JPH0361702B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyphenylene sulfide composition containing an inorganic filler and an epoxy resin, which exhibits particularly excellent performance in mechanical strength, dimensional stability, thermal properties, etc., and is useful as an engineering plastic. This invention relates to a resin composition with high properties. Polyphenylene sulfide (hereinafter abbreviated as PPS)
PPS is attracting attention as a high-performance engineering plastic with excellent heat resistance, moldability, chemical resistance, and rigidity, but PPS alone has the disadvantage of low elongation and brittleness, and it is usually used with various materials such as glass fiber. It is used with inorganic fillers added. However, if a large amount of inorganic filler is blended, molding processability may deteriorate and the appearance of the molded product may be impaired, so there are limitations to its use. On the other hand, if the amount of inorganic filler is small, not only will the reinforcing effect be reduced, but there will also be problems such as voids occurring in the molded product, and many proposals have been made to improve these problems. There is. For example, Japanese Patent Publication No. 53-13391 proposes improving mechanical strength, heat distortion temperature, etc. by blending an uncured epoxy resin with PPS containing an inorganic filler. However, in some cases, with this formulation, the fluidity of the composition decreases significantly as the epoxy resin itself progresses to three-dimensional crosslinking.
The disadvantage is that it becomes impossible to supply a stable quantity of resin to the mold cavity, and that the epoxy resin bleeds onto the surface of the molded product even in an atmosphere with a temperature of about 50 to 150℃, which significantly impairs the appearance of the molded product. be. Furthermore, even if a large amount of epoxy resin is blended, problems such as a decrease in heat distortion temperature and loss of rigidity at high temperatures are observed, and it has been found that there is much room for improvement in terms of practicality. Polymer blends of PPS and various thermoplastic resins have also been proposed. For example, the
No. 13468 blends PPS with polycarbonate resin to improve moldability and impact resistance. Japanese Patent Publication No. 53-13469 proposes blending polystyrene with PPS to improve moldability and impact resistance.
Furthermore, JP-A-50-156561 proposes a resin composition which is made of PPS and polyphenylene oxide and has excellent moldability and flame retardant effect. However, it has been found that even these proposals have problems such as solvent resistance, thermal properties, melt flow characteristics, etc., which are lower than PPS resin alone, and there is still room for improvement. did. As a result of intensive research, the present inventors have discovered a highly practical PPS composition that greatly improves the above-mentioned drawbacks of PPS and has excellent mechanical strength, dimensional stability, thermal properties, etc. That is, the present invention uses 30 to 90 parts by weight of PPS and an inorganic filler.
A PPS composition comprising 70 to 10 parts by weight and 0.1 to 100 parts by weight of a cured epoxy resin (based on 100 parts by weight of PPS) is provided. The composition of the present invention does not lose the excellent properties of PPS, has improved mechanical strength and thermal properties, has excellent moldability, and has a molded product with an excellent appearance without bleeding even at 150°C. It is something that can bring about. The general formula for PPS used in the present invention is

A composition containing 70 mol% or more of the structural unit represented by the formula is preferable because it provides a composition with excellent properties. PPS polymerization methods include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or polymerizing p-dichlorobenzene in the presence of sodium sulfide, sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Polymerization methods include self-condensation of p-chlorothiophenol, but sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane. The method is appropriate.
At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide.
If it is less than 30 mol% as a copolymer component, it is a meta bond.

[Formula] Ortho bond

[Formula] Ether bond

[Formula] Sulfone bond

[Formula] biphenyl join

[Formula] Substituted phenyl sulfide bond

[Formula] where R represents alkyl, nitro, phenyl, alkoxy, carboxylic acid or a metal base of carboxylic acid), trifunctional phenyl sulfide bond

[Formula] and the like may be contained as long as they do not significantly affect the crystallinity of the polymer, but preferably the copolymerization component is 10 mol% or less. In particular, when trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bonds, etc. are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less. Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368) (2) ) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3274165, British Patent No. 1160660)
(3) Condensation reaction of aromatic compounds with sulfur chloride in the coexistence of a Lewis acid catalyst (Special Publication No. 46-27255)
(see Belgian Patent No. 29437), and can be arbitrarily selected depending on the purpose. Inorganic fillers used in the present invention include glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber,
Fibrous reinforcement such as silicon nitride; barium sulfate,
Calcium sulfate, kaolin, clay, pyrofluorite, bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, attalpargite, wollastonite,
PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass balloon, quartz powder, etc. Examples include inorganic fillers. In addition, when adding these inorganic fillers, it is preferable to use a known silane coupling agent together. The blending ratio of PPS and inorganic filler in the composition of the present invention is generally in the range of 70 to 10 parts by weight of inorganic filler to 30 to 90 parts by weight of PPS. The cured epoxy resin used in the present invention is produced by a curing reaction between an epoxy resin and a curing agent such as a phenolic resin, amines, or acid anhydride. The epoxy resin preferably contains one or more epoxy groups, especially two or more. Typical examples include a condensate of bisphenol A and epichlorohydrin, and a halogenated bisphenol instead of bisphenol A. Examples thereof include those using A, resorcinol, bisphenol F, and bisphenol S, novolac types, and polyhydric alcohol types other than those mentioned above. This epoxy resin cured product is obtained by melting and heating the epoxy resin and a curing agent such as a phenol resin, amines, acid anhydride, etc. together with a normal reaction catalyst such as a tertiary amine as needed, and then carrying out addition polycondensation. It can be easily produced by cooling and grinding. The most important thing when adding a cured epoxy resin is that the cured epoxy resin is uniformly dispersed in the composition. It is thought that uniform dispersion progresses at the stage of kneading into pellets or at the stage of kneading in the molding machine cylinder, but
It is reasonable to add it after pulverizing it to 300 μm or less, since the object of the present invention can be easily achieved. At this time, the particle size of the cured epoxy resin may be further increased.
It is more convenient to achieve the object of the present invention if it is pulverized to 100 μm or less. If the cured epoxy resin is unevenly dispersed in the composition or the particle size is too large, the appearance and mechanical strength of the molded product may be impaired.
Both are disadvantageous for the purpose of the present invention. In the present invention, the epoxy resin cured product is
It is used in a proportion of 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, based on 100 parts by weight of PPS. If this amount is too small, the effect of the addition will be reduced, and if it is too large, the high temperature properties of the molded article and the fluidity of the composition will become too poor, both of which are disadvantageous. Furthermore, the composition of the present invention may contain tetrafluoroethylene, polyamide, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyimide, polyamideimide, epoxy resin, polyethylene,
Polymers such as polypropylene, polyester, polyphenylene oxide, polystyrene, and small amounts of mold release agents, lubricants, heat stabilizers, colorants, weather stabilizers, and blowing agents may be added. In the present invention, the composition can be prepared by various known methods. For example, all the raw materials are uniformly mixed in advance using a mixer such as a tumbler or Henschel mixer, then fed to a single or twin screw extruder, etc., melted and kneaded at 280°C to 360°C, and then prepared as pellets. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples. Example 1 (Production of cured epoxy resin powder) Novolac type epoxy resin, Epicron N-
670 (manufactured by Dainippon Ink and Chemicals, melting point 73°C, epoxy equivalent 212) 100 parts by weight, novolac type phenol-formaldehyde resin (Burcam TD-
2093, manufactured by Dainippon Ink and Chemicals, melting point 100℃,
50 parts by weight of OH equivalent (104) were uniformly melted at temperatures of 100°C and 120°C, respectively, and homogeneously melt-mixed with 2 parts by weight of the curing reaction catalyst 2-methylimidazole (manufactured by Kishida Chemical Co., Ltd.), and heated at 140°C for 2 hours. A curing reaction was then carried out at 180°C for 4 hours. The obtained cured product was coarsely pulverized with a hammer mill, then finely pulverized with a micropulperizer, and passed through a 200 mesh screen to obtain an epoxy resin cured product powder. The particle size of the obtained cured epoxy resin powder is 100 μm or less, and its heat distortion temperature according to ASTM D-648 is 5% of that measured at 160°C and 10°C/min.
The weight loss temperature was 320°C. Examples 1 to 3, Comparative Examples 1 to 6 PPS (manufactured by Philips Corporation, RYTON P-6 and P-4), glass beads as a filler (manufactured by Toshiba Balloteini, EGB731B), glass fiber (manufactured by Asahi Glass Co., Ltd., Glasslon CS03 MA497), epoxy resin cured powder (prepared in Reference Example 1) as a polymer additive, epoxy resin [Epiclon
7050 (bisphenol type) produced by Dainippon Ink & Chemicals Co., Ltd.] Epiclon N-670 and polycarbonate resin (manufactured by Mitsubishi Kasei Co., Ltd., Novarex 7025) were uniformly premixed in the proportions shown in Table 1, and then mixed in the same direction rotating type.
Screw rotation speed in a 50m/m twin screw extruder
Pellets were obtained by melt-kneading at 100 rpm and a barrel temperature of 320°C. The pellets were molded using a screw-type injection molding machine (manufactured by Toshiba Machine Co., Ltd.) at a temperature of 320℃ and a mold temperature of 130℃.
°C, injection pressure (primary/secondary) 1700/600 (Kg/cm ² )
A test piece for measuring bending strength and appearance change was molded. In addition, in order to evaluate the flow stability of the composition, the flow rate (g/10 min) of the pellets was measured according to ASTM D-1238 (measurement conditions: 300
°C/load 5Kg). Furthermore, in order to measure the heat bleed resistance and solvent resistance of the molded products, each test piece was immersed in toluene at 150°C/hour during hot air drying.
I did a 24 hour test. The results are summarized in Table 1. As shown in Table 1, the composition according to the present invention has excellent mechanical strength, flow stability, bleed resistance, and solvent resistance, while the comparative examples other than the composition according to the present invention have decreased mechanical strength and poor flow stability. It was observed that there was a change in fluidity with the passage of time at high temperatures. Furthermore, poor appearance of the molded product was noticeable due to bleeding under high temperatures or immersion in toluene.

【table】

Claims (1)

[Claims] 1 30 to 90 parts by weight of polyphenylene sulfide, 70 to 10 parts by weight of inorganic filler, and cured epoxy resin
0.1 to 100 parts by weight (polyphenylene sulfide 100
parts by weight).