JP2014065842A - Polyphenylene sulfide resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin and a molded article excellent in thermal conductivity and fire resistance, without requiring a painting process to white color and suitable for LED heat radiation members.SOLUTION: The polyphenylene sulfide resin is obtained by blending 100 pts.mass of a polyphenylene sulfide resin (A) and 160 pts.mass or more and 250 pts.mass or less of an inorganic filler, contains magnesium hydroxide (B) and titanium oxide (C) with blending ratio (mass ratio) of 100:10 or more and 100:75 or less, and has the total blending amount of the magnesium hydroxide (B) and the titanium oxide (C) is 60 pts.mass or more and 160 pts.mass or less based on 100 pts.mass of the polyphenylene sulfide resin (A).

Description

  The present invention relates to a polyphenylene sulfide resin composition useful for applications requiring heat conductivity, whiteness, and flame retardancy such as a heat radiating member for lighting, and a molded product thereof.

  Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to high-heat-resistant super engineering plastics, and has mechanical strength, rigidity, flame resistance, chemical resistance, electrical properties, dimensional stability, and the like. Therefore, it is widely used for various electric / electronic parts, home appliance parts, automobile parts and machine parts, mainly for injection molding.

  On the other hand, as compared with fluorescent lamps and light bulbs, many LEDs (Light Emitting Diodes) have been developed and put on the market as light sources having long-life performance and power saving compared to fluorescent lamps and light bulbs. In particular, LEDs with high luminous efficiency used for illumination and the like are attracting attention because they have excellent power saving and long life, and their applications are being expanded.

  In order to increase the intensity of the light emitted from the LED, it is necessary to increase the current supplied. However, the element is vulnerable to heat, and since it begins to deteriorate at 80 ° C. or higher, the life of the LED decreases, and the brightness increases accordingly. There is a characteristic that it decreases. In order to prevent a decrease in LED life and a decrease in brightness, it is preferable to use a member that appropriately dissipates heat. If the heat is not properly dissipated, the advantages of the LED are lost due to the reduction in light emission efficiency and the shortening of the life described above.・ There is a risk of fire and other accidents.

  Conventionally, as a heat dissipation measure for high luminous efficiency LEDs, metal materials such as aluminum die casting have been used as LED heat dissipation members for LED substrates and housings. However, metal materials such as die-casting are expensive because they require cutting one by one and painting them into white when manufacturing parts, which takes time for processing. Moreover, since the product weight is increased as compared with fluorescent lamps and light bulbs, there is a problem in that there is a risk that the socket and the ceiling holding fixture cannot withstand the weight and fall.

  For this reason, a new resin material that has thermal conductivity, whiteness, flame retardancy, and can be reduced in weight is demanded for the problem of the LED heat dissipation member.

  As an LED heat dissipating member, Patent Document 1 discloses, as a main component, polyphenylene sulfide resin, magnesium hydroxide, glass fiber, and olefin resin, molding processability, thermal conductivity, fillability in a molded product thin portion, and mechanical properties. An LED heat radiating member having excellent strength is disclosed. However, since the natural color of the member of Patent Document 1 is beige, a painting process is required for white, and there is no description about a method for obtaining a member for radiating LED heat having whiteness.

  Patent Document 2 discloses a polyphenylene sulfide resin composition that is excellent in light discoloration resistance and is useful for parts for electric lighting and outdoors, which is formed by blending a polyphenylene sulfide resin, a reinforcing material, titanium oxide, and a triazine compound. Has been. However, the resin composition of Patent Document 2 does not have a flame retardancy suitable for an LED heat dissipation member, has a whiteness, and has a flame retardance suitable for an LED heat dissipation member. There is no mention of how to obtain it.

  Further, Patent Document 3 discloses a polyphenylene sulfide resin composition having excellent tracking resistance, which is made of a polyphenylene sulfide resin and magnesium hydroxide and a fibrous and / or non-fibrous filler. However, since the natural color of the resin composition is beige, a white coating process is necessary, and no method for obtaining a white LED heat-dissipating member is described.

JP 2011-228685 A JP 2000-136305 A JP 2001-288363 A

  The present invention has been made in view of the above, and obtains a polyphenylene sulfide resin composition suitable for an LED heat radiating member, which is excellent in thermal conductivity and flame retardancy and does not require a white coating step. Is an issue.

  As a result of intensive studies to achieve the above object, the present inventors have blended magnesium hydroxide and titanium oxide in a predetermined ratio and a predetermined ratio to the PPS resin, thereby having whiteness and thermal conductivity. The present inventors have found that a polyphenylene sulfide resin composition excellent in flame retardancy and suitable for an LED heat radiating member is obtained, and thus completed the present invention.

  In order to solve the above-mentioned problems and achieve the object, the polyphenylene sulfide resin composition of the present invention is blended with 160 to 250 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyphenylene sulfide resin (A). The inorganic filler contains magnesium hydroxide (B) and titanium oxide (C), and is a total formulation of the magnesium hydroxide (B) and the titanium oxide (C). The amount is 60 to 160 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide resin (A), and the mixing ratio (mass ratio) of the magnesium hydroxide (B) and the titanium oxide (C). Is 100: 10 or more and 100: 75 or less.

  Further, the polyphenylene sulfide resin composition of the present invention is the above invention, further comprising a blue pigment (D), and the amount of the blue pigment (D) is 100 parts by mass of the polyphenylene sulfide resin (A). On the other hand, it is 0.05 mass part or more and 0.5 mass part or less.

In the polyphenylene sulfide resin composition of the present invention, the object color of the molded product obtained by molding the polyphenylene sulfide resin composition is the same as that of the International Illuminating Commission (CIE) standard illuminant C light source for colorimetry. In the CIE-LAB color system, the L ^* value is 82 or more, and the b ^* value is 0 or more and 8 or less.

  The polyphenylene sulfide resin composition of the present invention is characterized in that, in the above invention, the flame retardant level of UL94 standard when the polyphenylene sulfide resin composition is molded to a thickness of 0.38 mm is V-0. .

  Moreover, the molded article of the present invention is obtained by injection molding the polyphenylene sulfide resin composition described in any one of the above.

  Moreover, the molded article of the present invention is the heat dissipating member for illumination in the above invention.

  According to the present invention, when injection molding is performed, a polyphenylene sulfide resin composition useful for applications requiring thermal conductivity, whiteness, mechanical strength, and flame retardancy, such as a heat radiating member for lighting, can be obtained.

  Hereinafter, the present invention will be described in detail.

  The polyphenylene sulfide resin composition of the present invention is a resin composition obtained by blending 160 to 250 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyphenylene sulfide resin (A). Contains magnesium hydroxide (B) and titanium oxide (C), and the total amount of magnesium hydroxide (B) and titanium oxide (C) is 100 parts by mass of the polyphenylene sulfide resin (A). On the other hand, it is 60 mass parts or more and 160 mass parts or less, and the compounding ratio (mass ratio) of the magnesium hydroxide (B) and the titanium oxide (C) is 100: 10 or more and 100: 75 or less. It is characterized by.

As polyphenylene sulfide resin (A) used in the present invention, in addition to polyarylene sulfide represented by polyphenylene sulfide, polyarylene sulfide sulfone, polyarylene sulfide ketone, and their random copolymers, block copolymers, and their Mixtures and the like are included. Of these, polyarylene sulfide is particularly preferably used. The polyphenylene sulfide resin (A) used in the present invention is a polymer containing a repeating unit represented by the following structural formula (I), preferably 70 mol% or more, more preferably 90 mol% or more. The polyphenylene sulfide resin (A) preferably contains 70 mol% or more of the repeating unit represented by the structural formula (I) because of excellent heat resistance.

  In addition, the polyphenylene sulfide resin (A) used in the present invention can be composed of 30 mol% or less of the repeating units with repeating units represented by the following structural formula. The polyphenylene sulfide resin (A) used in the present invention is a random copolymer composed of a repeating unit represented by the structural formula (I) and at least one repeating unit represented by the following structural formula: It may be a block copolymer, or a mixture of a polymer having a repeating unit represented by the structural formula (I) and a polymer having at least one repeating unit represented by the following structural formula. There may be.

  The polyphenylene sulfide resin (A) used in the present invention is a generally known method, 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 or It can be produced by, for example, a method for obtaining a polymer having a relatively large molecular weight as described in JP-A 61-7332.

  In the method for producing the polyphenylene sulfide resin (A) used in the present invention, after the polymerization is completed, a solid is recovered from the polymerization reaction product containing a polymer, a solvent and the like. Any known recovery method may be employed for the polyphenylene sulfide resin (A) used in the present invention.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. There is no need for slow cooling at the same rate in the entire process of the slow cooling step, and a method of slow cooling at a rate of 0.1 to 1 ° C./minute until the polymer particles crystallize and then 1 ° C./minute or more is used. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on rapid cooling conditions, and flush method is mentioned as one of the preferable methods of collection | recovery under rapid cooling conditions. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery. This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere in which the polymerization reaction product is flushed include nitrogen or water vapor at normal pressure, and the temperature is usually selected in the range of 150 ° C to 250 ° C.

  In the present invention, the polyphenylene sulfide resin (A) obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, organic solvent, heat Of course, it is also possible to use after performing various treatments such as washing with water, aqueous acid solution, etc., activation with a functional group-containing compound such as acid anhydride, amine, isocyanate, functional group-containing disulfide compound. However, since cross-linking / high molecular weight by heating in the air leads to oxidative coloring of the polyphenylene sulfide resin (A), in order to achieve the whiteness target, it is substantially linear without performing cross-linking / high molecular weight by heating. It is preferable that the PPS is in the form of a plate.

  When the polyphenylene sulfide resin (A) is washed with an organic solvent, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the polyphenylene sulfide resin (A). For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as tetrahydrofuran, halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol / phenolic solvents such as cresol and polyethylene glycol, benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are particularly preferably used. These organic solvents are also preferably used alone or in combination of two or more.

  As a specific method for washing the polyphenylene sulfide resin (A) with an organic solvent, there is a method of immersing the polyphenylene sulfide resin (A) in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide resin (A) 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 (A) 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 water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin (A) is treated with hot water. That is, in order to express the preferable chemical modification effect of the polyphenylene sulfide resin (A) 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 adding a predetermined amount of polyphenylene sulfide resin (A) to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The proportion of the polyphenylene sulfide resin (A) and water should be high, and the polyphenylene sulfide resin (A) is preferably used at a bath ratio of 200 g or less per liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating polyphenylene sulfide resin (A). That is, there is a method of immersing the polyphenylene sulfide resin (A) in an acid or an aqueous solution of an acid, and stirring or heating can be appropriately performed as necessary. The acid to be used is not particularly limited as long as it does not have an action of decomposing the polyphenylene sulfide resin (A). Aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid Halo-substituted aliphatic saturated carboxylic acids such as, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid And dicarboxylic acids 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-treated polyphenylene sulfide resin (A) is preferably washed several times with water in order to remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of preferred chemical modification of the polyphenylene sulfide resin (A) by acid treatment.

  Although there is no restriction | limiting in particular in the melt viscosity of the polyphenylene sulfide resin (A) used by this invention, The one where the melt viscosity is low is preferable from the meaning which obtains the more outstanding fluidity | liquidity. For example, it is preferably 1 Pa · s or more (die length 10 mm, die hole diameter 1 mm, 310 ° C., shear rate 1216 / s), more preferably 2 Pa · s or more. From the viewpoint of moldability, the upper limit is preferably 25 Pa · s or less, and more preferably 20 Pa · s or less.

  The melt viscosity of the polyphenylene sulfide resin (A) can be measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of a die length of 10 mm, a die hole diameter of 1 mm, 310 ° C., and a shear rate of 1216 / s.

  The polyphenylene sulfide resin (A) used in the present invention may be used in combination with two types of polyphenylene sulfide resins having different melt viscosities for the purpose of obtaining better fluidity. For example, the low melt viscosity polyphenylene sulfide resin is 1 Pa · s or more, more preferably 2 Pa · s or more, and the upper limit b is 25 Pa · s or less, more preferably 20 Pa · s or less (die length 10 mm, die hole diameter 1 mm, 310 ° C, And a high melt viscosity polyphenylene sulfide resin of 30 Pa · s or more, more preferably 40 Pa · s or more, and an upper limit of 90 Pa · s or less, more preferably 60 Pa · s or less (die length: 10 mm, die) It is preferable to use those having a hole diameter of 1 mm, 310 ° C., and a shear rate of 1216 / s. The combined ratio (mass ratio) of the low melt viscosity polyphenylene sulfide resin / high melt viscosity polyphenylene sulfide resin is preferably 95: 5 to 70:30, and more preferably 95: 5 to 65:35.

The magnesium hydroxide (B) used in the present invention is preferably a magnesium hydroxide having a relatively high purity containing an inorganic substance represented by the chemical formula Mg (OH) ₂ in an amount of 80% by mass or more, having a thermal conductivity, mechanical strength and melt viscosity. In view of this, preferably, the inorganic substance represented by Mg (OH) ₂ is contained in an amount of 80% by mass or more, the content of CaO is 5% by mass or less, and the content of chlorine is 1% by mass or less, more preferably Mg (OH) ₂ containing 95% by mass or more, CaO content of 1% by mass or less, chlorine content of 0.5% by mass or less, more preferably 98% by mass of Mg (OH) ₂ High-purity magnesium hydroxide having a CaO content of 0.1% by mass or less and a chlorine content of 0.1% by mass or less is suitable.

  The shape of magnesium hydroxide (B) used in the present invention may be any of particles, flakes, and fibers, but from the viewpoint of dispersibility and the like, particles and flakes are most preferable. The particle size of magnesium hydroxide (B) is not particularly limited, but the average particle size measured by a laser diffraction method is 0.1 to 10 μm because of the balance of mechanical strength and melt viscosity of the polyphenylene sulfide resin composition. It is preferable that the thickness is in the range, more preferably in the range of 0.3 to 4 μm.

  Further, as the magnesium hydroxide (B) used in the present invention, the above magnesium hydroxide (B) is converted into a vinylsilane compound such as vinyltriethoxysilane or vinyltrichlorosilane, γ-glycidoxypropyltrimethoxysilane, γ- Epoxysilane compounds such as glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) It is possible to use an aminosilane compound such as aminopropyltrimethoxysilane or γ-aminopropyltrimethoxysilane, a long-chain fatty acid such as stearic acid, oleic acid, montanic acid or stearyl alcohol or a surface-treated product with a long-chain aliphatic alcohol. preferable. As magnesium hydroxide (B) used in the present invention, application of magnesium hydroxide surface-treated with an epoxy silane compound or an amino silane compound is particularly suitable in terms of thermal conductivity improvement effect and mechanical strength.

  There is no restriction | limiting in particular as titanium oxide (C) used for this invention, A well-known thing can be used. Titanium oxide has a crystal form such as a rutile type or an anatase type, and the rutile type crystal form is preferably used because it is excellent in white colorability and thermal stability.

  The average particle diameter of titanium oxide (C) measured by the laser diffraction method is preferably in the range of 0.05 to 5 μm, and more preferably in the range of 0.05 to 1 μm. If the average particle diameter exceeds 5 μm, the surface smoothness of the molded product tends to decrease, which is not preferable.

  Moreover, what formed the coating | coated part which consists of inorganic compounds, such as a silica, an alumina, aluminum phosphate, a zirconia, aluminum, can be used as said titanium oxide (C) as a titanium oxide (C) used by this invention. In addition, as titanium oxide (C) used in the present invention, titanium oxide particles having the coating part or titanium oxide particles not having the coating part are added to organosilane compounds such as silanol and silane coupling agent, siloxane, and aminosilane. A titanium coupling agent, an alcohol amine, a surface treated with an organic compound such as a polyol such as polyethylene glycol, a titanium oxide particle having the coating part, or a titanium oxide particle having no coating part, and an alcohol What formed the coating part which consists of organic compounds, such as polyols, such as amine and polyethyleneglycol, can also be used.

The blue pigment (D) used in the present invention may be inorganic, organic, natural or synthetic as long as it can be used as a blue color pigment. Examples of the blue pigment (D) used in the present invention include ultramarine blue, rock ultramarine blue, and bitumen. Among them, ultramarine blue which is a synthetic blue inorganic pigment is preferable. Ultramarine is fine particles of aluminosilicate complex containing sulfur. An example is Na _(8-9) Al ₆ Si ₆ O ₂₄ S _(2-4) . For the purpose of lowering the yellowness and improving the whiteness, it is preferable to add 0.05 parts by weight or more of the blue pigment (D) to 100 parts by weight of the polyphenylene sulfide resin (A). 1 part by mass or more. Moreover, it is preferable that the upper limit of the compounding quantity of a blue pigment (D) shall be 0.5 mass part or less with respect to 100 mass parts of polyphenylene sulfide resin (A), More preferably, it is 0.4 mass part or less.

  In the polyphenylene sulfide resin composition of the present invention, it is preferable to add an inorganic filler other than magnesium hydroxide (B) and titanium oxide (C) from the viewpoint of improving mechanical strength. Specific examples of such inorganic fillers include glass fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone Fibrous fillers such as kou fiber, metal fiber, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, Metal compounds such as alumina and zirconium oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide and aluminum hydroxide, glass beads Glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, and non-fibrous fillers such as silica are used, it may be hollow. Furthermore, two or more of these inorganic fillers can be used in combination. From the viewpoint of improving the mechanical strength, it is preferable to use glass fibers.

  In addition, these inorganic fillers may be used after being pretreated 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.

  In the polyphenylene sulfide resin composition of the present invention, an inorganic filler containing magnesium hydroxide (B) and titanium oxide (C) is added to 100 parts by mass of the polyphenylene sulfide resin (A) for the purpose of improving thermal conductivity. Therefore, it is essential to contain 160 parts by mass or more, preferably 180 parts by mass or more. Moreover, it is essential that the upper limit of the compounding quantity of an inorganic filler shall be 250 mass parts or less, Preferably it is 240 mass parts or less. If it is less than 160 parts by mass, the thermal conductivity is low, and the heat dissipation effect due to the temperature rise of the LED is low, so the brightness, light emission efficiency, and life when the LED is turned on are not preferable. Moreover, when it mixes exceeding 250 mass parts, extrusion processability will worsen and pelletization will be difficult and is unpreferable.

  Further, the polyphenylene sulfide resin composition of the present invention must contain at least 60 parts by mass of magnesium hydroxide (B) and titanium oxide (C) in total for the purpose of improving whiteness and thermal conductivity. Preferably, it is 80 parts by mass or more. Moreover, it is essential that the upper limit of the total amount of magnesium hydroxide (B) and titanium oxide (C) is 160 parts by mass or less, and preferably 140 parts by mass or less. If it is less than 60 mass parts, since whiteness falls and it is not suitable for a LED heat radiating member, it is unpreferable. Moreover, when it mixes exceeding 160 mass parts, extrusion processability will worsen and pelletization will be difficult and is unpreferable.

  Furthermore, the polyphenylene sulfide resin composition of the present invention is prepared by changing the mixing ratio (mass ratio) of magnesium hydroxide (B) and titanium oxide (C) to magnesium hydroxide (for the purpose of improving both whiteness and flame retardancy. B) It is essential that the titanium oxide (C) is 10 parts by mass or more with respect to 100 parts by mass, and preferably the titanium oxide (C) is 12 parts by mass or more. Moreover, it is essential that the upper limit of the compounding amount of titanium oxide (C) with respect to 100 parts by mass of magnesium oxide (B) is 75 parts by mass or less, and preferably 70 parts by mass or less. If the blending ratio (mass ratio) of magnesium hydroxide (B) and titanium oxide (C) is less than 100: 10, the whiteness is lowered and it is not suitable for the LED heat radiating member. Moreover, since the flame retardance falls and it is not suitable for a LED heat radiating member at the compounding ratio exceeding 100: 75, it is not preferable.

  The polyphenylene sulfide resin composition of the present invention includes a plasticizer such as a polyalkylene oxide oligomer compound, an ester compound, and an organic phosphorus compound, inorganic fine particles, an organic phosphorus compound, and a metal oxide as long as the effects of the present invention are not impaired. Products, crystal nucleating agents such as polyether ether ketone, polyethylene, polypropylene, olefin copolymers having functional groups such as carboxyl groups, carboxylic acid ester groups, acid anhydride groups and epoxy groups, polyolefin elastomers, montanic acid waxes, Montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea, polyethylene wax, lithium stearate, aluminum stearate and other metal soaps, ethylenediamine, Phosphoric acid / sebacic acid polycondensates, release agents such as silicone compounds, anti-coloring agents such as hypophosphites, phosphorous antioxidants, antioxidants such as sulfur antioxidants, weathering agents and ultraviolet rays Inhibitors (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), heat stabilizers (hindered phenols, hydroquinones, phosphites, and their substitutes), foaming agents, dyes, fluorescence Whitening agent (benzoxazole type), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, Betaine amphoteric antistatic agents), flame retardants (eg red phosphorus, melamine cyanurate, aluminum hydroxide) Ordinary additives such as hydroxides such as um, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide) Can be added.

  The polyphenylene sulfide resin composition of the present invention is usually produced by a known method. For example, (A) component, (B) component, (C) component, (D) component and, if necessary, an inorganic filler and other necessary additives are premixed or without premixing It is prepared by supplying to etc. and fully melt-kneading. Specific examples include a method of kneading a mixture of raw materials at a temperature of 260 to 400 ° C. using a commonly known melt kneader such as a single or twin screw extruder, a Banbury mixer, a kneader, and a mixing roll. be able to. Further, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are melt-kneaded by the above method, a method in which some raw materials are melt-kneaded by the above method, and the remaining raw materials are melt-kneaded, or Any method may be used, such as a method in which the remaining raw materials are mixed using a side feeder during melt kneading of a part of raw materials with a single-screw or twin-screw extruder. 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 object color of the molded product obtained by molding the polyphenylene sulfide resin composition of the present invention is reflected light when the molded product is irradiated with C light under a standard illuminant C light source for colorimetry of the International Lighting Commission (CIE). Is a CIE-LAB color system having an L ^* value of 82 or more and a b ^* value of 0 or more and 8 or less. When the object color of the molded product is CIE-LAB color system and the L ^* value is 82 or more and the b ^* value is 0 or more and 8 or less, the white coating process is not necessary, which is suitable for the LED heat dissipation member. . More preferably, those having an L ^* value of 83 or more and a b ^* value of 0 or more and 4 or less are used. The L ^* value represents lightness, L ^* = 0 indicates black, and L ^* = 100 indicates white diffused color. b ^* represents yellowness, negative values indicate blue, positive values indicate yellow, and larger values indicate higher saturation.

  The polyphenylene sulfide resin composition of the present invention contains magnesium hydroxide (B) and titanium oxide (C) in an amount of 100: 10 or more, preferably 100: 12 or more, and the upper limit is 100: 75 or less, preferably 100: 70. Since it is used in the following blending ratio (mass ratio), the flame resistance level of UL94 standard when the polyphenylene sulfide resin composition of the present invention is molded to a thickness of 0.38 mm is V-0, which is suitable for LED heat dissipation members. It is.

  The polyphenylene sulfide resin composition of the present invention can be melt-molded by an ordinary molding method (injection molding, press molding, injection press molding, etc.), and the resulting molded product is suitable for an LED heat radiation member. Among these, from the viewpoint of mass productivity, it is preferable to form by injection molding or injection press molding.

  The polyphenylene sulfide resin composition of the present invention is excellent in thermal conductivity and flame retardancy, and has whiteness. Therefore, a member that requires heat dissipation against the heat generated by the LED, dissipates the generated heat. Suitable for members, components, peripheral parts, and cases that come into contact with metal. In particular, it can be used as a heat dissipating member for LEDs with high luminous efficiency in recent years. Specifically, the luminous efficiency of the LED (luminous efficiency (lm / W) = total luminous flux (lm) / power consumption (W)) can be suitably used as a heat radiating member of an LED having 20 lm / W or more. Preferably, it can be used for a member for heat dissipation of LED of 30 lm / W or more, more preferably 40 lm / W or more. Specific examples of the heat dissipating member include an LED package mounting substrate in which the LED element is sealed, a heat dissipating plate in contact with the mounting substrate, a case for dissipating heat from the heat dissipating plate, and a case for protecting the LED power supply circuit. . These LED heat radiating members can also be used as an LED heat radiating member as a composite of a molded body made of the polyphenylene sulfide resin composition of the present invention and a metal.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Reference Example 1 Preparation of polyphenylene sulfide resin (A) (PPS-1)
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (hereinafter also abbreviated as NMP) 11.45 kg (115.50 mol) and 10.5 kg of ion-exchanged water were charged and gradually heated to 245 ° C over about 3 hours while passing nitrogen at normal pressure. After distilling out 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Thereafter, the mixture was cooled to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C for 100 minutes, the bottom valve of the autoclave is opened, the contents are flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and stirred for a while at 250 ° C to remove most of the NMP. did. The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake. The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes.

  Thereafter, the autoclave was cooled and the contents were taken out. The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS-1. The obtained PPS-1 had a melt viscosity of 10 Pa · s. The melt viscosity is a value measured using a capilograph manufactured by Toyo Seiki Co., Ltd. under the conditions of a die length of 10 mm, a die hole diameter of 1 mm, 310 ° C., and a shear rate of 1216 / s.

(Reference Example 2) Preparation of polyphenylene sulfide resin (A) (PPS-2)
In a 70 liter autoclave equipped with a stirrer, 8.75 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.96 kg (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11.45 Kg (115.50 mol), sodium acetate 0.86 K (10.5 mol), and ion-exchanged water 10.50 Kg were charged and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. After distilling off 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10.24 Kg (69.63 mol) of p-dichlorobenzene and 9.01 Kg (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After reacting at 270 ° C. for 100 minutes, 1.26 Kg (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26.30 Kg of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31.90 Kg of NMP and filtered off. This was washed several times with 56.00 Kg of ion-exchanged water and filtered, and then washed with 70.00 Kg of 0.05% by mass acetic acid aqueous solution and filtered. After washing with 70.00 kg of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-2 was linear and had a melt viscosity of 50 Pa · s (die length 10 mm, die hole diameter 1 mm, 310 ° C., shear rate 1216 / s).

(raw materials)
・ Magnesium hydroxide (B)
As magnesium hydroxide (B), “KISUMA (registered trademark)” 5EU manufactured by Kyowa Chemical Industry Co., Ltd. was used. The specific gravity is 2.4, and the average particle diameter is 0.7 μm.

・ Titanium oxide (C)
As the titanium oxide (C), “Taipec (registered trademark)” CR-60-2 manufactured by Ishihara Sangyo Co., Ltd. was used. The specific gravity is 4.2, and the average particle diameter measured by the laser diffraction method is 0.2 μm. “Typaque (registered trademark)” CR-60-2 is rutile titanium oxide surface-treated with aluminum as an inorganic compound and polyhydric alcohol as an organic compound.

・ Blue pigment (D)
As the blue pigment (D), CAS Registration No. An ultramarine of 57455-37-5 was used.

Inorganic filler As the inorganic filler, glass fiber “ECS03T-747H” manufactured by Nippon Electric Glass Co., Ltd., having an average fiber diameter of 10.5 μm was used.

Examples 1-9
A polyphenylene sulfide resin composition was prepared using a twin screw extruder with a screw diameter of 44 mm (TEX-44, manufactured by Nippon Steel Works). The polyphenylene sulfide resin composition was prepared by using polyphenylene sulfide resin (A), titanium oxide (C) of Reference Example 1 (PPS-1) and / or Reference Example 2 (PPS-2) in the blending amounts shown in Table 1 and their use. In order to do so, ultramarine (D) is charged from the raw material supply port of the above twin screw extruder, magnesium hydroxide (B) and glass fiber are charged from the intermediate addition port, and melted at a resin temperature of 320 ° C. and a screw rotation speed of 150 rpm. Kneading was performed to obtain pellets. Extrusion processability was evaluated by ○ ×. ○ can be pelletized, and x cannot be pelletized. The pellets obtained were then dried with a hot air dryer at 130 ° C. for 3 hours, and then evaluated as described later. The results are shown in Table 1.

Comparative Examples 1-6
A polyphenylene sulfide resin composition was prepared using a twin screw extruder with a screw diameter of 44 mm (TEX-44, manufactured by Nippon Steel Works). The polyphenylene sulfide resin composition was prepared by adjusting the blending amounts shown in Table 2 for Reference Example 1 (PPS-1) and / or Reference Example 2 (PPS-2) polyphenylene sulfide resin (A) and titanium oxide (C). The material was introduced from the raw material supply port of the twin screw extruder, magnesium hydroxide (B) and glass fiber were introduced from the intermediate addition port, and melt kneading was performed at a resin temperature of 320 ° C. and a screw rotation speed of 150 rpm to obtain pellets. Subsequently, the obtained pellets were dried with a hot air dryer at 130 ° C. for 3 hours, and then evaluated as described later. Extrusion processability was evaluated by ○ ×. ○ can be pelletized, and x cannot be pelletized. The results are shown in Table 2. In Comparative Example 4, the strand was brittle and could not be pelletized.

(1) Measurement of object color of molded product Using an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.), the polyphenylene sulfide resin compositions of Examples 1 to 9, Comparative Examples 1 to 3, 5 and 6 were injection molded. Sample. Under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., a test piece of a square-shaped product (80 mm × 80 mm × 3 mm thickness, film gate) is prepared, and color computer SM-5-IS-2B (Suga Test Instruments Co., Ltd.) By using C light as the standard light, φ30 as the condenser lens, and φ30 as the sample stage, L ^* and b ^* were determined according to JIS-Z-8722 and JIS-Z-8729.

(2) Flame retardant test of UL94 standard The injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.) was used to injection-mold the polyphenylene sulfide resin compositions of Examples 1 to 9, Comparative Examples 1 to 3, 5 and 6. A sample was obtained. A test piece for flame retardancy evaluation was injection molded under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and the flame retardancy was evaluated according to the evaluation criteria defined in the UL94 vertical test. Flame retardancy falls and ranks in the order of V-0>V-1>V-2> HB. The thickness of the test piece was 0.38 mm.

(3) Thermal conductivity Using an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.), the polyphenylene sulfide resin compositions of Examples 1 to 9, Comparative Examples 1 to 3, 5 and 6 were injection molded to prepare samples. Obtained. A square-shaped product (80 mm × 80 mm × 3 mm thickness, film gate) was produced under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., and a 20 mm × 20 mm × 3 mmt test piece was cut out from the center of the molded product. The thermal conductivity was measured with a heat flow meter method thermal conductivity measuring device (GH-1S manufactured by Rigaku Corporation). The higher this value, the better the thermal conductivity. Examples 1 to 9 show a value of 1.0 to 1.4 W / m · K, and when used with an LED heat dissipation member, the heat dissipation effect due to the temperature rise of the LED increases, so the brightness when the LED is lit, It was found that the luminous efficiency and life were improved.

  Since the polyphenylene sulfide resin composition of the present invention has excellent thermal conductivity and flame retardancy, and further has whiteness, a white coating step is not required. Therefore, an LED heat radiating member having a high degree of freedom can be made in terms of shape, structure and mechanical strength, and the LED heat radiating member manufactured according to the present invention is useful for weight reduction and simplification of the manufacturing process.

Claims (6)

A resin composition formed by blending 160 to 250 parts by mass of an inorganic filler with respect to 100 parts by mass of the polyphenylene sulfide resin (A),
The inorganic filler contains magnesium hydroxide (B) and titanium oxide (C),
The total amount of the magnesium hydroxide (B) and the titanium oxide (C) is 60 parts by mass or more and 160 parts by mass or less with respect to 100 parts by mass of the polyphenylene sulfide resin (A).
The polyphenylene sulfide resin composition, wherein a blending ratio (mass ratio) of the magnesium hydroxide (B) and the titanium oxide (C) is 100: 10 or more and 100: 75 or less. Blue pigment (D) is further blended,
The blending amount of the blue pigment (D) is 0.05 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the polyphenylene sulfide resin (A). A polyphenylene sulfide resin composition. The object color of the molded product obtained by molding the polyphenylene sulfide resin composition is the reflected light when the molded product is irradiated with C light under the International Illuminating Commission (CIE) standard illuminant C light source for colorimetry. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the L ^* value is 82 or more and the b ^* value is 0 or more and 8 or less in the CIE-LAB color system.   4. The polyphenylene sulfide resin according to claim 1, wherein the flame retardant level of UL94 standard when the polyphenylene sulfide resin composition is molded to a thickness of 0.38 mm is V-0. 5. Composition.   A molded article obtained by injection molding the polyphenylene sulfide resin composition according to any one of claims 1 to 4.   The molded product according to claim 5, wherein the molded product is a heat radiating member.