JPH10182913A - Thermoplastic elastomer composition, its production and molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer(TPE) using a general-purpose fluororesin and fluorine rubber and improved in tensile characteristics while retaining flexibility. SOLUTION: This thermoplastic elastomer composition comprises (A) a crosslinked or uncrosslinked fluorine rubber, (B) a tetrafluoroethylene/ perfluoroalkyl vinyl ether copolymer and/or an ethylene/tetrafluoroethylene copolymer and (C) a partially crosslinked tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride terpolymer having >=1.90 specific gravity, and a weight ratio of the component A to the component B is (90-10):(10-90) and the component C is compounded in an amount of 0. 05-50.0 pts.wt. based on 100 pts.wt. total amount of the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorine-based thermoplastic elastomer composition, a method for producing the same, and a molded product obtained by molding the thermoplastic elastomer composition. In particular, the fluorine-based thermoplastic elastomer composition contains a tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (PFA) and / or an ethylene / tetrafluoroethylene copolymer (ETFE) as a component, and its advantage is that it has good tensile properties. It is easy to manufacture.

[0002]

2. Description of the Related Art A composition comprising a rubber portion and a thermoplastic resin portion is useful as a material which can be melt-molded and has rubber elasticity and flexibility, and is called a thermoplastic elastomer (TPE). Among these, a composition comprising a crosslinked rubber and a thermoplastic resin is particularly called a dynamically crosslinked TPE.
U.S. Pat.Nos. 4,348,502; 4,130,535;
Nos. 4,173,556, 4,207,404, and 4,409,365. Here, a composition using a fluororubber (particularly, crosslinked fluororubber) as a rubber component and a fluororesin as a resin component has heat resistance,
It is expected to be an excellent TPE such as chemical resistance, and several research examples have been reported.

[0003] For example, Japanese Patent Application Laid-Open No. 61-57641 discloses a two-phase composition having a continuous phase and a dispersed phase, wherein the continuous phase contains a minimum of 38% by weight of fluorine. Disclosed are thermoplastic fluorocarbon resins, wherein the dispersed phase is about 50-90% of the two-phase composition and is an amorphous, cross-linked fluoroelastomer. In this publication, as the crystalline thermoplastic fluorocarbon resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polyvinylidene fluoride (PVdF), chlorotrifluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (FE
P) is used.

JP-A-5-14041 discloses a continuous phase of a thermoplastic fluorocarbon resin capable of being melt-molded and a vulcanized dispersed phase of a fluoroelastomer having a vulcanized site selected from a specific derivative group. Wherein the dispersed phase is 50 to 90% by weight based on the total of the continuous phase and the dispersed phase.
A PE composition is disclosed.

[0005]

SUMMARY OF THE INVENTION
In the invention described in JP-A-5-14041, it is necessary to use a special product obtained by copolymerizing glycidyl vinyl ether or the like as the fluororubber. In the invention described in JP-A-61-57641, general-purpose fluororesins and fluororubbers are also used, but the obtained TPE may not show satisfactory tensile strength in some cases.

[0006] TPEs generally tend to be significantly harder with increasing tensile strength. Further, as shown in the examples described later, in the fluorine-based dynamically crosslinked TPE, the maximum strength at the time of tension (in the present application, referred to as the ultimate strength) appears at low elongation, and thereafter, the stress accompanying the elongation increases. May exhibit non-rubber-like tensile properties that are significantly reduced.

An object of the present invention is to provide a TPE using a general-purpose fluororesin or fluororubber, which has improved tensile properties while maintaining flexibility.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies on the above-mentioned objects, and as a result, have found that fluororubber and PFA
And / or FEP and TPE
When the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride of 1.90 or more is blended,
The inventors have found that the tensile properties are improved while maintaining the flexibility substantially, and completed the present invention.

That is, the thermoplastic elastomer composition of the present invention comprises (A) a crosslinked or uncrosslinked fluororubber,
(B) a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and / or an ethylene / tetrafluoroethylene copolymer, and (C) a tetrafluoroethylene / hexafluoropropylene /
It is composed of a vinylidene fluoride terpolymer, the weight ratio of the component (A) to the component (B) is 90 to 10:10 to 90, and the component (C) is composed of the components (A) and (B). It is characterized in that it is blended in a ratio of 0.05 to 50.0 parts by weight based on 100 parts by weight in total.

The process for producing the thermoplastic elastomer composition of the present invention comprises the steps of (A ') 90 to 10 parts by weight of an uncrosslinked fluororubber, (B) a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and / or 10 to 90 parts by weight of ethylene / tetrafluoroethylene copolymer and (C) specific gravity
1.90 or more terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride 0.05 to 50.0
[1st Production Method] Component (A '), (B) and (C) are combined with component (B) tetrafluoroethylene / perfluoroalkylvinyl ether copolymer and / or ethylene / tetra A step of kneading at a temperature equal to or higher than the melting temperature of the fluoroethylene copolymer and cross-linking at least a part of the fluororubber component. [Second Production Method] The components (B) and (C) A step of obtaining a mixture by previously kneading the mixture at a temperature not lower than the melting temperature thereof, and at least partially crosslinking the fluororubber component while kneading the mixture and (A ′) at a temperature not lower than the melting temperature of the mixture. [Third production method] An ethylene / tetrafluoroethylene copolymer of the components (A '), (C) and (B), and further a tetrafluoroethylene / tetrafluoropropylene copolymer Adding 50 parts by weight or less of propylene, kneading at a temperature equal to or higher than the melting temperature of these components, and crosslinking at least a part of the fluororubber component to obtain a mixture; and 10 to 90 parts of the mixture and (B). Parts by weight of tetrafluoroethylene /
A step of kneading the perfluoroalkyl vinyl ether copolymer at a temperature not lower than the melting temperature of the component (B) tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer.

Here, the specific gravity of the component (C) is 1.90 or more,
The use of a tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer is an important requirement of the present invention. This improves the tensile properties without substantially compromising the flexibility of the TPE. These are completely unexpected.

The terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride is -C ₂ F ₄
—, —C ₃ F ₆ —, and —CF ₂ CH ₂ — in which various units are combined at various molar ratios. Of these, —C ₂ F
_{4 -: - C 3 F 6} -: - CF 2 CH 2 - mole ratio of from 0 to
30: 15-60: 40-80, especially, 0-25: 25-50: 50-75
Is a ternary fluororubber. Since the molar ratio of vinylidene fluoride units is high in the ternary fluororubber, the specific gravity is usually in the range of about 1.85 to 1.88. When these tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymers having a specific gravity of less than 1.90 are used, the improvement in tensile properties aimed at by the present invention is not achieved.

Among the terpolymers of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, those having a specific gravity of 1.90 or more used as the component (C) in the present invention are:
For example, it is commercially available from Sumitomo 3M Co., Ltd. under the brand name of THV fluoroplastic. The polymer is the type of the structural unit is identical to the ternary copolymer _{fluororubber, -C 2 F 4 -: -} C 3 F 6 -: - CF 2 CH 2 -
Is 30 to 70:15 to 40:10 to 50, and the molar ratio of vinylidene fluoride units is lower than that of fluororubber. Therefore, the specific gravity is as high as about 1.90 or more, and the heat resistance and chemical resistance are good. Also, while ordinary ternary fluororubber is amorphous at room temperature and does not show a small strength unless crosslinked, a terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.90 or more (hereinafter referred to as “terpolymer”) is used. Terpolymer) is a thermoplastic resin that is hardly plastically deformed at room temperature, has a tensile strength of about 200 kgf / cm ² , and is a thermoplastic resin. In particular, terpolymers having a specific gravity of about 1.95 or more have high chemical resistance, and ordinary tertiary fluororubbers are easily soluble in ketone and ester solvents, but are insoluble in these solvents. Further, the terpolymer in the present invention is different from fluororesins such as PFA and ETFE in that it is difficult to crystallize, and has a crystallinity of about 30% and is amorphous. In the present invention, any component (C) tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer can be used as long as it has a specific gravity of 1.90 or more. It is also possible to use a plurality of the terpolymers having a specific gravity of 1.90 or more in combination. However, tetrafluoroethylene / hexafluoropropylene /
As vinylidene fluoride terpolymer, -C ₂ F ₄ -:
The molar ratio of —C ₃ F ₆ —: — CF ₂ CH ₂ — is approximately 40 to 7
Those in the range of 0:15 to 35:10 to 40 or having a specific gravity of about
It is preferable to use one having a specific gravity of 1.93 or more, especially about 1.95 or more. This significantly improves the tensile properties of the TPE composition. Further, a TPE composition having higher heat resistance and chemical resistance can be obtained. In particular, resistance to ketone and ester solvents becomes remarkable.

As the (A ') uncrosslinked fluororubber used in the present invention, any rubber having a fluorine atom in the molecule can be used without any particular limitation. For example, hexafluoropropylene / vinylidene fluoride binary copolymer (Viton A manufactured by Showa Denko DuPont, Florel manufactured by Sumitomo 3M, etc.), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer (Viton B manufactured by Showa Denko DuPont, Florel manufactured by Sumitomo 3M, etc.), copolymer mainly composed of tetrafluoroethylene / propylene (Afras manufactured by Asahi Glass Co., Japan Synthetic Rubber Co., Ltd.), pentafluoropropylene / fluoride Vinylidene binary copolymer, chlorotrifluoroethylene / vinylidene fluoride binary copolymer, polymer having a perfluoroalkoxy group (such as Daikin Perfluoro manufactured by Daikin), and fluorosilicone rubber (Silastic LS manufactured by Dow Corning)
And the like, and these can be used in combination. As the component (A ') uncrosslinked fluororubber, one having a main chain composed of carbon atoms and containing no chlorine atom, more preferably a binary or ternary fluororubber having vinylidene fluoride as a constitutional unit Alternatively, a copolymer consisting mainly of tetrafluoroethylene / propylene can be used. By using a ternary fluororubber having vinylidene fluoride as a constituent unit, a TPE composition having more excellent tensile properties and chemical resistance can be obtained. By using a binary fluororubber having vinylidene fluoride as a constitutional unit, the compression set of the TPE composition can be reduced. Also, the use of a copolymer consisting primarily of tetrafluoroethylene / propylene makes the TPE composition more flexible.

The (B) tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) used in the present invention is not particularly limited, and has a molecular weight, a melt viscosity, a crystallinity, a terminal group, a melting temperature, and a glass transition temperature. Various PFAs having different polymerization ratios of tetrafluoroethylene: perfluoroalkyl vinyl ether and the like can be used. For example, Daikin Industries AP201,
AP210, AP211, AP230, AP210AS,
340J, 345 manufactured by Mitsui Dupont Fluorochemicals
J, 451HP-J, MP10, Aflon P made by Asahi Glass
66P and the like.

The ethylene / tetrafluoroethylene copolymer (ETFE) is not particularly limited, and has a molecular weight,
Various ETFEs having different melt viscosities, crystallinities, terminal groups, melting temperatures, glass transition temperatures, polymerization ratios of ethylene: tetrafluoroethylene, and the like can be used. As an example, EP521, EP541, EP manufactured by Daikin Industries, Ltd.
610, EP620, Tefzel 280 manufactured by Mitsui Dupont Fluorochemicals, Aflon COP C5 manufactured by Asahi Glass
5A, Aflon COP C55AX, Aflon COP C88
A, Aflon COP C88 APM, Aflon COP Z882
0, Aflon COP C885A and the like.

In the TPE composition of the present invention, component (A) a crosslinked or uncrosslinked fluororubber: component (B)
The composition ratio of FA and / or ETFE (hereinafter sometimes abbreviated as fluororesin) is 90:10 to 10:90 by weight. When the ratio of the component (B) fluororesin is smaller than this,
The melt molding targeted by the present invention is difficult or impossible, and the tensile strength of the obtained TPE composition is low.
If the proportion of the component (A) fluororubber is smaller than this, the resulting TPE composition will have poor flexibility and rubber elasticity. Considering the tensile properties, rubber elasticity, melt molding easiness, etc., the weight ratio of component (A) fluororubber: component (B) fluororesin is in the range of 80:20 to 20:80, especially 75:25.
~ 25: 75 is preferable.

Component (B) PFA: E in fluororesin
There is no particular limitation on the ratio of TFE. By increasing the ratio of PFA, TPE with excellent heat resistance, chemical resistance,
When the ratio of FE is increased, TPE having a large tensile strength and easy to be melt-processed can be obtained. As the proportion of PFA in the component (B) fluororesin is higher, the effect of blending the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride with the specific gravity of component (C) of 1.90 or more increases. In particular, when the component (B) fluororesin comprises only PFA, the effect is remarkable.

The thermoplastic elastomer composition of the present invention contains, in addition to PFA and / or ETFE, a tetrafluoroethylene / hexafluoropropylene copolymer (FEP)
Can also be blended. As a result, the melt processability can be improved without impairing the flexibility of the TPE. The amount of FEP is 1 to 100 parts by weight based on 100 parts by weight of the component (B), or 1 to 50 parts by weight, particularly 10 to 30 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). It is preferable to use a part. The present invention is also characterized in that 1 to 50 parts by weight of a tetrafluoroethylene / hexafluoropropylene copolymer is further blended with respect to a total of 100 parts by weight of (A) and (B). It also includes a plastic elastomer composition.

The composition ratio of the tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer having a specific gravity of component (C) of 1.90 or more is 0.05 parts by weight based on 100 parts by weight of the total of components (A) and (B). 550.0 parts by weight. When the amount of the component (C) terpolymer is less than 0.05 part by weight,
It is difficult to improve the tensile properties aimed at by the present invention, and if it is more than 50 parts by weight, problems such as an increase in hardness, a decrease in melting temperature, and shrinkage of a molded article due to heating occur. Generally, the higher the molecular weight of the component (B) fluororesin used,
The higher the proportion of PFA, the lower the blending amount of the component (C) terpolymer, the more the objective of the present invention can be achieved. However, the hardness, melting temperature, moldability, dimensional stability, etc. In view of the properties, the amount of component (C) is 1 to 30 parts by weight, especially 2 to 100 parts by weight of the total of components (A) and (B).
To 20 parts by weight; or 1 to 80 parts by weight, more preferably 2 to 50 parts by weight, especially 3 to 100 parts by weight of component (B) fluororesin.
It is preferably used in an amount of up to 30 parts by weight.

In the TPE composition of the present invention, the component (A) at least partially crosslinked fluororubber and part of the component (C) terpolymer become a dispersed phase, and the component (C) terpolymer It is preferable that a part of the polymer and the component (B) the fluororesin be a continuous phase. Further, the average particle size of the fluororubber dispersed phase is preferably 30 μm or less, particularly preferably 10 μm or less. By setting the average particle size of the fluororubber dispersed phase at this level, more preferably at 5 μm, particularly at most about 3 μm, the moldability, chemical resistance, tensile properties, etc. of the TPE composition of the present invention can be further improved. Things.

The method for producing the TPE composition of the present invention includes:
It can be obtained by melting and kneading the components (A '), (B) and (C) at a temperature not lower than the melting temperature of the component (B) fluororesin. In the case of using a terpolymer having a specific gravity in the range of about 1.90 to 1.95 as the component (C), the component (A ') uncrosslinked fluororubber and the component (C)
A mixed solution obtained by dissolving and mixing the terpolymer in a solvent such as a ketone (for example, acetone, methyl ethyl ketone, methyl butyl ketone) or an ester (for example, propyl acetate or butyl acetate); (AD2CR, manufactured by Daikin Industries, Ltd.) and removing the solvent. You may use the dispersion of component (C) ternary copolymer (THV350C by Sumitomo 3M etc.).

In the TPE composition of the present invention, the fluororubber component of component (A) may be crosslinked or uncrosslinked, but is preferably at least partially crosslinked. In the case of crosslinking the component (A ') uncrosslinked fluororubber, a crosslinking agent or the like may be added to the melt-kneaded product or the mixed solution and heated.

In a preferred embodiment of the present invention, the fluororubber component of the component (A ') is crosslinked by kneading with the component (B) of the fluororesin or the component (C) of the terpolymer.
It is preferably crosslinked by a so-called dynamic crosslinking technique. This makes it possible to easily obtain a TPE composition in which the component (B) the fluororesin is used as the continuous phase and the (A) at least partially crosslinked fluororubber is used as the dispersed phase. According to this technique, the average particle size of the fluororubber dispersed phase can be adjusted to the above range by adjusting conditions such as a kneading speed and a crosslinking speed. Those skilled in the art will easily find the conditions under which the average particle size of the fluororubber dispersed phase has a desired value.

The crosslinking agent for the fluororubber used in the present invention is not particularly limited, and examples thereof include a polyamine crosslinking agent, a polyol crosslinking agent, and a peroxide. Examples of the polyamine crosslinking agent include triethylenetetramine, hexamethylenediamine, hexamethylenediaminecarbamate, tetraethylenepentamine, 1,3-diaminocyclohexane, 1,3-
Diaminocyclohexane / carbamate, bis (p-aminocyclohexyl), hexamethylenediamine / carbamate (Dupont, Diak No. 1), ethylenediamine / carbamate (Dupont, DiakN)
o. 2), N, N'-dicinamylidene-1,6-hexanediamine (Diak No. 3 manufactured by DuPont), N, N '
-Bis (o-methoxybenzylidene) -1,6-hexanediamine, N, N'-bis (p-methoxybenzylidene)
-1,6-hexylenediamine, N, N'-bis (o-hydroxybenzylidene) -1,6-hexylenediamine, N,
N'-bis (N, N'-dimethyl-p-aminobenzylidene) -1,6-hexylenediamine, 4,4'-bis (aminocyclohexyl) methane carbamate, 4,4'-methylene-bis (2- Chloroaniline) (manufactured by DuPont, Mo
ca) and the like. Examples of the polyol crosslinking agent include bisphenol AF, bisphenol A, p, p'-
Examples include biphenol, 4,4'-dihydroxydiphenylmethane, hydroquinone, dihydroxybenzophenone, and alkali metal salts thereof. The peroxide used depending on the type of fluororubber is, for example, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 1,1-di (t-butylperoxy).
−3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-di (t-butylperoxyisopropyl) benzene, 2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane,
t-butyl peroxyisopropyl carbonate, n-
Butyl-4,4-di (t-butylperoxy) valerate,
α, α'-bis (t-butylperoxy-m-isopropyl) benzene and benzoyl peroxide. As these crosslinking agents, those previously mixed with fluororubber, carbon black, calcium carbonate or the like can be used.

When the fluororubber component is at least partially crosslinked by the polyamine, the elasticity of the TPE composition, particularly elasticity with respect to tensile strength, becomes remarkable. These polyamines are used per 100 parts by weight of the component (A ') fluororubber,
Preferably 0.05-10 parts by weight, more preferably 0.1-8
Parts by weight, particularly preferably 0.5 to 7 parts by weight. 0.0
If the amount is less than 5 parts by weight, the improvement in physical properties due to crosslinking does not appear so much.
Also, when the content is 10 parts by weight or more, the obtained TPE composition may be hardened. At the time of polyamine crosslinking, a crosslinking accelerator such as a quaternary ammonium salt may be used in combination. When the fluororubber component is crosslinked with a peroxide, a TPE composition having a small compression set and excellent heat resistance and chemical resistance can be obtained. The amount of peroxide used is determined by the amount of component (A ')
0.05 to 10 parts by weight, especially 100 parts by weight of fluoro rubber
Preferably it is 1 to 8 parts by weight.

When the amount is less than 0.05 part by weight, the physical properties are not significantly improved by crosslinking, and when the amount is more than 10 parts by weight, the rubber composition may be hardened. At the time of peroxide crosslinking, a crosslinking accelerator such as triallyl isocyanurate or trimethylolpropane trimethacrylate may be used in combination.

In the present invention, when crosslinking is carried out with a polyamine or a peroxide, the components (A ') and (B)
It is preferable to perform dynamic crosslinking by adding a polyamine or a peroxide crosslinking agent after kneading the component (C) and the component (C) to some extent. If the crosslinking agent is present from the start of kneading, the dispersion of each component may be non-uniform. Further, as a cross-linking accelerator, magnesium oxide (MgO), calcium hydroxide (Ca (OH) ₂ ), calcium oxide (CaO),
It is desirable to use an acid acceptor such as lead oxide (PbO). Preferably, 1 to 10 parts by weight, particularly 2 to 8 parts by weight of magnesium oxide, or 1 to 10 parts by weight, particularly 2 to 8 parts by weight of calcium hydroxide is added to 100 parts by weight of the component (B ') fluororubber. use. A plurality of these acid acceptors may be used in combination. The cross-linking accelerator and the cross-linking accelerator may be added simultaneously with the cross-linking agent. However, in order to improve the dispersion, it is preferable to add them at the beginning of the kneading or in the preceding step.

When the fluororubber component is at least partially crosslinked by a polyol, the tensile strength and elongation of the TPE composition increase, and the compression set decreases. In the present invention, various known polyols can be used, but it is preferable to use an aromatic polyol, particularly bisphenol AF. In the polyol crosslinking, an organic phosphonium salt such as benzyltriphenylphosphonium chloride, a quaternary ammonium salt such as tetrabutylammonium chloride, DBU (1,8-diazabicyclo [5,4,0] -7-undecene), hexa It is preferable to use a crosslinking accelerator such as methylenetetramine and / or a crosslinking accelerator such as an acid acceptor in combination. Also, the use of an acid acceptor is essential. As the acid acceptor used, magnesium oxide (MgO), calcium hydroxide (Ca (OH)
₂ ), calcium oxide (CaO), lead oxide (PbO), and the like, but are not limited thereto. A plurality of these acid acceptors may be used in combination. The amounts of the polyol and the crosslinking accelerator are not particularly limited, and those skilled in the art can arbitrarily determine the intended degree of crosslinking and the type of the crosslinking accelerator. However, usually
Preferably, about 0.1 to 10 parts by weight of a polyol and about 0.01 to 10 parts by weight of a crosslinking accelerator, more preferably about 0.5 to 7 parts by weight of a polyol and about 0.05 to 7 parts by weight, per 100 parts by weight of the component (A ') fluororubber. Parts by weight of a crosslinking accelerator, particularly preferably about 1 to 5 parts by weight of a polyol and about 0.1 to 5 parts by weight of a crosslinking accelerator, about 1 to 10 parts by weight, in particular about 2 to 8 parts by weight of magnesium oxide, or It is used with about 1 to 10 parts by weight, especially about 2 to 8 parts by weight of calcium hydroxide. If the amounts of the polyol and the crosslinking accelerator (assistant) are too small, the physical properties are not significantly improved by crosslinking, and if the amounts are too large, it may be difficult to melt-mold the TPE composition obtained.

When the polyol is crosslinked in the present invention, all three components of a crosslinking agent, a crosslinking accelerator and a crosslinking accelerator may be added after the kneading of each component is started. However, in the polyol crosslinking, even if the polyol is present before the start of kneading, a TPE composition in which each component is uniformly dispersed is obtained by adding a crosslinking accelerator and / or a crosslinking promotion auxiliary after the start of kneading. be able to. However, in order to improve the dispersion, a crosslinking accelerator and a crosslinking accelerator, or only the crosslinking accelerator, are added from the start of kneading or in the previous step, and then, After kneading to some extent, it is preferable to adopt a method of adding only a crosslinking agent or a crosslinking agent and a crosslinking accelerator.

The polyol crosslinking agent and the polyamine crosslinking agent may also be used in the presence of the crosslinking accelerator and the crosslinking accelerator described above, in the presence of the above-mentioned crosslinking accelerator, a ternary copolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.90 or more. The coalescence can also be crosslinked. In the TPE composition of the present invention, the component (C) terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.90 or more may be at least partially crosslinked. As a result, the tensile strength and chemical resistance of the TPE composition of the present invention are further improved.

The TPE composition of the present invention can be obtained by the above-mentioned production method. The kneading of each component and the crosslinking of the component (A ') fluororubber component are preferably carried out by the component (B) or the component (C). ) About 1-100 than the melting temperature
° C, more preferably about 5 to 80 ° C, particularly preferably about 10 to 80 ° C.
Perform at 60 ° C higher temperature. If the kneading temperature is just below the melting temperature of the resin component, kneading with each component may not proceed well. On the other hand, if the kneading temperature is too high, the component (A) fluororubber may be deteriorated during the production, leading to a decrease in the physical properties of the obtained TPE composition.

The TPE composition of the present invention can be produced using various known kneading apparatuses. Examples include a Banbury mixer, a pressure kneader, a twin screw extruder, and the like. Those skilled in the art will readily be able to adjust the kneading conditions in various ways to obtain the desired TPE composition. For example, taking a case where a fluororesin having a melting temperature of about 300 ° C. is used as the component (B) and the component (B) is manufactured using a Banbury mixer,
At a temperature of about 300-350 ° C, especially about 310-330 ° C, component (A ') fluororubber, component (B) PFA, component (C) terpolymer, acid acceptor, and optional amounts Of a crosslinking accelerator, an antioxidant, a reinforcing material, and the like. After about 10 seconds to 3 minutes, or after the melt has become almost uniform, a crosslinking agent for fluororubber is added under kneading, for example, in three batches every 1 minute. After adding the cross-linking agent in its entirety,
The desired TPE composition can be obtained by kneading and crosslinking for 3 to 20 minutes, especially for about 5 to 10 minutes.

The order of kneading the component (A ') uncrosslinked fluororubber, component (B) fluororesin, and component (C) terpolymer is not particularly limited. For example, the component (B) and the component (C) terpolymer may be melt-kneaded first, and then the mixture may be kneaded with the component (A ') uncrosslinked fluororubber. The present invention also relates to 100 parts by weight of tetrafluoroethylene / perfluoroalkylvinyl ether copolymer and / or ethylene / tetrafluoroethylene copolymer, which are intermediate products in the production method, and tetrafluoroethylene having a specific gravity of 1.90 or more. Component (A ') uncrosslinked fluororubber and component (C) terpolymer are also included, including a resin composition consisting mainly of 1 to 80 parts by weight of terpolymer / hexafluoropropylene / vinylidene fluoride. And then kneading with the component (B) fluororubber resin. In particular, when PFA and ETFE are used in combination as component (B), component (A ′) uncrosslinked fluororubber, component (C) terpolymer and component (B) ET
FE and kneading can be performed first, and then kneading with PFA can be performed. In that case, the crosslinking of the fluororubber is carried out by the component (C)
It is preferably carried out at the time of kneading with the terpolymer. The component (C) terpolymer generally has a lower softening temperature than the component (B) fluororubber resin. Among fluoro rubber resins, ET
FE has a lower softening temperature than PFA. Therefore, according to this method, kneading and crosslinking can be performed with almost no deterioration of the fluororubber. In addition, conditions such as temperature and time for kneading and crosslinking of the fluororubber can be set more freely. Component (A) and component (C) or ETFE
And then the component (B) PFA and PF
The TPE composition of the present invention can be obtained by mixing at a temperature not lower than the melting temperature of A for a short time, for example, 1 to 5 minutes.
In addition to these, tetrafluoroethylene with a specific gravity of 1.90 or more
A method in which the hexafluoropropylene / vinylidene fluoride terpolymer is added and kneaded later may be adopted.

Although the present invention is not limited by a particular theory, the reason why the present invention is effective is that tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.90 or more used as the component (C) is used. It is considered that the original copolymer functions as a compatibilizer between the component (A) fluororubber and the component (B) fluororesin. The terpolymer is common to PFA and ETFE in that it contains tetrafluoroethylene as a monomer unit (particularly, PFA is similar in that it has a high fluorine content). At the same time, the presence of vinylidene fluoride units in the molecule makes the polarity closer to fluororubber, so the terpolymer is fluororubber, PFA,
It may be highly compatible with each of the ETFEs. In addition, since the terpolymer is essentially amorphous, precipitation of a crystal phase and macroscopic phase separation associated therewith do not occur, and the terpolymer is not tack-free like a normal fluororesin. It is difficult to peel off from the rubber phase or fluororesin phase, and therefore the TPE composition of the present invention containing the terpolymer will exhibit good tensile properties.

The composition of the present invention further comprises reinforcing agents such as carbon black and silica, coloring agents, softeners, reinforcing fibers,
In addition, various additives according to the purpose can be added. It is also possible to mix other resins such as PVdF. Those skilled in the art will be able to determine the type and amount of the various additives and the method of addition depending on the properties of the desired composition.

The composition of the present invention can be formed into O-rings, tubes, hoses, films, and other arbitrary shapes by various known molding methods, for example, injection molding, extrusion molding, cast molding, blow molding and the like. Can be molded into The present invention also encompasses molded articles comprising these compositions of the present invention.

After molding the above molded article according to the present invention, at a temperature lower than the melting temperature, for example, at a temperature of about 150 to 250 ° C.
Heat treatment for up to 50 hours can be performed for secondary vulcanization. By the secondary vulcanization, it is possible to further improve the good mechanical properties that are characteristic of the TPE composition of the present invention and the molded article comprising the same.

As described above, the TPE composition of the present invention comprises:
It has the advantages of excellent mechanical properties represented by good tensile properties, flexibility, good chemical resistance, and easy melt molding. Therefore, the molded article comprising the TPE composition according to the present invention is useful for applications where ordinary fluororubber vulcanizates are difficult to apply, for example, ketone and ester resistant parts, such as O-rings, tubes, hoses and the like. Although the TPE composition of the present invention can also be used as a substitute for a fluororubber vulcanizate, it has the advantage of being capable of being melt-molded, so that it is an article having a complicated and difficult-to-mold shape, and a thickness that is difficult to heat. It is particularly useful as a material for objects and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[0041]

【Example】

Examples 1 to 15 and Comparative Examples 1 to 12 (Preparation of Samples) Among the blended materials shown in Tables 1 to 5, components other than the vulcanizing agent or the vulcanization accelerator were used in combination with Labo Plastomill of Toyo Seiki Co., Ltd. (Mixing volume 60 ml), 260-34
The mixture was kneaded at 80 rpm while being heated to a temperature of about 0 ° C. (Each component was used in an amount such that the total volume became about 50 ml). After about 2 to 3 minutes, the mixture was turned into a homogeneous melt, and the vulcanizing agent or vulcanization accelerator was divided into three portions.
Dosing at 1 minute intervals and at a specific temperature for 5-6 minutes (total
10 minutes) to obtain a sample.

Next, the obtained mixture was injection-molded into a JIS No. 6 dumbbell shape at a cylinder temperature of 280 to 350 ° C. using an injection molding machine. The flow direction of the molten sample during molding was made to coincide with the longitudinal direction of the dumbbell. (Physical property test) Using the sample molded as described above, hardness measurement, tensile test and thermal analysis were performed by the following methods. Measurement of hardness: Shore A hardness was measured according to JIS K6253.
(The hardness test method of the vulcanized rubber) was measured. Tensile test: Conducted at about 25 ° C. and 500 mm / min according to JIS K6251 (test method for tensile strength of vulcanized rubber). The ultimate strength indicates the strength at the point where the tensile stress reaches the maximum, and the breaking strength indicates the strength when the sample breaks.

Table 1 shows the composition of each sample and the results of physical properties tests.
It is shown in FIG. In these tables, E represents an example,
C shows each comparative example. The properties of the fluororubber, FEP and cross-linking agent indicated by the abbreviations and trademarks are as follows. (Description of compounding materials) Fluoro rubber-1: Binary fluoro rubber, peroxide cross-linked grade (Polyamine, polyol cross-linkable) Fluoro rubber-2: Ternary fluoro rubber, specific gravity 1.81, polyamine, polyol cross-linked grade Fluorine Rubber-3: tetrafluoroethylene / propylene /
Vinylidene fluoride copolymer, specific gravity 1.60, peroxide crosslinking grade (Polyamine, polyol crosslinking is also possible) PFA-1: MFR (372 ° C., 5000 g / 10 min):
1.0 to 3.0 PFA-2: MFR (372 ° C, 5000g / 10min): 10
-15 PFA-3: MFR (372 ° C, 5000g / 10min): 20
-30 ETFE-1: MFR (372 ° C, 5000g / 10min):
25-35 ETFE-2: MFR (372 ° C, 5000g / 10min):
4 to 8 FEP-1: MFR (372 ° C, 5000g / 10min): 4.
5 to 8.5 Curative 20: Crosslinking accelerator for polyol crosslinking (pure content
Curative 30: Polyol-based cross-linking agent (50% pure) Peroximon F40: Peroxide cross-linking agent (40% pure) TAIK-M60: Cross-linking aid for peroxide cross-linking (60 pure)
%) Terpolymer-1: Tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer, specific gravity
1.99 (catalog value: 1.98) Terpolymer-2: Tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer, specific gravity
1.96 (Same as catalog value) Terpolymer-3: Tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer, specific gravity
1.93 (catalog value: 1.95) Ternary copolymer-4: Ternary copolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, specific gravity
1.92 (Catalog value: 1.91)

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5] #A, b, c of E16: The composition is the same, but the order of kneading is different.

T-containing terpolymers according to the invention
The tensile strength of the PE composition is higher than that of the TPE composition not containing the terpolymer; the strength at break becomes closer to the ultimate strength due to the blending of the terpolymer. it is obvious. In addition, it was shown that these effects can be exhibited by using any kind of fluororubber, fluororesin, and crosslinking agent. Example 9 and Comparative Example 8
Compared with the above, the ultimate strength and the tensile strength are greatly improved by the addition of a small amount of the component (C) terpolymer.
In Examples and Comparative Examples compared here, the total amount of the component (B) fluororesin and the component (C) terpolymer in the total components hardly changed; and Example 8 and Comparative Examples As shown in FIG. 7, even if the total amount of the (B) fluororesin and the component (C) terpolymer is the same, the tensile properties such as the breaking strength are improved, considering that the tensile properties are improved. It is apparent that the reason for this is not merely the increase in the ratio of the resin component due to the addition of the terpolymer (C). Further, from Example 9 and Comparative Examples 8 and 9, when a terpolymer having a specific gravity of less than 1.90 (fluororubber-2, specific gravity 1.81) was used instead of the terpolymer, the tensile strength was reduced. It turns out that it is not actually improved. Example 7,
8 and Comparative Example 7 show that the effect of the present invention is exerted even in a composition containing FEP as the fourth component.

REFERENCE EXAMPLE 1 This reference example shows that the composition of the present invention contains the component (C)
It indicates that a part of the terpolymer may be crosslinked.

100.0 parts by weight of terpolymer-3, 5.00
Parts by weight of Ca (OH) ₂ and 4.00 parts by weight of Curative 20 were kneaded in a Labo Plastomill at 170-190 ° C. Three minutes, four minutes, and five minutes after the start of kneading, 2.00 parts by weight of bisphenol AF was added in about 1/3 each, and kneading was further performed for 5 minutes (total 10 minutes). When the solubility of the obtained kneaded material in MEK was measured, 48% of the kneaded material was measured.
Dissolved. The untreated terpolymer-3 was MEK
Dissolve completely in It is estimated that about half of the total molecular chains of the sample obtained in this example were crosslinked.

Reference Example 2 100.0 parts by weight of terpolymer-1 and 5.00 parts by weight of Mg
O and 4.00 parts by weight of Curative 20 were kneaded in a Labo Plastomill at 180-210 ° C. After 3 minutes, 4 minutes and 5 minutes from the start of kneading, add 2.00 parts by weight of bisphenol AF in about 1/3 each, and further 5 minutes (total 10 minutes)
Kneaded. The obtained mixture was injection-molded into a JIS No. 6 dumbbell shape, and a tensile test and a thermal analysis were performed. The results are shown in Table 6 together with the test results for the untreated terpolymer-1.

[0053]

[Table 6]

The resin obtained in Reference Example 2 has a higher weight loss start temperature and a higher 10% loss temperature than the untreated resin, and is excellent in heat resistance. Regarding the DTA peak, the untreated product had one peak but had two peaks (the strength was almost 1: 1), and it is clear that the DTA was partially crosslinked.

Example 16 The same operation as in Examples 1 to 15 was carried out except that the kneading order of the fluororubber, PFA, ETFE and the terpolymer was changed.
Melt kneading of each component shown in Table 5 was attempted. Example 16a
The order of kneading in to 16c is as follows. 16a: Same as in Examples 1 to 15 16b: Fluorine rubber, ETFE and terpolymer were added to about 26
The sample was melt-kneaded at 0 to 290 ° C., dynamically crosslinked in the same manner as in Examples 1 to 15, and then melt-kneaded with PFA at a temperature of about 300 to 330 ° C. for 3 minutes to obtain a sample. 16c: PFA, ETFE and terpolymer were added to about 310
The sample was melt-kneaded at a temperature of about 350 DEG C. and dynamically crosslinked at a temperature of about 290 DEG to 310 DEG C. in the same manner as in Examples 1 to 15 using the obtained resin composition and fluororubber to obtain a sample.

The results of the physical property tests are as shown in Table 5. It is clear that the effects of the present invention are exhibited even if the kneading order of the raw materials is changed.

[0057]

As described above, according to the present invention, a fluorine-based thermoplastic elastomer composition having improved tensile strength, rubber-like tensile properties, and easy production, and production of the fluorine-based thermoplastic elastomer composition And a molded article comprising the fluorine-containing thermoplastic elastomer composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 29/10 C08L 29/10 // (C08L 27/12 27:18 23:08 27:16)

Claims (10)

[Claims] (A) a crosslinked or uncrosslinked fluororubber,
(B) a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and / or an ethylene / tetrafluoroethylene copolymer, and (C) a tetrafluoroethylene / hexafluoropropylene /
It is composed of a vinylidene fluoride terpolymer, the weight ratio of the component (A) to the component (B) is 90 to 10:10 to 90, and the component (C) is composed of the components (A) and (B). A thermoplastic elastomer composition, which is blended in an amount of 0.05 to 50.0 parts by weight based on 100 parts by weight in total. 2. The thermoplastic elastomer composition according to claim 1, wherein the tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer of component (C) is partially crosslinked. 3. The thermoplastic elastomer composition according to claim 1, wherein the tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer of the component (C) has a specific gravity of 1.95 or more. 4. The composition further comprises 50 parts by weight or less of a tetrafluoroethylene / hexafluoropropylene copolymer per 100 parts by weight of the total of the components (A) and (B).
The thermoplastic elastomer composition according to claim 1. 5. The thermoplastic elastomer composition according to claim 1, wherein the component (B) is a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer. 6. A tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and / or ethylene /
100 parts by weight of tetrafluoroethylene copolymer and specific gravity
6. A resin composition comprising 1 to 80 parts by weight of a terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, which is contained in the thermoplastic elastomer of claim 1 or more. 7. (A ') 90 to 10 parts by weight of an uncrosslinked fluororubber, and (B) 10 to 90 parts by weight of a tetrafluoroethylene / perfluoroalkylvinyl ether copolymer and / or an ethylene / tetrafluoroethylene copolymer. And (C) specific gravity
1.90 or more terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride 0.05 to 50.0
Parts by weight and kneading the component (B) at a temperature equal to or higher than the melting temperature of the tetrafluoroethylene / perfluoroalkylvinyl ether copolymer and / or the ethylene / tetrafluoroethylene copolymer. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 5, further comprising a step of crosslinking at least a part of the components. 8. (B) 10 to 90 parts by weight of a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer and / or an ethylene / tetrafluoroethylene copolymer;
(C) terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.90 or more
A step of kneading 0.05 to 50.0 parts by weight in advance at a temperature not lower than the melting temperature of the two to obtain a mixture; and mixing the mixture and 90 to 10 parts by weight of (A ') uncrosslinked fluororubber at a temperature not lower than the melting temperature of the mixture. And kneading at a temperature equal to or higher than the melting temperature of the mixture, and crosslinking at least a part of the fluororubber component while kneading at a temperature equal to or higher than the melting temperature of the mixture. A method for producing a plastic elastomer composition. 9. A mixture of (A ′) 90 to 10 parts by weight of an uncrosslinked fluororubber and (C) a tetrafluoroethylene /
0.05 to 50.0 parts by weight of hexafluoropropylene / vinylidene fluoride terpolymer, 90 parts by weight or less of ethylene / tetrafluoroethylene copolymer of (B), and tetrafluoroethylene / hexafluoropropylene copolymer Adding not more than 50 parts by weight of the combined, kneading in advance at a temperature equal to or higher than the melting temperature of these components, and kneading at a temperature equal to or higher than the melting temperature to crosslink at least a part of the fluororubber component to obtain a mixture; And 10 to 90 parts by weight of the tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer of (B) are kneaded at a temperature equal to or higher than the melting temperature of the component (B) tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer. The method for producing a thermoplastic elastomer composition according to any one of claims 1 to 4, comprising a step. 10. A molded article obtained by molding the thermoplastic elastomer composition according to claim 1.