JPH07252418A - Resin composition and molding comprising the same composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition, comprising a resin containing sulfone groups, a fluororesin and a polyimide resin containing fluorine, excellent in strength and useful as bushings, piston rings, seal rings, etc. CONSTITUTION:This resin composition comprises (A) a resin containing sulfone groups such as a poly(ether) sulfone or polyphenyl sulfone, (B) a fluororesin such as a hexafluoropropylene-vinylidene fluoride copolymer rubber, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a tetrafluoroethylene- hexafluoropropylene copolymer, an ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride or polychlorotrifluoroethylene and (C) a polyimide resin containing fluorine. Furthermore, the components (A), (B) and (C) are preferably blended in the following amounts based on 100 pts.wt. component (A): 1-170 pts.wt. component (B) and 0.1-30 pts.wt. component (C).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition and a molded article made of this composition.

[0002]

2. Description of the Related Art Parts such as a bush, a piston ring, and a seal ring, which are formed by molding a resin composition into a predetermined shape, are incorporated in various devices such as a hydraulic device and a compressor. These parts may be required to have sliding characteristics (for example, low friction and abrasion resistance), and in order to meet these requirements, it has been proposed to mold the following resin composition.

(1) Thermosetting polyimide resin 4 to 25% by weight, polytetrafluoroethylene (PTFE) 5-1
A resin composition comprising 5% by weight, 2 to 15% by weight of lubricating oil, and the balance thermoplastic resin (JP-A-55-135163).

(2) A resin composition comprising 5 to 60% by weight of a fluororesin, 1 to 20% by weight of boron nitride (BN) and the balance of an aromatic polysulfone resin (JP-A-58-58).
No. 138747).

(3) 30-95% by weight of aromatic polysulfone, 2.5-60% by weight of fluororesin and carbon fiber 2.
Resin composition consisting of 5 to 60% by weight (JP-A-60-38)
465).

(4) 100 parts by weight of aromatic polysulfone,
A resin composition comprising 3 to 60 parts by weight of a fluororesin and 3 to 60 parts by weight of a ceramic fiber (JP-A-63-97).
663).

[0007]

By the way, in recent years, there has been a strong demand for improvement in the reliability of these devices, and there is a strong demand for high performance such as improvement in the strength of the components incorporated therein. However, a molded product made of the above resin composition has not been able to sufficiently meet this demand.

Therefore, it is an object of the present invention to provide a resin composition and a molded product made of the composition, which enables to obtain a molded product having high strength.

[0009]

The resin composition according to the present invention is characterized by containing a sulfone group-containing resin, a fluororesin and a fluoropolyimide.

In the present invention, the blending ratio of the sulfone group-containing resin, the fluororesin and the fluorine-containing polyimide, which are the essential components, can be appropriately set. Usually, the fluororesin is 1 to 170 parts by weight relative to 100 parts by weight of the sulfone group-containing resin. The fluorine-containing polyimide is 0.1 to 30 parts by weight, preferably the fluororesin is 5 to 120 parts by weight and the fluorine-containing polyimide is 0.2 to 25 with respect to 100 parts by weight of the sulfone group-containing resin.
Parts by weight.

Examples of the above-mentioned sulfone group-containing resin include polysulfone, polyether sulfone, polyphenyl sulfone, etc. These can be used alone or in combination of two or more kinds.

As the fluororesin, hexafluoropropylene-vinylidene fluoride copolymer rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), Examples thereof include ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVdF) and polychlorotrifluoroethylene (PCTFE). This fluororesin may be used alone or in combination of two or more kinds.

In the present invention, it is important to further add a fluorine-containing polyimide to the above-mentioned sulfone group-containing resin and fluororesin. This fluorine-containing polyimide may be any one that contains at least one fluorine atom in the molecule.

Such a fluorine-containing polyimide is, for example,
Using a fluorine-containing compound as at least one of tetracarboxylic acid dianhydride and diamine as a monomer, a fluorine-containing polyamic acid is synthesized by reacting these acid components and approximately equimolar amounts of the diamine in an organic polar solvent. It can be obtained by a method of imide conversion of an acid.

Specific examples of the fluorine-containing tetracarboxylic dianhydride include 3-trifluoromethyl-1,2,4,5.
-Pyromellitic dianhydride, 3,6-trifluoromethyl-1,2,4,5-pyromellitic dianhydride, 4,4
Examples thereof include'-hexafluoroisopropylidene-phthalic acid dianhydride, and these may be used alone or in combination of two or more kinds.

Specific examples of the fluorine-containing diamine include 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoro. Propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino4-methylphenyl) hexafluoropropane, 3,3-difluorobenzidine and the like can be mentioned. These may be used alone or in combination of two or more.

As described above, when a fluorine-containing diamine is used to obtain a fluorine-containing polyimide, tetracarboxylic dianhydride (which does not contain fluorine) can be used as an acid component to react with the fluorine-containing diamine. When carboxylic acid dianhydride is used, diamine (which does not contain fluorine) can be used as a component to react with it.

Specific examples of such a tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ', 4.
4'benzophenone tetracarboxylic dianhydride, 3,3
′, 4,4′-biphenyltetracarboxylic dianhydride,
2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1 , 4,5,8-Tephthalenetetracarboxylic dianhydride, 2,2'-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride , Perylene-3,4,9,
Examples thereof include 10-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, and ethylenetetracarboxylic dianhydride. These may be used alone or in combination of two or more. You may use together.

Specific examples of the diamine are 4,4 '.
-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3-dichlorobenzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 1,5-diamino Naphthalene, m-phenylenediamine, p-phenylenediamine, 3,3'-dimethyl-4,4'-diphenyldiamine, benzidine, 3,
3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 4,4'-diaminophenyl sulfone, 4,4
′ -Diaminodiphenylpropane, 2,4-bis (β-
Amino-tert-butyl) toluene, bis (p-β-amino-tert-butylphenyl) ether, bis (p-β-methyl-δ-aminophenyl) benzene, bis-p- (1,
1-dimethyl-5-amino-pentyl) benzene, 1-
Isopropyl-2,4-m-phenylenediamine, m-
Xylylenediamine, p-xylylenediamine, di (p
-Aminocyclohexyl) methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, diaminopropyltetramethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2, 11-diaminododecane, 1,2-bis-3-aminopropoxyethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5
-Dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonamethylenediamine,
2,11-diaminododecane, 2,17-diaminoeicosadecane, 1,4-diaminocyclohexane, 1,1
0-diamino-dimethyldecane, 1,12-diaminooctadecane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, piperazine, H ₂ N (C
H ₂ ) ₃ O (CH ₂ ) ₂ O (CH ₂ ) NH ₂ , H ₂ N
(CH ₂ ) ₃ S (CH ₂ ) ₃ NH ₂ , H ₂ N (CH ₂ )
₃ N (CH ₃ ) (CH ₂ ) ₃ NH _{2 and the} like can be mentioned, and these may be used alone or in combination of two or more kinds.

The organic polar solvent used when the acid component and the diamine component are reacted to synthesize the polyamic acid is N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N
-Diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone and the like can be used.
If desired, at least one of phenols such as cresol, phenol and xylenol, benzonitrile, dioxane, butyrolactone, xylene, cyclohexane, hexane, benzene and toluene may be mixed with these organic polar solvents. However, addition and mixing of water induces hydrolysis of the generated polyamic acid and lowers the molecular weight of the polyamic acid, so it should be avoided.

A fluorine-containing polyamic acid is obtained by reacting the above-mentioned acid component and diamine in an organic polar solvent. Although the monomer concentration at that time is set according to various conditions, it is usually about 5 to 30% by weight. The reaction temperature is usually about 80 ° C or lower, preferably 5 to 50 ° C.

As described above, a fluorine-containing compound is used as a monomer of at least one of an acid component and a diamine component, and both monomers are reacted in an organic polar solvent to synthesize a fluorine-containing polyamic acid. As the reaction proceeds, Solution viscosity increases (reaction time is usually about 0.5-10)
It's time). In addition, in the present invention, although not limited thereto, as the fluorine-containing polyamic acid, the logarithmic viscosity η
It has been found preferable to synthesize and use those having inh of 0.1 dl / g or more. This logarithmic viscosity was measured by a conventional method using a capillary viscometer to measure the falling time of each of the polyamic acid solution and the solvent used in the solution.
The value calculated by However, in Formula 1, “T ₀ ” is the solvent drop time, “T ₁ ” is the solution drop time, and “C” is the polyamic acid concentration (g / dl) in the solution.

[0023]

[Equation 1]

After the fluorine-containing polyamic acid solution was obtained in this manner, the polyamic acid concentration was about 0.1 to 10% by weight.
And then dilute the diluted solution into a large amount of non-solvent (liquid that does not dissolve polyamic acid, such as alcohols such as methanol and ethanol, hexane, toluene, petroleum ether, water, etc.). And the fluorinated polyamic acid coagulates and precipitates in powder form,
This is separated and dried.

To obtain the resin composition according to the present invention using this fluorinated polyamic acid, for example, a predetermined amount of each of the sulfone group-containing resin, the fluororesin and the fluorinated polyamic acid is prepared by using a kneader or the like. A method of mixing while heating to a temperature of imide conversion temperature (usually about 300 to 400 ° C.) or higher, cooling this, and then pelletizing or powdering it can be adopted. During the above heating and mixing, the fluorinated polyamic acid is imide-converted to form a fluorinated polyimide and is mixed with the sulfone group-containing resin and the fluororesin. Although ring-closing water is generated during the imide conversion, it is not necessary to give special consideration to the ring-closing water because it is evaporated and removed by the heat during heating and mixing.

The resin composition can be obtained also by converting the fluorinated polyamic acid into an imide by heating or the like to give a fluorinated polyimide, and mixing the fluorinated polyimide with a sulfone group-containing resin and a fluororesin. .

In the present invention, if desired, additives such as a filler, a coloring agent, and a filler can be mixed in appropriate amounts. When these additives are used, the proportion in the weight of the resin composition is usually 0.1 to 30% by weight.

The above-mentioned filler is added in order to impart a function to the molded product obtained from the resin composition or improve its performance. For example, glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, glass beads, silicon carbide whiskers, silicon nitride whiskers, potassium titanate whiskers, etc. for improving strength, graphite, nitric acid Molybdenum sulfide,
Tungsten disulfide, boron nitride, mica, aromatic polyester resin, silicone resin, calcium fluoride, fluorinated graphite, glass flakes, carbon black, graphite, bronze, etc. are used for imparting conductivity to metal powder, metal flakes, metal. Beryllium oxide, aluminum nitride, alumina, magnesia, titania, or the like can be used as the fiber or the like for improving thermal conductivity.

In order to mold the resin composition according to the present invention into a predetermined shape, conventional injection molding, melt extrusion molding, hot press molding, blow molding, transfer molding or the like can be adopted.

[0030]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 69.2 parts by weight of 4,4'-hexafluoroisopropylidene-phthalic acid dianhydride and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane 9
7.1 parts by weight is dissolved in 850 parts by weight of N, N-dimethylacetamide and reacted at a temperature of 25 ° C. for 3 hours to obtain a fluorinated polyamic acid solution, which is adjusted to have a polyamic acid concentration of 5% by weight. Dilute with dimethylacetamide.
And this diluted fluorine-containing polyamic acid solution 100
1 part by weight is poured into 1000 parts by weight of ion-exchanged water to coagulate and precipitate the polyamic acid, and the precipitate is separated by filtration and dried at a temperature of 150 ° C. for 10 hours to obtain a powder (particle size 1
Fluorine-containing polyamic acid having a diameter of 00 μm is obtained. The polyamic acid had an inherent viscosity ηinh of 0.71 dl / g.

Polyphenylsulfone pellets (particle size 2 to
3 mm) 1467 parts by weight, hexafluoropropylene-
Vinylidene fluoride copolymer rubber pellets (particle size 2-3 m
m) 533 parts by weight and 6 parts by weight of the fluorine-containing polyamic acid powder were melt-kneaded for 15 minutes in a kneader maintained at 360 ° C. (during this kneading, imide conversion of the fluorine-containing polyamic acid occurred, and 5.8 parts by weight of fluorine-containing polyamic acid was produced. Will be polyimide).
After kneading, the mixture is cooled to room temperature and cut into pellets having a particle diameter of 2 to 3 mm to obtain a resin composition.

This resin composition was heated and pressed for 15 minutes under the conditions of a temperature of 320 ° C. and a pressure of 200 kg / cm ² using a hot press machine, and had a length of 150 mm, a width of 12.6 mm and a thickness of 6.
It was molded into a 3 mm plate shape. The bending strength of this molded body is 5.
It was 12 kg / cm ² . The bending strength is measured by a tensile tester (manufactured by Toyo Baldwin Co., Ltd., Tensilon CR-
700 / UTM), temperature 23 ° C, fulcrum distance 10
The maximum bending load was measured under the conditions of 0 mm and the pressing speed of 5 mm / min, and it is a value calculated by the following formula 2. In Formula 2, “F” is the maximum bending load (kg), “L” is the distance between fulcrums (100 mm), and “H” is the thickness of the compact (6.3 m).
m) and “B” are the width (12.6 mm) of the molded body.

[0034]

[Equation 2]

Example 2 When melt-kneading 1467 parts by weight of polyphenyl sulfone pellets, 533 parts by weight of hexafluoropropylene-vinylidene fluoride copolymer rubber pellets, and 6 parts by weight of fluoropolyamic acid powder, carbon fibers (diameter 7 μm, long length) 40
μm) 60 parts by weight and molybdenum disulfide powder (particle size 3
[mu] m) The same operation as in Example 1 except that 50 parts by weight was added to obtain a pellet-shaped resin composition and a molded product made of the composition. The bending strength of this molded product is 5.09k.
It was g / cm ² .

Example 3 44.4 parts by weight of pyromellitic dianhydride and 88.5 parts by weight of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane were added to N, N-dimethylacetamide 531. It is dissolved in 0.6 part by weight and reacted at a temperature of 25 ° C. for 3 hours to obtain a fluorine-containing polyamic acid solution, which is diluted with N, N-dimethylacetamide so that the polyamic acid concentration becomes 5% by weight. Then, 100 parts by weight of this diluted fluorinated polyamic acid solution was poured into 1000 parts by weight of ion-exchanged water to coagulate and precipitate the polyamic acid, and the precipitate was separated by filtration and dried at a temperature of 150 ° C. for 10 hours. A powdery fluorinated polyamic acid is obtained. The polyamic acid had an inherent viscosity ηinh of 0.66 dl / g.

Polyphenyl sulfone pellets (particle size 2 to
3 mm) 1467 parts by weight, hexafluoropropylene-
Vinylidene fluoride copolymer rubber pellets (particle size 2-3 m
m) 533 parts by weight and 6 parts by weight of the fluorine-containing polyamic acid powder were melt-kneaded for 15 minutes in a kneader maintained at 360 ° C. (during this kneading, imide conversion of the fluorine-containing polyamic acid occurred, and 5.7 parts by weight of fluorine-containing polyamic acid. Will be polyimide). After kneading, cool to room temperature and make this a particle size of 2-3 mm.
To obtain a resin composition. Then, this resin composition was molded into a plate shape in the same manner as in Example 1.
The bending strength of this molded product was 5.02 kg / cm ² .

Example 4 12 Polyethersulfone pellets (particle size 2-3 mm)
Same as Example 1 except that 57 parts by weight, 743 parts by weight of hexafluoropropylene-vinylidene fluoride copolymer rubber pellets (particle diameter 2 to 3 mm) and 6 parts by weight of the fluorine-containing polyamic acid obtained in Example 1 are used. Melt kneading,
Cooling, cutting and hot press molding were performed to obtain a pellet-shaped resin composition and a molded body. The bending strength of this molded body was 4.21 kg / cm ² .

Example 5 Polyethersulfone pellets (particle size 2-3 mm) 12
98 parts by weight, ETFE pellets (particle size 2-3 mm) 70
2 parts by weight and the fluorinated polyamic acid 6 obtained in Example 1
Melt kneading as in Example 1 except that parts by weight were used,
Cooling, cutting and hot press molding were performed to obtain a pellet-shaped resin composition and a molded body. The bending strength of this molded body was 4.01 kg / cm ² .

Example 6 A pelletized resin composition and a molded product were obtained in the same manner as in Example 1 except that the blending amount of the fluorinated polyamic acid powder at the time of melt kneading was 20 parts by weight. The bending strength of this molded product was 5.05 kg / cm ² .

Example 7 1039 parts by weight of polysulfone pellets (particle size 2 to 3 mm), 961 parts by weight of ETFE pellets (particle size 2 to 3 mm) and 6 parts by weight of the fluorinated polyamic acid obtained in Example 1 were used. Melt kneading, cooling and hot press molding were carried out in the same manner as in Example 1 to obtain a pelletized resin composition and a molded product. The bending strength of this molded body is 1.53 kg / c
It was m ² .

Comparative Example 1 Melt kneading, cooling, cutting and hot press molding were carried out in the same manner as in Example 1 except that the fluorine-containing polyamic acid powder was not blended to obtain a pelletized resin composition and a molded product. The bending strength of this molded body was 4.51 kg / cm ² .

Comparative Example 2 52.9 parts by weight of pyromellitic dianhydride and 97.1 parts by weight of 3,3'-bis (aminophenoxy-4,4'-phenyl) sulfone were added to N, N-dimethylacetamide 850.
It is dissolved in 1 part by weight and reacted at a temperature of 25 ° C. for 3 hours to obtain a polyamic acid solution, which is diluted with N, N-dimethylacetamide so that the polyamic acid concentration becomes 5% by weight. Then, 100 parts by weight of this diluted polyamic acid solution is added to 10
After pouring into 100 parts by weight of ion-exchanged water to coagulate and precipitate the polyamic acid, the precipitate was separated by filtration and the temperature was raised to 15
It is dried at 0 ° C. for 10 hours to obtain a powdery polyamic acid. The logarithmic viscosity ηinh of this polyamic acid is 0.68d.
It was 1 / g.

Polyphenylsulfone pellets (particle size 2 to
3 mm) 1467 parts by weight, hexafluoropropylene-
Vinylidene fluoride copolymer rubber pellets (particle size 2-3 m
m) 533 parts by weight and 6 parts by weight of the above polyamic acid powder were melt-kneaded for 15 minutes in a kneader maintained at 360 ° C. (The imide conversion of polyamic acid occurred during this kneading,
This gives 5.7 parts by weight of polyimide). After kneading, the mixture is cooled to room temperature and cut into pellets having a particle diameter of 2 to 3 mm to obtain a resin composition.

This pellet-shaped resin composition was hot press molded in the same manner as in Example 1. The bending strength of this molded body was 4.40 kg / cm ² .

[0046]

EFFECTS OF THE INVENTION The present invention is configured as described above, and since a fluorinated polyimide is further mixed with a sulfone group-containing resin and a fluororesin, a molded product having high strength can be obtained.

Claims (5)

[Claims] 1. A resin composition containing a sulfone group-containing resin, a fluororesin and a fluorine-containing polyimide. 2. The resin composition according to claim 1, wherein 1 to 170 parts by weight of a fluororesin and 0.1 to 30 parts by weight of a fluorine-containing polyimide are mixed with 100 parts by weight of a resin containing a sulfone group. 3. The resin composition according to claim 1 or 2, wherein the sulfone group-containing resin is at least one selected from polysulfone, polyether sulfone, and polyphenyl sulfone. 4. The fluororesin is hexafluoropropylene-vinylidene fluoride copolymer rubber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer,
Tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer,
At least one selected from polyvinylidene fluoride and polychlorotrifluoroethylene.
The resin composition according to any one of 3 above. 5. A molded body made of the resin composition according to claim 1.