JPH093325A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE: To markedly improve the compatibility between polyphenylene sulfide and a polysulfone, otherwise incompatible with each other, to thereby give a thermoplastic resin compsn. in which the sizes of dispersed particles are fine and which gives a molded item excellent in stiffness, appearance, and impact strength by using an alkali metal salt. CONSTITUTION: This compsn. contains 10-90 pts.wt. polyphenylene sulfide, 90-10 pts.wt. polysulfone, and an alkali metal salt in an amt. of 0.01-10wt.% of the sum of the foregoing two resins.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing polyphenylene sulfide, and more particularly to a thermoplastic resin composition which is useful as an industrial material excellent in balance of mechanical properties of molded articles and appearance.

[0002]

2. Description of the Related Art Polyphenylene sulfide has a fluidity,
It is a high melting point heat resistant resin with excellent organic solvent resistance, electrical characteristics and flame retardancy. However, when it is used as a molding material for a sliding member, an optical disk carriage, etc., it has a drawback that the polymerization degree is low and the extrusion molding stability and the injection molding stability are poor. Further, since the glass transition temperature is not so high as about 90 ° C., there is also a drawback that the rigidity of the molded product is greatly reduced at a high temperature.

Therefore, glass fiber, carbon fiber, talc,
Rigidity improvement by compounding with an inorganic filler such as silica has been carried out (USP 4,737,539, USP 4,
However, in this case, there are problems that the appearance of the molded product is deteriorated and warpage is likely to occur in the molded product.

Further, as one method for improving the high temperature rigidity and toughness of polyphenylene sulfide, other thermoplastic resins such as polyamide, polyester, polyarylate, polycarbonate, polyphenylene ether, polyimide, polyamide imide, polysulfone, polysulfone, and polysulfone are used. Many blends with ether ketone have been tried. Among them, polysulfone is a resin having excellent heat resistance, high-temperature rigidity, toughness, dimensional stability, non-hygroscopicity, electrical characteristics, and the like, and is a preferable resin as a resin to be blended with polyphenylene sulfide. However, in a simple blend system, the compatibility at the interface is poor because of poor affinity at the interface, and further phase separation occurs during molding. Therefore, the resulting molded article has improved rigidity, but insufficient impact resistance, and cannot obtain a balance of mechanical properties, resulting in poor appearance.

For this reason, as a technique capable of improving the compatibility of the two, for example, Japanese Patent Laid-Open No. 59-164360 discloses.
A resin composition in which a novolac type epoxy resin is added to improve the compatibility and the impact resistance is disclosed. However, even with this method, the compatibility of polyphenylene sulfide and polysulfone is not sufficiently improved, and the effect of improving impact resistance is small.

[0006]

DISCLOSURE OF THE INVENTION The present invention has an extremely excellent compatibility between polyphenylene sulfide and polysulfone.
An object of the present invention is to provide a thermoplastic resin composition having excellent appearance of molded articles, balance of mechanical properties, and moldability.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have remarkably improved the compatibility of both resins by adding an alkali metal salt to polyphenylene sulfide and polysulfone, and The present invention has been completed by finding that an excellent resin composition can be obtained. That is, the present invention is a polyphenylene sulfide-based resin composition containing the following components (a), (b) and (c).

(A) 10 to 90 parts by weight of polyphenylene sulfide (b) 90 to 10 parts by weight of polysulfone (c) 0.01 to 10 parts by weight of an alkali metal salt based on 100 parts by weight of the total of the components (a) and (b). Parts by Weight The present invention will be described in detail below. Component (a) Polyphenylene sulfide The polyphenylene sulfide used in the present invention has the general formula (I)

[0009]

Embedded image Is a crystalline resin containing a repeating unit represented by as a main constituent element.

In the present invention, a polymer having the above repeating unit as a main constituent, that is, a homopolymer comprising the above repeating unit, or a main constituent (80 mol% or more, more preferably 90 mol% or more) is used as a main constituent. For example, a copolymer having one or more repeating units represented by the following general formulas (II) to (VIII) in a proportion of 20 mol% or less can be used.

[0011]

Embedded image (In the formula, R ¹ represents an alkyl group, a phenyl group or an alkoxy group.)

The polyphenylene sulfide used in the present invention preferably has a substantially linear structure from the viewpoint of the physical properties of the molded product. As long as the physical properties are not substantially reduced, for example, a polymerized cross-linked product obtained by using an effective amount of a cross-linking agent (for example, trihalobenzene) at the time of polymerization, or a polymer obtained by heat treatment in the presence of oxygen to cross-link the heat. Crosslinked products can also be used.

The polyphenylene sulfide used in the present invention has a melt viscosity at 300 ° C. and a shear rate of 10 ³ sec ⁻¹ of 100 to 100,000 poise, preferably 500 to
50,000 poise, more preferably 500-3
Those in the range of 000 poise are preferred. If the melt viscosity is less than 100 poise, the fluidity is too high and molding is difficult, which is not preferable. The melt viscosity is 100,000.
On the contrary, even if it exceeds the poise, the fluidity is too low and molding is difficult.

The polyphenylene sulfide used in the present invention can be produced by any method. For example, a method for producing a polymer having a relatively small molecular weight as disclosed in JP-B-45-3368, Kosho 52-12
No. 240, a method for producing a linear polymer having a relatively high molecular weight or a method for obtaining a crosslinked product by heating a low molecular weight polymer in the presence of oxygen, or by adding necessary modifications thereto. Can be manufactured. Polysulfone used for the component (b) Polysulfone present invention have the general formula ^{(IX) -A-SO 2 -} (IX) ( wherein A is interrupted ether oxygen atoms, and / or by a divalent aliphatic group Which represents a divalent aromatic group which may be present) as a main constituent element.

Specific examples thereof include polysulfones containing repeating units represented by the general formulas (X), (XI) and (XII) as main constituents.

[0016]

Embedded image

The polysulfone used in the present invention includes:
Although the polysulfones of the general formulas (X) to (XII) may be used alone or in combination of two or more, the polysulfone of the general formula (XI) is preferable from the viewpoint of high temperature rigidity.
These polymers are obtained, for example, by reacting 4,4'-dichlorodiphenyl sulfone with a sodium salt of 2,2'-bis (4-hydroxyphenyl) propane.
It can be manufactured according to the methods disclosed in Japanese Patent Laid-Open No. 9-52, Japanese Patent Laid-Open No. 52-38000, and the like.

Component (c) Alkali metal salt The alkali metal salt used in the present invention is an alkali metal (Li,
It is a compound consisting of a cation of an element selected from Na, K, Rb, Cs and Fr) and a conjugate base of a monobasic acid. The alkali metal is preferably Li, Na, K, Cs, and more preferably N.
a, K, Cs. As the conjugate base of monobasic acid, hydroxide ion, carbonate ion, acetate ion and alkoxyl ion are preferred. Specific examples of the alkali metal salt include hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate, potassium carbonate and cesium carbonate, acetates such as sodium acetate, potassium acetate and cesium acetate, and sodium methoxy. And alcoholates such as sodium ethoxide, sodium-n-butoxide, potassium-tert-butoxide and the like.

The alkali metal salts used in the present invention may be added alone or in combination of two or more. Among the alkali metal salts used in the present invention, preferred are sodium methoxide, sodium ethoxide, sodium hydroxide, potassium carbonate and cesium acetate.

Additional component The polyphenylene sulfide resin composition of the present invention comprises
Other additional components besides the above components (a) to (c) can be added. For example, as a filler, metal oxides (silicon oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, etc.), silicates (kaolin, clay, mica, pentonite, silica, talc, wollastonite, montmorillonite). Etc.), iron hydroxide, hydrotalcite, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, boron nitride, silicon carbide, glass beads, glass fiber, alumina fiber, silica / alumina fiber, zirconia fiber, silicon nitride fiber, Boron nitride fiber, asbestos fiber, silicon carbide fiber, calcium silicate fiber, gypsum fiber, polyamide fiber, phenol fiber, silicon carbide whisker, potassium titanate whisker,
A total of 10 carbon fibers (a), (b) and (c)
40 parts by weight or less, 20 parts by weight or less of various flame retardants with respect to 0 parts by weight, crystallization accelerator (nucleating agent), phenol-based, sulfur-based and phosphorus-based antioxidant, heat stabilizer, ultraviolet absorber, 5 parts by weight or less of a hindered amine light stabilizer and a colorant may be added as additional components. For the purpose of controlling the degree of crosslinking of polyphenylene sulfide, up to 5 parts by weight of a metal salt of thiophosphinic acid as a crosslinking accelerator, a dialkyltin dicarboxylate as a crosslinking inhibitor, aminotriazole and the like can be added.

Further, in order to improve impact strength, the thermoplastic elastomer is added in an amount of 2 to 40 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of the components (a) and (b). You can The thermoplastic elastomer is a polymer having an elastic modulus at room temperature of 10 ⁸ (dyn / cm ² ) or less, and examples thereof include a polyolefin-based elastomer, a diene-based elastomer, a polystyrene-based elastomer, a polyamide-based elastomer, a polyester-based elastomer, and a polyurethane-based elastomer. Known examples include fluorine-based elastomers and silicone-based elastomers, with preference given to polyolefin-based elastomers, diene-based elastomers and polystyrene-based elastomers.

Suitable polyolefin elastomers include, for example, the following copolymers and modified products of the copolymers. For example, as the copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer,
Examples thereof include ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-maleic anhydride copolymer and the like. As the modified product of the copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene copolymer and ethylene-
Maleic anhydride modified product of butene-1 copolymer, glycidyl methacrylate modified product or N- [4- (2,3-epoxypropoxy) -2,5-dimethylphenylmethyl]
Examples include acrylamide modified products.

Suitable diene elastomers include modified polymers of the following. For example, polybutadiene containing a carboxyl group or an epoxy group, a hydrogenated product of polybutadiene and a hydrogenated product of polyisoprene are modified with maleic anhydride, modified with glycidyl methacrylate or N- [4- (2,3-epoxypropoxy)-
2,5-dimethylphenylmethyl] acrylamide modified products and the like.

Suitable polystyrene-based elastomers include the following copolymers and modified products of the copolymers. Examples of the copolymer include a styrene-butadiene block copolymer, a hydrogenated block copolymer thereof, a styrene-isoprene block copolymer and a hydrogenated block copolymer thereof. As the modified product of the copolymer, a maleic anhydride modified product, a glycidyl methacrylate modified product, or N-modified product of a styrene-butadiene hydrogenated block copolymer and a styrene-isoprene hydrogenated block copolymer is used.
-[4- (2,3-epoxypropoxy) -2,5-dimethylphenylmethyl] acrylamide modified product and the like. The thermoplastic elastomer used in the present invention may be used alone or in combination of two or more.

Composition Ratio of Constituent Components The composition ratio of the components (a) to (c) of the present invention is as follows with respect to a total of 100 parts by weight of the component (a) and the component (b). Ingredient (a)
Is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight. component
If (a) is less than 10 parts by weight, the organic solvent resistance to polar solvents such as dimethylsulfoxide and nitrobenzene and chlorinated hydrocarbons such as dichloromethane and chloroform is poor, and if it exceeds 90 parts by weight, the heat resistance and rigidity are not sufficient, which is preferable. Absent.

The component (b) is 90 to 10 parts by weight, preferably 80 to 20 parts by weight, more preferably 70 to 30 parts by weight.
Parts by weight. If component (b) exceeds 90 parts by weight, the organic solvent resistance to polar solvents such as dimethyl sulfoxide and nitrobenzene and chlorinated hydrocarbons such as dichloromethane and chloroform is poor, and if it is less than 10 parts by weight, heat resistance and rigidity are insufficient. Not preferable.

The component (c) is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. Addition in excess of 10 parts by weight is not preferable because gas is generated during molding and physical properties such as impact strength of the molded product deteriorate. If it is less than 0.01 parts by weight, physical properties such as impact strength of the molded product are deteriorated and appearance is deteriorated, which is not preferable.

Manufacturing Method and Molding Method of Resin Composition The manufacturing method of the resin composition of the present invention is not limited to a particular method, but preferably, melt kneading. As the melt-kneading method, a kneading method generally used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components, together with the additives described in the additional components section, are uniformly mixed by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial. It can be kneaded with a kneading extruder, roll, Banbury mixer, or the like. Each component including the above-mentioned additional components may be fed all at once during kneading or sequentially. Alternatively, a mixture of two or more components may be used. The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, molding methods such as injection molding, blow molding, extrusion molding, press molding, etc. Applicable.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. . The components used are as follows. Component (a) Polyphenylene sulfide: Polyphenylene sulfide manufactured by Topren Co., Ltd. (Brand name: Toprene T-7)
Was used. (Represented by PPS in the table.) Component (b) Polysulfone: Polyethersulfone manufactured by Sumitomo Chemical Co., Ltd. (trade name: Victorex 4100G) was used. (Indicated by PSF in the table.)

Component (c) Alkali metal salt: sodium ethoxide (represented by NaOEt in the table), sodium hydroxide (represented by NaOH in the table) and cesium acetate (CH3COO in the table).
Expressed as Cs. ) Was used. Additional components Novolac type epoxy resin: Epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. (Product name: Epicoat 180S8
0) was used. (Indicated by epoxy resin in the table.)

<Examples 1 to 6 and Comparative Examples 1 to 4> The above components were dry blended in the composition shown in Table 1 and then, using a Labo Plastomill manufactured by Toyo Seiki Co., Ltd., at a temperature of 310.
Kneading was carried out for 5 minutes at a rotation speed of the rotor of 180 rpm. After the kneading was completed, it was crushed by a crusher into particles. Using a compression molding machine manufactured by Toyo Seiki Co., Ltd., the granular sample was molded into a sheet having a thickness of 2 mm at a temperature of 310 ° C. This sheet was heated in a hot air drier at 120 ° C. for 4 hours to sufficiently crystallize polyphenylene sulfide. A test piece for physical property evaluation was cut from this sheet.

Upon kneading and molding, polyphenylene sulfide was used which had been previously vacuum dried at 100 ° C. for 24 hours. Also, the test piece for physical property evaluation is for 2 days,
Evaluation was carried out after storage in a desiccator. The rigidity is JIS-
Bending rigidity was measured at 23 ° C. according to K-7106. The Izod impact strength was measured with an Izod impact tester according to JIS-K-7110 by stacking three 2 mm thick test pieces. For the dispersed form, a part of the sheet was cut out and observed with a scanning electron microscope S-2400 manufactured by Hitachi, Ltd. at a magnification of 1000 times and 5000 times. From the observed morphological photograph, SPICC manufactured by Nippon Avionics Co., Ltd.
The number average dispersed particle diameter Dn was determined by the following equation using an A II type image analyzer.

Dn = Σnidi / Σni di is the measured value of the dispersed particle diameter ni is the number of dispersed particles of the dispersed particle diameter di The appearance is good, ○ is worse, but there is no problem in practical use, and the surface is rough. Therefore, there is a problem in practical use. The results are shown in Table 1.

[0034]

[Table 1]

[0035]

INDUSTRIAL APPLICABILITY The polyphenylene sulfide-based resin composition of the present invention is a thermoplastic resin that gives a molded article excellent in rigidity, appearance and impact strength because the compatibility of polyphenylene sulfide and polysulfone is remarkably improved by using an alkali metal salt. It is a resin composition.

Claims (1)

[Claims] 1. A polyphenylene sulfide-based resin composition containing the following components (a), (b) and (c). (a) Polyphenylene sulfide 10 to 90 parts by weight (b) Polysulfone 90 to 10 parts by weight (c) 0.01 to 10 parts by weight of alkali metal salt based on 100 parts by weight of the total of components (a) and (b).