JP3069288B2 - Fluorine-based resin composition, method for producing the same, and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluororesin composition which can be melt-molded, has rubber elasticity, has good tensile properties and is excellent in heat resistance, a process for producing the same, and the fluororesin composition. A molded article comprising:

[0002]

2. Description of the Related Art A composition comprising a rubber and a thermoplastic resin is useful as a material which can be melt-molded and has rubber elasticity and flexibility, and is called a thermoplastic elastomer. Among these, a composition comprising a crosslinked rubber and a thermoplastic resin is particularly called a dynamically crosslinked thermoplastic elastomer. In recent years, various compositions having a composition of Coran
U.S. Pat.Nos. 4,348,502, 4,130,535, 4,17
Nos. 3,556, 4,207,404 and 4,409,365 are known. Here, a resin composition in which the rubber component is a fluororubber (particularly, a crosslinked fluororubber) and the thermoplastic resin component is a fluororesin is expected to be a thermoplastic elastomer having excellent heat resistance, chemical resistance, and the like. , Several studies 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. Characterized essentially by a thermoplastic fluorocarbon resin, wherein said dispersed phase comprises an amorphous, cross-linked fluoroelastomer, said dispersed phase comprising about 50-90% of said two-phase composition. A two-phase composition is disclosed. In this publication, as a crystalline thermoplastic fluorocarbon resin, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer (PFA), polyvinylidene fluoride (PVdF), chlorotrifluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer (FE
P) is used.

JP-A-5-14041 discloses a vulcanized dispersion of a continuous phase of a melt-moldable thermoplastic fluorocarbon resin and a fluoroelastomer having a vulcanized site selected from specific derivative groups. Disclosed is a fluorine-containing thermoplastic elastomer composition comprising a phase, wherein the dispersed phase is 50 to 90% by weight based on the total of the continuous phase and the dispersed phase.

[0005]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
As in JP 61-57641, PF
When A is used, the kneading temperature with the fluororubber must be about 300 ° C. or higher, and the deterioration of the fluororubber during kneading cannot be ignored when manufacturing using a general-purpose device. In the examples of the publication, kneading of both components is performed under nitrogen. Further, the resin composition containing PVdF as a resin component has drawbacks in that the Shore A hardness is as high as about 90 and the elongation at break in tension is small. Further, the resin composition obtained using chlorotrifluoroethylene has a disadvantage that the decomposition temperature is low and heat resistance is hardly obtained. When FEP is used as the fluororesin, the above problems are somewhat reduced, but the tensile strength is still unsatisfactory unless expensive perfluoro rubber is used as the fluororubber.

The composition described in JP-A-5-14041 has good properties such as hardness, tensile strength and elongation, but uses a special product obtained by copolymerizing glycidyl vinyl ether or the like as a fluorine rubber. There is a need. Production of the composition is also 300
It is considered to be performed at about ° C, and the deterioration of the fluoro rubber during that time cannot be ignored.

[0007] A resin composition obtained by using a normal fluororesin such as PFA has a disadvantage that it has a high melt viscosity and is difficult to mold. Difficulties with melt molding are one of the reasons that fluorine-based dynamically crosslinked thermoplastic elastomer compositions are not marketed.

[0008]

Means for Solving the Problems The present inventors have a specific gravity of 1.9.
3 or more thermoplastic resins , tetrafluoroethylene /
When the hexafluoropropylene / vinylidene fluoride terpolymer is used as the fluororesin component, the above-mentioned deterioration during kneading and the problem of the flexibility of the product do not occur, the tensile properties are good, and the melt molding is easy. It has been found that a suitable resin composition can be obtained.

That is, the present invention relates to (A) 10 to 90% by weight of a terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, which is a thermoplastic resin having a specific gravity of 1.93 or more, and (B) a specific gravity of 1.91.
A resin composition comprising: 90 to 10% by weight of a crosslinked or uncrosslinked fluororubber.

The method for producing the resin composition of the present invention has a specific gravity of 1.9.
3 or more thermoplastic resins, tetrafluoroethylene /
10 to 90% by weight of a hexafluoropropylene / vinylidene fluoride terpolymer and 90 to 10% by weight of an uncrosslinked fluororubber having a specific gravity of 1.91 or less, together with optional components, are mixed with the above tetrafluoroethylene / hexafluoropropylene / a step of kneading at a temperature above the melting temperature of vinylidene fluoride terpolymer, while kneading in the temperature, characterized in that comprising the step of crosslinking at least a part of the fluororubber ingredient. Further, the molded article of the present invention is a molded article molded using such a resin composition.

Here, the use of a terpolymer of tetrafluoroethylene / hexafluoropropylpyrene / vinylidene fluoride (hereinafter referred to as terpolymer) having a specific gravity of 1.93 or more as a fluororesin component is described in the present invention. This is an important requirement of the invention. When a terpolymer is used, PDdF, ethylene /
Hardness and poor rubber elasticity when using a tetrafluoroethylene copolymer (ETFE) or the like are improved. Also, P
Deterioration of fluoro rubber when using FA etc., deterioration of physical properties,
Melt molding difficulties are improved. The specific gravity of the terpolymer is
If it is less than 1.93, the resulting resin composition has low strength, and melt molding is impossible or extremely difficult. On the other hand, when the terpolymer having a specific gravity of 1.93 or more according to the present invention is used, the resin is easily melt-molded without deterioration of the fluororubber during production, and is flexible and stretchable, and has good tensile properties and heat resistance. A composition can be obtained. This is completely unexpected.

[0012] The present invention specific gravity 1.93 or more terpolymers to be used in, for example, from Sumitomo 3M (Co.), is commercially available under the trade name of THV fluoroplastic, -C ₂ F _{4
-: - C 3 F 6 -} : - CF 2 CH 2 - molar ratio schematic of 40
~ 70: 15 ~ 40: 10 ~ 40 and normal ternary fluororubber (molar ratio 0 ~ 30: 25 ~ 60: 40 ~ 80, specific gravity 1.80 ~ 1.91
), The molar ratio of vinylidene fluoride units is lower.

The terpolymer of the present invention has such a low molar ratio of vinylidene fluoride units, and therefore has a high specific gravity of about 1.93 or more, and has good heat resistance and chemical resistance. Also, the ternary fluororubber is amorphous at room temperature,
The terpolymer according to the present invention does not show a small strength unless crosslinked, but does not show rubber elasticity at room temperature, has a tensile strength of about 200 kgf / cm ² , and is a thermoplastic resin. In particular, those having a specific gravity of about 1.95 or more have high chemical resistance, and the ternary fluororubber is easily soluble in ketone-based and ester-based solvents, but is insoluble in these solvents. On the other hand, unlike fluorinated resins such as PFA and ETFE, they are hardly crystallized, and the terpolymer in the present invention has a crystallinity of about 30% and is essentially amorphous.

As the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride (A) in the present invention, any copolymer having a specific gravity of 1.93 or more can be used. It is also possible to use a plurality of original copolymers in combination. In particular, the specific gravity is about
It is preferable to use a terpolymer of 1.95 or more, and it is possible to obtain a resin composition having higher heat resistance and higher chemical resistance. In particular, resistance to ketone and ester solvents becomes remarkable.

The uncrosslinked fluororubber of the component (B ') used in the present invention is not particularly limited, but has a specific gravity of 1.93 or more.
(A) Specific gravity of 1.91 or less so that it can be more clearly distinguished from component
The following is assumed. As an example of such unvulcanized fluoro rubber ,
Hexafluoropropylene / vinylidene fluoride binary copolymer (Viton A, Sumitomo 3M, manufactured by Showa Denko DuPont)
Co., Ltd.), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer (Viton B, Sumitomo 3M, manufactured by Showa Denko DuPont)
Co., Ltd.), tetrafluoroethylene / propylene copolymer (Asahi Glass Co., Ltd., Nippon Synthetic Rubber Co., Ltd.)
Etc.), pentafluoropropylene / vinylidene fluoride binary copolymer, chlorotrifluoroethylene / vinylidene fluoride binary copolymer, perfluoroalkoxy group-containing polymer (Daikin Perflo And fluorosilicone rubber (Silastic LS manufactured by Dow Corning Co., Ltd.), and a plurality of fluorine rubbers can be used in combination.

Preferred uncrosslinked fluororubbers include those having a main chain of carbon atoms and containing no chlorine atoms, and more preferred are binary or ternary systems having a vinylidene fluoride unit as a constitutional unit. Fluoro rubber and tetrafluoroethylene / propylene copolymer are exemplified. By using vinylidene fluoride-based ternary fluororubber, a resin composition with more excellent tensile properties and chemical resistance can be obtained, and by using the same type of binary fluororubber, compression set can be reduced. Can be reduced.
Further, by using the tetrafluoroethylene / propylene copolymer, the resin composition becomes more flexible.

The composition ratio of the terpolymer of the component (A) to the fluororubber of the component (B) in the resin composition of the present invention is from 10:90 to 90:10 by weight. If the ratio of the component (A) terpolymer is smaller than this, melt molding becomes difficult or impossible, and the tensile strength of the resin composition decreases. If the ratio of the component (B) fluororubber is smaller than this, the resin composition becomes poor in flexibility and rubber elasticity. Considering the tensile properties, rubber elasticity, ease of melt molding, etc., the weight ratio is about 20: 80-80: 20, especially 25: 75-75:
It is preferably about 25.

In the resin composition of the present invention, the ternary copolymer having a specific gravity of 1.93 or more as the component (A) becomes a continuous phase,
Preferably, the at least partially crosslinked fluororubber is the dispersed phase. And the average particle size of the fluororubber dispersed phase is preferably 30 μm or less, more preferably 10 μm or less,
More preferably, it is 5 μm or less. By reducing the average particle size of the fluororubber dispersed phase, the moldability, chemical resistance, and tensile properties of the resin composition can be further improved.

The resin composition of the present invention can be produced by a known method. For example, by melting and kneading the component (A) terpolymer having a specific gravity of 1.93 or more and the component (B ') uncrosslinked fluororubber at a temperature not lower than the melting temperature of the component (A) terpolymer. When the specific gravity of the component (A) terpolymer is in the range of about 1.93 to 1.95, the component (A) terpolymer and the component (B ′) are not used. It is also produced by dissolving and mixing a crosslinked fluororubber with a solvent such as a ketone (eg, acetone, methyl ethyl ketone, methyl butyl ketone) and an ester (eg, propyl acetate, butyl acetate), and removing the solvent. be able to. In the resin composition of the present invention, the fluororubber component may be crosslinked or uncrosslinked, but is preferably at least partially crosslinked. In the case of crosslinking the component (B) fluororubber component, 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 is preferably obtained by a so-called dynamic crosslinking technique of crosslinking under kneading with a fluororesin. This makes the component (A) terpolymer a continuous phase,
A resin composition containing at least partially crosslinked fluororubber as a dispersed phase can be easily obtained. According to this technique, it is possible to adjust the conditions such as the kneading speed and the cross-linking speed so that the average particle size of the fluororubber dispersed layer is within the above range. 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.

As the crosslinking agent for fluororubber used in the present invention, a polyamine crosslinking agent such as triethylenetetramine, hexamethylenediamine, hexamethylenediamine-carbamate, tetraethylenepentamine, 1,3-diaminocyclohexane, 1,3 -Diaminocyclohexane carbamate, bis (p-aminocyclohexyl), hexamethylenediamine carbamate (DuPont
iak No. 1), ethylenediamine carbamate (Diak No. 2 from DuPont), N, N'-dicinamylidene-1,6-hexanediamine (Diak No. 3 from 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) (Moca from DuPont) , Cumene diamine, m-phenylenediamine, p-phenylenediamine and the like; polyol crosslinking agents such as bisphenol AF, bisphenol A, p, p'-biphenol, 4,4'-dihydroxydiphenylmethane, hydroquinone, dihydroxybenzophenone and alkali metals thereof And the like. Depending on the type of fluoro rubber, peroxide,
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-butylperoxy) Isopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyisopropyl carbonate, n-butyl-4,4-di (t-butylperoxy) valerate, α, α′- Crosslinking can also be carried out using bis (t-butylperoxy-m-isopropyl) benzene, benzoyl peroxide or the like. As these crosslinking agents, those previously mixed with fluororubber, carbon black, calcium carbonate or the like can also be used.

When the fluororubber component is at least partially crosslinked by the polyamine, the resin composition has a higher tensile strength and, moreover, has a remarkable elasticity, particularly elasticity against tensile strength. These polyamines can be used as component (B)
Preferably, about 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, particularly preferably 2 to 10 parts by weight per 100 parts by weight of the fluororubber.
Use up to 7 parts by weight. If the amount is less than about 0.5 part by weight, the improvement in physical properties by crosslinking is not so significant, and if the amount is about 10 parts by weight or more, the obtained resin composition may be hardened. At the time of 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 resin composition having small compression set and excellent heat resistance and chemical resistance can be obtained. The amount of peroxide is about 0.5 to 100 parts by weight of the component (B) fluororubber.
It is preferred to use 10 parts by weight, especially about 1 to 8 parts by weight. about
If the amount is less than 0.5 part by weight, the physical properties are not significantly improved by crosslinking, and if the amount is more than 10 parts by weight, the rubber composition may be hardened. At the time of peroxide crosslinking, triallyl isocyanurate,
A crosslinking accelerator such as 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 ')
After kneading to some extent, it is preferable to add a polyamine or peroxide crosslinking agent to perform dynamic crosslinking.
If the crosslinking agent is present from the start of kneading, the dispersion of the component (A) and the component (B) may be non-uniform. In addition, as a crosslinking promoting aid, magnesium oxide (MgO), calcium hydroxide (Ca (OH) ₂ ), calcium oxide (Ca
It is desirable to use an acid acceptor such as O) and lead oxide (PbO). Preferably, about 1 to 10 parts by weight, especially about 2 to 8 parts by weight of magnesium oxide, or about 1 to 10 parts by weight, especially about 2 to 8 parts by weight of water, per 100 parts by weight of the component (B) fluororubber. Use calcium oxide. A plurality of these acid acceptors may be used in combination. Crosslinking accelerator, crosslinking accelerator,
It may be added simultaneously with the cross-linking agent, but it is preferable to add it at the beginning of kneading or in a previous step in order to improve the dispersion.

When the fluororubber component is (at least partially) crosslinked by a polyol, the resin composition has an increased tensile strength and elongation and a reduced compression set. 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, a quaternary ammonium salt,
It is preferable to use a crosslinking accelerator such as DBU (1,8-diazabicyclo [5,4,0] -7-undecene) and hexamethylenetetramine 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 to be used, magnesium oxide (MgO), calcium hydroxide (Ca (OH) ₂ ), calcium oxide (Ca
O), lead oxide (PbO), and the like, but are not limited thereto. A plurality of these acid acceptors may be used in combination. There is no particular limitation on the amounts of the polyol and the crosslinking accelerator, and those skilled in the art will understand that
It can be arbitrarily determined according to the type of the agent and the like. However, usually, about 0.1 to 10 parts by weight of polyol and about 0.1 to 10 parts by weight of component (B) fluororubber are preferably used.
About 10 to 10 parts by weight of a crosslinking accelerator, more preferably about 0.5 to 7 parts by weight of a polyol and about 0.3 to 7 parts by weight of a crosslinking accelerator, particularly preferably about 1 to 5 parts by weight of a polyol and about 0.5 to 5 parts by weight.
Parts by weight of the crosslinking accelerator, about 1 to 10 parts by weight, especially about 2 to 8 parts by weight
Used with parts by weight of magnesium oxide, or 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 improvement of the physical properties by crosslinking is not appreciably exhibited. If the amounts are too large, melt molding of the obtained resin composition may be difficult.

When polyol crosslinking is carried out in the present invention, all three components of a crosslinking agent, a crosslinking accelerator and a crosslinking accelerator may be added at the start of kneading of components (A) and (B '). However, in polyol crosslinking, even if the polyol is present before the start of kneading, the components (A) and (B) can be uniformly mixed by adding a crosslinking accelerator and / or a crosslinking promoting aid after the start of kneading. To obtain a resin composition dispersed therein. However, in order to improve the dispersion, a crosslinking accelerator and a crosslinking promoting aid or only a crosslinking promoting aid are added from the start of kneading or in the previous step, and then the component (A) ) And the component (B ') are kneaded to some extent, and 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.
Component (A) A terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.93 or more can also be crosslinked. In the resin composition of the present invention, component (A), a terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride having a specific gravity of 1.93 or more, may be at least partially crosslinked. Thereby, the tensile strength and chemical resistance of the resin composition of the present invention are further improved. The present invention also provides, in addition to the above resin composition, a specific gravity which is at least partially crosslinked by a polyol or a polyamine.
The tertiary resin of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride of 1.93 or more is also included.

The resin composition of the present invention can be obtained by the above-mentioned production method, and comprises the components (A) and (B ').
And the crosslinking of the component (B ') fluororubber component is preferably carried out at about 10 to 100 ° C, more preferably about 20 to 80 ° C, more preferably at a melting temperature of the terpolymer of component (A). It is preferably carried out at a temperature about 30-60 ° C. higher. If the kneading temperature is just below the melting temperature of component (A), kneading of component (A) and component (B) may not proceed well. Also,
Specific gravity of 1.93 to 1.96 as a terpolymer of component (A)
When the melting temperature is about 120 ° C. to about 150 ° C., the crosslinking of the component (B) fluororubber may be insufficient. On the other hand, if the kneading temperature is too high, the component (B) fluororubber is deteriorated during production, which may lead to a decrease in physical properties of the obtained resin composition.

The resin 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. It will be easy for those skilled in the art to adjust the kneading conditions in various ways to obtain the desired resin composition. For example,
For example, when a ternary copolymer having a specific gravity of 1.98 and a melting temperature of about 180 ° C. is used as the component (A) and is produced using a Banbury mixer, at a temperature of about 185 to 280 ° C., particularly about 200 to 240 ° C., The component (A) terpolymer, component (B ') fluororubber, acid acceptor, and optional amounts of a crosslinking accelerator, an antioxidant, a reinforcing material, and an alkenylalkoxysilane are kneaded. After about 10 seconds to 3 minutes, or after the melt is almost uniform, a crosslinking agent for fluororubber is kneaded, for example,
Add 3 times every 1 minute. After adding the cross-linking agent in its entirety, kneading and cross-linking at the above-mentioned temperature for about 3 to 20 minutes, particularly about 5 to 10 minutes, the desired resin composition can be obtained.

It is to be noted that blends of two or more tertiary fluororubbers and blends of tertiary fluororubbers with other fluororubbers are known. Essentially different from blended rubber and blending methods. These blended rubbers are prepared by using an amorphous fluororubber having a specific gravity of less than 1.93, usually less than 1.90 as a ternary copolymer, and kneading it with a rubber roll, a closed mixer or the like. On the other hand, even if the component (A) terpolymer having a specific gravity of 1.93 or more and the component (B) fluororubber are kneaded at room temperature with a rubber roll, a closed mixer or the like according to a usual fluororubber blending method, the component (B ) Only a composite in which the component (A) terpolymer is roughly dispersed in fluororubber can be obtained. Conventional known fluororubber blends develop strength only after being vulcanized (crosslinked) and are not thermoplastic after crosslinking, whereas the resin composition of the present invention is a non-crosslinked vulcanized fluororubber. It shows a strength equal to or higher than that of, and is thermoplastic even if crosslinked. In particular, among the resin compositions of the present invention, those using a resin having a specific gravity of about 1.95 or more as the terpolymer of component (A) and those crosslinked to some extent have not only excellent strength but also chemical resistance. It differs from ordinary fluororubber blends in that it is good and is not easily attacked by solvents such as ketones and esters.

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 1.93 or more used as the component (A) is used. It is believed that the source copolymer has the amorphous properties, adhesion, melting temperature, flexibility, and molecular structure suitable for the blend as in the present invention. Since the terpolymer is essentially amorphous, no precipitation of a crystal phase and the accompanying macroscopic phase separation do not occur, and the terpolymer is not tack-free like a normal fluororesin. The resin composition of the present invention containing polymerization as a component is not easily broken by an external force such as tension,
It will show good tensile properties. The terpolymer is
Unlike ETFE, PFA, etc., it melts at about 150-180 ° C. Therefore, in the melt-kneading step, the fluororubber hardly deteriorates due to exposure to high temperatures. Also, PV
Unlike dF and the like, since it is flexible, the obtained resin composition does not become very hard. Further, since the terpolymer has a vinylidene fluoride unit and a tetrafluoroethylene unit in the molecule, it is well compatible with a general-purpose vinylidene fluoride rubber and a tetrafluoroethylene / propylene copolymer rubber, Alternatively, it is considered that physical properties such as tensile properties are improved as a result of part of the resin component being cross-linked or co-cross-linked with fluororubber. At the same time, since the constituent ratio of vinylidene fluoride units is low in the terpolymer composed of the above three units, the component (A) is significantly crosslinked in the step of crosslinking the fluororubber like ordinary fluororubber. And a continuous thermoplastic phase would result.

The alkenylalkoxysilane and / or aminoalkylalkoxysilane can be further added to the resin composition of the present invention. By adding these silane compounds, the tensile properties and the like of the resin composition of the present invention can be further improved. These silane compounds are preferably added before or during the mixing of the component (A) and the component (B '). Usually, at least a part of the added alkenylalkoxysilane reacts with a fluorine rubber chain, a functional group on the surface of carbon black, or the like to form another silane compound. The alkenylalkoxysilane and aminoalkylalkoxysilane are not particularly limited, and various known ones can be used. It is also possible to use a plurality of these silane compounds in combination. Preferably, monoalkenyl trialkoxysilanes, especially vinyltrialkoxysilanes, allyltrialkoxysilanes, such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane; or monoaminoalkyl trialkoxysilane For example, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Aminopropyltrimethoxysilane, γ- (polyethyleneamino) propyltrimethoxysilane and the like are used.
These silane compounds comprise a total of 10 components (A) and (B ').
0 parts by weight, preferably about 0.01 to 10 parts by weight, more preferably about 0.1 to 5 parts by weight, particularly preferably about 0.3 to 5 parts by weight.
Use 3 parts by weight. If the addition amount of the silane compound is less than about 0.01 part by weight, the effect of addition is not so much exhibited, and
If the amount exceeds the weight part, the strength of the resin composition may be reduced.

The resin composition of the present invention may further contain a reinforcing agent such as carbon black and silica, a coloring agent, a softening agent, a reinforcing fiber, and other various additives depending on purposes. Those skilled in the art will be able to determine the types and amounts of various additives and the method of addition depending on the properties of the intended resin composition.

The resin composition of the present invention can be prepared by various known molding methods such as injection molding, extrusion molding, cast molding, blow molding, etc.
It can be formed into a hose, film, or any other shape. The present invention also includes a molded article comprising the resin composition of the present invention.

After the above-mentioned molded article according to the present invention is melt-molded,
The secondary vulcanization can be performed by heating at a temperature lower than the melting temperature, for example, at a temperature lower by about 30 ° C. than the melting temperature for 2 to 24 hours. Further, the fluororubber component and the resin component can be further cross-linked by irradiating a radiation, an electron beam or the like.
By the secondary vulcanization, it is possible to further improve the good mechanical properties characteristic of the resin composition of the present invention and the molded article comprising the same.

As described above, the resin composition of the present invention has excellent mechanical properties represented by good tensile properties, flexibility,
It has the advantage that it has good chemical resistance and is easy to melt-mold. Therefore, the molded article made of the resin composition according to the present invention is useful for applications where ordinary fluororubber vulcanizates are difficult to apply, for example, parts for ketones and esters, for example, O-rings, tubes, hoses and the like. The resin composition of the present invention can also be used as a substitute for a fluororubber vulcanizate, but has the advantage of being capable of being melt-molded, so that it is an article having a complicated shape that is difficult to mold, and a thickness that is difficult to pass 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.

[0036]

【Example】

Examples 1 to 6 and Comparative Examples 1 to 6 (Preparation of Samples) Unless otherwise specified, the samples were produced by the following methods.

Of the ingredients shown in Tables 1 and 3, components other than the vulcanizing agent or the vulcanization accelerator were heated to 80 r using a Labo Plastomill (mixing amount: 60 ml) of Toyo Seiki Co., Ltd.
The mixture was kneaded at pm (each component was used in an amount such that the total volume was about 50 ml). After about 2 to 3 minutes, when the mixture has become a homogeneous melt, the vulcanizing agent or vulcanization accelerator is divided into three portions and charged at intervals of about 1 minute. The mixture was kneaded for 6 minutes (total 10 minutes) to obtain a sample (approximate kneading temperature and time are shown in Tables 2 and 4). The obtained mixture was passed between cold rolls to form a sheet, and then subjected to the following molding and testing.

(Molding of Sample) Using an injection molding machine, J
It was injection molded into the shape of a dumbbell IS6. The flow direction of the molten sample during molding was made to coincide with the longitudinal direction of the dumbbell. In addition, as the temperature at the time of molding, a temperature close to the minimum was selected as long as it could be easily injected to some extent. This is to prevent both decomposition of the sample and deterioration in physical properties that can be caused by uneven melting and coagulation. Table 2 shows the cylinder temperature of the molding machine during molding and the ease of injection molding.
It is shown in FIG. Here, the state represented by each stage of injection molding easiness is as follows: 0: The molten sample hardly flows into the mold 1: The mold can be molded only to the middle of the neck of the dumbbell 2: The dumbbell Can be formed only a little past the neck part 3: One side of the dumbbell gripping part can be formed to about half 4: Dumbbells with a somewhat incomplete shape can be formed 5: Clean dumbbells can be formed Samples of steps 1-5 Indicates that the hardness can be measured, and the samples of steps 3 to 5 can be subjected to the tensile test. Tables 2 and 4 show the cylinder temperature of the molding machine and the ease of molding during injection molding.

(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.
It was measured according to K6253 (test method for hardness of vulcanized rubber).

Tensile test: Conducted in accordance with 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.

Thermal analysis: "T" manufactured by Seiko Electronic Industry Co., Ltd.
The measurement of TG / DTA was performed in the air using G / DTA300 ″. The temperature rising rate was 5 ° C./min.

The temperature at which the weight starts to decrease is a temperature at which the weight starts to decrease sharply, and the 10% loss temperature is a temperature at which the weight of the sample decreases by 10%.

MEK extraction rate: Approximately 1 g of a molded sample was formed into granules of about 0.3 mm square, and methyl ethyl ketone (ME
K) Boiled in 100 ml for 8 hours. After cooling, the mixture was filtered, the filtrate was distilled off, the weight of the extract was measured, and the ratio to the original sample weight was calculated. Samples and extracts were weighed to the nearest 0.1 mg.

Tables 2 and 4 show the results of the physical property tests. It is clear that the resin composition according to the present invention is soft and has a large elongation at break as compared with the resin compositions containing PVdF and ETFE (Comparative Examples 1 and 2). Also, ETF
It was shown that the production and molding can be performed at a lower temperature than the resin composition containing E and PFA as components. The resin composition containing PFA as a component (Comparative Example 5) generated remarkable smoke during production and molding, and was virtually impossible to mold.

In Comparative Examples 3 and 4, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymers (hereinafter simply referred to as terpolymers) having specific gravities of 1.91 and 1.87, respectively, were used. For example,
In any case, injection molding is impossible, which is in contrast to the resin compositions of Examples according to the present invention. The MEK extraction rate is also high.

In the resin composition of Example 5, although the rubber component is substantially uncrosslinked in view of the MEK extraction rate, the excellent flexibility, injection moldability, and good tensile strength which are the objects of the present invention are aimed at. The characteristics have been developed.

Example 6 is an example in which tetrafluoroethylene / propylene copolymer rubber was used as the fluoro rubber component. Even when a fluororubber containing no vinylidene fluoride unit is used, it is shown that a resin composition which is easy to melt-mold, and which is flexible, stretchable and has high tensile strength, which is the object of the present invention, can be obtained. Was done.

In Comparative Examples 1 and 6, PVd was used as the resin component.
F is used. In contrast to the resin compositions of the examples according to the present invention, each of them is hard, has small elongation, and has a low weight loss starting temperature and a low 10% weight loss temperature.

Examples 7 to 16 and Comparative Examples 7 and 8 Examples 1 to 6 except that the formulations were as shown in Tables 5 and 7.
The same operation was performed. Tables 6 and 8 show the test results and the like.

In Examples 7 to 9, the composition ratio of the component (A) and the component (B) was variously changed. In any of the composition ratios, the object of the present invention, that is, melt molding easiness, flexibility, extensibility, and high tensile strength are achieved.

In Examples 10 and 11, the type of the terpolymer having a specific gravity of 1.93 or more was changed. Terpolymer-
Although the tensile strength is slightly lowered as compared with the case where No. 1 is used, the melt-forming easiness, flexibility, extensibility and high tensile strength which are the objects of the present invention are achieved. Example 13 is an example relating to a ternary resin containing no fluorine rubber. The ternary copolymer-3 used in Examples 11 and 13 was dissolved in MEK, but the MEK extraction rates of the samples obtained in Examples 11 and 13 were 25% and 45%, respectively. (About 40% and about 100%, respectively). It is clear that component (A) terpolymer was crosslinked.

As shown in Examples 12 and 14, a plurality of types can be used in combination as the component (A) terpolymer or the component (B ') fluororubber.

Examples 15 and 16 show that the object of the present invention can be achieved even when the component (B) fluororubber is crosslinked with a substance other than the polyol.

Examples 17 to 27 and Comparative Example 9 Examples 1 to 27 were repeated except that the formulations were as shown in Tables 9 and 11.
The same operation as in No. 6 was performed. Tables 10 and 12 show the test results and the like.

Tables 9 to 12 Example 18 is an example in which the number of rotations of the blade during sample preparation was reduced. Although the obtained resin composition has somewhat deteriorated physical properties, it still shows good tensile properties and heat resistance.

Examples 19 to 21 examine changes in physical properties due to the addition of a silane coupling agent. It is clear that the addition of the silane coupling agent improved the physical properties.

Examples 22 to 27 are examples in which carbon black as an optional component was added. Even with the addition of carbon black, a resin composition having good characteristics was obtained.
Comparative Example 8 is a system in which PVdF is used as a resin and carbon black is added, but injection molding is difficult. On the other hand, the resin composition of Example 27 is still easy to mold.

[0060]

As described above, according to the present invention, a fluororesin composition which can be melt-molded, has rubber elasticity, is excellent in tensile properties and heat resistance, a method for producing the fluororesin composition, Further, a molded article comprising the fluororesin composition is provided. The effect of the present invention is remarkable in view of the fact that the above-mentioned properties cannot be obtained with a resin composition containing a normal fluororesin such as PFA, ETFE, PFdV or the like as one component or a mere blend of a plurality of fluororubbers. .

[0061]

[Table 1] Fluoro rubber-1: Viton A, manufactured by Showa Denko Dupont, binary fluorine rubber, specific gravity 1.82, Fluoro rubber 2: Viton B, manufactured by Showa Denko Dupont, ternary fluoro rubber, specific gravity 1.86, Fluororubber-3: Florel FT2481, Sumitomo 3M
Co., Ltd., ternary fluororubber, specific gravity 1.87, fluororubber-4: Viton B-70, manufactured by Showa Denko Dupont, ternary fluororubber, specific gravity 1.77, fluororubber-5: Afras 210, Asahi Glass Co., Ltd./Nippon Synthetic Rubber Co., Ltd., tetrafluoroethylene / propylene copolymer, terpolymer-1: THV500G, Sumitomo 3M Co., Ltd.
Made, specific gravity 1.993 (catalog value: 1.98), melting temperature 165
-180 ° C, terpolymer-low specific gravity: THV200P, Sumitomo 3M
Co., Ltd., specific gravity 1.913, melting temperature 115-125 ° C, PVdF: KF1000, Kureha Chemical Industry Co., Ltd., melting temperature about 170 ° C, ETFE: COP-88AX, Asahi Glass Co., Ltd., melting temperature about 260 ° C , PFA: P-66P, manufactured by Asahi Glass Co., Ltd., melting temperature about 300
C., Crosslinking aid-1: Curative 20, a mixture of an organic phosphonium salt and Viton A (weight ratio 1: 2).

[0062]

[Table 2]

[0063]

[Table 3] Fluoro rubber-1: Viton A, manufactured by Showa Denko Dupont, binary fluoro rubber, specific gravity 1.82, Fluoro rubber-2: Viton B, manufactured by Showa Denko Dupont, ternary fluoro rubber, specific gravity 1.86, Fluororubber-3: Florel FT2481, manufactured by Sumitomo 3M Co., Ltd., ternary fluorine rubber, specific gravity 1.87, Fluororubber-4: Viton B-70, manufactured by Showa Denko DuPont, Sangen -Based fluoro rubber, specific gravity 1.77, fluoro rubber-5: Afras 210, manufactured by Asahi Glass Co., Ltd./Nippon Synthetic Rubber Co., Ltd., tetrafluoroethylene / propylene copolymer, terpolymer-1: THV500G, Sumitomo 3M Co., Ltd., specific gravity 1.993 (catalog value: 1.98), melting temperature 165-180 ° C, terpolymer-low specific gravity: THV200P, Sumitomo 3M Co., specific gravity 1.913, melting temperature 115-125 ° C, PVdF: KF1 00, manufactured by Kureha Chemical Industry Co., Ltd., melting temperature: about 170 ° C., ETFE: COP-88AX, manufactured by Asahi Glass Co., Ltd., melting temperature: about 260 ° C., PFA: P-66P, manufactured by Asahi Glass Co., Ltd., melting temperature: about 300 C., Crosslinking aid-1: Curative 20, a mixture of organic phosphonium salt and Viton A (weight ratio 1: 2).

[0064]

[Table 4] *: Injection molding was attempted at 270 to 380 ° C, but little or no melting occurred and injection was not possible. The MEK extraction rate is a measured value for an unformed sample.

[0065]

[Table 5] Fluoro rubber-6: Afras 200, manufactured by Asahi Glass Co., Ltd./Nippon Synthetic Rubber Co., Ltd., tetrafluoroethylene / propylene copolymer, terpolymer-2: THV400G, Sumitomo 3M Co., Ltd.
Manufacture, specific gravity 1.961, melting temperature 150-160 ° C, terpolymer-3: THV200G, Sumitomo 3M Co., Ltd.
, Specific gravity 1.934 (catalog value: 1.95), melting temperature 115-125 ° C, crosslinking aid-2: Afras MA-30, manufactured by Asahi Glass Co., Ltd./Nippon Synthetic Rubber Co., Ltd., a mixture of DBU and Afras 210 Polyamine-1: DIAK No. 3, N, N'-dicinamylidene-1,6-hexanediamine, manufactured by Showa Denko DuPont.

[0066]

[Table 6] # Showed the highest stress at break.

[0067]

[Table 7] Fluoro rubber-6: Afras 200, manufactured by Asahi Glass Co., Ltd./Nippon Synthetic Rubber Co., Ltd., tetrafluoroethylene / propylene copolymer, terpolymer-2: THV400G, manufactured by Sumitomo 3M, specific gravity 1.961 Melting temperature 150-160 ° C, Ternary copolymer-3: THV200G, manufactured by Sumitomo 3M Co., Ltd., specific gravity 1.934 (catalog value: 1.95), Melting temperature 115-125 ° C, Crosslinking assistant-2: Afras MA- 30, manufactured by Asahi Glass Co., Ltd., Nippon Synthetic Rubber Co., Ltd., a mixture of DBU and Afras 210, polyamine-1: DIAK No.3, manufactured by Showa Denko Dupont, N, N'-dicinamylidene-1,6 -Hexanediamine.

[0068]

[Table 8] # Showed the highest stress at break.

[0069]

[Table 9] Alkenylalkoxysilane-1: vinyl tris (β-methoxyethoxy) silane, alkenylalkoxysilane-2: vinyltriethoxysilane, aminoalkylalkoxysilane: γ-aminopropyltriethoxysilane, polyamine-2: DIAK No. 1. Hexamethylenediamine carbamate manufactured by Showa Denko DuPont.

[0070]

[Table 10]

[0071]

[Table 11] Alkenylalkoxysilane-1: vinyl tris (β-methoxyethoxy) silane, alkenylalkoxysilane-2: vinyltriethoxysilane, aminoalkylalkoxysilane: γ-aminopropyltriethoxysilane, polyamine-2: DIAK No. 1, Showa Hexamethylenediamine carbamate manufactured by Denko Dupont Co., Ltd.

[0072]

[Table 12]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-57-135871 (JP, A) JP-A-59-68363 (JP, A) JP-A-64-16852 (JP, A) 117478 (JP, A) JP-A-6-25500 (JP, A) JP-A-7-97457 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/12-27 / 20 C08J 3 / 24,5 / 00 C08K 5/54-5/549 CA (STN)

Claims (7)

(57) [Claims] 1. A thermoplastic resin having a specific gravity of 1.93 or more.
A terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride, and 10 to 90% by weight of a crosslinked or uncrosslinked fluororubber having a specific gravity of 1.91 or less. Fluorinated resin composition. 2. The fluororesin composition according to claim 1, wherein the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride is partially crosslinked. 3. The fluororesin composition according to claim 2, wherein the partial crosslinking in the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride is caused by a polyol or a polyamine. 4. The resin composition according to claim 1, which contains alkenylalkoxysilane and / or aminoalkylalkoxysilane. 5. The resin composition according to claim 1, wherein (A) the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride has a specific gravity of 1.95 or more. . 6. A thermoplastic resin having a specific gravity of 1.93 or more.
An uncrosslinked fluororubber having a tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride terpolymer of 10 to 90% by weight and a specific gravity (B ') of 1.91 or less;
Kneading 10% by weight, optionally together with alkenylalkoxysilane and / or aminoalkylalkoxysilane, at a temperature not lower than the melting temperature of the terpolymer of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride (A) And a step of crosslinking at least a part of the fluororubber component while kneading at the temperature. 7. A molded article characterized by being molded using the resin composition according to any one of claims 1 to 5.