JPH0611863B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a PPS resin composition comprising polyphenylene sulfide (hereinafter referred to as PPS), a thermoplastic polyester resin (hereinafter referred to as polyester), an epoxy resin and the like.

Many blend compositions of PPS and polyester are known. However, since most of these compositions have insufficient compatibility, they have problems such as a large decrease in mechanical strength such as bending strength and impact strength, deterioration of the surface condition of a molded article, and the like. It turned out that it was hard to say that the original purpose of blending was achieved.

As a result of intensive studies, the present inventors have found that a composition comprising PPS, polyester and a specific epoxy resin has excellent compatibility,
In addition, it has been found that the characteristics of both blended polymer components, such as the improvement of the brittleness of PPS and the improvement of heat resistance and hydrolysis resistance of polyester, can be exhibited, and a highly practical molding material can be provided. Invented.

That is, the present invention includes (A) 90 to 40 parts by weight of PPS, and (B) polyester 1
0-60 parts by weight, (C) novolac type epoxy resin 0.1
.About.20 parts by weight (based on 100 parts by weight of A and B above) and (D) 0 to 300 parts by weight of reinforcing filler (based on 100 parts by weight of total above A, B and C). Provided is a PPS resin composition having excellent compatibility.

The PPS used in the present invention has the general formula It is preferable that the content of the structural unit represented by is 70 mol% or more, and if the amount is less than 70 mol%, it is difficult to obtain a composition having excellent properties. This polymer can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydroxide. Examples of the method include polymerization of p-chlorothiophenol, and self-condensation of p-chlorothiophenol. Sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane. The method of causing is suitable. At this time, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid or to add an alkali hydroxide in order to adjust the degree of polymerization. If less than 30 mol% as a copolymerization component, a meta bond Ortho-join Ether bond Sulfone bond Biphenyl bond Substituted phenyl sulfide bond Here, R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of carboxylic acid), trifunctional bond Although it may be contained within a range that does not significantly affect the crystallinity of the polymer, the content of the copolymerization component is preferably 10 mol% or less. Particularly, when a phenyl, biphenyl, naphthyl sulfide bond or the like having a functionality of 3 or more is selected for the copolymerization, the content is preferably 3 mol% or less, more preferably 1 mol% or less.

As a specific method for producing such PPS, for example, (1) a reaction of a halogen-substituted aromatic compound with an alkali sulfide (US Pat. No. 2,513,188, JP-B-44-2767).
No. 1 and Japanese Patent Publication No. 45-3368) (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or a copper salt (US Pat. No. 3,274,165, British Patent No. 11)
No. 60660) (3) Condensation reaction of an aromatic compound with sulfur chloride in the presence of a Lewis acid catalyst (Japanese Patent Publication No. 46-27).
255, Belgian Patent No. 29437)) and the like.

In order to improve the compatibility of the composition, which is the main object of the present invention, PPS having a low crosslink density and / or a crystallinity reduced by copolymerization can be used. However, since a decrease in crosslink density and / or a decrease in crystallinity may result in a decrease in heat resistance, moldability, rigidity, etc., which are inherent properties of PPS, consideration must be taken according to the purpose.

PPS is currently available from Philips under the trade name Ryton. When
And it is put on the market. Ryton The bridge is dense
Depending on the degree, V-1, P-2, P-3, P-4, R-6
There are types. Furthermore, JP-A-50-84698,
High molecular weight P known from Kai 51-144495
PS can also be used.

On the other hand, as polyester, terephthalic acid, isophthalic acid, orthophthalic acid, naltalenedicarboxylic acid, 4,
4'-diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, adipic acid, sebacic acid, azelaic acid,
Decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, dicarboxylic acids such as dimer acid or ester-forming derivatives thereof and ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, Cyclohexanedimethanol, hydroquinone, bisphenol A, 2,2-
A polyester obtained from glycols such as bis (4-hydroxyethoxyphenyl) propane, xylylene glycol, polyethylene ether glycol, polytetramethylene ether glycol, and aliphatic polyester oligomers having hydroxyl groups at both ends. In a mixed solvent of phenol and ethane tetrachloride in a weight ratio of 6: 4, the intrinsic viscosity [η] measured at 30 ° C. is 0.3 to
Those having a range of 1.5 d / g are used.

As a comonomer component, it retains a hydroxycarboxylic acid such as glycolic acid, hydroxybutyric acid, hydroxybenzoic acid, hydroxyphenylacetic acid, or naphthylglycolic acid, a lactone compound such as propiolactone, butyrolactone, valerolactone, or caprolactone, or thermoplasticity. Trimethylolpropane within the range possible,
It may contain a polyfunctional ester-forming component such as trimethylolethane, glycerin, ventaerythritol, trimellitic acid, trimesic acid and pyromellitic acid.

Further, dibromoterephthalic acid, tetrabromoterephthalic acid, tetrabromophthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, 1,4-dimethyloltetrabromobenzene, tetrabromobisphenol A, and tetrabromobisphenol A ethylene oxide adducts. A thermoplastic polyester resin obtained by copolymerizing a halogen compound having a halogen compound such as chlorine or bromine as a substituent in the aromatic nucleus and having an ester-forming group is also included.

Particularly preferred polyesters include polybutylene terephthalate, polyhexamethylene terephthalate, poly (ethylene, butylene terephthalate), poly (cyclohexane dimethylene terephthalate), poly (butylene tetramethylene terephthalate), 2,2-bis (β-hydroxy). Examples include ethoxytetrabromophenyl) propane copolymerized porobutylene terephthalate and the like.

The novolak type epoxy resin, which is an essential component for improving the compatibility between PPS and polyester, contains two or more epoxy groups, and is a glycidyl ether such as phenol novolac or phenol derivative novolac such as cresol novolac. The thing of a system is illustrated. You may use these epoxy resins individually and / or as a mixture of 2 or more types. The epoxy resin may be used in combination with general amines, acid anhydrides, phenols, polysulfides and other curing agents.

The amount of such a curing agent used is preferably smaller than that for usual purposes, and when it is used in a large amount, the melt fluidity of the composition of the present invention may be significantly lowered. As a combined effect with the curing agent, it can be expected to prevent the deterioration of bleeding property, thermal property, etc. due to the addition of the epoxy resin.

The epoxy resin may be added by mixing with other raw materials (PPS and polyester) constituting the composition of the present invention at the same time. However, the epoxy resin and PPS or polyester may be previously kneaded, and the polyester or PPS may be further added. Mixing and kneading is preferable in consideration of the possibility of reaction between the epoxy resin and PPS and / or polyester.
Alternatively, the epoxy resin may be added after the PPS and the polyester are kneaded in advance.

The mixing ratio of PPS and polyester is 10 to 60 parts by weight with respect to 90 to 40 parts by weight of PPS, and preferably 10 to 50 parts by weight with respect to 90 to 50 parts by weight of PPS. If the proportion of the polyester is less than 10 parts by weight, the compounding effect of the polyester is small, and if it exceeds 60 parts by weight, the excellent thermal properties and rigidity of PPS are lost, which is not preferable. The amount of epoxy resin added is PP
0.1 to 100 parts by weight of S and polyester
20 parts by weight, preferably 1 to 10 parts by weight. If the amount is less than 0.1 parts by weight, the effect is small, and if it exceeds 20 parts by weight, the properties of PPS such as rigidity are lost, and depending on the epoxy resin added, bleeding to the surface of the molded article and melt flowability of the composition may occur. It is not preferable because it may significantly decrease.

In addition to the above components, the composition of the present invention further includes the following reinforcing fillers, so-called reinforced compositions are also included, and such reinforcing fillers include glass fibers. , Carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, silicon nitride and other fibrous reinforcing agents; barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, sericite, zeolite, mica , Mica, nepheline sinite, talc, atalpulgite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, nitric oxide Molybdenum sulfide, graphite, gypsum, glass beads,
Examples thereof include inorganic reinforcing fillers such as glass balloons, quartz and quartz glass, and organic reinforcing fillers such as aramid fibers. The amount of these fillers added is usually 1 to 300 parts by weight, preferably 5 to 20 parts by weight, relative to 100 parts by weight of the resin component (the total of PPS, polyester and epoxy resin).
0 parts by weight. If the addition amount exceeds 300 parts by weight, there is a problem that the melt fluidity of the composition deteriorates and the appearance of the molded product is impaired.

The following thermoplastic resins can be mixed and used in the composition of the present invention within a range not departing from the object of the present invention. As the thermoplastic resin, ethylene, propylene, butylene,
Homopolymers or copolymers of vinyl monomers such as pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, methacrylic acid ester, (meth) acrylonitrile, polyurethane system Polymer, polyamide polymer, polyester elastomer, polycarbonate,
Homopolymers such as polyacetal, polysulfone, polyarylsulfone, polyethersulfone, polyarylate, polyphenylene oxide, polyetheretherketone, polyimide, polyamideimide, silicone resin, phenoxy resin, fluororesin, polyarylether, etc. Mention may be made of block or graft polymers. In addition, a small amount of a releasing agent, a coupling agent, a colorant, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a foaming agent, a flame retardant, a flame retardant auxiliary agent such as antimony trioxide may be added.

In the present invention, the composition of the above-mentioned invention can be prepared by various known methods. For example, there is a method in which the raw materials are mixed in advance by a mixer such as a tumbler or a Henschel mixer, and then fed into a uniaxial or biaxial extruder or the like, melt-kneaded, and then prepared as pellets.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Examples 1-2, Comparative Examples 1-2 PPS (Ryton V-1 or Ryton R-6: Ph
(Manufactured by Lips) and polybutylene terephthalate resin (hereinafter
Later, abbreviated as PBT, Novadoul 5010: Mitsubishi Kasei Co., Ltd.
Made) and epoxy resin (cresol novolac grease
Zylether: Epicron N-695: Dainippon Ink and Chemicals
(Manufactured by Kogyo Co., Ltd.) were mixed in the proportions shown in Table 1. Then
Extruded and kneaded at a cylinder temperature of 300 ° C to obtain pellets.
It was Injection molding machine (cylinder temperature 2
Mold the test piece at 90 ℃, mold temperature 100 ℃
It was However, in the formulation of Comparative Example 1, the melt viscosity of the composition was notable.
It is very fragile and it is very fragile.
The shape was impossible.

The results of physical property evaluation are summarized in Table 1.

Examples 3 to 4, Comparative Examples 3 to 5 PPS, epoxy resin, ethylene / glycidyl methacrylate copolymer [LEX Pearl RA4100 manufactured by Japan Petrochemical Industry Co., Ltd., glycidyl methacrylate content 10% by weight), PBT and glass. Fiber (Glaslon CSO3MA 497:
Asahi Glass Co., Ltd. was mixed in the ratio shown in Table-2. Then, extrusion kneading was performed at a cylinder temperature of 320 ° C. to obtain pellets. A test piece was molded by an injection molding machine (cylinder temperature: 300 ° C., mold temperature: 100 ° C.) for performance evaluation. The results of physical property evaluation are summarized in Table 2.

As is clear from the results shown in Tables 1 and 2, the composition obtained according to the present invention had good compatibility and exhibited an excellent appearance, and the heat distortion temperature, the bending strength, the impact strength and the PCT.
The results are excellent in physical properties such as hydrolyzability.

On the other hand, comparative examples outside the scope of the present invention are compatibility, heat distortion temperature,
The bending strength and the hydrolyzability were extremely poor, and it was not practical at all.

Claims (1)

[Claims] 1. A polyphenylene sulfide (A) 90-4
0 parts by weight, (B) thermoplastic polyester resin 10 to 60
Parts by weight, (C) 0.1 to 20 parts by weight of novolac type epoxy resin (relative to 100 parts by weight of A and B above) and (D) 0 to 300 parts by weight of reinforcing filler (total of A, B and C above). A polyphenylene sulfide-based resin composition containing 100 parts by weight).