JP2005082760A - Resin composition for precision molded products - Google Patents

Abstract

As a precision molded product such as optical device mechanism parts, optical fiber connector ferrules, printer parts, copier parts, automobile lamp parts, or engine room parts, it has excellent fluidity and generates less burrs during molding. Provide resin compositions with excellent accuracy and anisotropy.
The resin component is (a) 1 to 99 parts by weight of a polyphenylene sulfide resin, (b) 99 to 1 part by weight of a polyphenylene ether resin, and (c) per 100 parts by weight in total of the component (a) and the component (b) (c ) Admixture 1-100 parts by weight of the basic resin composition 100 parts by weight of filler (d) fly ash, (e) fibrous filler and / or (f) flaky inorganic filler 40 to 400 parts by weight and (d) 5 to 95% by weight of fly ash in all filler components.
[Selection] No selection.

Description

  The present invention is excellent in dimensional accuracy during cooling and its anisotropy required for optical device mechanism parts, optical fiber connector ferrules, printer parts, copying machine parts, automobile lamp parts, automobile engine compartment parts, etc. The present invention relates to a resin composition for precision molded products that gives a precision molded product.

Polyphenylene sulfide resin is blended with fillers such as glass fiber as one of crystalline resins with high heat resistance, and is a resin molding material with excellent heat resistance, chemical resistance, rigidity and flame resistance. It is used as parts and automotive electrical parts.
Among them, the optical pickup base built in a compact disk, which is one of the optical device mechanism parts, and the optical system housing of the copying machine were manufactured by metal die casting such as aluminum and zinc. Conversion to resin is being studied from the viewpoint of improving productivity and productivity. In order to convert to these resins, resin molded products are required to have high heat resistance and high dimensional accuracy associated with thermal changes.

For this reason, many improvements from the material viewpoint are proposed about the polyphenylene sulfide resin composition which is a raw material of the molded article of these uses.
These technologies consist of specific inorganic compounds, fibrous fillers and other inorganic fillers for resin components consisting of polyphenylene sulfide and polyphenylene ether. An excellent resin composition (see, for example, Patent Documents 1 and 2) has been proposed. Further, in order to obtain the same effect, a resin composition (for example, Patent Documents 3 to 4) including a silane coupling agent, a fibrous filler, and other inorganic fillers with respect to a resin component composed of polyphenylene sulfide and polyphenylene ether. In addition, in order to obtain a resin composition having a small optical axis deviation as an optical component (for example, see Patent Document 5), the volume fraction of polyphenylene sulfide and polyphenylene ether to be used is defined, and an inorganic filler is used. Including resin compositions have been proposed. In order to reduce the occurrence of burrs during injection molding, a resin composition (for example, see Patent Document 6) in which the ratio of each component of polyphenylene sulfide, polyphenylene ether and glass fiber is specified has been proposed.
In order to obtain an optical disk mechanism component having excellent heat resistance and dimensional accuracy, the applicant of the present invention used a scaly inorganic filler or scaly for a resin component using polyphenylene sulfide, polyphenylene ether and a specific compatibilizer. The composition which consists of a fibrous inorganic filler and a fibrous reinforcement filler (for example, refer patent documents 7-8) was proposed.

Japanese Patent Laid-Open No. 9-157525 Japanese Patent Laid-Open No. 11-106655 Japanese Patent Laid-Open No. 11-158374 JP 2002-69298 A JP 2001-294751 A JP 2002-179915 A JP 2002-249661 A JP 2002-352542 A

  In these documents, by adding a composition containing various inorganic fillers to the resin component consisting of polyphenylene sulfide and polyphenylene ether as a base, the dimensional accuracy due to temperature change, which is a defect of the resin, is improved. Anisotropy (when the ratio of the linear expansion coefficient of the molded product in the direction perpendicular to the resin flow / the linear expansion coefficient of the molded product in the resin flow direction increases, the anisotropy of the molded product is poor. In this case, it can be said that there is no anisotropy), burrs are generated in the molded product, and the excellent fluidity of the resin is remarkable by adding a large amount of inorganic filler to further improve the dimensional accuracy. The actual condition is that it has many problems that have not yet been solved as a molded product, such as the deterioration of the appearance of the molded product and the appearance of the molded product.

  The problems to be solved by the present invention are as follows: (1) high concentration inorganic fillers as precision molded products such as optical device mechanism parts, optical fiber connector ferrules, printer parts, copier parts, automobile lamp parts, automobile engine compartment parts, etc. (2) Remarkably less burrs when molded, (3) Dimensional accuracy due to temperature change (-30 ° C to 100 ° C) and its anisotropy (perpendicular to resin flow) If the ratio of the linear expansion coefficient of the molded product in the direction / the linear expansion coefficient of the molded product in the resin flow direction is large, the anisotropy of the molded product is poor. If this ratio is 1, it can be said that there is no anisotropy) Another object of the present invention is to provide a resin composition.

In order to solve the above-mentioned problems, the present invention has been intensively studied on a resin composition comprising a polyphenylene sulfide resin, a polyphenylene ether resin and a filler material. As a result, a specific admixture is used, and fly ash and other fillers are used as filler types. When using a specific filler consisting of an agent, it was found that the fluidity at the time of molding was excellent, the occurrence of burrs in the molded product was remarkably small, the dimensional accuracy and its anisotropy were also excellent, and the present invention was achieved. .
That is, the present invention
[1] The resin component is (a) 1 to 99 parts by weight of a polyphenylene sulfide resin, (b) 99 to 1 part by weight of a polyphenylene ether resin, and (c) per 100 parts by weight in total of the components (a) and (b). Admixture 1 to 20 parts by weight of basic resin composition, 100 parts by weight of the basic resin composition with 40 fillers (d) fly ash and (e) fibrous filler A resin composition for precision molded products, comprising -400 parts by weight and containing 5 to 95% by weight of component (d) in all filler components;

[2] With respect to 100 parts by weight of the basic resin composition, 40 to 400 parts by weight of a filler composed of (d) component and (f) flaky inorganic filler are included, and the total filler component ( d) A resin composition for precision molded products comprising 5 to 95% by weight of a component,
[3] The filler comprising 40 to 400 parts by weight of the component (d), the component (e), and the component (f) with respect to 100 parts by weight of the basic resin composition, and in all the filler components (D) A resin composition for precision molded products comprising 5 to 95% by weight of a component,
[4] The resin composition for precision molded products according to any one of the above [1] to [3], wherein the melt viscosity of the component (a) is 1 to 10000 poise (however, the melt viscosity conforms to JISK-7210. Then, using a flow tester, measured value after holding at 300 ° C., load 196 N, die length (L) / die diameter (D) = 10 mm / 1 mm for 6 minutes),

[5] The component (a) has an extraction amount by methylene chloride of 0.7% by weight or less, and the —SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom) is 20 μmol / g or more. A resin composition for precision molded products according to any one of the above [1] to [4],
[6] The above [1] to [5], wherein the component (b) is a constituent ratio of 100% by weight of polyphenylene ether or polyphenylene ether / styrene resin = 1 to 99% by weight / 99 to 1% by weight. A resin composition for precision molded products according to any one of
[7] The component (c) is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline. -The resin composition for precision molded products according to any one of the above [1] to [6], which is at least one selected from the group consisting of acrylonitrile copolymers,

[8] The resin composition for precision molded products according to any one of the above [1] to [7], wherein the fly ash of component (d) is a fly ash type II specified in JIS A6201-1999,
[9] The component (e) is selected from the group consisting of glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber, metal fiber, potassium titanate whisker, calcium carbonate whisker, and wollastonite. The resin composition for precision molded products according to any one of [1] and [3] to [8], which is at least one kind,
[10] The above (2) and [3] to [8], wherein the component (f) is at least one selected from the group consisting of glass flakes, mica, talc, graphite, boron nitride, and molybdenum disulfide. The resin composition for precision molded products according to any one of the above,
[11] The above [1] to [10], wherein the precision molded product is at least one of an optical device mechanism part, an optical fiber connector ferrule, a printer part, a copier part, an automobile lamp part, or an automobile engine compartment part. The resin composition for precision molded products according to any one of the above.

  The resin composition of the present invention is (1) excellent in fluidity at the time of molding even if it contains an inorganic filler at a high concentration, (2) remarkably little burrs are produced when molded, and (3) temperature change (−30 A precision molded product excellent in dimensional accuracy and anisotropy by (° C. to 100 ° C.) can be provided, which is very useful industrially.

Hereinafter, the present invention will be described in detail.
The basic resin composition that is the resin component of the resin composition for precision molded products of the present invention comprises the following (a) component polyphenylene sulfide resin, (b) component polyphenylene ether resin, and (c) admixture. Composed.
The polyphenylene sulfide resin (hereinafter abbreviated as PPS) used as the component (a) for use in the present invention is usually 50 mol%, preferably 70 mol% of an arylene sulfide repeating unit represented by the following general formula (formula 1). Preferably it is a polymer containing 90 mol% or more.
[—Ar—S—] (Formula 1)
(Here, Ar represents an arylene group, and as the arylene group, for example, a p-phenylene group, an m-phenylene group, and a substituted phenylene group (the alkyl group having 1 to 10 carbon atoms and the phenyl group are preferable as the substituent), and p, p′-diphenylenesulfone group, p, p′-biphenylene group, p, p′-diphenylenecarbonyl group, naphthylene group, etc.).

  PPS may be a homopolymer having one type of arylene group as a structural unit, and is a copolymer obtained by mixing two or more different arylene groups from the viewpoint of processability and heat resistance. May be. Among these, a polyphenylene sulfide resin having a repeating unit of p-phenylene sulfide as a main constituent element is preferable because it is excellent in processability and heat resistance and is easily available industrially. Further, the PPS structure may be either linear or branched, and may be a mixture of these structures, but it is preferable to use PPS having a linear structure.

In the present invention, those having a melt viscosity of 1 to 10,000 poise at 300 ° C. can be suitably used. In the present invention, the melt viscosity is JISK-7210 as a reference test method, and after preheating PPS at 300 ° C. for 6 minutes using a flow tester (CFT-500 manufactured by Shimadzu Corporation), a load of 196 N, Die length (L) / die diameter (D) = 10 mm / 1 mm.
The most preferable PPS among PPSs having these structures has an extraction amount of 0.7% by weight or less with methylene chloride, and a terminal-SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom). The polyphenylene sulfide resin is 20 μmol / g or more, preferably 20 to 60 μmol / g.

  Here, the amount of extraction with methylene chloride can be determined by the following method. That is, 5 g of PPS powder is added to 80 ml of methylene chloride, subjected to Soxhlet extraction for 6 hours, cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above extraction is washed in three portions with a total of 60 ml of methylene chloride, and the washing liquid is collected in the weighing bottle. Next, the methylene chloride in the weighing bottle is evaporated and removed by heating to about 80 ° C., the residue is weighed, and the amount extracted from the methylene chloride from the amount of the residue, that is, the proportion of the oligomer present in the PPS. Can be requested.

  And quantification of -SX group said here can be calculated | required with the following method. That is, after the PPS powder is previously dried at 120 ° C. for 4 hours, 20 g of the dried PPS powder is added to 150 g of N-methyl-2-pyrrolidone, and the mixture is vigorously stirred and mixed at room temperature for 30 minutes so that the powder agglomerates are eliminated. . After the slurry is filtered, washing is repeated seven times using 1 liter of warm water of about 80 ° C. each time. The filter cake obtained here is slurried again in 200 g of pure water, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Next, after stirring for 30 minutes at 25 ° C. and filtration, washing is repeated 6 times using 1 liter of warm water of about 80 ° C. each time. The obtained filter cake is slurried again in 200 g of pure water, then titrated with 1N sodium hydroxide, and the amount of -SX groups present in the PPS can be determined from the amount of sodium hydroxide consumed.

  Further, this PPS may be acid-modified PPS. Here, the acid-modified PPS is obtained by modifying the PPS with an acid compound, and the acid compound includes unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and maleic anhydride. Examples thereof also include carboxylic acids or anhydrides thereof, saturated aliphatic carboxylic acids and aromatic substituted carboxylic acids. In addition, inorganic acid compounds such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid and carbonic acid can also be mentioned as the acid compound.

  The above PPS production method is usually a method in which a halogen-substituted aromatic compound such as p-dichlorobenzene is polymerized in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent, or Examples include polymerization in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, amide solvents such as N-methylpyrrolidone and dimethylacetamide, sulfolane, etc. A method in which sodium sulfide and p-dichlorobenzene are reacted in a sulfone solvent is suitable. These production methods are known methods, for example, US Pat. No. 2,513,188, Japanese Examined Patent Publication No. 44-27671, Japanese Examined Patent Publication No. 45-3368, Japanese Examined Patent Publication No. 52-12240, Japanese Unexamined Patent Publication No. Sho 61-61. No. 225217 and US Pat. No. 3,274,165, British Patent No. 1160660, Japanese Patent Publication No. Sho 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-222196, etc. The PPS can be obtained by the prior art method exemplified in (1).

Here, a specific example of a method for producing PPS satisfying an extraction amount by methylene chloride of 0.7% by weight or less and a terminal-SX group of 20 μmol / g or more is described in JP-A-8-253588. In the organic amide solvent, alkali metal sulfide and dihaloaromatic compound are reacted, and during the reaction, the gas phase part of the reaction vessel is cooled to condense part of the gas phase in the reaction vessel. And a method of reducing the oligomer component by refluxing it to the liquid layer above the reaction solution.
Next, the polyphenylene ether resin of the component (b) of the present invention comprises a repeating unit represented by the following bond unit (Formula 2), and is a number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography). Is a polyphenylene ether resin (hereinafter abbreviated as PPE) which is a homopolymer and / or copolymer in the range of 1000 or more, preferably 1500 to 50000, more preferably 1500 to 30000.

(Where R ₁ , R ₂ , R ₃ and R ₄ are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group, It is selected from the group consisting of a hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different. )

  Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl ether). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,6- Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) may also be mentioned. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, and It can be easily produced by the method described in JP-A-50-51197 and JP-A-63-152628.

  The polyphenylene ether resin of component (b) provided in the present invention can be used even with the above-mentioned PPE component of 100% by weight, but in the present invention, polyphenylene ether (PPE) / styrene resin = 1 to 99% by weight / 99. Those having a ratio of ˜1% by weight can be preferably used. Among them, in the resin composition of the present invention, the total amount of the fillers of the components (d) to (f) described later is 65 parts by weight. When exceeding, when improving the workability of the resin composition, the ratio of the polyphenylene ether (PPE) / styrene resin is most preferably used at a ratio of 80/20 to 20/80 (unit: wt%). . Such a styrene resin is a rubber polymer dispersed in the form of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds and a polymer of a styrene compound. Examples thereof include rubber-modified styrene resin (high impact polystyrene). Examples of the styrenic compound that gives these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4- Examples thereof include dimethyl styrene, monochloro styrene, and p-tert-butyl styrene.

These styrenic compounds may be copolymers obtained by using two or more kinds in combination, but among them, polystyrene obtained by polymerization using styrene alone is preferable. As these polymers, polystyrene having a stereoregular structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used. The styrene resin used in combination with this PPE does not include the styrene copolymer of component (c) shown below.
In the present invention, the blending ratio of the polyphenylene sulfide resin as the component (a) and the polyphenylene ether resin as the component (b) is (a) / (b) = 1 to 99 parts by weight / 99 to 1 part by weight. From the viewpoint of molding processability and suppression of burr generation during molding, 20 to 90 parts by weight / 80 to 10 parts by weight is preferable, and 40 to 80 parts by weight / 60 to 20 parts by weight is more preferable.

  Next, the admixture used as the component (c) of the present invention acts as an emulsifying dispersant when the PPS of the component (a) and the polyphenylene ether resin of the component (b) are mixed, and the resin composition of the present invention is used. This has the effect of significantly reducing the occurrence of burrs in the molded product when it is molded. Examples of the admixture of the component (c) include (1) an epoxy resin, (2) a silane coupling agent, (3) a compound containing an epoxy group and / or a compound containing an oxazonyl group. A copolymer of an unsaturated monomer having a group and / or an oxazonyl group and a monomer having styrene as a main component can be preferably used. As used herein, the monomer having styrene as the main component has no problem if the styrene component is 100% by weight, but when there is another monomer copolymerizable with styrene, the copolymer chain is component (b). In order to maintain the miscibility with the polyphenylene ether-based resin, it is necessary to contain at least 65% by weight of styrene monomer, more preferably 75 to 95% by weight. Specific examples thereof include a copolymer of an unsaturated monomer having an epoxy group and / or an oxazonyl group and a styrene monomer. Examples thereof include an unsaturated monomer having an epoxy group and / or an oxazonyl group and a copolymer of styrene / acrylonitrile = 90 to 75% by weight / 10 to 25% by weight.

  Examples of the epoxy group-containing unsaturated monomer include glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, glycidyl ether of hydroxyalkyl (meth) acrylate, glycidyl ether of polyalkylene glycol (meth) acrylate, glycidyl itaconate, and the like. Of these, glycidyl methacrylate is preferred. Moreover, as said oxazonyl group containing unsaturated monomer, 2-isopropenyl-2-oxazoline is industrially available and can be used preferably, for example.

  Other unsaturated monomers that copolymerize with the unsaturated monomer having an epoxy group and / or oxazonyl group include vinyl aromatic compounds such as styrene as an essential component and vinyl cyanide such as acrylonitrile as a copolymerization component. Monomer, vinyl acetate, (meth) acrylic acid ester and the like can be mentioned, but in the present invention, it is essential that at least 65% by weight or more of styrene monomer is contained in the component excluding unsaturated monomer having epoxy group and / or oxazonyl group. It is. Further, the unsaturated monomer having an epoxy group and / or an oxazonyl group is 0.3 to 20% by weight, preferably 1 to 15% by weight, more preferably 3 to 10% by weight in the copolymer of component (c). Must be contained. The amount of the unsaturated monomer having an epoxy group and / or oxazonyl group of the copolymer of component (c) is required to be 0.3% by weight or more from the viewpoint of mechanical properties of a molded product obtained from the resin composition obtained. When the content is 20% by weight or less, the miscibility of the component (b) with the polyphenylene ether-based resin is maintained, whereby the miscibility of the component (a) and the component (b) is improved. Generation | occurrence | production of the burr | flash of the molded article shape | molded using the composition can be suppressed significantly.

Examples of the copolymer of component (c) obtained by copolymerizing these copolymerizable unsaturated monomers include, for example, styrene-glycidyl methacrylate copolymer, styrene-glycidyl methacrylate-methyl methacrylate copolymer, styrene- Examples thereof include a glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline-acrylonitrile copolymer.
The compounding amount of the component (c) is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight based on 100 parts by weight of the total of the components (a) and (b). Part by weight is required. If the blending amount of the component (c) is 1 part by weight or more, the miscibility of the component (a) and the component (b) is improved. If the blending amount is 20 parts by weight or less, the obtained resin composition is used. Generation of burrs in the molded product can be greatly suppressed.

The resin composition for precision molding of the present invention is a filler of the components (d) to (f) shown below with respect to the basic resin composition composed of the resin components (a) to (c) described above. It is the resin composition obtained by mix | blending. The fillers of the components (d) to (f) provided in the present invention will be described below.
The fly ash used as the component (d) of the present invention is capable of maintaining high dimensional accuracy due to temperature change (-30 ° C to 100 ° C) of a precision molded product molded using the resin composition of the present invention. More specifically, there is an effect that the anisotropy of the molded product due to the orientation during the melt flow of the resin-filler composition of the molded product can be remarkably reduced.
The fly ash of component (d) is coal ash that is usually generated in a thermal power plant or the like that burns coal by a pulverized coal combustion method, and is baked at high temperature. Therefore, unlike natural inorganic fillers, Melting, dispersion, and solidification occur, resulting in glassy fine spherical particles with a smooth surface. The two components, silica and alumina, occupy 70 to 80% by weight, and other components include iron oxide and oxidation. Contains magnesium and calcium oxide.

  The fly ash used in the present invention may be a product whose quality standard is industrially quality-controlled by JIS A 6201-1999, and classification according to this standard is fly ash type I, fly ash type II, fly ash III. These are classified into four types, fly ash type IV, and any of these can be used. Among them, fly ash type II can be supplied industrially stably, and the flow of the resulting resin composition It is preferable from the viewpoint of the dimensional accuracy of the obtained molded product. The size of this fly ash type II contains 40% or less of a 45 μm sieve residue obtained by a mesh sieving method. These fly ash are further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent or an aliphatic metal salt, or treated with an ammonium salt or the like by an intercalation method, or urethane. What processed resin as resin, a resin, such as an epoxy resin, may be used.

  Next, the fibrous filler used as the component (e) of the present invention is a filler used in combination with the fly ash of the above component (d), and the mechanical strength of the composition obtained by fly ash alone is insufficient. It is an important ingredient in making up for this. Examples of the fibrous filler include glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber, metal fiber, potassium titanate whisker, calcium carbonate whisker, and wollastonite. The fibrous filler of the component (e) used in the present invention usually has a fiber diameter of 1 to 50 μm and a fiber length of about 1 to 10 mm, and only one kind is selected from the group consisting of the above-described fibrous fillers. Of course, two or more kinds may be used in combination. This fibrous filler is further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, an aliphatic metal salt, or an organic treatment with an ammonium salt by an intercalation method. Further, a product obtained by treating a resin such as urethane resin or epoxy resin as a binder may be used.

  Further, the scaly inorganic filler used as the component (f) of the present invention is a filler used in combination with the fly ash of the above component (d), and the mechanical strength of the composition obtained by fly ash alone is insufficient. Therefore, it is an important component in making up for this. Examples of the scaly inorganic filler include glass flake, mica, talc, graphite, boron nitride, molybdenum disulfide and the like. The scale-like inorganic filler of the component (f) used in the present invention has a plate-like structure or a layered structure having an aspect ratio (average particle diameter / thickness ratio) of at least 10 or more, preferably 15 or more. These scale-like inorganic fillers may be used alone or in combination of two or more. This scaly inorganic filler is further treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent or an aliphatic metal salt, or an organic treatment with an ammonium salt or the like by an intercalation method. Or what processed resin, such as urethane resin and an epoxy resin, as a binder may be used.

The characteristic of the resin composition of the present invention is that the above-mentioned fillers of the components (d) to (f) are used in combination, and (1) the component (d) and the component (e) are used together as the filler component. ,
(2) System in which component (d) and component (f) are used in combination,
(3) A resin composition containing a filler corresponding to the three system embodiments in which the component (d), the component (e) and the component (f) are used in combination. What is common to these three embodiment systems is that the blending ratio of the fly ash of the component (d) is 5 to 95% by weight, preferably 25 to 95% by weight, more preferably 35 to 90% by weight in the total filler. %. When the blending amount of the component (d) is 5% by weight or more, the dimensional accuracy in the thickness direction of a molded product obtained by molding using the obtained resin composition is improved, and sink marks are reduced, and 95% by weight or less. If it is, the outstanding dimensional accuracy by the temperature change (-30 degreeC-100 degreeC) of the molded article shape | molded using the obtained resin composition will be obtained, and the anisotropy (perpendicular to resin flow) of a molded article will be obtained. When the ratio of the linear expansion coefficient of the molded product in the direction / the linear expansion coefficient of the molded product in the resin flow direction becomes large, the anisotropy regarding the dimensional accuracy of the molded product is bad. Can be said to be greatly improved.

In addition, the blending amount of all fillers in these three aspect systems described above is 40 to 400 parts by weight, more preferably, 100 parts by weight of the basic resin composition comprising the components (a) to (c). 50 to 250 parts by weight, more preferably 60 to 200 parts by weight. If the blending amount is 40 parts by weight or more, the dimensional accuracy of a molded product obtained by molding using the resulting resin composition is improved, and if the blending amount is 400 parts by weight or less, the resulting resin composition is molded. The molded product obtained in this manner has few sink marks and can be a molded product that retains excellent dimensional accuracy and anisotropy due to temperature change (-30 ° C to 100 ° C).
In the present invention, in addition to the above components, other thermoplastic elastomers (hydrogenated block copolymers and polyolefin-based elastomers), thermal stabilizers, antioxidants may be used as long as the characteristics and effects of the present invention are not impaired. Known releasing agents such as stabilizers, stabilizers such as UV absorbers, crystal nucleating agents, antistatic agents, flame retardants, colorants such as pigments and dyes, polyethylene wax, polypropylene wax, montanate wax, stearate wax Agents can also be added as appropriate.

The production method of the resin composition of the present invention is usually a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. Among them, the melt kneading method using a twin screw extruder is preferable.
Although the melt kneading temperature in this case is not particularly limited, it can usually be arbitrarily selected from 290 to 350 ° C. As one of the specific methods for producing the resin composition of the present invention by a preferred twin-screw extruder, for example, blending of (a) component polyphenylene sulfide resin, (b) component polyphenylene ether resin and (c) component The agent is simultaneously supplied to the first supply port of the twin screw extruder set at 300 ° C., and melt-kneaded at a screw rotation speed of 100 to 1200 rpm, preferably 200 to 500 rpm. With these components (a) to (c) Examples thereof include a method in which the fillers of the components (d) to (f) are supplied from the second supply port of the twin-screw extruder and further melt-kneaded in a state where the basic resin composition to be constituted is melt-kneaded. Moreover, the position which supplies each filler of (d)-(f) component to a twin-screw extruder may supply collectively from the 2nd supply port of an extruder as mentioned above, and a 2nd supply port And a third supply port may be provided to divide and supply the components (d) to (f), or (d) to (d) together with the components (a) to (c) from the first supply port of the extruder. (F) You may supply a component. The resin composition of the present invention thus obtained as a molding material that can be a precision molded product, for example, injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, hot press molding, A molding method such as rotational molding or lamination molding can be applied.

Hereinafter, the present invention will be described by way of examples.
In addition, the used raw material is as follows.
(A) Polyphenylene sulfide resin as component a-1: Melt viscosity (value measured after holding for 6 minutes at 300 ° C., load 196 N, L / D = 10/1 using a flow tester) is 500 poise, chloride A linear type PPS having a repeating unit of p-phenylene sulfide having an extraction amount by methylene of 0.4% by weight and a -SX group amount of 29 μmol / g was defined as a-1.
a-2: Linear type having a repeating unit of p-phenylene sulfide having a melt viscosity of 300 poise measured in the same manner as in a-1, an extraction amount by methylene chloride of 0.7% by weight, and an amount of —SX group of 30 μmol / g Of PPS was designated as a-2.

(B) Component Polyphenylene Ether Resin b-1: Polyphenylene ether having a reduced viscosity of 0.54 obtained by oxidative polymerization of 2,6-xylenol was designated as b-1.
b-2: In order to make a polyphenylene ether / styrene resin mixture as the polyphenylene ether resin, atactic polystyrene (polystyrene 685 manufactured by PS Japan) used as b-2 was used as the styrene resin.
Component (c) Admixture c-1: A styrene-glycidyl methacrylate copolymer (weight average molecular weight 110,000) containing 5% by weight of glycidyl methacrylate was defined as c-1.
c-2: A styrene-2-isopropenyl-2-oxazoline copolymer (weight average molecular weight 146,000) containing 5% by weight of 2-isopropenyl-2-oxazoline was defined as c-2.

(D) Component fly ash d-1: Fly ash having a quality standard of JIS A6201-1999 of fly ash type I (manufactured by Techno Chubu Co., Ltd., middle fly ash) was defined as d-1.
d-2: Fly ash having a quality standard of JIS A6201-1999 of fly ash type II (manufactured by Techno Chubu Co., Ltd., middle fly ash) was defined as d-2.
d-3: Fly ash (medium part fly ash manufactured by Techno Chubu Co., Ltd.) whose quality standard of JIS A6201-1999 is fly ash type III was defined as d-3.
d-4: Fly ash having a quality standard of JIS A6201-1999 of fly ash type IV (manufactured by Techno Chubu Co., Ltd., middle fly ash) was designated as d-4.

(E) Component fibrous filler e-1: An average diameter of 13 μm, a length of 3 mm, a surface treatment with an aminosilane coupling agent, and a glass fiber treated with an epoxy resin as a binder was defined as (e-1). .
(F) Component scale-like inorganic filler f-1: Glass flakes having an average plate diameter of 600 μm, surface-treated with an aminosilane coupling agent, and further treated with an epoxy resin as a binder were designated as (f-1).
(Other inorganic fillers)
As other inorganic filler, 1.5 parts by weight of a silane coupling agent [β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane] is added to 100 parts by weight of calcium carbonate having an average particle diameter of 7 μm, Calcium carbonate obtained by blending using a blender. In addition, evaluation of the molded article shape | molded using the resin composition obtained from the said component was performed as follows.

(1) Molding fluidity: A resin composition is supplied to a screw in-line injection molding machine set at 310 ° C., and tested using an ASTM-D638-1 dumbbell test piece mold at a mold temperature of 130 ° C. The molding lower limit pressure (gauge pressure) of the piece was measured to evaluate the molding fluidity.
(2) Presence or absence of occurrence of molded product burrs: The ASTM-D638-1 dumbbell test piece molded by the above-described molding fluidity test was visually checked for burrs.
(3) Linear expansion coefficient (dimensional accuracy): Using a molded product for tensile test with a thickness of 3.17 mm, in accordance with ASTM-D696, the linear expansion coefficient in the direction perpendicular to the flow direction and flow of the resin (−30 C. to 100.degree. C.). The anisotropy is represented by the ratio of the linear expansion coefficient of the molded product in the direction perpendicular to the resin flow / the linear expansion coefficient of the molded product in the resin flow direction. Judge.

[Examples 1 to 10, Comparative Examples 1 to 10]
Tables 1 and 2 show the polyphenylene sulfide resin of component (a), the polyphenylene ether resin of component (b), the admixture of component (c), the fillers of components (d) to (f), and other fillers. (A) to (a) to (a) to (a)-() c) While supplying the total amount of the components, the components (d) to (f) and other fillers are supplied from the second supply port, and melt-kneaded under conditions of a screw rotation speed of 300 rpm to obtain a resin composition as pellets. It was. Using this pellet, it was supplied to a screw in-line type injection molding machine set at 300 to 320 ° C., and a 3.17 mm-thick molded product for tensile testing in accordance with ASTM-D638 was obtained under the condition of a mold temperature of 130 ° C. In order to know the dimensional accuracy at −30 ° C. to 100 ° C. of the molded product obtained here, the linear expansion coefficient was measured using a molded product for a tensile test having a thickness of 3.17 mm. These results are shown in Tables 1-2.

  Precision molded products molded with the resin composition of the present invention are (1) excellent in fluidity at the time of molding even if containing an inorganic filler at a high concentration, and (2) the occurrence of burrs is remarkably small when molded ( 3) Compact disk read-only memory (CDROM), digital versatile disk read-only memory (DVDROM) to maintain excellent dimensional accuracy and anisotropy against temperature changes (-30 ° C to 100 ° C) , Compact Disc Recordable (CDR), Digital Versatile Disc Recordable -R Standard (DVD-R), Digital Versatile Disc Recordable + R Standard (DVD + R), Compact Disc Rewritable ( CDRW), digital versatile disc rewritable -R standard (DVD-RW) Chassis and cabinets such as digital versatile disk rewritable + R standard (DVD + RW), digital versatile disk random access memory (DVDRAM), optical equipment mechanism parts such as optical pickup slide base, optical fiber connector ferrule, laser It can be used as at least one of a beam printer internal part, an inkjet printer internal part, a copier internal part, an automobile lamp part, and an automobile engine room internal part.

Claims (11)

The resin component is (a) 1 to 99 parts by weight of a polyphenylene sulfide resin, (b) 99 to 1 part by weight of a polyphenylene ether resin, and (c) an admixture 1 per 100 parts by weight in total of the components (a) and (b). A basic resin composition comprising ˜20 parts by weight, and 40 to 400% by weight of a filler comprising (d) fly ash and (e) a fibrous filler with respect to 100 parts by weight of the basic resin composition A resin composition for precision molded articles, comprising 5 parts by weight to 5 parts by weight of component (d) in all filler components. 40 to 400 parts by weight of a filler comprising (d) component and (f) flaky inorganic filler with respect to 100 parts by weight of the basic resin composition, and (d) component in the total filler component 5 to 95% by weight of a resin composition for precision molded products. 40 to 400 parts by weight of a filler consisting of the component (d), the component (e) and the component (f) is included with respect to 100 parts by weight of the basic resin composition, and (d) in the total filler component A resin composition for precision molded products comprising 5 to 95% by weight of a component. The resin composition for precision molded products according to any one of claims 1 to 3, wherein the melt viscosity of the component (a) is 1 to 10000 poise.
(However, melt viscosity is based on JISK-7210, and measured using a flow tester after holding for 6 minutes at 300 ° C., load 196 N, die length (L) / die diameter (D) = 10 mm / 1 mm) ) The component (a) has an extraction amount by methylene chloride of 0.7% by weight or less, and -SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom) is 20 μmol / g or more. The resin composition for precision molded products according to any one of 1 to 4. The component (b) has a constituent ratio of 100% by weight of polyphenylene ether or polyphenylene ether / styrene resin = 1 to 99% by weight / 99 to 1% by weight, according to any one of claims 1 to 5. The resin composition for precision molded products as described. Component (c) is a styrene-glycidyl methacrylate copolymer, a styrene-glycidyl methacrylate-methyl methacrylate copolymer, a styrene-glycidyl methacrylate-acrylonitrile copolymer, a styrene-vinyl oxazoline copolymer, and a styrene-vinyl oxazoline-acrylonitrile copolymer. It is at least 1 sort (s) chosen from the group which consists of polymers, The resin composition for precision molded products of any one of Claims 1-6. The resin composition for precision molded products according to any one of claims 1 to 7, wherein the component (d) is a fly ash type II specified in JIS A6201-1999. (E) at least one selected from the group consisting of glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, ceramic fiber, gypsum fiber, metal fiber, potassium titanate whisker, calcium carbonate whisker and wollastonite The resin composition for precision molded products according to any one of claims 1 and 3 to 8. The component (f) is at least one member selected from the group consisting of glass flakes, mica, talc, graphite, boron nitride, and molybdenum disulfide. 9. Resin composition for precision molded products. The precision molded product is at least one of an optical device mechanism part, an optical fiber connector ferrule, a printer part, a copier part, an automobile lamp part, or an automobile engine compartment part. The resin composition for precision molded products as described.