JP2008163221A - Polyphenylene sulfide resin composition and molded article therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition being excellent in flowability during molding, tracking resistance and mechanical strength, and being reduced in the occurrence of burr. <P>SOLUTION: The polyphenylene sulfide resin composition comprises 15-45 wt.% polyphenylene sulfide resin (A), 5-25 wt.% vinyl cyanide copolymer (B), 5-20 wt.% modified vinyl copolymer (C), 10-45 wt.% fibrous filler (D), and 5-30 wt.% nonfibrous filler (E) on the basis of 100 wt.% of the total amount of (A) to (E), and is added with 0.01-3 pts.wt. silane-based coupling agent (F), based on 100 pts.wt. total amount of (A) to (E), and has a spiral flow length in a mold cavity having a breadth of 5 mm and a thickness of 1 mm at a conditioned temperature of 130°C, when the temperature of the cylinder of an injection molding machine is set at 320°C and the injection pressure is set at 98 MPa, of not shorter than 200 mm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition containing a polyphenylene sulfide resin, a vinyl copolymer such as acrylonitrile / styrene resin, and a modified vinyl copolymer such as acrylonitrile / styrene / glycidyl methacrylate copolymer, and more particularly to a metallized film. The present invention relates to a resin composition suitable for a hybrid vehicle member such as a capacitor part. More specifically, the present invention relates to a resin composition suitable for various parts used as a metallized film capacitor member provided with 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. Polyphenylene sulfide resin is a resin that has excellent mechanical strength, heat resistance, and water resistance, and can withstand harsh usage conditions. 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 increasing rapidly. However, they have high capacity and 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. Along with this, there is a concern that if a resin with poor resin flowability at the time of melting is used, there will be a problem that filling failure will occur at the time of molding the capacitor element case, and it will be impossible to collect good products. Resins with excellent properties have been demanded. 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 cyanide copolymer, a modified vinyl copolymer, a fibrous filler, a non-fibrous filler, and a silane coupling agent. Patent Document 1 discloses a resin composition obtained by blending a polyarylene sulfide resin with a polystyrene polymer and a filler as a resin composition close to. Further, Patent Document 2 discloses a resin composition in which a polyphenylene sulfide resin, a graft copolymer composed of a thermoplastic elastomer segment and a vinyl copolymer segment, and a silane coupling agent are blended.
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 resin, and has a significant effect on metallized film capacitor performance. No mention is made of the fluidity and the fluidity which are important for collecting good products during production. 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 a description of the polystyrene polymer in the text, but there is no description about the addition of the modified vinyl copolymer.

  The resin composition described in Patent Document 2 is intended to reduce the coefficient of linear expansion of polyarylene sulfide resin, improve heat and humidity resistance, and impact resistance. No mention is made of insulation which has a great influence on performance and fluidity which is important for collecting good products during production. Further, in this publication, unlike the present invention, a graft copolymer comprising a thermoplastic elastomer segment and a vinyl copolymer segment is added, and even if these are added, the excellent fluidity of the present invention cannot be obtained. .

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 insulation and fluidity, which will be important in the future for the reasons described above.
JP 7-316428 A Japanese Patent Laid-Open No. 2002-053752 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 a polyphenylene sulfide resin composition for metallized film capacitor parts that is excellent in fluidity during molding, mechanical strength of molded products, tracking resistance, and low burr properties.

The inventors made the total amount of (A) to (E) 100% by weight, (A) 15 to 45% by weight of polyphenylene sulfide resin, (B) vinyl cyanide monomer (a), aromatic vinyl 5 to 25% by weight of a vinyl cyanide copolymer consisting of a monomer (b) and another vinyl monomer (c) copolymerizable therewith, (C) a vinyl cyanide monomer ( a), a modified vinyl comprising an aromatic vinyl monomer (b) and a monomer (d) having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group and an amide group 5 to 20% by weight of a copolymer, (D) 10 to 45% by weight of a fibrous filler, and (E) 5 to 30% by weight of a non-fibrous filler, and (A) to (E) (F) Silane coupling agent 0.01 to 3 parts by weight relative to 100 parts by weight Compositions obtained by adding the amount unit, fluidity during molding, mechanical strength of the molded article, tracking resistance and low burr properties were found that excellent well-balanced. That is, in the present invention, (1) the total amount of (A) to (E) is 100% by weight, (A) 15 to 45% by weight of polyphenylene sulfide resin, (B) vinyl cyanide monomer (a), 5 to 25% by weight of vinyl cyanide copolymer comprising aromatic vinyl monomer (b) and other vinyl monomer (c) copolymerizable therewith, (C) vinyl cyanide monomer From the monomer (d) having at least one functional group selected from the group consisting of a monomer (a), an aromatic vinyl monomer (b) and a carboxyl group, an epoxy group, an amino group and an amide group 5 to 20% by weight of a modified vinyl copolymer, (D) 10 to 45% by weight of a fibrous filler, and (E) 5 to 30% by weight of a non-fibrous filler. (F) Silane coupling agent with respect to 100 parts by weight of the total amount of (E) 0. 1 to 3 parts by weight of a composition, which is 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. A polyphenylene sulfide resin composition having a spiral flow length of 200 mm or more.
(2) (B) a vinyl cyanide monomer comprising a vinyl cyanide monomer (a), an aromatic vinyl monomer (b) and another vinyl monomer (c) copolymerizable therewith. The blending amount of the copolymer is selected from the group consisting of (C) vinyl cyanide monomer (a), aromatic vinyl monomer (b) and carboxyl group, epoxy group, amino group and amide group. More than the blending amount of the modified vinyl copolymer comprising the monomer (d) having at least one functional group selected, and the total amount of (B) + (C) is (A) to (E) The polyphenylene sulfide resin composition according to (1), wherein the total amount is 25% by weight or less with respect to 100% by weight.
(3) The amount of (D) fibrous filler is greater than the amount of (E) non-fibrous filler, and the total amount of (D) + (E) is the total amount of (A) to (E) The polyphenylene sulfide resin composition according to (1) or (2), wherein the polyphenylene sulfide resin composition is 60% by weight or less based on 100% by weight.
(4) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (3).
(5) An 80 mmφ × 2 mmt disk-shaped mold having 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. (B) Protrusion when molding by adding 10 MPa to the lowest pressure at which the protrusion of (a) is filled when injection molding is performed at a set temperature of 320 ° C. at a molding machine cylinder temperature of 130 ° C. The molded product according to (4), wherein the filling length of the part is 130 μm or less.
(6) The molded article according to (4) or (5), wherein the tracking resistance index is 225 V or more.
(7) A metallized film capacitor part comprising the molded product according to any one of (4) to (6).
(8) The metallized film capacitor part according to (7), wherein the molded product thickness is 2 mm or less.
It is about.

  According to the present invention, it is possible to obtain a polyphenylene sulfide resin composition that is excellent in balance in fluidity during molding, mechanical strength of molded products, tracking resistance, and low burr properties. Since it has such characteristics, it is suitable as a material for in-vehicle parts, particularly a metallized film capacitor member.

  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 compounding quantity of the polyphenylene sulfide resin used by this invention is 15 to 45 weight%, Preferably it is 12 to 42 weight%, More preferably, it is 10 to 40 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. In order to balance mechanical strength such as fluidity and toughness, it is preferable to use a mixture of two or more polyphenylene sulfide resins having different degrees of polymerization and fluidity.

  Examples of the (B) vinyl cyanide copolymer used in the present invention include a vinyl cyanide monomer (a), an aromatic vinyl monomer (b), and other vinyl copolymers copolymerizable therewith. A monomer (c) is mentioned, These can be used by 1 or more types, Both a powdery thing and a pellet-like thing can be used.

  Here, examples of the vinyl cyanide monomer (a) include acrylonitrile and methacrylonitrile, 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, and these may be used alone or in combination of two or more. it can. Examples of other vinyl monomers (c) copolymerizable therewith include maleimide compounds such as N-methylmaleimide, N-cyclohexylmaleimide and N-phenylmaleimide, and unsaturated dicarboxylic acids such as maleic acid. And copolymerizable vinyl compounds typified by unsaturated dicarboxylic anhydrides such as maleic anhydride and unsaturated amide compounds such as acrylamide. These may be used alone or in combination of two or more.

  The intrinsic viscosity of the vinyl cyanide copolymer in the present invention is preferably 0.2 to 1.2 dl / g. If it is less than 0.2 dl / g, the resulting thermoplastic resin composition has insufficient chemical resistance and impact resistance. If it exceeds 1.2 dl / g, the molding processability of the resulting thermoplastic resin composition Is inferior. Further, the dispersibility is deteriorated and the surface of the molded product and the coated surface are inferior, which is not preferable.

  The amount of the vinyl cyanide copolymer used in the present invention is 5 to 25% by weight, preferably 6 to 20% by weight. If the blended amount of the vinyl cyanide copolymer is too small, the tracking resistance index is lowered, while if it is too much, the mechanical strength and heat resistance are lowered.

  The (C) modified vinyl copolymer used in the present invention comprises a vinyl cyanide monomer (a), an aromatic vinyl monomer (b), a carboxyl group, an epoxy group, an amino group, and an amide group. A modified vinyl copolymer composed of a monomer (c) having at least one functional group selected from the group having a structure obtained by copolymerizing two or more vinyl monomers. And having at least one functional group of carboxyl group, epoxy group, amino group, and amide group in the molecular chain. The content of these functional groups may be minimal, and may be contained in a large amount as long as the performance such as appearance and fluidity is not impaired. It is sufficient that more than one species of functional group is present.

  Here, examples of the vinyl cyanide monomer (a) include acrylonitrile and methacrylonitrile, 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, and these may be used alone or in combination of two or more. it can. Examples of the monomer (c) having at least one functional group selected from the group consisting of carboxyl group, epoxy group, amino group and amide group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride Monomers having a carboxyl group such as acid and itaconic acid, monomers having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, and glycidyl itaconate, aminoethyl acrylate, ethylaminopropyl methacrylate, methacrylic acid Aminoalkyl ester derivatives of (meth) acrylic acid such as phenylaminoethyl, vinylamine derivatives such as N-acetylvinylamine, allylamine derivatives such as methallylamine, and monomers having amino groups such as aminostyrene, acrylamide, N-methyl methacrylate Monomers include having an amide group of de such, they can be used singly or in combination.

  The intrinsic viscosity of the modified vinyl copolymer in the present invention is preferably 0.2 to 1.2 dl / g. If it is less than 0.2 dl / g, the resulting thermoplastic resin composition has insufficient chemical resistance and impact resistance. If it exceeds 1.2 dl / g, the molding processability of the resulting thermoplastic resin composition Is inferior. Further, the dispersibility is deteriorated and the surface of the molded product and the coated surface are inferior, which is not preferable.

  The amount of the modified vinyl copolymer used in the present invention is 5 to 20% by weight, preferably 6 to 18% by weight. If the amount of the modified vinyl copolymer is too small, the tracking resistance index will be low. On the other hand, if it is too large, the mechanical strength, heat resistance, and fluidity will decrease.

  In the present invention, in order to obtain excellent fluidity, the blending amount of (B) the vinyl cyanide copolymer is larger than the blending amount of (C) the modified vinyl copolymer, and (B) + ( The total amount of C) is preferably 25% by weight or less. Specifically, it is preferably 3% by weight or less, more preferably 5% by weight or more. Further, if the total amount of (B) + (C) is large, the mechanical strength, heat resistance, and low burr properties are adversely affected. Therefore, the total of both materials is preferably 25% by weight or less, and 20% by weight or less. More preferably.

  In the present invention, it is essential to add (D) 10 to 45% by weight of fibrous filler and (E) 5 to 30% by weight of non-fibrous filler and blend the fibrous filler together with the non-fibrous filler. It is. 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. Is preferable in terms of obtaining Of these, glass fiber and carbon fiber are more preferably used. The amount of the fibrous filler used in the present invention is 10 to 45% by weight, preferably 12 to 43% by weight, and 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.

  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 amount of the non-fibrous filler used in the present invention is 5 to 30% by weight, preferably 7 to 28% by weight, and more preferably 10 to 25% by weight. If the amount of the non-fibrous filler is too small, the dimensional stability of the molded product will be insufficient, and if it is too large, the strength, rigidity and impact resistance will be insufficient, and the fluidity during molding will be reduced. .

  In the present invention, in order to obtain excellent fluidity, the content of the non-fibrous filler is preferably less than the content of the fibrous filler. Specifically, it is preferably 5 parts by weight or more, more preferably 10 parts 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 55% by weight or less. preferable.

  In the polyphenylene sulfide resin composition of the present invention, it is essential to add (F) a silane coupling agent in order to further improve the low burr and high toughness. Examples of such silane coupling agents include alkoxysilane compounds having at least one functional group selected from an epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and 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 coupling agent used in the present invention is from 0.01 to a total amount of 100 parts by weight of the above (A) to (E) from the viewpoint of obtaining more excellent low burr and high toughness. The addition in the range of 3 parts by weight is preferably selected, and the range of 0.1 to 1.5 parts by weight is more preferably selected. If the amount is too small, the improvement effect of low burrs and high toughness due to the addition of the silane coupling agent will not be fully manifested. It tends to make it.

  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 acid ester groups, acid anhydride anhydride groups, and epoxy groups, polyolefins Based 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.
The polyphenylene sulfide resin composition of the present invention is intended to be used as a material for in-vehicle components, particularly metalized film capacitor case members. However, in this application, the product has recently been made smaller and thinner. ing. Further, in this application, there are many examples that are used as an outer case, but because of the box shape, the molded product itself is large, and further fluidity is required for injection molding a good product. Further, when molding is performed with 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 characterized by being 200 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 300 mm.

Also, as materials for automotive parts, especially metalized film capacitor members, when assembling metal terminals due to downsizing associated with downsizing, for example, the distance between the terminals has to be shortened, and as a result, tracking resistance has been increasing recently. There is a tendency that insulation characteristics such as Molded articles obtained by molding the polyphenylene sulfide resin composition of the present invention by injection molding are characterized by having 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 excellent in balance with respect to the above-mentioned characteristics, it is particularly suitably used for materials for metallized film capacitor members such as automotive parts, particularly exterior cases. It is done.

  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 hot 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 cyanide copolymer: AS resin “1800B” manufactured by Toray Industries, Inc.
Acrylonitrile / styrene copolymer, intrinsic viscosity 0.49 [dl / g]. The intrinsic viscosity was measured using a Ubbelohde viscometer from a methyl ethyl ketone solution having a measurement temperature of 30 ° C. and a sample concentration of 0.4 g / dl.

Modified vinyl copolymer: AS resin “AS-3G” manufactured by Toray Industries, Inc.
Acrylonitrile / styrene / glycidyl methacrylate copolymer, intrinsic viscosity 0.60 [dl / g].

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]
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 and 2 and the cylinder temperature was set to 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, 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 type injection molding machines, cylinder temperature: 320 ° C., mold temperature: 140 ° C., injection-cooling time: 13-15 seconds, injection speed: 75%. Injection pressure: It was prepared by injection molding under the setting condition of filling lower limit pressure + 10 kg / cm ² (G).

[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 Injection molding was performed using a disk-shaped mold of 80 mmφ × 2 mm thickness having two projections of 20 mm long × 500 μm deep, (b) 4 mm wide × 20 mm long × 20 μm deep, 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 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., which was 80 mm wide × 80 mm long × 3 mm thick. 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]
Table 1 shows examples. In Examples 1 to 3, each characteristic when the addition amount of the silane coupling agent was changed is shown, but all show excellent mechanical strength, spiral flow length, burr length, and tracking resistance index. In Examples 2 and 3, the amount of the silane coupling agent is increased and the fluidity is inferior to that of Example 1, but the mechanical strength and the low burr property are on the contrary. In Examples 4 and 5, the addition ratio of the vinyl cyanide copolymer and the modified vinyl copolymer is changed, and the modified vinyl is compared with Example 2 in which the addition amount of the silane coupling agent is the same. Although the addition ratio of the copolymer is increased, the spiral flow length is inferior to that of Example 2, but all show excellent mechanical strength, spiral flow length, burr length, and tracking resistance index. In Example 6, the blending ratio of PPS-1 and PPS-2 was changed, and the fluidity of PPS itself was reduced due to the increase in the ratio of PPS-2. However, good fluidity was achieved with the composition of the present invention. It can be seen that it retains sex. Example 7 has the same addition ratio of the fibrous reinforcing material and the non-fibrous reinforcing material, and compared with Example 2 in which the fibrous reinforcing material was added more than the non-fibrous reinforcing material, the mechanical strength and spiral Although it is inferior in flow length, it can be seen that it exhibits excellent mechanical strength, spiral flow length, burr length, and tracking resistance index. In addition, about tracking-proof index | exponent, all Examples 1-7 show 250 [V] or more, and the effect of addition of a vinyl cyanide copolymer and a modified vinyl copolymer can be confirmed.

[Comparative Examples 1 to 7]
Table 2 shows a comparative example. Comparative Example 1 does not contain a vinyl cyanide copolymer and a modified vinyl copolymer, and the mechanical strength is improved as compared with the case where it is contained, but it can be seen that the tracking resistance index and the spiral flow length are lowered. In Comparative Example 2, only the vinyl cyanide copolymer is added, and the mechanical strength is lowered and the burr length is deteriorated as compared with the case where both the vinyl cyanide copolymer and the modified vinyl copolymer are added. . On the other hand, in Comparative Example 3, only the modified vinyl copolymer is added, and the mechanical strength is improved as compared with the case where both the vinyl cyanide copolymer and the modified vinyl copolymer are added. It turns out that the spiral flow length decreases. In Comparative Example 4, no silane coupling agent is contained, and the burr length is deteriorated. On the other hand, in the case of Comparative Example 5 containing 5 parts of a silane coupling agent, the burr length is reduced, but the fluidity is greatly deteriorated. In Comparative Example 6, the addition amounts of the fibrous filler and the non-fibrous filler are both out of the claims, the fibrous filler is less than the non-fibrous filler, the mechanical strength is reduced, and the spiral flow You can see that the length has dropped. On the other hand, in Comparative Example 7, the addition amounts of the fibrous filler and the non-fibrous filler are both out of the claims, the fibrous filler is larger than the non-fibrous filler, and the mechanical strength and the spiral flow length are Although it is excellent, it turns out that the burr length deteriorates.

  The present invention can be expected to be developed as various parts such as an outer case, which is used for a metallized film capacitor member provided with a capacitor element in an outer case and filled with resin in the outer case. It is not limited to.

Claims (8)

The total amount of (A) to (E) is 100% by weight, (A) 15 to 45% by weight of polyphenylene sulfide resin, (B) vinyl cyanide monomer (a), aromatic vinyl monomer ( 5 to 25% by weight of a vinyl cyanide copolymer comprising b) and other vinyl monomers (c) copolymerizable therewith, (C) a vinyl cyanide monomer (a), aromatic Modified vinyl copolymer 5 comprising vinyl monomer (b) and monomer (d) having at least one functional group selected from the group consisting of carboxyl group, epoxy group, amino group and amide group -20 wt%, (D) 10-45 wt% of fibrous filler, and (E) non-fibrous filler, 5-30 wt%, and the total amount of (A)-(E) is 100 wt% (F) 0.01-3 parts by weight of silane coupling agent is added to parts The spiral flow length in a mold cavity having a width of 5 mm and a thickness of 1 mm adjusted to 130 ° C. when the injection molding machine cylinder set temperature is 320 ° C. and the injection pressure is 98 MPa is 200 mm or more. A polyphenylene sulfide resin composition characterized by the above. (B) Vinyl cyanide copolymer comprising vinyl cyanide monomer (a), aromatic vinyl monomer (b) and other vinyl monomers (c) copolymerizable therewith. At least selected from the group consisting of (C) vinyl cyanide monomer (a), aromatic vinyl monomer (b) and carboxyl group, epoxy group, amino group and amide group The total amount of (B) + (C) is larger than the blending amount of the modified vinyl copolymer composed of the monomer (d) having one kind of functional group, and the total amount of (A) to (E). 2. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is 25% by weight or less as 100% by weight. (D) The amount of fibrous filler is greater than the amount of (E) non-fibrous filler, and the total amount of (D) + (E) is 100 weights of the total amount of (A) to (E). The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is 60% by weight or less. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 3. An 80 mmφ × 2 mmt disk-shaped mold having 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 at 130 ° C. When the temperature is controlled and injection molding is performed at a molding machine cylinder set temperature of 320 ° C., filling of the protrusion of (b) when molding is performed by adding 10 MPa to the lowest pressure at which the protrusion of (a) is filled. The molded article according to claim 4, wherein the length is 130 μm or less. The molded article according to claim 4 or 5, wherein the tracking resistance index is 225V or more. A metallized film capacitor component comprising the molded product according to claim 4. The metallized film capacitor component according to claim 7, wherein the molded product has a thickness of 2 mm or less.