JPH05132621A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for electrical components, etc., excellent in stress cracking resistance, heat resistance, elastic modulus, coefficient of friction, abrasion resistance, moldability, chemical resistance, composed of a specific aromatic polysulfone copolymer and a polyether ketone resin. CONSTITUTION:The object resin composition comprises (A) preferably 1-99wt.% polyether ketone resin and (B) preferably 99-1wt.% aromatic polysulfone copolymer obtained by polymerizing 1-49mole%, preferably 5-40mole% structural unit corresponding to a monomer of formula I [(n) is 3 and 4] and 51-99mole%, preferably 60-95mole% structural unit corresponding to a monomer of formula II and III [R<1> and R<2> are H, halogen 1-8C hydrocarbon; (a) and (b) are 1-4; X and Y are halogen{9147/28}. A resin composition is obtained by compounding component (B) with an aromatic polycarbonate resin, a polyphenylene sulfide resin or a fluororesin.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an aromatic polysulfone copolymer and a polyetherketone resin; an aromatic polysulfone copolymer and an aromatic polycarbonate resin; an aromatic polysulfone copolymer and a polyphenylene sulfide resin; or an aromatic polysulfone. It relates to a resin composition comprising a copolymer and a fluororesin.

[0002]

2. Description of the Related Art Aromatic polysulfone resins are engineering plastics excellent in heat resistance, strength, rigidity, toughness, flame retardancy, chemical properties, wear resistance, etc., and are expected to be used in a wide range of fields. ing. For example, it has been attracting attention as an engineering plastic having excellent creep resistance at high temperatures in applications such as electric parts and automobile parts. Alternatively, the resin exhibits excellent resistance to aliphatic hydrocarbons, alcohols, gasoline and some aromatic chemicals, and may therefore be used in applications such as parts of chemical plant equipment. Further, since it has excellent wear resistance, it is expected to be applied to various sliding materials.

However, aromatic polysulfone resins also have some drawbacks. For example, this resin is relatively excellent in chemical resistance as described above, but is affected by certain organic chemicals, in particular, highly polar chemicals such as ketones and esters, and chlorinated hydrocarbons, for example, stress. When loaded under, the impact strength decreases and cracks are likely to occur (stress cracking resistance is inferior). In recent years, it has been strongly demanded in the electric field, automobile field, etc. to maintain the above-mentioned excellent properties of the aromatic polysulfone resin and improve the stress cracking resistance. Furthermore, since aromatic polysulfone resin has low fluidity, thin-walled molded products,
Molding defects such as delamination of layers and appearance of flow marks occur during the molding of precision molded products, and their applications have been limited.

Further, although application to a sliding material is desired as described above, an aromatic polysulfone resin alone cannot be used as it is as a sliding material because it has a high friction coefficient. Therefore, attempts have been made to lower the friction coefficient by using a resin having a low friction coefficient such as a tetrafluoroethylene resin together. However, on the other hand, the wear resistance deteriorates as the friction coefficient decreases, and it has been difficult to obtain a sliding material composition having a low friction coefficient and good wear resistance as a sliding material.

As an attempt to maintain the excellent characteristics of the aromatic polysulfone resin and improve the stress cracking resistance, a method of blending the aromatic polysulfone resin with a polyetherketone resin is disclosed in JP-A-59-202256. is there. Polyetherketone resins are a relatively new class of engineering plastics. This resin has crystallinity and excellent physical properties such as high impact strength, heat resistance, hydrolysis resistance, radiation resistance, and chemical resistance.
Nuclear power field, fields such as industrial plants using hot water,
It has attracted attention in applications such as the electric / electronic field and the automobile field. However, while the polyetherketone resin has high heat resistance, it has a glass transition point of about 150 ° C., so that the elastic modulus is greatly reduced at a temperature of 150 ° C. or higher, and high strength and elastic modulus are required under high load. Its application is restricted to the mechanical parts etc. Therefore, in the method of the above publication, stress cracking resistance is improved when the polyetherketone resin is blended in a high proportion, but when the aromatic polysulfone resin is blended in a high proportion, strength at high temperature and elasticity are improved. The rate is insufficient.

As described above, the aromatic polysulfone resin has a low fluidity, which causes poor molding and its use is limited. However, as an attempt to improve the drawback, it is disclosed in JP-A-1-141945. Thus, compositions containing aromatic polysulfones, aromatic polycarbonates, polybutylene terephthalates, butadiene elastic copolymers, and polyolefins have been proposed. As described above, this composition contains polybutylene terephthalate for the purpose of improving chemical resistance, and as a result, it has a drawback that the deflection temperature under load is lowered.

Further, in order to make up for some of the drawbacks of the aromatic polysulfone resin, JP-A-58-98362, JP-A-62-295957 and JP-A-61-2 are used.
Japanese Patent No. 47755 discloses that the polysulfone resin and the polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) are blended or made into a block copolymer. As a result, for example, moldability and heat resistance are improved to some extent. However, the heat resistance of such a blended product or block copolymer cannot be said to be sufficient.

In addition, as a resin composition in which the friction coefficient is lowered while maintaining the abrasion resistance of the aromatic polysulfone resin, JP-A-63-97663 discloses an aromatic polysulfone resin, a fluororesin and a ceramic fiber. A composition containing is disclosed. Furthermore, JP-A-5
Japanese Patent Application Laid-Open No. 9-202260 discloses a method of adding an aromatic polyamide fiber and the like. However, the addition of the reinforcing fibers can maintain the wear resistance, but deteriorates the molding processability, so that it has a drawback that the setting of the manufacturing conditions becomes complicated and the cost increases.

[0009]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned conventional problems, and the object thereof is to
An object of the present invention is to provide a resin composition having stress cracking resistance, heat resistance and various mechanical properties.

Another object of the present invention is to provide a resin composition having excellent moldability and chemical resistance.

Still another object of the present invention is to provide a resin composition having excellent moldability and sufficient heat resistance.

[0012] Still another object of the present invention is to provide a resin composition having excellent wear resistance and a low friction coefficient.

[0013]

DISCLOSURE OF THE INVENTION As a result of intensive research conducted by the present inventors in view of the above situation, a polyetherketone resin, an aromatic polycarbonate resin, a PPS resin or a fluororesin was added to a certain aromatic polysulfone copolymer. By blending, in addition to various excellent properties of the aromatic polysulfone resin such as heat resistance, mechanical properties, and flame retardancy, a resin composition having stress cracking resistance; a resin composition having excellent moldability; Alternatively, they have found that a resin composition having excellent wear resistance and a low friction coefficient can be obtained, and completed the present invention.

The first resin composition of the present invention comprises a polyetherketone resin and an aromatic polysulfone copolymer, and the aromatic polysulfone copolymer has the following general formulas (I), (II) and ( Obtained by polymerizing the monomer represented by the formula (III), and containing 1 to 49 mol% of a structural unit corresponding to the monomer represented by the formula (I), and
And structural units 51 to 99 mol% corresponding to the monomers represented by (III).

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

(In the above formula, n represents an integer of 3 or 4, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a straight or branched chain having 1 to 8 carbon atoms. Represents a hydrocarbon group, and a and b are each independently 1 to
It is an integer of 4 and X and Y represent a halogen atom. ) The aromatic polysulfone copolymer contained in the resin composition of the present invention is a copolymer of the monomers represented by the general formulas (I), (II) and (III), and X, Y, And the structural units excluding the hydroxyl group are linearly linked via an ether bond.

The molar fraction of the units of the monomer (I) is 1 to 4
It is 9 mol%, preferably 5 to 40 mol%. When the mole fraction is less than 1%, the stress cracking resistance of the resin composition is insufficient and the moldability is poor. If it exceeds 49%, the composition is difficult to melt by heat, and kneading and molding cannot be performed, which is not practical. Regarding the molecular weight of the aromatic polysulfone copolymer, the reduced viscosity can be used as a guide, and the reduced viscosity of the present copolymer is 30% in dimethylformamide.
When measured at a concentration of 0.5 g / dl at
It is preferably 0.2 dl / g or more. Reduced viscosity is 0.2 dl
If it is less than / g, the mechanical properties of a molded product made from the resin composition will be poor and it will not be practical.

Preferred examples of the monomer represented by the general formula (I) include dihydroxy compounds such as 4,4 '"-dihydroxy-p-terphenyl and 4,4"'-dihydroxy-p-quaterphenyl. Used for.
In addition, 4,4 ′ ″-dihydroxy-p-quaterphenyl is, for example, Journal of Chemical.
It can be synthesized according to the method described in al Society 1379-85 (1940).

As the monomer represented by the general formula (II), for example, a monohalogen monohydroxysulfone compound represented by the following formula is preferably used.

[0022]

[Chemical 7]

X in the monomer represented by the general formula (III)
Examples of the halogen atom represented by are fluorine, chlorine and iodine, and fluorine and chlorine are particularly preferable. R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a linear or branched hydrocarbon group having 1 to 8 carbon atoms. Chlorine and bromine are preferred as the halogen atom. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl,
Examples thereof include n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, neopentyl, hexyl, heptyl, n-octyl and isooctyl. As a preferable compound, a dihalodiphenyl sulfone compound represented by the following formula can be exemplified.

[0024]

[Chemical 8]

A preferred method for producing the aromatic polysulfone copolymer used in the present invention is a nucleophilic substitution polycondensation method in which polymerization is carried out in a polar solvent in the presence of an alkali metal or a metal salt. A method of polymerizing in an aprotic polar solvent in the presence of a metal carbonate can be mentioned.

The above-mentioned alkali metal carbonate is preferably one capable of reacting with the above-mentioned general formulas (I), (II) and (III) to form an alkali metal salt, specifically sodium carbonate and potassium carbonate. , Rubidium carbonate, cesium carbonate and the like. Particularly preferred is potassium carbonate or sodium carbonate. Further, potassium bicarbonate or sodium bicarbonate can also be used for producing carbonate by the thermal decomposition reaction represented by the following formula.

[0027]

[Chemical 9]

The amount of the alkali metal carbonate used is the total molar amount of the compounds represented by the above general formulas (I), (II) and (III) in order to obtain a polymer and to increase the polymerization reaction rate. It is preferable that the molar amount is excessive. When the amount of the alkali metal carbonate used is small, it is not preferable because only a low molecular weight product is obtained due to the free hydroxyl group.

Examples of the aprotic polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and 1,3-
Amide solvents such as dimethyl-2-imidazolidinone and dimethylimidazoline, or dimethylsulfoxide,
Examples thereof include sulfone solvents such as sulfolane and diphenyl sulfone. If necessary, an azeotropic dehydration solvent such as benzene, toluene, xylene, chlorobenzene, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane, monochloroethylene, dichloroethylene or trichloroethylene may be added.

In the production of the copolymer, the polymerization reaction temperature is usually 80 to 400 ° C., preferably 100 to 350 ° C., though it varies depending on the reaction raw materials, the types of components, the type of polymerization reaction and the like. Will be implemented in. When the reaction temperature is lower than the above temperature range, the intended polymerization reaction does not proceed at a rate that can be practically used, and it is difficult to obtain a polymer having a required molecular weight. On the other hand, when the reaction temperature is higher than the above range, side reactions other than the intended polymerization reaction cannot be ignored and coloring of the obtained polymer becomes remarkable.
The time required for the polymerization reaction varies depending on the type of reaction raw material components, the type of polymerization reaction, etc., but is usually in the range of 10 minutes to 100 hours, and preferably in the range of 1 hour to 24 hours.

Further, in the polymerization, the monomer units are mixed such that all the halogen groups are 90 to 1 with respect to all the hydroxyl groups.
It is preferably used within the range of 10 mol%. In order to obtain a higher polymer, it is preferably used within the range of 95 to 105 mol%.

In the manufacturing method, it is preferable that oxygen is not present as the atmosphere for carrying out the reaction, and if the reaction is carried out in nitrogen or other inert gas, good results can be obtained. This is because the alkali metal salt that has reacted with the hydroxyl group
This is because when heated in the presence of oxygen, it is easily oxidized, which hinders the intended polymerization reaction, making it difficult to increase the molecular weight and also causing coloring of the produced polymer.

In the production method, the reaction product is usually cooled to stop the polymerization reaction. However,
If necessary, addition reaction of an aliphatic halide, an aromatic halide or the like may be carried out in order to stabilize the phenoxide group which may be present at the terminal of the polymer. Specific representative examples of the above-mentioned halides include methyl chloride, ethyl chloride, methyl bromide, 4-chlorodiphenyl sulfone, 4-chlorobenzophenone, 4,4′-dichlorophenyl sulfone, 4-
Examples thereof include chloronitrobenzene.

In the production method, known methods can be applied to the method for separating and purifying the polymer. For example, after filtering the salt precipitated in the reaction solvent and the excess alkali metal carbonate, the polymer solution which is the filtrate is usually added dropwise to the non-solvent of the polymer, or conversely, the non-solvent of the polymer is added to the polymer. The target polymer can be precipitated by adding it to the solution. Representative examples of those usually used as a non-solvent of the polymer, methanol, ethanol, isopropanol,
Acetone, methyl ethyl ketone, water and the like can be mentioned, but these may be used alone or as a mixture of two or more kinds.

The polyetherketone resin contained in the first resin composition of the present invention comprises a repeating unit represented by the following formula, or

[0036]

[Chemical 10]

Examples thereof include those composed of the repeating unit represented by the above formula and at least one selected from the group of repeating units represented by the following formula.

[0038]

[Chemical 11]

The intrinsic viscosity of the polyetherketone resin is preferably 0.3 or more, more preferably 0.5 or more. Here, the intrinsic viscosity is a viscosity of a 0.1 g / dl sulfuric acid solution measured at 25 ° C.

The first resin composition of the present invention preferably contains 1 to 99% by weight of a polyetherketone resin and 99 to 1% by weight of an aromatic polysulfone copolymer. When the content of the polyetherketone resin is less than 1% by weight and the content of the aromatic polysulfone copolymer exceeds 99% by weight, the stress cracking resistance of the aromatic polysulfone copolymer cannot be improved. On the contrary, when the content of the polyetherketone resin exceeds 99% by weight and the content of the aromatic polysulfone copolymer is less than 1% by weight, the rigidity at high temperature is insufficient.

The first composition of the present invention may contain various additives as long as the effects of the present invention are not impaired. For example, antioxidants, heat stabilizers, UV absorbers, release agents,
One or more of colorant, crystal nucleating agent, filler (clay, mica, silica, graphite, glass beads, alumina, calcium carbonate, etc.), reinforcing fiber (glass fiber, carbon fiber, potassium titanate fiber, etc.) Can be included.

The means for mixing the components of the first composition of the present invention is not particularly limited. It is possible to separately supply the aromatic polysulfone copolymer and the polyether ketone resin to the melt mixer, and preliminarily mix these raw materials with a mortar, a Henschel mixer, a ball mill, a ribbon blender, etc. It is also possible to supply it to the melt mixer afterwards.

The first resin composition of the present invention can be molded into a predetermined molded article by a molding method such as an injection molding method, an extrusion molding method and a compression molding method.

The second resin composition of the present invention is characterized by comprising an aromatic polycarbonate resin and an aromatic polysulfone copolymer.

The aromatic polysulfone copolymer contained in the second resin composition of the present invention is the same as the aromatic polysulfone copolymer contained in the first resin composition of the present invention.

The aromatic polycarbonate resin contained in the second resin composition of the present invention is a polymer composed of repeating units represented by the following general formula.

[0047]

[Chemical 12]

(In the formula, R ³ and R ⁴ each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ⁵ and R ⁶ each independently represent 1 to 10 carbon atoms.
Is an alkyl group, chlorine, bromine or hydrogen, and p and r are each independently an integer of 0-4. ) This aromatic polycarbonate resin is a solvent method, for example, in the presence of an acid acceptor and a molecular weight modifier in a solvent such as methylene chloride,
It can be produced by a reaction between a dihydric phenol and phosgene or a transesterification reaction between a dihydric phenol and diphenyl carbonate.

The dihydric phenol which can be particularly preferably used here is 2,2-bis (4-hydroxyphenyl).
Propane (bisphenol A), bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3)
-Methylphenyl) propane, 2,2- (3,5,
3 ', 5'-tetrachloro-4,4'-dihydroxyphenyl) propane, 2,2- (3,5,3', 5'-tetrachloro-4,4'-dihydroxydiphenyl) propane and the like can be mentioned. And particularly preferably bisphenol A
Is. The aromatic polycarbonate resin may be a homopolymer of these dihydric phenols, a copolymer of two or more dihydric phenols, or a blended product.

The second resin composition of the present invention contains 1 to 99% by weight of an aromatic polycarbonate resin and 99 to 1% by weight of an aromatic polysulfone copolymer. The content of aromatic polycarbonate resin is less than 1% by weight,
When the content of aromatic polysulfone exceeds 99% by weight, the moldability of the resulting resin composition is poor, the content of aromatic polycarbonate resin exceeds 99% by weight, and the content of aromatic polysulfone copolymer Is less than 1% by weight,
The resulting resin composition has insufficient chemical resistance and heat resistance.

If necessary, the second composition of the present invention may contain the same additives as those of the above-mentioned first composition within a range not impairing the object of the present invention.

The means for mixing the components of the second composition of the present invention is not particularly limited. For example, the mixing means in the first composition can be adopted.

The second resin composition of the present invention can be molded by the same method as the first resin composition.

The third resin composition of the present invention is characterized by comprising a polyphenylene sulfide resin and an aromatic polysulfone copolymer.

The aromatic polysulfone copolymer contained in the third resin composition of the present invention is the same as the aromatic polysulfone copolymer contained in the first resin composition of the present invention.

The polyphenylene sulfide resin (hereinafter referred to as PPS resin) contained in the third resin composition of the present invention is a polymer composed of repeating units represented by the general formula -R ⁷ -S-, Examples of R ⁷ include those represented by the following formula.

[0057]

[Chemical 13]

(In the above formula, Q represents a fluorine, chlorine, bromine or methyl group, and m represents an integer of 1 to 4.) Particularly, a typical PPS resin has a repeating unit represented by the following general formula. One that is composed of.

[0059]

[Chemical 14]

The manufacturing method thereof is, for example, US Pat.
54129 and corresponding Japanese Patent Publication No. 45-336
No. 8 publication. According to this, a PPS resin having desired properties can be produced by subjecting a PPS resin having no cross-linking (cross-linking) bond to a PPS resin having a partial cross-link with various degrees of polymerization to a post heat treatment step. .. These are marketed under the trademark "Ryton" by Philippe Petroleum Company, USA. PP
As the S resin, a resin having melt viscosity characteristics suitable for the target melt blending is arbitrarily selected.

The third resin composition of the present invention preferably contains 1 to 50% by weight of a PPS resin and 99 to 50% by weight of an aromatic polysulfone copolymer. When the content of the PPS resin is less than 1% by weight and the content of the aromatic polysulfone copolymer exceeds 99% by weight, the moldability of the obtained resin composition is poor and the content of the PPS resin is 5%.
When the content of the aromatic polysulfone copolymer is more than 0% by weight and the content of the aromatic polysulfone copolymer is less than 50% by weight, a continuous phase of PPS is formed in the resin composition. The effect of maintaining physical properties and suppressing the molding shrinkage cannot be expected. In general, PPS resin has been attracting attention as a high-performance engineering plastic due to its excellent chemical resistance and rigidity, and it has been considered to be used for sliding applications such as gears, cams, and bearings by taking advantage of the characteristic of self-lubrication. However, since this resin has an extremely high degree of crystallinity, it has the drawbacks that the molding shrinkage is large and the dimensional accuracy is low, and that the glass transition point is low, and the elastic modulus at the glass transition temperature or more sharply decreases. is doing. In recent years, further high temperature heat resistance has been demanded, but conventional polyether sulfone resins have not been obtained with sufficient heat resistance. On the other hand, the composition of the present invention having a PPS resin content of 1 to 50% by weight and an aromatic polysulfone copolymer content of 99 to 50% by weight has excellent mechanical properties and molding properties. It has heat resistance, heat resistance, and dimensional accuracy.

If necessary, the third composition of the present invention may contain the same additives as those of the above-mentioned first composition within the range not impairing the object of the present invention.

The means for mixing the components of the third composition of the present invention is not particularly limited. For example, the mixing means in the first composition can be adopted.

The third resin composition of the present invention can be molded by the same method as the first resin composition.

The fourth resin composition of the present invention is characterized by comprising a fluororesin and an aromatic polysulfone copolymer.

The aromatic polysulfone copolymer contained in the fourth resin composition of the present invention is the same as the aromatic polysulfone copolymer contained in the first resin composition of the present invention.

The fluororesin contained in the fourth resin composition of the present invention is a polymer containing a fluorine atom (F) in its molecule, and generally has a higher heat resistance than other synthetic resins. It is a resin that has excellent chemical resistance, electrical characteristics (especially high frequency characteristics), and also has unique low friction characteristics and non-adhesiveness. For example, polytetrafluoroethylene (PT
FE), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer Resin (EPE), tetrafluoroethylene-ethylene copolymer resin (ETFE), trifluoroethylene chloride resin (ECTFE), vinylidene fluoride resin (PVDF), polychlorotrifluoroethylene (PC)
TFE), polyvinyl fluoride (PVF), and the like, and at least one kind or a mixture of two or more kinds thereof is used.

Among the above-mentioned fluororesins, PTFE which is completely fluorinated is excellent in these properties and is most preferably used in the fourth composition. In this composition, 2 to 60% by weight of these fluororesins and 98 to 40% of the above-mentioned aromatic polysulfone copolymer are contained.
It is preferably contained in a weight percentage. If the blending amount of the fluororesin is less than 2% by weight, the friction coefficient of the obtained resin composition becomes large, which is not preferable. On the other hand, if the content of the fluororesin is more than 60% by weight, the abrasion resistance is decreased, which is not preferable.

If necessary, the following may be added to the fourth composition of the present invention as long as the effects of the present invention are not impaired: Reinforcing fiber (eg, carbon fiber, glass fiber, titanic acid). Potassium fiber, metal fiber, etc.), filler (eg calcium carbonate, clay, talc, silica, etc.),
Antioxidants, heat stabilizers, UV absorbers, lubricants and mold release agents (eg stearic acid and its salts, esters,
Half ester, stearyl alcohol, stearamide, etc.), dyes (eg, nitrocin), pigments (eg, cadmium sulfide, phthalocyanine, carbon black, etc.), other thermoplastic resins (eg, polyamide, polycarbonate, polyphenylene sulfide, polyetherimide) , PET, PBT, polyacetal, polyetherketone, etc.), thermosetting resin (for example, phenol resin, epoxy resin, silicone resin, polyimide resin, polyamideimide resin, etc.).

The means for mixing the components of the fourth composition of the present invention is not particularly limited. For example, the mixing means in the first composition can be adopted. Further, it is also possible to employ a method in which the respective components of the composition are dispersed in an aqueous medium or an organic medium and mixed by a wet mixing method.

The fourth resin composition of the present invention can be molded by the same method as the first resin composition.

[0072]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto.

Example 1 [Production Method of Aromatic Polysulfone Copolymer] In a 200 ml eggplant-shaped flask equipped with a stirrer, a gas introduction tube, a thermometer and a condenser with a receiver at the end, 4-chloro- 4 '-(p
-Hydroxyphenyl) diphenyl sulfone 10.33
g (30 mmol), 4,4 ′ ″-dihydroxy-p
-Quaterphenyl 3.39 g (10 mmol),
2.88 g of 4,4'-dichlorodiphenyl sulfone (1
0 mmol), anhydrous potassium carbonate 3.46 g (25 mm
ol), 60 g of diphenyl sulfone, and toluene 2
5 ml was charged and the atmosphere was replaced with nitrogen. Next, stirring and temperature increase were started in a nitrogen atmosphere, and toluene azeotropy was performed at 150 to 170 ° C. to remove water in the system. Approximately 1 hour later, after confirming that distillation stopped, 1 hour at 220 ° C for 25 hours
30 minutes at 0 ℃, 30 minutes at 280 ℃, 3 at 320 ℃
A time reaction was performed. After completion of the reaction, the reaction solution was cooled to room temperature, potassium chloride precipitated in the reaction solution was removed by filtration, and the filtrate was poured into a large amount of methanol to precipitate a polymer. The reduced viscosity of the obtained polymer was 0.40 dl / g (3
It was 0.5 g / dl in dimethylformamide at 0 ° C.

[Production of Resin Composition Organism] The above aromatic polysulfone copolymer and polyether ketone resin (IC
Victrex PEEK (trade name) manufactured by Company I was charged into a Brabender plastograph with the composition shown in Table 1 and melt-kneaded. After confirming that the torque became stable after about 5 minutes, the mixture was taken out and quickly press-molded at 350 ° C. to obtain a molded product. This molded product was used to measure the heat distortion temperature, the bending regeneration ratio, and the stress cracking resistance test (each test method will be described later).

The results of the above test are shown in Table 1. The results of Examples 2 to 3 and Comparative Examples 1 to 4 described later are also shown in Table 1.

(Examples 2 and 3) The same as Example 1 except that the aromatic polysulfone copolymer and the polyetherketone resin were blended in the proportions shown in Table 1.

Comparative Examples 1 and 2 As shown in Table 1,
Same as Example 1 except that no aromatic polysulfone copolymer or polyetherketone resin was used.

Comparative Examples 3 and 4 The aromatic polysulfone copolymer was changed to the composition ratio shown in Table 1, and the aromatic polysulfone copolymer and the polyetherketone resin were changed to Table 1.
The same procedure as in Example 1 was carried out except that a molded product was prepared with the blending ratio shown in. In Comparative Example 4, the aromatic polysulfone copolymer could not be melted and kneaded.

[0079]

[Table 1]

In Table 1, 1) to 7) show the following matters.

1) A: 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone molar fraction 2) B: 4,4 "'-dihydroxy-p-quarterphenyl molar fraction 3) C : Mole fraction of 4,4'-dichlorodiphenyl sulfone 4) D: Weight fraction of aromatic polysulfone resin 5) E: Polyether ketone (Victrex PEE)
Weight fraction of K) 6) Tested according to ASTM D-648.

7) The test was conducted according to ASTM D-790.

8) Autograph 100 k on the test piece
The cracking resistance when a stress of g / cm ² was applied and a predetermined chemical was brought into contact was evaluated.

◯: No change in the test piece for 20 minutes after contact with the chemical C20: Fine cracks were formed 20 minutes after contact with the chemical.

R40S, R55S: Cracks were formed 40 seconds and 55 seconds after contact with the chemical.

(Example 4) [Preparation of resin composition] Aromatic polycarbonate resin (Panlite L-1225 (trade name) manufactured by Teijin Chemicals Ltd.)
The aromatic polysulfone copolymer obtained by the same method as in Example 1 was charged into a Brabender Plastograph with the composition shown in Table 2 and melt-kneaded. After confirming that the torque became stable after about 5 minutes, the mixture was taken out and quickly press-molded at 350 ° C. to obtain a molded product. This molded product was used for heat distortion temperature, melt flow index, and toluene resistance tests.

The results of the above tests are shown in Table 2. The results of Examples 5 to 8 and Comparative Examples 5 to 8 described later are also shown in Table 2.

(Examples 5 and 6) The same as Example 4 except that the blending ratio of the aromatic polysulfone copolymer and the aromatic polycarbonate resin was set as shown in Table 2.

Comparative Examples 5 and 6 As shown in Table 2,
Same as Example 4 except that no aromatic polysulfone copolymer or aromatic polycarbonate resin was used.

(Examples 7 and 8) The same as Example 10 except that the aromatic polysulfone copolymer and / or the blending ratio was as shown in Table 2.

Comparative Examples 7 and 8 The same as Example 4 except that the aromatic polysulfone copolymer and / or the blending ratio was as shown in Table 2. In Comparative Example 8, it was impossible to melt and knead the aromatic polysulfone copolymer.

[0092]

[Table 2]

In Table 2, 1) to 7) indicate the following matters.

1) A: 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone molar fraction 2) B: 4,4'''-dihydroxy-p-quaterphenyl molar fraction 3) C : Mole fraction of 4,4'-dichlorodiphenyl sulfone 4) D: Weight fraction of aromatic polysulfone resin 5) E: Aromatic polycarbonate resin (Panlite L-
1225) Weight fraction 6) Tested according to ASTM D-648.

7) According to JIS K 7210, a test was conducted under a load of 2.16 kg and a temperature of 300 ° C.

8) A toluene resistance test was conducted as a chemical resistance test. First, it was immersed in toluene at 30 ° C. for 10 minutes, and then appearance change by visual inspection and breaking elongation by tensile test were measured.

Example 9 [Preparation of Resin Composition] Aromatic polysulfone copolymer and PPS resin obtained by the same method as in Example 1 (Ryton P-4 (trade name) manufactured by Philip Petroleum Co., Ltd.) 2) was dry-blended with the composition shown in Table 3 and then extruded while melt-kneading with a 40 mm extruder equipped with a screw to obtain a uniform blended pellet.

Next, the uniformly compounded pellets obtained above were put into a normal injection molding machine to prepare molding test pieces (barrel temperature 3
60 ° C., mold temperature 150 ° C.), and the injection pressure at this time was used as a measure of moldability. In addition, physical and thermal characteristics were measured using this molded product (each test method will be described later). The above results are shown in Table 3. The results of Examples 10 to 12 and Comparative Examples 9 to 12 described later are also shown in Table 3.

(Examples 10 and 11, Comparative Examples 9 and 10) The same as Example 9 except that the aromatic polysulfone copolymer and the PPS resin were blended in the proportions shown in Table 3.

(Example 12, Comparative Examples 11 and 12)
The amount of the aromatic polysulfone copolymer was changed to the composition ratio shown in Table 3, and the aromatic polysulfone copolymer and PPS were changed.
The same procedure as in Example 9 was carried out except that a molded product was prepared by mixing the resins in the blending ratio shown in Table 3.

[0101]

[Table 3]

In Table 3, 1) to 7) indicate the following matters.

1) A: 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone molar fraction 2) B: 4,4 "'-dihydroxy-p-quaterphenyl molar fraction 3) C : Mole fraction of 4,4'-dichlorodiphenyl sulfone 4) D: Weight fraction of aromatic polysulfone resin 5) E: Weight fraction of PPS resin (Ryton P-4) 6) According to ASTM D-955 The test was conducted.

7) The test was conducted according to ASTM D-638.

8) A test was carried out under a load of 18.6 kg in accordance with ASTM D-648.

Example 13 Preparation of Resin Composition Polysulfone copolymer and fluororesin powder obtained by the same method as in Example 1 (tetrafluoroethylene resin, Teflon PL manufactured by Mitsui Fluorochemical Co., Ltd.)
After dry blending P-10 (trade name) with the composition shown in Table 4, a 40 mm diameter extruder (extrusion temperature 360 ° C to 39 ° C)
The mixture was extruded at 0 ° C. while being melt-kneaded to obtain a uniform blended pellet.

Next, a molding test piece was prepared from the above uniformly blended pellets under the temperature conditions of a cylinder temperature of 390 ° C. and a mold temperature of 180 ° C. by using an ordinary injection molding machine, and the friction coefficient and wear coefficient were measured as sliding characteristics. It was measured. The results are shown in Table 4.

The friction coefficient was measured at room temperature using a Matsubara friction tester under the conditions of a surface pressure of 10 kg / cm ² and a speed of 6 m / min, using stainless steel as the mating material. The measurement was performed at room temperature using a cylindrical abrasion tester under the conditions of 5 kg / cm ² and a speed of 100 m / min.

The results of the above tests are shown in Table 4. The results of Examples 14 to 18 and Comparative Examples 13 to 16 described later are also shown in Table 4.

Examples 14 and 15 The same as Example 13 except that the aromatic polysulfone copolymer and the fluororesin were blended in the proportions shown in Table 4.

Comparative Examples 13 and 14 Example 13 is the same as Example 13 except that the aromatic polysulfone copolymer and the fluororesin were blended in the proportions shown in Table 4.

(Examples 16 to 18) The same as Example 13 except that the composition and / or blend ratio of the aromatic polysulfone copolymer was set to the values shown in Table 4.

Comparative Examples 15 and 16 Same as Example 13 except that the composition of the aromatic polysulfone (co) polymer was as shown in Table 2 and the moldings were prepared at the blending ratios shown in Table 4. Is. In Comparative Example 17, melting and kneading of the aromatic polysulfone copolymer was impossible.

[0114]

[Table 4]

In Table 4, 1) to 4) indicate the following matters.

1) A: 4-chloro-4 '-(p-hydroxyphenyl) diphenylsulfone molar fraction 2) B: 4,4 "'-dihydroxy-p-quaterphenyl molar fraction 3) C : Molar fraction of 4,4'-dichlorodiphenyl sulfone 4) D: Weight fraction of aromatic polysulfone resin 5) E: Weight fraction of fluororesin (Teflon PLP-10)

[0117]

According to the present invention, the aromatic polysulfone copolymer is blended with the polyetherketone resin, the aromatic polycarbonate resin, the PPS resin or the fluororesin as described above, so that the aromatic polysulfone resin has A composition that maintains excellent properties and has various excellent properties can be obtained. The composition containing the polyetherketone resin has a sufficient resistance to stress cracking, and the elastic modulus at high temperature, which is insufficient when the polyetherketone resin alone is insufficient, is improved. A composition containing an aromatic polycarbonate resin is excellent in moldability and has improved chemical resistance to an organic solvent and the like, which was insufficient with the aromatic polycarbonate resin alone. The composition containing the PPS resin has excellent moldability and sufficient heat resistance. A composition containing a fluororesin has a low friction coefficient and good wear resistance, and is therefore suitable for use as a sliding material.

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[Procedure amendment]

[Submission date] December 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Chemical 1]

[Chemical 2]

[Chemical 3] (However, in the above formula, n represents an integer of 3 or 4, and R ¹
And R ² each independently represent a hydrogen atom, a halogen atom, or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and a and b are each independently an integer of 1 to 4, X and Y represent a halogen atom. )

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction content]

[0015]

[Chemical 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hiroki Kakumachi, 1-11-3 Minamikasugaoka, Ibaraki-shi, Osaka (72) Inventor Daishiro Kishimoto 2--11-20, Mishimaoka, Ibaraki, Osaka

Claims (4)

[Claims] 1. A resin composition comprising a polyetherketone resin and an aromatic polysulfone copolymer, wherein the aromatic polysulfone copolymer has the following general formulas (I) and (I
I) and (III) are obtained by polymerizing the monomers, and 1 to 49 mol% of a structural unit corresponding to the monomer represented by the general formula (I), and general formulas (II) and (II
Structural units 51 to 99 corresponding to the monomer represented by I)
A resin composition, characterized in that it is composed of mol%. [Chemical 1] [Chemical 2] [Chemical 3] (However, in the above formula, n represents an integer of 3 or 4, and R ¹
And R ² each independently represent a hydrogen atom, a halogen atom, or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and a and b each independently represent an integer of 1 to 4, X and Y represent a halogen atom. ) 2. A resin composition comprising an aromatic polycarbonate resin and the aromatic polysulfone copolymer according to claim 1. 3. A resin composition comprising a polyphenylene sulfide resin and the aromatic polysulfone copolymer according to claim 1. 4. A resin composition comprising a fluororesin and the aromatic polysulfone copolymer according to claim 1.