JP3478371B2 - Polyphenylene sulfide resin composition for precision molding - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has no or extremely few burrs at the time of molding, has excellent dimensional accuracy and rigidity, and particularly has good moldability such as injection molding. The present invention relates to a precision molding material comprising an improved polyphenylene sulfide resin composition. 2. Description of the Related Art Conventionally, metals such as aluminum die-cast and zinc die-cast have been used for precision parts represented by optical parts, electronic / electric parts, automobile parts and the like. However, the cost of processing into a given shape with high dimensional accuracy leads to an increase in product cost,
In recent years, the use of thermoplastic resins centering on engineering plastics has been increasing. In other words, a large number of components can be continuously produced by injection molding even with a complicated shape, so that component production costs can be reduced, and the number of components can be reduced by integrating a plurality of components. Among the thermoplastic resins, polyphenylene sulfide resin (hereinafter abbreviated as PPS) has heat resistance,
Excellent dimensional stability, chemical resistance, flame retardancy, moldability, rigidity,
In applications where dimensional stability is demanding, fibrous,
PPS filled with a plate-like or granular inorganic filler at a high concentration is used. However, a disadvantage of PPS is that burrs are easily generated during molding. This is PP
The cause is that the melt viscosity is relatively low even in the places where the shear rate of the resin is low, such as the terminal of the cavity or the minute clearance portion of the mold, where the melt viscosity of S has low shear rate dependence. As for molded products using PPS, burrs are currently removed by blasting, such as by spraying fine nylon beads at a high speed, and the man-hours involved are not negligible. Also, as a recent trend, switching to the integral molding method with other metal foils etc. has been actively promoted for the purpose of further reducing the cost of parts. Since the situation is inevitable, there is a strong demand for non-validating PPS used for this purpose. Various methods have been studied to reduce burrs in PPS. For example, to improve the flow characteristics of PPS, PPS is added to polyamide or liquid crystal polymer,
Although there is a method of adding other specific polyester compounds and silane compounds, the definitive burr has not been reduced, and at that time, the rigidity of the material significantly decreases, especially when a polyamide system is added, the water absorption of the material increases. There is a fatal problem such as dimensional stability of PPS being impaired. on the other hand,
Polyphenylene ether (hereinafter abbreviated as PPE) for PPS
(For example, JP-A-7-53865) has been proposed. It is possible to reduce burrs by adding PPE, but in order to extremely suppress the generation of burrs or to prevent burrs from occurring, PP
It is necessary to increase the compounding amount of E,
There is a problem that the rigidity is significantly reduced. [0005] A PPS resin composition for precision molding which has excellent dimensional accuracy and rigidity, is excellent in moldability such as injection molding and the like, and has little or no burrs during molding. . SUMMARY OF THE INVENTION The present invention relates to (a) 300
C., a shear rate of 500 sec ^-1 and a polyphenylene sulfide resin having a melt viscosity of 300 to 3,000 poise at a shear rate of 500 to 300%.
A resin composition comprising 5 to 40% by weight of a polyphenylene ether resin having a melt viscosity of 5,000 to 50,000 poise in sec- ¹ , (b) an inorganic filler composed of kaolin and spherical silica, and (c) a fibrous filler. (B) to 100 parts by weight of the component (a) in a polyphenylene sulfide resin composition comprising a material, another inorganic filler or a mixture thereof.
50-200 parts by weight of the component, 10-300 of the component (c)
Parts by weight (however, the total of (b) and (c) is 400 parts by weight or less), and the inorganic filler of (b) is kaolin 20
20 to 80% by weight of spherical silica is blended with respect to 80 to 80% by weight, and the kaolin has an average particle diameter of 0.05 μm to 0.5 μm, and the spherical silica has an average particle diameter of 0.0
A polyphenylene sulfide resin composition for precision molding having a size of 6 μm or more and 0.6 μm or less. DETAILED DESCRIPTION OF THE INVENTION The PPS resin used as the component (a) in the present invention is as follows: Preferably, the composition contains at least 70 mol% of the structural unit represented by the formula. If the amount is less than 70 mol%, it is difficult to obtain a composition having excellent properties. As a polymerization method of the PPS resin, a method of reacting sodium sulfide with p-dichlorobenzene in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable.
At this time, an alkali metal salt of a carboxylic acid or a sulfonic acid is added to adjust the degree of polymerization, or an alkali hydroxide, an alkali metal carbonate, or an alkaline earth metal oxide is added. If the amount of the copolymer component is less than 30 mol%, a meta bond, an ortho bond, an ether bond, a sulfone bond, a biphenyl bond, a substituted phenylene sulfide bond (where the substituent is an alkyl group, nitro group, phenyl group, alkoxy group Carboxylic acid group, metal base of carboxylic acid), 3
Even if it contains a functional bond or the like, it may be in a range that does not significantly affect the crystallinity of the polymer, but preferably the copolymer component is 10 mol% or less. [0008] The PPS resin is generally used in the presence of oxygen in the range of 200 to
It is used after thermal crosslinking at a temperature of 250 ° C. to adjust the melt viscosity. Desirable melt viscosity of the PPS used in the present invention is 300 to 3 at 300 ° C. and a shear rate of 500 sec ⁻¹ .
000 poise, more preferably in the range of 600 to 2500 poise. If the melt viscosity is less than 300 poise, burrs are likely to occur, and if it exceeds 3000 poise, moldability deteriorates. When compounding a filler at a high concentration, it is desirable to use a filler having a relatively low viscosity within the above range in consideration of extrusion processability and moldability. The PPE resin used in the component (a) is also (Wherein at least one of R1 and R2 in the formula is a linear or primary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, and a halogen atom. May be the same or different from each other), a homopolymer comprising a repeating unit represented by the general formula (1) and a repeating unit represented by the general formula (1) (In the formula, R3, R4, R5, and R6 each represent a linear or primary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a hydrogen atom, or the like. And R3 and R4 may not be hydrogen atoms at the same time, although they may be the same or different from each other). Graft copolymers in which styrene is graft-polymerized to copolymers or copolymers. Representative examples of homopolymers of PPE include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether and poly ( 2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-) (Phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene)
Ether, poly (2-ethyl-6-isopropyl-1,
4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6) -Chloroethyl-1,4-
Homopolymers such as phenylene) ether are exemplified. The PPE copolymer is o-cresol or a compound of the general formula (Wherein R 3, R 4, R 5, R 6 have the same meaning as described above), and mainly comprises a polyphenylene ether structure obtained by copolymerization with an alkyl-substituted phenol such as 2,3,6-trimethylphenol. Polyphenylene ether copolymers. Desirable melt viscosity of the PPE used in the present invention is 5,000 to 50,000 poise at 300 ° C. and a shear rate of 500 sec ⁻¹ , more preferably 100 to 50,000 poise.
It is in the range of 00 to 30,000 poise. If it is less than 5,000 poise, the effect of reducing burrs is small, and if it exceeds 50,000 poise, moldability deteriorates. The mixing ratio of PPS and PPE is 60 to 95% by weight of PPS and PPE5
-40% by weight, more preferably 70-90% by weight of PPS
10 to 30% by weight of PPE. PPE is 5
If the amount is less than 40% by weight, the effect of reducing burrs is small, and if it exceeds 40% by weight, moldability deteriorates. [0011] (b) kaolin used in the components of the present invention is white fine clay minerals, typically formula 2SiO ₂ · A
The average particle diameter represented by l ₂ O ₃ .2H ₂ O is 0.05 μ
m to 0.5 μm, more preferably 0.1 μm to 0.4 μm. Average particle size 0.05μ
If it is less than m, a problem of moldability occurs, and if it exceeds 0.5 μm, the effect of reducing burr is reduced. Spherical silica is added to improve moldability during molding. Spherical silica is high-purity spherical synthetic silica (SiO2) obtained by igniting metallic silicon powder in an oxygen stream to continuously form a self-combustion flame and performing a gas phase reaction at a high temperature of 4000 ° C. It is from 0.06 μm to 0.6 μm, more preferably from 0.1 μm to 0.5 μm. When the average particle diameter of the spherical silica is less than 0.06 μm, the effect of improving the moldability is reduced, and when it exceeds 0.6 μm, burrs are easily generated. The mixing ratio of kaolin and spherical silica is 20 to 80% by weight of kaolin and 20 to 80% by weight of spherical silica, more preferably 30 to 70% by weight of kaolin and 30 to 70% by weight of spherical silica. When the amount of the spherical silica is less than 20% by weight, the effect of improving the moldability is small.
If it exceeds 0% by weight, the strength is reduced. The amount of the component (b) is 50 to 200 parts by weight, more preferably 60 to 180 parts by weight, per 100 parts by weight of the component (a). If the amount is less than 50 parts by weight, the effect of reducing burrs is small, and if it exceeds 200 parts by weight, the moldability is reduced. The fibrous filler which is the component (c) of the present invention /
Other inorganic fillers are used to improve various physical properties such as mechanical strength, heat resistance, dimensional stability, and electrical properties of the material (b)
It is desirable to use in combination with the components. Examples of the fibrous filler include glass fiber, carbon fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and stainless steel, Inorganic fibrous materials such as fibrous materials of metals such as aluminum, titanium, copper, and brass can be used. Other inorganic fillers include carbon black, quartz powder, glass beads, glass powder, glass flake, calcium silicate, aluminum silicate,
Silicates such as clay, mica, diatomaceous earth, wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; calcium sulfate; barium sulfate And the like, and other metal powders such as silicon carbide, silicon nitride, boron nitride, and various metal powders. Two or more of these fillers can be used in combination. In use, it is desirable to modify the particle surface with a surface treatment agent. Examples of the surface treatment agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and the like. The filler may be surface-treated with these compounds in advance or used at the same time as mixing the materials. The amount of these fillers is (a) component 10
The amount is 10 to 300 parts by weight, more preferably 50 to 250 parts by weight, per 0 parts by weight. When the amount is less than 10 parts by weight, the effect of improving various properties is small, and when it exceeds 300 parts by weight, the moldability is significantly reduced. In particular, in the case of a fibrous filler, this tendency is strong, and anisotropy tends to be developed when the molded product shrinks. Therefore, it is desirable to keep the content within the above-mentioned range. Further, the composition of the present invention generally contains thermoplastic resin, and known substances added to the thermosetting resin, that is, stabilizers such as antioxidants and ultraviolet absorbers,
Antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants and the like can also be added as needed. The method for producing the composition according to the present invention is not limited. For example, it is also possible to measure the components, mix them with a blender, a mixer, or the like, and melt-knead them with an extruder to form pellets. Alternatively, the glass fiber may be kneaded and pelletized by being supplied in a fixed amount by a side feeder. The pellet-shaped molding material thus obtained is
It is usually molded into a desired shape by a widely used thermoplastic resin molding machine, injection molding machine, injection compression molding machine or the like and used. The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. The components used in Examples 1 to 8 and Comparative Examples 1 to 13 are as shown below. PPS resin: Product name, manufactured by Topren Co., Ltd. K-4 PPE resin: Melt viscosity: 18000, powder (at 300 ° C, 500sec-1) Kaolin: Product name, manufactured by ENGELHARD (USA) ASP200 Spherical silica: Product name, manufactured by Admatex Co., Ltd. Fine SO-25R Glass fiber: Nippon Sheet Glass Co., Ltd. Product name RES03-TP29 Calcium carbonate: Shiraishi Calcium Co., Ltd. Product name Whiten P-30 The above components are blended in the composition shown in Tables 1 and 2, and biaxial The mixture was melted and kneaded with a kneader to form pellets. After the obtained molding material was dehumidified and dried at 140 ° C. for 5 hours, the cylinder temperature was 300 ° C., the injection pressure was 1200 kg / cm ² , the injection speed was medium, and the injection molding machine (TOSHIBA MACHINE IS80EPN) was used.
Molding was performed under the condition of a mold temperature of 140 ° C. to prepare various test pieces. Using each test piece, flexural strength, flexural modulus,
The molding shrinkage was measured according to the ASTM test method. Also,
Regarding the burr characteristics, a clearance portion (width of 5 mm) provided around the cavity when each was molded at the minimum injection speed for filling was used.
(mm, depth: 20 μm). Further, the melt viscosity of the material was measured with a capillograph (manufactured by Toyo Seiki) (310 ° C., shear rate)
20-6000sec- ¹ ). The results are shown in Tables 1 to 3. [Table 1] [Table 2] [Table 3] According to the present invention, it is possible to provide a PPS resin composition which has good dimensional accuracy and rigidity, is particularly excellent in moldability, and does not generate or has very few burrs during molding. Such a resin composition can be used for precision parts such as optical parts of an optical pickup.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 71:12) (58) Investigation field (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 71 / 10-71/12 C08K 3/34 C08K 3/36 C08K 7/02

Claims (1)

(57) [Claims] (1) (a) 300 ° C., shear rate 500 sec ⁻¹
To 60 to 95% by weight of polyphenylene sulfide resin having a melt viscosity of 300 to 3000 poise
5000-500 at 00 ° C and shear rate 500 sec ^-1
Resin composition 100 containing 5 to 40% by weight of polyphenylene ether resin having a melt viscosity of 00 poise
(B) The average particle diameter is 0.05 μm or more with respect to parts by weight.
Kaolin of 0.5 μm or less and average particle size of 0.06 μm
consisting of a mixture of spherical silica of m or more and 0.6 μm or less ,
20 to 80% by weight of kaolin, 20 to 80% by weight of spherical silica
50 to 200 parts by weight of an inorganic filler compounded at 80% by weight (c) 10 to 300 parts by weight of a fibrous filler, another inorganic filler, or a mixture thereof (however, the total of (b) and (c)
Is 400 parts by weight or less) . A polyphenylene sulfide resin composition for precision molding, characterized in that: