JP4973097B2 - Polyphenylene sulfide resin composition and molded article - Google Patents

Description

  The present invention relates to a resin composition containing a vinyl copolymer such as polyphenylene sulfide resin and acrylonitrile-styrene resin, and more particularly to a resin composition suitable for optical storage device parts and metallized film capacitor parts. More specifically, such as CD, CD-ROM, CD-R, CD-RW, DVD, DVD-ROM, DVD ± R, DVD ± RW, DVD-RAM, etc., which write and read using laser light. The present invention relates to a resin composition suitable for various parts used as a metallized film capacitor member provided with an optical recording device and a capacitor element in an outer case and filled with resin in the outer case.

  Polyphenylene sulfide resin belongs to high-heat-resistant super engineering plastics and has mechanical strength, rigidity, flame retardancy, chemical resistance, electrical properties and dimensional stability, etc., mainly for injection molding, It is widely used for various electric / electronic parts, home appliance parts, automobile parts and machine parts. One such application is an optical pickup which is an electric / electronic component. In this application, the optical axis stability of the laser focus is required (the laser focus is stable when the environmental temperature changes), and so far, polyphenylene sulfide resin compositions with a high filler content have been used for CD applications. . However, in DVD applications that have recently become widespread, better optical axis stability of the laser focus is required, and the conventional polyphenylene sulfide resin composition is insufficient in terms of optical axis stability of the laser focus. . In addition, the parts can be obtained by injection molding, but if the fluidity at the time of injection molding is poor, good products cannot be obtained or molding is performed by applying excessive pressure. Problems such as poor shaft stability occur. Further, since the component plays a role of reading a digital signal recorded on a DVD or the like, if a burr is generated at the time of molding, it causes a reading error or the like, which is not preferable.

  In addition, polyphenylene sulfide resin is a resin that has excellent mechanical strength, heat resistance, and water resistance, and can withstand harsh use conditions, and is therefore one of the resins that have been used in applications such as automotive parts. One such application is a metallized film capacitor. Metallized film capacitors have been deployed in various fields from the conventional home appliance field to industrial and vehicle fields. Among them, metalized film capacitors for vehicles are often used in power unit parts of modern hybrid vehicles, and the demand is rapidly increasing. However, they have high capacity, high voltage and high current capability and high reliability. In addition to performance, downsizing is required. Since the capacity is proportional to the amount of film used as a dielectric, the capacity increases as the capacity increases. Therefore, in order to achieve miniaturization, it is necessary to reduce the thickness of the case containing the capacitor element and the thickness of the filling resin covering the element. In addition, with the trend toward miniaturization, the tendency to design the distance between the metal terminals to be shorter has become stronger, and insulation has also been required.

  The present invention is a resin composition containing a polyphenylene sulfide resin, a vinyl copolymer, a fibrous filler, a non-fibrous filler, and a silane coupling agent. As a resin composition close to the present invention, a polyphenylene sulfide resin is used. Patent Document 1 discloses a resin composition in which a polystyrene polymer and a filler are blended. A resin composition containing a polyphenylene sulfide resin, an epoxysilane compound, a fibrous filler, an inorganic filler or a mixture thereof is known from Patent Document 2.

  However, the resin composition described in Patent Document 1 is a composition devised for the purpose of improving the impact properties, toughness, and flame retardancy of polyphenylene sulfide resins, and is particularly an optical pickup slide base among optical recording apparatus components. Although the stability of the laser optical axis has a great influence on the reliability of the optical recording apparatus, this is not mentioned at all. In addition, although the text mentions the combined use of a fibrous filler and a non-fibrous filler, in the composition specifically described as an example of the publication, an example of using both fillers in combination. There is no description. Furthermore, there is no mention of the fluidity of each composition that is important for moldability.

  The resin composition described in Patent Document 2 is intended to reduce burrs of polyphenylene sulfide resin, and although mention is made in the text regarding application to optical components, the stability of the laser optical axis Is not mentioned at all. In addition, among the compositions specifically described as examples of the publication, all the compositions using glass fiber and calcium carbonate in combination have a glass fiber content higher than that of calcium carbonate. If the blending amount is too high, the orientation of the glass fiber is too strong and the optical axis stability is lowered, so that only the laser optical axis stability in the optical recording apparatus is insufficient.

On the other hand, as a metallized film capacitor, there is a description in Patent Document 3, and an exterior case in which one or more capacitor elements and an epoxy resin are filled inside, and the capacitor element is fixed inside by curing the epoxy resin with a curing agent. Describes an example in which a polyphenylene sulfide resin having an adhesive strength with an epoxy resin of 3 MPa or more and 10 MPa or less is used as a material. However, Patent Document 3 does not mention fluidity and insulation, which will be important in the future for the reasons described above.
JP 7-316428 A JP 2000-198924 A JP 2004-146724 A

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue. That is, the present invention provides an excellent polyphenylene sulfide resin composition for optical recording device parts in balance with optical axis stability of laser focus, fluidity during molding, and low burr properties, and fluidity and tracking resistance during molding. An excellent polyphenylene sulfide resin composition for metalized film capacitor parts is provided.

  The inventors have (A) 15-45% by weight of polyphenylene sulfide resin, (B) 5-25% by weight of vinyl copolymer, (C) 10-50% by weight of fibrous filler, (D) non-fibrous. A polyphenylene sulfide resin composition comprising 10 to 50% by weight of a filler, wherein 0.01 to 3 parts by weight of (E) silane coupling agent is added to 100 parts by weight of the present composition. It was found that the optical axis stability of the laser focus is excellent, and the fluidity at the time of molding and low burr properties are balanced and excellent. Moreover, it discovered together that this composition was excellent in the fluidity | liquidity at the time of shaping | molding, and tracking resistance.

That is, in the present invention, the total of (1) (A), (B), (C) and (D) is 100% by weight, (A) 15-45% by weight of polyphenylene sulfide resin, (B ) modified with glycidyl methacrylate Acrylonitrile-styrene resin 5-25% by weight, (C) fibrous filler 10-50% by weight, (D) non-fibrous filler 10-50% by weight , and ( A), (B), (C) And (D) 0.01-3 parts by weight of (E) silane coupling agent is added to 100 parts by weight of the total , and (C) the amount of fibrous filler is (D) non-fibrous filling The amount of spiral flow in a mold cavity with a width of 5 mm and a thickness of 1 mm adjusted to 130 ° C. when the cylinder setting temperature is 320 ° C. and the injection pressure is 98 MPa is less than the blending amount of the agent is 90 mm or more. Some polyphenylene Rufido A molded article comprising a resin composition, an optical recording apparatus part comprising the molded article, characterized in that the optical axis deviation amount at the time of changing the temperature to 80 ° C. from 23 ° C. is not more than 2.5 minutes,
( 2 ) The optical recording device component according to (1), comprising a molded product having a tracking resistance index of 225 V or more ,
( 3 ) The molded product according to (1), wherein two protrusions (a) 4 mm wide × 20 mm long × 500 μm deep and (b) 4 mm wide × 20 mm long × 20 μm deep on the circumference. When an 80 mmφ × 2 mmt disk-shaped mold having a temperature is adjusted to 130 ° C. and injection molding is performed at a molding machine cylinder set temperature of 320 ° C., the minimum pressure at which the protrusion of (a) is filled is set to 10 MPa. In addition, an optical recording device component comprising a molded product characterized in that the filling length of the protruding portion of (b) when molded is 130 μm or less, and the molded product according to ( 4 ) (1), An optical recording device part comprising a molded product having a molded product thickness of 2 mm or less .
Is to provide.

  According to the present invention, it is possible to obtain a polyphenylene sulfide resin composition which is excellent in environmental stability of a laser focus and is excellent in balance with fluidity at molding, low burr properties, mechanical strength and the like. It is also possible to obtain a polyphenylene sulfide resin composition excellent in fluidity and tracking resistance during molding. Since it has such characteristics, it is suitable as an optical recording device component, particularly as an optical pickup slide base material, and as an in-vehicle component, particularly as a metalized film capacitor member material.

  The polyphenylene sulfide resin (A) used in the present invention is a repeating unit represented by the following structural formula

Is a polymer containing 70 mol% or more, preferably 90 mol% or more. When the above repeating unit is less than 70 mol%, the heat resistance tends to be impaired. In addition, the polyphenylene sulfide resin can be composed of 30 mol% or less of the repeating unit with a repeating unit having the following structural formula.

  Such polyphenylene sulfide resins are generally known methods, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. Can be produced by, for example, a method for obtaining a polymer having a relatively large molecular weight.

  In the present invention, the polyphenylene sulfide resin obtained as described above is washed with an aqueous acid solution (acid washing), treated with an organic solvent or hot water, washed with water containing an alkaline earth metal salt, an acid anhydride, and the like. Various treatments such as activation with functional group-containing compounds such as amines, isocyanates, functional group-containing disulfide compounds, cross-linking / high molecular weight by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure Of course, it is possible to use them after applying them, and to repeat these treatments a plurality of times, or to combine different treatments, but at least acid cleaning exhibits the effect of the present invention more remarkably. It is particularly effective on the above.

  The following method can be illustrated as a specific method in the case of acid-washing polyphenylene sulfide resin. That is, there is a method of immersing a polyphenylene sulfide resin in an acid or an acid aqueous solution, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide resin, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acid such as aromatic saturated carboxylic acid, acrylic acid, crotonic acid, aromatic carboxylic acid such as benzoic acid, salicylic acid, dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, And inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The acid or acid aqueous solution used for the acid cleaning of the polyphenylene sulfide resin preferably has a pH of 2.5 to 5.5, and the amount used is 2 to 100 kg with respect to 1 kg of the dried polyphenylene sulfide resin. It is preferably 4 to 50 kg, more preferably 5 to 15 kg. There is no restriction | limiting in particular in washing | cleaning temperature, Usually, it can carry out at room temperature, and when heating, it can carry out at 50-90 degreeC. The washing time is usually preferably 30 minutes or longer, and more preferably 45 minutes or longer. The upper limit is not particularly limited, but is preferably about 90 minutes from the viewpoint of cleaning efficiency. For example, when acetic acid is used, it is preferable to immerse the polyphenylene sulfide resin powder in a pH 4 aqueous solution kept at room temperature and stir for 45 to 90 minutes. The acid-treated polyphenylene sulfide resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The temperature of the water washing is preferably 50 to 100 ° C, and more preferably 60 to 95 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of the polyphenylene sulfide resin by acid washing.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl sulfoxide , Sulfoxide / sulfone solvents such as dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol Propylene glycol, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, and benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a polyphenylene sulfide resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyphenylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is treated with hot water. That is, in order to express the preferable chemical modification effect of the polyphenylene sulfide resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by charging a predetermined amount of polyphenylene sulfide resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyphenylene sulfide resin to water is preferably larger, but usually a bath ratio of 200 g or less of polyphenylene sulfide resin is selected per 1 liter of water.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with water containing an alkaline earth metal salt. There are no particular restrictions on the type of alkaline earth metal salt, but alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. Are preferable examples, and alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate are particularly preferable. The temperature of the water is preferably room temperature to 200 ° C, more preferably 50 to 90 ° C. The amount of the alkaline earth metal salt used in the water is preferably 0.1 g to 50 g, more preferably 0.5 g to 30 g, relative to 1 kg of the dried polyphenylene sulfide resin. The cleaning time is preferably 0.5 hours or longer, and more preferably 1.0 hour or longer. The preferred washing bath ratio (weight of warm water containing alkaline earth metal salt per unit weight of dry polyphenylene sulfide resin) depends on the washing time and temperature, but warm water containing the above alkaline earth metal per kg of dry polyphenylene sulfide is preferred. It is preferable to wash using 5 kg or more, and it is more preferable to wash using 10 kg or more. There is no restriction | limiting in particular as an upper limit, Although it may be high, it is preferable that it is 100 kg or less from the point of the usage-amount and the effect acquired. Such warm water cleaning may be performed a plurality of times.

  Specific methods for crosslinking / high molecular weight polyphenylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Thus, a method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. In this case, the heat treatment temperature is usually in the range of 150 to 280 ° C., preferably 200 to 270 ° C., and the treatment time is usually in the range of 0.5 to 100 hours, preferably 2 Although it is ˜50 hours, the target viscosity level can be obtained by controlling both. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary blade or a stirring blade. However, for efficient and more uniform treatment, a heating device with a rotary blade or a stirring blade is used. Is more preferable.

  As a specific method for heat-treating the polyphenylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200, under an inert gas atmosphere such as nitrogen or under reduced pressure. The method of heat-processing on the conditions of -270 degreeC and the heat time of 0.5-100 hours, Preferably it is 2-50 hours can be illustrated. The heat treatment apparatus may be a normal hot air drier or a heating apparatus with a rotary or stirring blade. However, for efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade may be used. More preferably it is used.

  The blending amount of the polyphenylene sulfide resin used in the present invention is 15 to 45% by weight, preferably 12 to 42% by weight, with the total of (A), (B), (C) and (D) being 100% by weight. More preferably, it is 10 to 40% by weight. If the blending amount of the polyphenylene sulfide resin is too small, it leads to a decrease in fluidity and toughness at the time of molding, while on the other hand, it leads to a decrease in rigidity and an increase in shrinkage during molding.

  When the blending amount of (C) fibrous filler described later is smaller than the blending amount of (D) non-fibrous filler, the total of (A), (B), (C) and (D) is 100% by weight. 15 to 35% by weight is preferable.

  Examples of the (B) vinyl copolymer used in the present invention include a vinyl copolymer obtained by copolymerizing a vinyl cyanide monomer (ii) and an aromatic vinyl monomer (b), and cyan. Vinyl-based monomers such as vinyl copolymers obtained by copolymerizing vinyl fluoride monomers (a), aromatic vinyl monomers (b) and other monomers copolymerizable with these (c) A copolymer is mentioned, These can be used by 1 or more types, Both a powdery thing and a pellet form can be used.

Here, examples of the vinyl cyanide monomer (i) include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more. Examples of the aromatic vinyl monomer (b) include styrene, α-methyl styrene, p-methyl styrene, propyl styrene, butyl styrene, and the like, which can be used alone or in combination of two or more. Specifically, AS resin modified with acrylonitrile-styrene resin (hereinafter referred to as AS resin) or glycidyl methacrylate (hereinafter referred to as GMA) as the vinyl copolymer (B) may be mentioned . The compounding amount of the vinyl copolymer used in the present invention is 5 to 25% by weight, preferably 7 to 22 with the total of (A), (B), (C) and (D) being 100% by weight. % By weight, more preferably 10 to 20% by weight. If the amount of the vinyl copolymer is too small, the stability of the laser optical axis is lowered, and the tracking resistance index is lowered. On the other hand, when too large, the strength and fluidity at the time of molding will decrease.

  In the present invention, the total of (A), (B), (C) and (D) is 100% by weight, (C) 10 to 50% by weight of fibrous filler, and (D) 10 to 50% of non-fibrous filler. It is essential to add weight percent and blend the fibrous filler with the non-fibrous filler. Specific examples of the fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, and ceramic. Fibers, asbestos fibers, stone-gypsum fibers, metal fibers, etc. are used, and these can be used in combination of two or more. In addition, it is better to use these fibrous fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound. It is preferable in the meaning which obtains. Of these, glass fiber and carbon fiber are more preferably used. The blending amount of the fibrous filler used in the present invention is 10 to 50% by weight, preferably 12 to 45, where the total of (A), (B), (C) and (D) is 100% by weight. % By weight, more preferably 15 to 40% by weight. If the blending amount of the fibrous filler is too small, the strength, rigidity and impact resistance are lowered, and if it is too much, the fluidity during molding is lowered and the stability of the laser optical axis is also lowered.

  In the present invention, it is also essential to add a non-fibrous filler. Specific examples of such non-fibrous fillers include talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, silicon oxide, magnesium oxide, alumina , Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, water such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide Oxides, glass beads, glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite and the like may be used. These may be hollow, and two or more kinds of these fillers may be used. Can be used togetherThese non-fibrous fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, silicates such as kaolin, clay and talc, alumina and graphite are particularly preferable. The blending amount of the non-fibrous filler used in the present invention is 10 to 50% by weight, preferably 12 to 100%, where the total of (A), (B), (C) and (D) is 100% by weight. 48% by weight, more preferably 15 to 45% by weight. If the amount of the non-fibrous filler is too small, the stability of the laser optical axis is insufficient, and if it is too large, the strength, rigidity and impact resistance are insufficient.

  In the present invention, in order to obtain excellent laser focus environmental stability, it is preferable that the content of the non-fibrous filler is larger than the content of the fibrous filler. Specifically, it is preferably 5% by weight or more, more preferably 10% by weight or more.

  On the other hand, in order to obtain excellent fluidity, the content of the non-fibrous filler is preferably smaller than the content of the fibrous filler. Specifically, it is preferably 5% by weight or less, and more preferably 10% by weight or more. Further, if the total amount of the non-fibrous filler and the fibrous filler is large, the fluidity is adversely affected. Therefore, the total of both materials is preferably 60% by weight or less, more preferably 50% by weight or less. preferable.

  In the polyphenylene sulfide resin composition of the present invention, it is necessary to further add (E) a silane compound in order to further improve the low burr property and high toughness. Examples of the silane compound include an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxy Examples thereof include hydroxyl group-containing alkoxysilane compounds such as silane, among which γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy Chlohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, ureido groups such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane are preferred. Particularly preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. . The content of the silane compound is from 0.01 to 3 with respect to a total of 100 parts by weight of (A), (B), (C) and (D) from the viewpoint of obtaining more excellent low burr and high toughness. The range of parts by weight is preferably selected, and the range of 0.2 to 1.5 parts by weight is more preferably selected. If the amount is too small, the improvement effect of low burr and high toughness due to the addition of the silane compound will not be sufficiently expressed.If the amount is too large, the above improvement effect will not only reach saturation, but the gas generation amount of the composition tends to increase. is there.

The polyphenylene sulfide resin composition of the present invention may further be blended with other resins as long as the effects of the present invention are not impaired. The blendable resin is not particularly limited, and specific examples thereof include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyamide such as aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, poly Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, olefin copolymers having functional groups such as carboxyl groups, carboxylic ester groups, acid anhydride groups, and epoxy groups, polyolefin elastomers , Polyether ester elastomers, polyether amide elastomers, polyamide imides, polyacetals and polyimides.

  In addition, the polyphenylene sulfide resin composition of the present invention includes a plasticizer such as a thioether compound, an ester compound, an organic phosphorus compound, a crystal nucleating agent such as an organic phosphorus compound, and a polyolefin as long as the effects of the present invention are not impaired. Release agents such as compounds, silicone compounds, long chain aliphatic ester compounds, long chain aliphatic amide compounds, antioxidants such as hindered phenol compounds and hindered amine compounds, heat stabilizers, calcium stearate, stearin Conventional additives such as lubricants such as aluminum oxide and lithium stearate, UV inhibitors, colorants, flame retardants and foaming agents can be added.

  The method for preparing the polyphenylene sulfide resin composition of the present invention is not particularly limited, but each raw material is supplied to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, A representative example is a method of kneading at a temperature of 280 to 380 ° C. There are no particular restrictions on the mixing order of the raw materials, a method in which all raw materials are blended and melt kneaded by the above method, a part of the raw materials are melted and kneaded by the above method, and the remaining raw materials are further blended and melt kneaded. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  The polyphenylene sulfide resin composition of the present invention thus obtained can be used for various moldings such as injection molding, extrusion molding, blow molding and transfer molding, and is particularly suitable for injection molding applications.

  Among the polyphenylene sulfide resin compositions of the present invention, particularly when the blending amount of the (C) fibrous filler is less than the blending amount of the (D) non-fibrous filler, the optical recording device parts, particularly CD, DVD It can be preferably used for optical pickup parts such as laser disks and magneto-optical disks. In this application, the product has recently been reduced in size and thickness. In this application, injection molding is generally used. However, if the fluidity is inferior, a good product cannot be formed. Further, when molding is performed by applying an excessive pressure due to poor fluidity, it is assumed that the optical axis stability is deteriorated due to stress distortion occurring in the molded product. The polyphenylene sulfide resin composition of the present invention has a spiral flow length in a mold cavity having a width of 5 mm and a thickness of 1 mm adjusted to 130 ° C. when an injection molding machine cylinder set temperature is 320 ° C. and an injection pressure is 98 MPa. It is 90 mm or more, and has excellent fluidity during injection molding. The upper limit value of the spiral flow length is not particularly limited, but it is preferably 150 mm or less in consideration of practicality because there is a concern that an increase in fluidity may lead to a decrease in mechanical properties.

On the other hand, in the polyphenylene sulfide resin composition of the present invention, in particular, the blending amount of (C) fibrous filler is larger than the blending amount of (D) non-fibrous filler, and the total of (C) and (D). However, when the total of (A), (B), (C) and (D) is 100% by weight and 60% by weight or less, it is preferably used as a material for in-vehicle parts, particularly metalized film capacitor case members. be able to. In this application as well, products have recently been made smaller and thinner. Furthermore, in many cases, it is used as an exterior case in this application, but unlike the optical recording member described above, it has a box-like shape, so the molded product itself is large, and further fluidity is required for injection molding good products. The In addition, when molding is performed by applying an excessive pressure due to poor fluidity, stress distortion occurs in the molded product, and there is a concern that the distortion is released when the temperature rises in an actual use environment, leading to deformation or warping. The polyphenylene sulfide resin composition of the present invention has a spiral flow length in a mold cavity having a width of 5 mm and a thickness of 1 mm adjusted to 130 ° C. when an injection molding machine cylinder set temperature is 320 ° C. and an injection pressure is 98 MPa. It is 150 mm or more, and has excellent fluidity at the time of injection molding of this shape product. The upper limit value of the spiral flow length is not particularly limited, but in the present composition, the upper limit value is considered to be around 220 mm.

  In optical pickup component applications, it is common to use a laser assembled on this component when reading a digital signal recorded on a disk or the like and discriminate the signal from its reflection intensity. Because of this structure, environmental stability of the laser focus is important, and it is necessary from the viewpoint of reading and writing error prevention that the amount of optical axis misalignment when the environmental temperature changes is small, which is an index indicating the environmental stability of this laser focus. It becomes. The molded product formed by injection molding of the polyphenylene sulfide resin composition of the present invention has an optical axis deviation of 2.5 minutes or less when the temperature is changed from 23 ° C. to 80 ° C. Has focus environmental stability. The lower limit value of the optical axis deviation amount is not particularly limited, and is preferably a smaller value. However, in the case of a resin composition, the optical axis deviation amount at the time of temperature environment change is larger than that of metal, 1.0 minute. The vicinity is considered to be the lower limit of ability value.

  On the other hand, in optical pickup component applications, when reading or writing signals with a laser, if dust such as burrs or dust adheres to the lens that adjusts the laser focus, it may lead to reading or writing errors. Since it is assumed, it is not preferable. A molded product obtained by injection molding of the polyphenylene sulfide resin composition of the present invention has a circumference of (a) width 4 mm × length 20 mm × depth 500 μm, (b) width 4 mm × length 20 mm × depth 20 μm. When the 80 mmφ × 2 mmt disk-shaped mold having two protrusions is temperature-controlled at 130 ° C. and injection molding is performed at a molding machine cylinder set temperature of 320 ° C., the lowest limit in which the protrusions in (a) are filled The protrusion length of (b) when molded by applying 10 MPa to the pressure is 130 μm or less, and is excellent in low burr properties. In addition, the protrusion of the shape shown in (b) has the same depth as the cavity end clearance of an injection-molded product that usually tends to generate burrs, and also flows when other parts are filled. Therefore, the filling length of the protrusions in (b) was determined to be in accordance with the burr length. In general, for the purpose of improving the mechanical properties of products, the molding is often performed by adding about 5 to 10 MPa to the minimum pressure at which a good product can be collected, and this evaluation was performed by adding 10 MPa to the minimum pressure. The lower limit value of the filling length of the protrusions in (b) is not particularly limited and is preferably a smaller value. However, in the case of a molded body formed by molding the polyphenylene sulfide resin composition, the actual value is around 50 μm. It is considered the lower limit.

Due to downsizing associated with miniaturization, for example, when assembling metal terminals, automotive parts, especially metalized film capacitor member materials, have to keep the distance between the terminals short. There is a tendency to ask more severely the insulation characteristics. Molded articles obtained by molding the polyphenylene sulfide resin composition of the present invention by injection molding have a tracking resistance index of 225 V or more, and are excellent as these members. The tracking resistance of the polyphenylene sulfide resin itself is never high, but the vinyl copolymer is excellent in tracking resistance, and this effect is considered to have led to an improvement in tracking resistance of the composition. Regarding the tracking resistance index, in the present composition, around 300 V is considered to be the upper limit of ability.

  As described above, since the polyphenylene sulfide resin composition of the present invention is balanced and excellent with respect to the above-described properties, it is an optical recording device component, particularly an optical pickup component such as a CD, DVD, laser disk, or magneto-optical disk. It is particularly preferably used as a material for metalized film capacitor members such as automotive parts, especially exterior parts.

  Other applicable applications of the polyphenylene sulfide resin composition of the present invention include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminal boards, and transformation. Electricity / electronics such as devices, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts Parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disks / compact disks, lighting parts, refrigerator parts, Houses represented by acon parts, typewriter parts, word processor parts, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, Machine-related parts such as typewriters: Optical instruments such as microscopes, binoculars, cameras, watches, precision machine-related parts; water faucet tops, mixing faucets, pump parts, pipe joints, water control valves, relief Water-related parts such as valves, hot water sensors, water sensors, water meter housings; valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, fuel related / exhaust systems, Intake system pipes, Ar intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad Wear sensor, thermostat base for air conditioner, heating warm air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer Nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil , Fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, cable liner, etc. Various applications such as related parts can be exemplified.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.

[Raw materials used]
PPS-1: 2.98 kg (25 mol) of 47% aqueous sodium hydrosulfide solution, 2.17 kg (26 mol) of 48% sodium hydroxide and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) in an autoclave equipped with a stirrer Was gradually heated to 205 ° C., and 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. This was filtered, poured into 25 liters of a pH 4 acetic acid aqueous solution, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and ionized at about 90 ° C. until the pH of the filtrate reached 7. After washing with exchange water, the polymer was dried under reduced pressure at 120 ° C. for 24 hours to obtain MFR6000 (g / 10 min) of PPS-1. The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). The heat loss of the polyphenylene sulfide resin was 0.5% by weight. In addition, 1 g of polyphenylene sulfide resin was put into an aluminum cup, preliminarily dried in an atmosphere of 150 ° C. for 1 hour, measured for weight, treated in air at 371 ° C. for 1 hour, and again weighed. . The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

  PPS-2: 6.005 kg (25 mol) of sodium sulfide 9 hydrate and 5 kg of NMP were charged into an autoclave equipped with a stirrer, and the temperature was gradually raised to 205 ° C. through nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.763 kg (25.6 mol) of 1,4-dichlorobenzene and 1.8 kg of NMP were added, sealed under nitrogen, heated to 274 ° C., heated at 274 ° C. It reacted for 0.8 hours. The extraction valve provided at the lower part of the autoclave was opened at room temperature and normal pressure, the contents were extracted, and washed with hot water at 80 ° C. This was filtered, poured into 25 liters of an aqueous solution containing 10.4 g of calcium acetate, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and the pH of the filtrate reached 7. After washing with ion-exchanged water at about 90 ° C., it was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-2 having an MFR of 3000 g / 10 min.

  Vinyl copolymer: GMA-modified AS resin “AS-3G” manufactured by Toray Industries, Inc.

  Silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd., β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane “KBM-303”

  Glass fiber (hereinafter abbreviated as GF): manufactured by Nippon Electric Glass Co., Ltd., glass chopped strand “ECS 03 T-747H”

  Calcium carbonate (hereinafter abbreviated as charcoal cal): Heavy calcium carbonate “KSS-1000” manufactured by Dowa Calfine Co., Ltd.

[Resin pellet adjustment method]
A screw-type twin screw extruder (TEX manufactured by Nippon Steel Works) in which the above raw materials were dry blended in advance at the ratios shown in Tables 1 to 3 and set to a cylinder temperature of 280 ° C. (lower hopper) to 310 ° C. (discharge port side). -44) was melt-kneaded and pelletized to prepare a pellet-shaped resin composition. Using this pellet, mechanical properties, optical axis stability, spiral flow length, and burr length were measured by the following means. In addition, it was common at the time of any measurement, and it preliminarily dried for 3 hours in the hot air dryer which temperature-controlled the pellet to 130 degreeC before shaping | molding.

[Measurement of mechanical properties]
Tensile properties: measured according to ASTM D638.

  Bending properties: measured according to ASTM D790.

  Izod impact strength: measured according to ASTM D256.

The test specimens for evaluating mechanical properties of all materials are Toshiba Machine IS80 injection molding machine, cylinder temperature: 320 ° C., mold temperature: 140 ° C., injection-cooling time: 13-15 seconds, injection speed: 75% Injection pressure: It was created by injection molding under the setting condition of filling lower limit pressure + 10 kg / cm ² (G).

[Measurement of optical axis stability evaluation (amount of optical axis deviation)]
The resin pellets were supplied to an injection molding machine (SG75-HIPRO · MIII) manufactured by Sumitomo-Nestal Co., which was set at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and injection molded under the conditions of a molding lower limit pressure + 5 kgf / cm ² gauge, An optical pickup model injection molded product 1 having the shape shown in FIG. 1 was obtained. A half mirror 2 (material: glass base material) is installed in the central notch portion of the optical pickup model injection molded product 1, and the semiconductor laser autocollimator has a focal length of 200 mm, a wavelength of 650 nm, and an output of 0.3 mW in a thermostatic chamber. The oscillated laser beam was applied and the reflected laser beam was received by a CCD camera. In addition, the optical axis inclination measuring machine made from Kubotec Co., Ltd. was used for these measurements. The position of the reflected laser beam at 23 ° C. was used as the origin, the temperature was raised to 80 ° C. over 20 minutes, and the optical axis fluctuation value after standing for 60 minutes was measured. It can be said that the smaller this value, the better the environmental stability of the laser focus.

  FIG. 1 shows a front view of the injection molded product. FIG. 2 is a perspective view of a state in which a molded product provided with a half mirror is set on a fixing jig. A half mirror 2 is installed in a central notch portion of the injection molded product 1, and these are fixed by a fixing jig 3 so that the half mirror is flat with respect to the floor surface. Laser light a oscillated from the semiconductor laser autocollimator is incident on the surface of the half mirror 2 at a right angle and is reflected at a right angle as reflected laser light b. Therefore, when the surface on which the half mirror is installed is displaced, the reflection angle of the reflected light also deviates from a right angle.

[Measurement of spiral flow length]
A mold having a spiral cavity with a width of 5 mm and a depth of 1 mm, which is supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO · MIII) with a cylinder temperature set at 320 ° C. and temperature-controlled at 130 ° C. Was used to measure the flow length when the injection pressure was 98 MPa, and this was used as the spiral flow length. The injection speed was fully opened, and the measurement was performed at a setting of 1 speed and 1 pressure. It can be said that the larger this value, the better the fluidity.

[Measurement of burr length]
The resin pellets were supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO · MIII) set at a cylinder temperature of 320 ° C., and the temperature was adjusted to a mold temperature of 130 ° C. (a) 4 mm wide × long on the circumference Injection molding was performed using a disk-shaped mold of 80 mmφ × 2 mm thickness having two protrusions of 20 mm depth × 500 μm depth, (b) width 4 mm × length 20 mm × depth 20 μm, and the protrusion of (a) The filling length of the protrusion in (b) when molding was performed by adding 10 MPa to the lowest pressure at which the part was filled, and the burr length was taken as a burr length, and the length was measured by enlarging it 100 times with an optical projector.

[Measurement of tracking resistance index]
The resin pellets were supplied to an injection molding machine (SG75-HIPRO · MIII) manufactured by Sumitomo-Nestal with a cylinder temperature set at 320 ° C., and the temperature was adjusted to a mold temperature of 130 ° C., with a width of 80 mm × length of 80 mm × thickness of 3 mm. Injection molding was performed using a square plate mold, and an applied voltage at which tracking occurred was measured using a test piece obtained by adding 10 MPa to the lowest pressure at which the cavity was filled, in accordance with IEC112 3rd edition. .

[Examples 1 7
The results are shown in Tables 1 and 3 . In Examples 1 to 3, PPS-1 is solely used as a base, and all exhibit excellent optical axis misalignment, bar flow flow length, burr length, and tracking resistance index. In Examples 2 and 3, the amount of the silane coupling agent is increased, and although fluidity is inferior to that of Example 1, it is excellent in low burr property and maintains a low optical axis deviation. Moreover, in Examples 4-6, PPS-1 and PPS-2 are used together, and although the fluidity | liquidity is inferior compared with PPS-1 alone, the same tendency as Examples 1-3 is shown .

[Comparative Examples 1 to 10]
The results are shown in Tables 2-3 . In Comparative Example 1, the amount of optical axis deviation is larger than that in the case where the fibrous filler is more than the non-fibrous filler and the fibrous filler is less than the non-fibrous filler. Further, the total of the fibrous filler and the non-fibrous filler is 70% by weight, and it is difficult to apply to the capacitor case in terms of fluidity.
Comparative Example 2 does not contain a GMA-modified AS resin , and the optical axis deviation increases and the tracking resistance index decreases as compared with the case of containing GMA-modified AS resin . Comparative Example 3 does not contain a silane coupling agent, and the burr length is deteriorated. On the other hand, in the case of Comparative Example 4 containing 4 % by weight of the silane coupling agent, the burr length is reduced, but the fluidity is greatly deteriorated. In Comparative Examples 5 to 6 , 30 % by weight of GMA-modified AS resin is contained, but it can be seen that both strength and fluidity are lowered. In Comparative Examples 7 to 8 , the fibrous filler and the non-fibrous filler are not used in combination, but are used alone. In Comparative Example 7 , the amount of optical axis deviation is large, and in Comparative Example 8 , the strength is greatly deteriorated. I understand that.

The ratio Comparative Examples 9-10 In the not contain GMA modified AS resin tracking resistance index significantly reduced, fluidity decreased.

  The present invention is represented by CDs, CD-ROMs, CD-Rs, CD-RWs, DVDs, DVD-ROMs, DVD ± Rs, DVD ± RWs, DVD-RAMs, etc. that perform writing and reading using laser light. Various parts such as an optical pickup slide base used for an optical recording apparatus, and an exterior case used for a metallized film capacitor member provided with a capacitor element in the exterior case and filled with resin in the exterior case However, the range of application is not limited to these.

It is a figure which shows the injection molded product 1 used for the optical axis stability evaluation in the Example. It is a perspective view which shows the state which fixed the injection molded product 1 which installed the half mirror 2 used for the optical axis stability evaluation in the Example on the fixing jig 3. FIG.

Explanation of symbols

1. 1. Injection molded product Half mirror 3, fixing jig a. Incident direction of laser light emitted from a semiconductor laser autocollimator b. Reflection direction of reflected laser light

Claims (4)

The total of (A), (B), (C) and (D) is 100% by weight, (A) 15 to 45% by weight of polyphenylene sulfide resin, and (B ) acrylonitrile-styrene resin 5 to 25 modified with glycidyl methacrylate. % By weight, (C) 10-50% by weight of fibrous filler, (D) 10-50% by weight of non-fibrous filler, and a total of 100% of ( A), (B), (C) and (D) (E) 0.01 to 3 parts by weight of silane coupling agent is added to the part , (C) the amount of fibrous filler is less than the amount of (D) non-fibrous filler, and injection A polyphenylene sulfide resin composition having a spiral flow length of 90 mm or more in a mold cavity having a width of 5 mm and a thickness of 1 mm adjusted to 130 ° C. when a molding machine cylinder set temperature is 320 ° C. and an injection pressure is 98 MPa. A Ranaru molded article, an optical recording apparatus part comprising the molded article, characterized in that the optical axis deviation amount at the time of changing the temperature to 80 ° C. from 23 ° C. is not more than 2.5 minutes. 2. The optical recording device component according to claim 1, wherein the optical recording device component comprises a molded product having a tracking resistance index of 225 V or more. The molded product according to claim 1, wherein the projection has two projections on the circumference: (a) width 4 mm × length 20 mm × depth 500 μm, (b) width 4 mm × length 20 mm × depth 20 μm. X2mmt disk-shaped mold is temperature-controlled at 130 ° C, and when injection molding is performed at a molding machine cylinder set temperature of 320 ° C, 10MP is added to the minimum pressure at which the protrusions in (a) are filled An optical recording device component made of a molded product, wherein the filling length of the protrusions in (b) is 130 μm or less. 2. An optical recording device component comprising the molded product according to claim 1, wherein the molded product has a thickness of 2 mm or less.

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