In addition, for example, when the crosslinkable functional group possessed by the rubber (b) is an anhydro carboxyl group, an amino compound can be used as the crosslinking agent (C); when the crosslinkable functional group possessed by the rubber (b) is a hydroxyl group, An isocyanate compound or a dehydrated carboxyl group-containing compound can be used as the crosslinking agent (C).

The compounding amount of the crosslinking agent (C) is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, based on 100 parts by weight of the rubber (b). If the crosslinking agent (C) is less than 0.1 parts by weight, the crosslinking of the rubber (b) will not proceed sufficiently, and the heat resistance and oil resistance of the resulting thermoplastic polymer composition will tend to decrease. If it exceeds 10 parts by weight, the moldability of the obtained thermoplastic polymer composition tends to decrease.

The term "under melting conditions" means at a temperature at which the fluorine-containing resin (A) and the rubber (b) melt. The melting temperature varies depending on the glass transition temperature and/or melting point of the fluororesin (A) and rubber (b), but the melting temperature is preferably 120°C to 330°C, more preferably 130°C to 320°C . If the temperature is lower than 120°C, the dispersion between the fluorine-containing resin (A) and the rubber (b) tends to be coarsened; if the temperature exceeds 330°C, the rubber (b) tends to undergo heat aging.

The resulting thermoplastic polymer composition may have the following structure: the fluorine-containing resin (A) forms a continuous phase, and the crosslinked rubber (B) forms a dispersed phase; or the fluorine-containing resin (A) and the crosslinked rubber (B) form a Co-continuous phases, wherein preferably the fluororesin (A) forms the continuous phase, and the crosslinked rubber (B) forms the dispersed phase.

When the rubber (b) forms a matrix at the beginning of dispersion, as the crosslinking reaction progresses, the rubber (b) becomes the crosslinked rubber (B), the melt viscosity increases, and the crosslinked rubber (B) forms a dispersed phase, or Together with the fluorine-containing resin (A), it forms a co-continuous phase.

If such a structure can be formed, the thermoplastic polymer composition of the present invention exhibits excellent heat resistance and oil resistance, and has good molding processability. In this case, the average dispersed particle diameter of the crosslinked rubber (B) is preferably 0.01 μm to 20 μm, more preferably 0.1 μm to 10 μm.

In addition, the ideal form of the thermoplastic polymer composition of the present invention is a structure in which the fluorine-containing resin (A) forms a continuous phase and the crosslinked rubber (B) forms a dispersed phase. For the thermoplastic polymer composition of the present invention, That is, a co-continuous structure of the fluorine-containing resin (A) and the crosslinked rubber (B) may be contained in a part of the structure.

In addition, when a flame retardant is further contained in the thermoplastic polymer composition of the present invention, good flame retardancy is exhibited. In this case, the flame retardant is not particularly limited, and generally used flame retardants can be used arbitrarily. Examples include metal hydroxides such as magnesium oxide and aluminum hydroxide; phosphoric acid-based flame retardants; halogen-containing flame retardants such as bromine-containing flame retardants and chlorine-containing flame retardants, etc., preferably metal hydroxides and phosphoric acid Department of flame retardants. In addition, flame retardant additives such as antimony trioxide and zinc borate, smoke prevention agents such as molybdenum oxide, and the like may be used together.

The compounding amount of the flame retardant is preferably 1 to 100 parts by weight with respect to a total of 100 parts by weight of the fluorine-containing resin (A) and the fluorine-free crosslinked rubber (B). If the above-mentioned flame retardant is less than 1 part by weight, the flame-retardant effect brought by adding the flame retardant is not obvious; if the above-mentioned flame retardant exceeds 100 parts by weight, there is a tendency to deteriorate moldability and flexibility. .

Regarding the proportioning amount of the above-mentioned flame-retardant auxiliary agent, relative to a total of 100 parts by weight of the fluorine-containing resin (A) and the fluorine-free cross-linked rubber (B), the above-mentioned flame-retardant auxiliary agent is preferably 1 to 70 parts by weight, more preferably 5 to 50 parts by weight. If the above-mentioned flame-retardant auxiliary agent is less than 1 weight part, the flame-retardant effect brought by adding the flame-retardant auxiliary agent is not obvious; There is a tendency to deteriorate sexually.

In addition, within the range that does not affect the effect of the present invention, the following substances can be added to the composition of the thermoplastic polymer of the present invention: polyethylene, polypropylene, polyamide, polyester, polyurethane and other polymers; carbonic acid Calcium, talc, clay, titanium oxide, carbon black, barium sulfate and other inorganic fillers; dyes, lubricants, light stabilizers, weather stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, release agents, foaming agents , spices, oils, softeners, etc.

The thermoplastic polymer composition of the present invention can be molded by general molding processing methods, molding processing equipment, and the like. As the molding method, for example, arbitrary methods such as injection molding, extrusion molding, compression molding, blow molding, roll molding, and vacuum molding can be employed. Depending on the purpose of use, the composition of the thermoplastic polymer of the present invention is processed into a molded body of any shape.

Further, the present invention also includes moldings such as sheets, films, and wire sheaths obtained by using the composition of the thermoplastic polymer of the present invention; Layers formed from compositions of , as well as layers formed from other materials.

The above-mentioned wire sheath is generally a material used to provide flame retardancy and prevent mechanical damage in wires/cables for electronic equipment such as computers, so it is a tubular body used to accommodate copper wires and their covering materials. The molding method is not particularly limited, and known methods such as extrusion molding using a crosshead and a single-screw extruder can be mentioned.

Since the electric wire sheath has the above structure, it has good formability and flexibility, and exhibits particularly excellent heat resistance, so it is also very suitable for the sheath of LCC (Limited Comb usable Cable), which has traditionally required high flame retardancy. The electric wire sheath of the present invention can have different thicknesses depending on the application and the like, and is usually within a range of 0.2 mm to 1.0 mm. Since the electric wire sheath of the present invention has a thickness within the above-mentioned range, it is particularly excellent in flexibility.

The electric wire sheath of the present invention is a molded article formed using the thermoplastic polymer composition of the present invention, and is excellent in flame retardancy, flexibility, and the like.

The electric wire sheath of the present invention is not particularly limited, and it can be used for electric wires for electronic equipment wiring, 600-volt insulated wires for electrical appliances, communication cables such as LAN cables, and the like. The above-mentioned LAN cable is equivalent to a LAN cable.

A cable for LAN also belongs to one aspect of the present invention, and the cable for LAN is characterized in that the cable has the wire sheath of the present invention. As a cable for LAN, a plenum cable can be mentioned, and the above-mentioned LCC is very suitable for this cable.

Although the LAN cable of the present invention can be set to an appropriate thickness, it is usually a molded product with a thickness of 0.2 mm to 1.0 mm. The LAN cable of the present invention has the wire sheath of the present invention, so it has flame retardancy and flexibility. And so on.

The thermoplastic polymer composition of the present invention and molded articles, sheets, and films formed from the composition can be used in the following articles: automobile parts, mechanical parts, electrical and electronic parts, office supplies, daily necessities, building materials, miscellaneous goods, etc. . The laminated structure of the present invention can be used as food containers, fuel containers, tubes, hoses, and the like.

Example

Next, the present invention will be described with reference to examples. However, the invention is not limited to the exemplary embodiments in question.

<hardness>

Using the granules of the thermoplastic polymer compositions produced in Examples and Comparative Examples, the granules were compression-molded by a hot press at 250° C. and 10 MPa to make sheet-like test pieces with a thickness of 2 mm. Using these test pieces, A hardness was measured based on JIS-K6301.

<Tensile strength at break and tensile elongation at break>

Using the granules of the thermoplastic polymer composition produced in Examples and Comparative Examples, the granules are compressed and molded by a hot press at 250°C and 10 MPa to make a sheet-like test piece with a thickness of 2mm, from which the thickness is punched out. 2mm, 5mm wide dumbbell-shaped test piece. Using the obtained dumbbell-shaped test piece, using an automatic plotter (manufactured by Shimadzu Corporation), according to JIS-K6301, under the condition of 50 mm/min, the tensile breaking strength and tensile breaking strength at 23° C. were measured. elongation, and tensile breaking strength at 140°C.

<Compression set>

Using the pellets of the thermoplastic polymer composition produced in Examples and Comparative Examples, using an injection molding machine, under the condition of a roller temperature of 250°C, a straight cylindrical molded product with a diameter of 29.0mm and a thickness of 12.7mm was formed. According to JIS-K6301, the compression set was measured after standing for 22 hours under the conditions of a temperature of 120° C. and a compression deformation of 25%.

<Chemical Resistance>

Using the granules of the thermoplastic polymer composition produced in Examples and Comparative Examples, the granules are compressed and molded by a hot press at 250°C and 10 MPa to make a sheet-like test piece with a thickness of 2mm, from which the thickness is punched out. A dumbbell-shaped test piece with a diameter of 2 mm and a width of 5 mm. The obtained dumbbell-shaped test piece was immersed in JIS No. 3 oil, and left at 100° C. for 70 hours. Then, take out the dumbbell-shaped test piece, use an automatic plotter (manufactured by Shimadzu Corporation), according to JIS-K6301, under the condition of 50mm/min, measure the tensile breaking strength at 23°C, and calculate the relative immersion The change ratio of the tensile breaking strength before.

<Flame Retardancy>

Using the granules of the thermoplastic polymer compositions produced in Examples and Comparative Examples, the granules were compressed and molded by a hot press at 250° C. and 10 MPa to make a sheet-like test piece with a thickness of 2 mm, from which the thickness was punched. 2mm, length 50mm, width 50mm sheet test piece. The obtained sheet-shaped test piece was subjected to a combustion test using a cone calorimeter (Cone Calorimeter, manufactured by Toyo Seiki Seisakusho Co., Ltd.), and the heat generation rate and smoke generation rate were determined.

The following fluorine-containing vinyl polymer (a-1), fluorine-containing vinyl polymer (a-2), rubber (b-1), rubber (b-2), rubber ( b-3), rubber (b-4), crosslinking agent (C-1), crosslinking agent (C-2), flame retardant (D) and flame retardant auxiliary (E).

<Fluorinated vinyl polymer (a-1)>

Tetrafluoroethylene-ethylene copolymer (melting point 220°C, manufactured by Daikin Industries, Ltd., NEOFLONETEE EP-620)

<Fluorinated vinyl polymer (a-2)>

Tetrafluoroethylene-hexafluoropropylene copolymer (weight ratio of tetrafluoroethylene to hexafluoropropylene = 75/25; melting point 192°C)

<rubber (b-1)>

Maleic anhydride-modified hydrogenated styrene-butadiene-styrene block copolymer (manufactured by Asahi Kasei Co., Ltd., Toughtec M1943)

<rubber (b-2)>

Ethylene-propylene rubber (manufactured by JSR Co., Ltd., EP57P)

<rubber (b-3)>

Cross-linked silicone rubber powder (Dow Corning Toray Co.Ltd., E-600)

<rubber (b-4)>

Unvulcanized silicone rubber (Dow Corning Toray Co.Ltd., SH851U)

<Crosslinking agent (C-1)>

6-aminohexyl carbamate (manufactured by Daikin Industries, Ltd., V-1)

<Crosslinking agent (C-2)>

2,5-Dimethyl-2,5-bis-(tert-butylperoxy)hexyne-3 (manufactured by NOF Corporation, Perhexyne 25B)

<Flame retardant (D)>

Brominated flame retardant (manufactured by Teijin Chemicals Co., Ltd., FIRE GUARD 7500)

<Flame Retardant Additive (E)>

Antimony trioxide (manufactured by Nippon Seiko Co., Ltd., PATOX-M)

Examples 1-3

After the above-mentioned fluorine-containing vinyl polymer (a-1), rubber (b-1) and crosslinking agent (C-1) are pre-mixed according to the ratio shown in Table 1, they are put into a twin-screw extruder, and the Melt-kneading was carried out under conditions of a cylinder temperature of 260° C. and a screw rotation speed of 100 rpm to produce pellets of thermoplastic polymer compositions.

Embodiment 4～6

After the above-mentioned fluorine-containing vinyl polymer (a-1), rubber (b-2) and crosslinking agent (C-2) are pre-mixed according to the ratio shown in Table 1, they are put into a twin-screw extruder, and the Melt-kneading was carried out under conditions of a cylinder temperature of 260° C. and a screw rotation speed of 100 rpm to produce pellets of thermoplastic polymer compositions.

Morphological examination was carried out by a scanning electron microscope (JEOL Ltd.), and it was found from the results that the thermoplastic polymer compositions obtained in Examples 1 to 6 had the fluorine-containing resin (A) forming a continuous phase and cross-linked rubber. (B) Formation of the structure of the dispersed phase.

Using the particles of the thermoplastic polymer composition obtained, the hardness, tensile strength at break, tensile breaking elongation and compression set were measured by the above-mentioned method, and the chemical resistance was evaluated. The results are shown in Table 1. Show.

Comparative example 1

Pellets of a thermoplastic polymer composition were produced in the same manner as in Example 3 except that the crosslinking agent (C-1) was not added.

Comparative example 2

Pellets of a thermoplastic polymer composition were produced in the same manner as in Example 6 except that the crosslinking agent (C-2) was not added.

According to the results of morphological inspection by scanning electron microscope (JEOL Ltd.), the compositions of thermoplastic polymers obtained in Comparative Example 1 and Comparative Example 2 have rubber (b) forming a continuous phase and containing fluorine The resin (A) forms the structure of the dispersed phase.

Using the particles of the thermoplastic polymer composition obtained, the hardness, tensile strength at break, tensile breaking elongation and compression set were measured by the above-mentioned method, and the chemical resistance was evaluated at the same time. The results are shown in Table 1. Show.

Comparative example 3

30 parts by weight of polypropylene (Grand Polymer Co. Ltd., J106W), 70 parts by weight of ethylene-propylene-diene rubber (JSR (strain), EPDM EP21), 0.5 parts by weight of crosslinking agent (NOF (strain), Parkmil D) After premixing, use a Plastmil mixing device to melt and knead for 10 minutes at 230 ° C and 50 rpm to synthesize a dynamically cross-linked rubber (TPV-1) formed of polypropylene and cross-linked EPDM.

According to the results of morphological examination by a scanning electron microscope (JEOL Ltd.), the resulting thermoplastic polymer composition has polypropylene as a continuous phase and cross-linked ethylene-propylene-diene rubber as a dispersed phase. phase structure.

Using the pellets of the obtained dynamic crosslinked rubber (TPV-1), the hardness, tensile breaking strength, tensile breaking elongation, and compression set were measured by the above-mentioned method, and the chemical resistance was evaluated at the same time. The results are shown in Table 1.

Table 1

Example Comparative example 1 2 3 4 5 6 1 2 3 Proportion amount (parts by weight) Fluorinated vinyl polymer (a) 50 40 30 50 40 30 30 30 Rubber (b-1) 50 60 70 70 Rubber (b-1) 50 60 70 70 Cross-linking agent (C-1) 0.12 0.15 0.20 Cross-linking agent (C-2) 0.10 0.12 0.14 Dynamic cross-linked rubber (TVP-1) 100 Evaluation results Hardness 99 92 84 90 85 78 79 73 78 Tensile strength at break (MPa) at 23°C 19 15 12 20 14 12 7 9 10 Tensile elongation at break (%)23℃ 93 125 140 102 137 156 255 234 155 Tensile breaking strength (MPa)140℃ 12 10 8 13 10 8 0 6 3 Compression set rate (%) 67 54 45 53 46 37 100 40 48 Chemical resistance (%) 68 51 38 73 60 47 0 29 3

Examples 7-10

After premixing the above-mentioned fluorine-containing vinyl polymer (a-2), rubber (b-3), flame retardant (D) and flame retardant additive (E) according to the ratio shown in Table 2, put them into the biaxial In the extruder, melt kneading was carried out under the conditions of a roller temperature of 250° C. and a screw rotation speed of 100 rpm to produce pellets of thermoplastic polymer compositions.

Morphological examination was carried out by a scanning electron microscope (JEOL Ltd.). According to the results, the thermoplastic polymer compositions obtained in Examples 7 to 9 had the fluorine-containing resin (A) to form a continuous phase and were crosslinked. The rubber (B) forms the structure of the dispersed phase.

Table 2 shows the tensile strength at break, tensile elongation at break, and flame retardancy evaluation results measured by the above-mentioned method using the obtained pellets of the thermoplastic polymer composition.

Comparative example 4, 5

The above-mentioned fluorine-containing vinyl polymer (a-2), rubber (b-4), flame retardant (D) and flame retardant auxiliary agent (E), in the case of not adding a crosslinking agent, according to Table 2 After pre-mixing at the indicated ratios, they were put into a twin-screw extruder, and melted and kneaded under the conditions of a roller temperature of 250° C. and a screw rotation speed of 100 rpm to produce pellets of thermoplastic polymer compositions.

Morphological examination was carried out by a scanning electron microscope (Japan Electronics Co., Ltd.). According to the results, the thermoplastic polymer compositions obtained in Comparative Examples 4 and 5 had a fluorine-containing resin (A) to form a continuous phase, and cross-linked The joint rubber (b-4) forms a dispersed phase structure.

Table 2 shows the evaluation results of tensile strength at break, tensile elongation at break, and flame retardancy by the above-mentioned method using the obtained pellets of the thermoplastic polymer composition.

Table 2

Example Comparative example 7 8 9 10 4 5 Proportion amount (parts by weight) Fluorinated vinyl polymer (a-2) 90 80 90 80 90 Rubber (b-3) 10 20 10 20 Rubber (b-3) 10 20 Flame retardant (D) 10 10 10 10 Flame Retardant Additive (E) 5 5 5 5 Evaluation results Tensile breaking strength (MPa)23℃ twenty one 15 19 14 12 10 Tensile elongation at break (%) 23°C 312 256 286 238 112 101 Heat generation rate (kW/m) 37 48 46 53 Smoke rate(l/sec) 3.1 3.8 3.7 4.2

Industrial availability

The thermoplastic polymer composition of the present invention is a composition having both excellent heat resistance and chemical resistance because crosslinked rubber particles are dispersed in the fluorine-containing vinyl polymer, and it is flexible and easy to mold and process. excellent.

Claims (20)

1. A thermoplastic polymer composition, which is a thermoplastic polymer composition containing a fluorine-containing resin (A) and a fluorine-free cross-linked rubber (B), wherein the fluorine-containing resin (A) contains fluorine-containing vinyl type In the polymer (a), at least a part of at least one rubber (b) is cross-linked in the fluorine-free cross-linked rubber (B). 2. The thermoplastic polymer composition according to claim 1, wherein the fluorine-containing vinyl polymer (a) has a melting point of 120°C to 310°C. 3. The thermoplastic polymer composition according to claim 1 or 2, wherein the rubber (b) is selected from olefin-based rubber, acrylic rubber, nitrile rubber, silicon-based rubber, polyurethane-based rubber and surface At least one rubber selected from the group consisting of chlorohydrin-based rubbers. 4. The thermoplastic polymer composition according to any one of claims 1 to 3, wherein the cross-linked rubber (B) is in the presence of the fluorine-containing resin (A) and the cross-linking agent (C). Rubber (b) is a cross-linked rubber subjected to dynamic cross-linking treatment. 5. The thermoplastic polymer composition according to any one of claims 1 to 4, wherein, in its structure, the fluorine-containing resin (A) forms a continuous phase, and the crosslinked rubber (B) forms a dispersed phase . 6. The thermoplastic polymer composition according to any one of claims 1 to 5, wherein the fluorine-containing resin (A) is a copolymer of tetrafluoroethylene and ethylene. 7. The thermoplastic polymer composition according to any one of claims 1 to 5, wherein the fluorine-containing resin (A) is tetrafluoroethylene and perfluoroethylene-type non-aqueous resin represented by the following general formula (1). Copolymers of saturated compounds; CF ₂ =CF-R _f ¹ (1) In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms. 8. The thermoplastic polymer composition according to claim 7, wherein the copolymer of tetrafluoroethylene and the perfluoroethylenically unsaturated compound represented by the general formula (1) has a melting point of 120°C to 245°C. 9. The thermoplastic polymer composition according to any one of claims 1 to 5, wherein the fluorine-containing resin (A) is a copolymer containing 19 mol% to 90 mol% of tetrafluoroethylene Fluoroethylene units, 9mol% to 80mol% of ethylene units, and 1mol% to 72mol% of perfluoroethylenically unsaturated compound units represented by the following general formula (1); CF ₂ =CF-R _f ¹ (1) In the formula, R _f ¹ represents -CF ₃ and/or -OR _f ² , and R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms. 10. The thermoplastic polymer composition according to any one of claims 1 to 5, wherein the fluorine-containing resin (A) is polyvinylidene fluoride. 11. The thermoplastic polymer composition according to any one of claims 1 to 10, wherein the rubber (b) is selected from the group consisting of ethylene-propylene-diene rubber, ethylene-propylene rubber, butyl rubber, halogen A group consisting of butyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, dimethyl silicone rubber, vinyl methyl silicone rubber, and styrene-diene-styrene block copolymer At least one rubber in. 12. The thermoplastic polymer composition according to any one of claims 4 to 11, wherein the crosslinking agent (C) is selected from organic peroxides, amino compounds, hydroxyl compounds, phenolic resin compounds, At least one compound selected from the group consisting of sulfur-containing compounds, bismaleimide-based compounds, and quinoid compounds. 13. The thermoplastic polymer composition according to any one of claims 4 to 12, wherein the rubber (b) is a compound having at least one functional group having at least one crosslinkable functional group in its molecule, And the crosslinking agent (C) can react with the above-mentioned functional groups. 14. The thermoplastic polymer composition according to any one of claims 1 to 13, further comprising a flame retardant. 15. A molded article comprising the thermoplastic polymer composition according to any one of claims 1 to 14. 16. A sheet comprising the thermoplastic polymer composition according to any one of claims 1-14. 17. A film comprising the thermoplastic polymer composition according to any one of claims 1-14. 18. A laminated structure comprising the thermoplastic polymer composition according to any one of claims 1 to 14. 19. An electric wire sheath comprising the thermoplastic polymer composition according to any one of claims 1 to 14. 20. A LAN cable, characterized in that the LAN cable has the wire sheath according to claim 19.