JP5433431B2 - High thermal conductive polycarbonate resin composition and molded product - Google Patents

Description

  The present invention relates to a high thermal conductivity thermoplastic resin composition and a molded article, and more particularly to a high thermal conductivity thermoplastic resin composition and a molded article excellent in whiteness, reflectivity, thermal conductivity, and heat dissipation.

  Thermoplastic resins have excellent physical and chemical properties, such as ease of molding, appearance, economy, mechanical strength, etc., so electrical, electronic and OA equipment, precision machinery, automotive parts, building materials, miscellaneous goods It is used in a wide range of fields.

  In the fields of electrical / electronic / OA devices, most devices are equipped with heat-generating components, but recently, with the higher performance of equipment and components, the amount of power consumption has increased and the amount of heat generated from the components has increased. There is a concern that local high temperatures may cause troubles such as malfunctions. At present, heat generated by using metal materials is diffused in the chassis, chassis, heat sink, etc., but by replacing these metal parts by increasing the thermal conductivity of the thermoplastic resin material and increasing the heat dissipation effect The demand for is increasing.

In recent years, light emitting diodes (LEDs) have long life, low power consumption, and low environmental load compared to incandescent lamps and fluorescent lamps, and many lighting devices using LEDs as light sources have been proposed. With the practical application of white LEDs, development has been increasingly intensive, including general lighting applications.
For illumination, a plurality of LED elements that have low light output but can be obtained at low cost are often integrated and mounted on a relatively small element mounting substrate. However, in the LED used for illumination, only about 15% to 20% of the electric power input to the LED is converted to light, and the remaining 80% to 85% is converted to heat, which is dissipated to the surroundings. If this is not possible, the temperature of the LED component will be excessively high. Therefore, the board on which the LED element is mounted needs to have high heat dissipation characteristics.

As a method for imparting heat dissipation and thermal conductivity to a resin material, many methods for mixing various thermal conductive fillers with a resin component have been reported.
For example, Patent Document 1 discloses a thermoplastic resin having excellent thermal conductivity in which both high thermal conductivity inorganic fibers and high thermal conductivity inorganic powders are filled. Vapor-grown carbon fiber whiskers are used as highly thermally conductive inorganic fibers. However, since the fiber diameter is small and the aspect ratio is large, uniform dispersion in the resin is difficult, and the fibers are broken during dispersion. For example, sufficient thermal conductivity cannot be obtained.

Patent Document 2 describes a method for producing vapor grown carbon fiber coated with boron nitride. Further, by using vapor grown carbon fiber as a filler, an insulating high thermal conductivity material is produced. It describes what you can do. However, in order to produce carbon fibers coated with boron nitride, not only the cost of equipment such as a heat treatment furnace is required, but also the productivity is poor and the practical level has not been reached.
Furthermore, Patent Document 3 proposes a polycarbonate-based resin composition that is blended with graphitized carbon fiber and boron nitride and has excellent thermal conductivity, insulation, and molding processability, and has little warpage of the molded product.

By the way, as an LED mounting board in the above-mentioned LED illumination, a function as a reflector having a high light reflectivity is required as well as a heat dissipation effect, and therefore a white heat conductive material with high whiteness is required.
However, in the above prior art, the filler to be blended in order to obtain thermal conductivity is basically carbon black of carbon-based carbon or carbon fiber, and white ceramics suitable for applications requiring insulation. However, there is a drawback that whitening is difficult because the hardness is high and dirt such as a screw of a molding machine is picked up during kneading and molding.

JP-A-8-283456 JP 2002-235279 A JP 2007-99799 A

  An object of the present invention is to provide a high thermal conductive thermoplastic resin composition and a molded product excellent in whiteness, reflectivity, thermal conductivity, and heat dissipation, in view of the above-mentioned problems of the prior art.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors use boron nitride and boron oxide at a specific ratio, and improve the whiteness by blending this with a specific amount in a thermoplastic resin. The inventors have found that a highly heat-conductive thermoplastic resin composition having improved reflectivity and excellent heat conductivity and heat dissipation can be obtained, and the present invention has been completed.

That is, according to 1st invention of this invention, 1-70 mass parts of boron nitride (B) , boron oxide (C), and calcium oxide (D) are contained with respect to 100 mass parts of aromatic polycarbonate resin (A). a polycarbonate resin composition, the amount of boron oxide (C), the amount of (B) and the total 100 mass% of (C), 1 to 20 wt% range, calcium oxide (D) is A highly heat-conductive polycarbonate resin composition is provided that is in the range of 2 to 5% by mass with respect to 100% by mass in total of (B), (C) and (D) .

Further, according to the second aspect of the present invention, in the first aspect, further, titanium oxide, zinc oxide, and one or more compounds selected from zinc sulfide (E), an aromatic polycarbonate resin (A) A highly heat conductive polycarbonate resin composition characterized by containing 0.1 to 20 parts by mass with respect to 100 parts by mass is provided.

Moreover, according to the third invention of the present invention, in the first or second invention, the phosphorus-based flame retardant (F-1) is further added in an amount of 3 to 20 with respect to 100 parts by mass of the aromatic polycarbonate resin (A). A highly heat-conductive polycarbonate resin composition characterized by containing a mass part is provided.

According to a fourth aspect of the present invention, there is provided a highly thermally conductive polycarbonate resin composition according to the third aspect , wherein the phosphorus flame retardant (F -1 ) is a phosphate ester compound. Provided.
According to the fifth invention of the present invention, in any one of the first to fourth inventions, the metal salt flame retardant (F-2) is added to 0 part by mass of the aromatic polycarbonate resin (A). 0.01-0.5 mass part is provided, The high heat conductive polycarbonate resin composition characterized by the above-mentioned is provided.

According to the sixth invention of the present invention, in any one of the first to fifth inventions, the fluororesin (G) is further added in an amount of 0.01 to 100 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). A highly heat-conductive polycarbonate resin composition comprising 1 part by mass is provided.

According to a seventh aspect of the present invention, there is provided a molded article obtained by molding the polycarbonate resin composition according to any one of the first to sixth aspects.

  According to the thermoplastic resin composition and the molded article of the present invention, a highly thermally conductive thermoplastic resin composition and a molded article excellent in whiteness, reflectivity, thermal conductivity, and heat dissipation can be obtained.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

[1. Overview]
The high thermal conductivity thermoplastic resin composition of the present invention is a thermoplastic resin composition containing 1 to 70 parts by mass of boron nitride (B) and boron oxide (C) with respect to 100 parts by mass of the thermoplastic resin (A). And the quantity of boron oxide (C) is the range of 1-20 mass% with respect to a total of 100 mass% of (B) and (C), It is characterized by the above-mentioned.

[2. Thermoplastic resin (component A)]
The thermoplastic resin used in the present invention is not particularly limited, and examples thereof include polycarbonate resins; polyester resins such as polyethylene terephthalate (PET) resins and polybutylene terephthalate (PBT) resins; polyamide resins such as polyamide 6, polyamide 66, and polyamide MXD. Resin; Polyphenylene ether (PPE) resin; Polyoxymethylene (polyacetal) resin; Polystyrene resin, High impact polystyrene resin (HIPS), Acrylonitrile-styrene copolymer (AS resin), ABS resin, Acrylonitrile-ethylene propylene rubber-styrene Styrenic resin such as copolymer (AES resin); Methacrylic resin such as PMMA resin; Polyphenylene sulfide resin; Thermoplastic resin such as liquid crystal polymer, or two or more of these thermoplastic resins Mention may be made of a polymer alloy consisting of.
Among them, a heat selected from the group consisting of a polycarbonate resin, a polyamide resin, a modified polyphenylene ether resin, a polyester resin, and a polymer alloy resin composition of polycarbonate resin / polyester resin and polycarbonate resin / styrene resin. It is preferable to use a plastic resin, and a polycarbonate resin is particularly preferable.

[2-1. Polycarbonate resin (A-1)]
The polycarbonate resin (A-1) preferably used in the present invention includes an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin, preferably an aromatic polycarbonate resin. Specifically, a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid is used.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetramethylbisphenol A, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, Resorcinol, 4,4′-dihydroxydiphenyl and the like can be mentioned. Further, as a part of the dihydroxy compound, when the above-mentioned aromatic dihydroxy compound is combined with one or more tetraalkylphosphonium sulfonates, or a polymer or oligomer containing both terminal phenolic OH groups having a siloxane structure, A highly flame-retardant polycarbonate resin can be obtained.

  Preferred examples of the polycarbonate resin (A) used in the present invention include 2,2-bis (4-hydroxyphenyl) propane as a dihydroxy compound, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy. The polycarbonate resin which used the compound together is mentioned. In the present invention, two or more polycarbonate resins may be used in combination as the component (A).

  The molecular weight of the polycarbonate resin (A) used in the present invention is a viscosity average molecular weight converted from a solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 14,000 to 30,000, more preferably 18,000 to 29,000. When the viscosity average molecular weight is within this range, a resin composition can be obtained that gives a molded article having good moldability and high mechanical strength. The most preferable molecular weight range of the polycarbonate resin (A) is 22,000 to 28,000.

  The method for producing the polycarbonate resin is not particularly limited, and a polycarbonate resin produced by any of the phosgene method (interfacial polymerization method) and the melting method (transesterification method) can also be used. Moreover, it is also preferable to use the polycarbonate resin which performed the post-process which adjusts the amount of terminal OH groups to the polycarbonate resin manufactured by the melting method.

The polycarbonate resin in the present invention preferably contains a certain percentage or more of a polycarbonate resin having a structural viscosity index N in a predetermined range.
The structural viscosity index N is an index for evaluating the flow characteristics of a melt as described in detail in the document “Rheology for chemists” (Chemical Doujin, 1982, pp. 15-16). . Usually, the melting characteristics of polycarbonate resin can be expressed by the formula: γ = a · σ ^N. In the above formula, γ: shear rate, a: constant, σ: stress, N: structural viscosity index.

  In the above formula, when N = 1, Newtonian fluidity is shown, and the non-Newtonian fluidity increases as the value of N increases. That is, the flow characteristics of the melt are evaluated by the magnitude of the structural viscosity index N. In general, a polycarbonate resin having a large structural viscosity index N tends to have a high melt viscosity in a low shear region. For this reason, when a polycarbonate resin having a large structural viscosity index N is mixed with another polycarbonate resin, dripping at the time of combustion of the obtained polycarbonate resin composition can be suppressed, and flame retardancy can be improved. However, in order to maintain the moldability of the obtained polycarbonate resin composition in a favorable range, the structural viscosity index N of the polycarbonate resin is preferably not excessively large.

Therefore, the polycarbonate resin in the polycarbonate resin composition of the present invention has a structural viscosity index N of usually 1.2 or more, preferably 1.25 or more, more preferably 1.28 or more, and usually 1.8 or less. It is preferable to contain a polycarbonate resin of 1.7 or less, preferably an aromatic polycarbonate resin in a certain ratio or more.
The high structural viscosity index N means that the polycarbonate resin has a branched chain. By containing the polycarbonate resin having a high structural viscosity index N in this way, the polycarbonate resin composition of the present invention burns. The dripping at the time can be suppressed and the flame retardancy can be improved.

The structural viscosity index N can also be expressed by Log η _a = [(1-N) / N] × Log γ + C, which is derived from the above equation, as described in, for example, JP-A-2005-232442. Is possible. In the above formula, N: structural viscosity index, γ: shear rate, C: constant, η _a : apparent viscosity. As can be seen from this equation, the N value can also be evaluated from γ and ηa in _a low shear region in which the viscosity behavior is greatly different. For example, the N value can be determined from η _a at γ = 12.16 sec ⁻¹ and γ = 24.32 sec ⁻¹ .

  An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is obtained by a melting method (transesterification method) as described in JP-A-8-259687 and JP-A-8-245782, for example. When reacting an aromatic dihydroxy compound and a carbonic acid diester, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolytic stability can be obtained without adding a branching agent by selecting catalyst conditions or production conditions. be able to.

An aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more can also be produced by a method using a branching agent when produced by a phosgene method or a melting method (a transesterification method) according to a conventional method. .
Specific examples of the branching agent include phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris (4-hydroxy). Phenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenylheptene-3,1,3,5-tris (4-hydroxyphenyl) ethane and the like, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like.
The amount used is in the range of 0.01 to 10 mol%, particularly preferably in the range of 0.1 to 3 mol%, based on the aromatic dihydroxy compound.

  The molecular weight of the aromatic polycarbonate resin having a structural viscosity index N of 1.2 or more is a viscosity average molecular weight in the range of 16,000 to 30,000 converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent. Is preferred.

In the polycarbonate resin composition of the present invention, the polycarbonate resin is a polycarbonate resin in which the structural viscosity index N described above is in a predetermined range (hereinafter, this polycarbonate resin may be referred to as “predetermined N polycarbonate resin”). In general, it is desirable to contain 20% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more. By combining with the predetermined N polycarbonate resin in this manner, the torque during extrusion is not increased more than necessary, so that the productivity is hardly lowered. That is, excellent moldability and productivity can be exhibited.
In addition, there is no restriction | limiting in the upper limit of content of predetermined N polycarbonate resin in polycarbonate resin, Usually, it is 100 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less.
Moreover, 1 type may be used for predetermined N polycarbonate resin, and it may use 2 or more types together by arbitrary combinations and a ratio.

  Further, the polycarbonate resin may include a polycarbonate resin having a structural viscosity index N outside the above predetermined range, in addition to the above predetermined N polycarbonate resin. Although there is no restriction | limiting in the kind, A linear polycarbonate resin is preferable especially. By combining the predetermined N polycarbonate resin and the linear polycarbonate resin, there is an advantage that it is easy to balance the flame retardancy (anti-dripping property) and moldability (fluidity) of the obtained polycarbonate resin composition. From this viewpoint, it is particularly preferable that the polycarbonate resin is composed of a predetermined N polycarbonate resin and a linear polycarbonate resin. In addition, the structural viscosity index N of this linear polycarbonate resin is usually about 1-1.15.

  When the polycarbonate resin contains a linear polycarbonate resin, the proportion of the linear polycarbonate resin in the polycarbonate resin is usually 80% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, Usually, it is more than 0% by mass, preferably 10% by mass or more, more preferably 15% by mass or more. By setting the content of the linear polycarbonate resin in the polycarbonate resin within the above range, it is easy to obtain good dispersibility of the additive, and there is an advantage that a polycarbonate resin excellent in flame retardancy and moldability is easily obtained. It is done.

The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination.
Polycarbonate resins such as polyamide 6 and polyamide 6,6; thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin) Styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin), etc. One or more thermoplastic resins may be used in combination. Further, two types of thermoplastic resins that form a two-phase structure of a polymer alloy may be used as the basic composition.

  Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[3. Boron nitride (component B)]
The thermoplastic resin composition of the present invention contains boron nitride (B).
Boron nitride has several stable structures such as c-BN (zinc blende structure), w-BN (wurtzite structure), h-BN (hexagonal crystal structure), and r-BN (rhombohedral crystal structure). It has been. In the present invention, any boron nitride may be used. Among them, hexagonal boron nitride is preferably used. Boron nitride includes spherical ones and scale-like ones, and any of them can be used in the present invention. However, when a scale-like one is used, a molded product having more excellent thermal conductivity can be obtained. At the same time, the mechanical properties are favorable, which is preferable.
Further, the average particle diameter of the scaly boron nitride powder is generally 1 to 50 μm, and it is also preferable to use a powder having an average particle diameter in such a range. However, the specific gravity and average particle diameter of boron nitride used in the present invention are not limited to this range.
Further, the thermal conductivity of boron nitride is preferably 10 W / m · K or more.

[4. Boron oxide (C component)]
The thermoplastic resin composition of the present invention further contains boron oxide (C).
Examples of boron oxide include diboron trioxide, boron trioxide, diboron dioxide, tetraboron trioxide, and tetraboron pentoxide.
Boron oxide may be pure or produced from a natural product. In the case of a natural product, boron oxide containing 80% by mass or more of a boron oxide component is preferably used. Although impurities such as silicon oxide, iron oxide, aluminum oxide, and magnesium oxide may be contained, the content of each is preferably 5% by mass or less. Moreover, the average particle diameter of boron oxide is generally 1 to 200 μm, and it is also preferable to use a powder having an average particle diameter in this range.

Content of boron nitride (B) and boron oxide (C) is 1-70 mass parts with respect to 100 mass parts of thermoplastic resins (A), Preferably, it is 3-50 mass parts. If it is less than 1 part by mass, the thermal conductivity is insufficient, and if it exceeds 70 parts by mass, the moldability of the resin composition becomes poor.
Moreover, the quantity of boron oxide (C) is the range of 1-20 mass% with respect to a total of 100 mass% of (B) and (C). When the amount of boron oxide is less than 1% by mass or more than 20% by mass, the whiteness becomes insufficient. Preferably, it is 3-15 mass%, More preferably, it is 5-15 mass%.

[5. Calcium oxide (component D)]
The thermoplastic resin composition of the present invention preferably further contains calcium oxide (D) CaO.
Calcium oxide can be used in any purity as long as it does not impair the characteristics of the present invention, but a specific preferred purity is 80% by mass or more as calcium oxide (CaO). More preferably, it is 90 mass% or more, Most preferably, it is 95 mass% or more.
Industrially available calcium oxide may contain SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , MgO, etc. as other oxide components, but the total content thereof is 10 It is preferably at most mass%, more preferably at most 5 mass%, particularly preferably at most 3 mass%.

  Further, the content of calcium oxide (D) is preferably in the range of 2 to 5% by mass when the total of boron nitride (B), boron oxide (C) and calcium oxide (D) is 100% by mass. When the amount of calcium oxide (D) is less than 2% by mass or exceeds 5% by mass, the whiteness tends to be insufficient, preferably 2 to 4.5% by mass, and more preferably 2.5 to 4%. % By mass.

[6. Titanium oxide, zinc oxide, zinc sulfide (E component)]
The thermoplastic resin composition of the present invention preferably contains one or more compounds (component E) selected from titanium oxide, zinc oxide or zinc sulfide.

[6-1. Titanium oxide additive]
Titanium oxide functions to improve the whiteness, light reflection characteristics and the like of a molded product obtained from the resin composition.
The production method, crystal form, average particle diameter, and the like of titanium oxide are not particularly limited. There are sulfuric acid method and chlorine method in the production method of titanium oxide, but titanium oxide produced by sulfuric acid method tends to be inferior in whiteness of the composition to which this is added, so the object of the present invention can be effectively achieved. To achieve this, those produced by the chlorine method are preferred.

  The crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferred from the viewpoint of light resistance. The average particle diameter of titanium oxide is preferably 0.1 to 0.7 μm, more preferably 0.1 to 0.4 μm. When the average particle diameter is less than 0.1 μm, the light shielding property of the molded product is poor, and when it exceeds 0.7 μm, the surface of the molded product is roughened or the mechanical strength of the molded product is lowered. In the present invention, two or more types of titanium oxide having different average particle diameters may be mixed and used.

  Titanium oxide is preferably pretreated with an alumina surface treatment agent before being surface treated with an organosiloxane surface treatment agent described later. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. The pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

  Titanium oxide pretreated with alumina hydrate and, if necessary, silicic acid hydrate can be further improved in thermal stability by surface treatment with an organosiloxane surface treatment agent. In addition, the uniform dispersibility in the polycarbonate resin composition and the stability of the dispersion state are improved.

  As the organosiloxane surface treating agent, a reactive functional group-containing organosilicon compound having a reactive functional group that reacts with the surface of the inorganic compound particles is particularly preferable. Examples of reactive functional groups include Si-H groups, Si-OH groups, Si-NH groups, and Si-OR groups, but those having Si-H groups, Si-OH groups, and Si-OR groups. More preferred are Si-H group-containing organosilicon compounds having Si-H groups.

  The Si—H group-containing organosilicon compound is not particularly limited as long as it is a compound having a Si—H group in the molecule, and may be appropriately selected and used. Among them, poly (methyl hydrogensiloxane), polycyclo (Methylhydrogensiloxane), poly (ethylhydrogensiloxane), poly (phenylhydrogensiloxane), poly [(methylhydrogensiloxane) (dimethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (ethylmethylsiloxane) )] Copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (hexylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (octylmethy) Siloxane)] copolymer, poly [(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethoxysiloxane)] copolymer, poly [(methylhydrogensiloxane) (dimethoxysiloxane)] Copolymer, poly [(methylhydrogensiloxane) (3,3,3-trifluoropropylmethylsiloxane)] copolymer, poly [(dihydrogensiloxane) ((2-methoxyethoxy) methylsiloxane)] copolymer, poly [( Polyorganohydrogensiloxanes such as dihydrogensiloxane) (phenoxymethylsiloxane)] copolymers are preferred.

  There are (1) a wet method and (2) a dry method as a surface treatment method using an organosiloxane-based surface treatment agent of titanium oxide. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Furthermore, it is a method of heat-processing at 100-300 degreeC after that. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxane are mixed with a Henschel mixer in the same manner as described above, and an organic solution of polyorganohydrogensiloxane is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C.

[6-2. Zinc oxide, zinc sulfide]
The thermoplastic resin composition of the present invention preferably contains zinc oxide or zinc sulfide.
The zinc oxide or zinc sulfide used preferably has an average particle size of 0.02 to 1 μm, more preferably an average particle size of 0.08 to 0.8 μm, and an average particle size of 0.2 to 0. A thickness of 0.5 μm is most preferable.

  By adding titanium oxide, zinc oxide or zinc sulfide (E), the whiteness can be further improved. The addition amount is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and particularly 0.5 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). If the amount added is large, elongation and low-temperature toughness tend to decrease.

[7. Flame retardant (F component)]
It is preferable to add a flame retardant to the resin composition of the present invention.
Examples of the flame retardant include a halogen flame retardant, a phosphorus flame retardant, a metal salt flame retardant, and an inorganic filler flame retardant. Among these, a phosphorus flame retardant or a metal salt flame retardant is preferable.

[7-1. Phosphorus flame retardant]
The thermoplastic resin composition of the present invention preferably contains 5 to 20 parts by mass of the phosphorus-based flame retardant with respect to 100 parts by mass of the thermoplastic resin (A). Thus, the flame retardance of a resin composition can be improved by containing a phosphorus flame retardant.
In the present invention, the phosphorus flame retardant is preferably a phosphate ester compound. The phosphate ester compound is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. For example, the following general formula (1) or (2 The phosphorus-based flame retardant represented by the general formula (1) is particularly preferable from the viewpoint of thermal stability.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、各々独立して、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を、Ｘはアリーレン基を示し、ｐ、ｑ、ｒおよびｓは、それぞれ０または１であり、ｋは１から５の整数である。）

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, X represents an arylene group, p, q, r and s are each 0 or 1, and k is an integer of 1 to 5.)

（式中、Ｒ_５、Ｒ_６及びＲ_７は、それぞれ、炭素数１〜６のアルキル基又はアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｈ、ｉ及びｊは、それぞれ０又は１を示す。）

(Wherein R ₅ , R ₆ and R ₇ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and h, i and j) Represents 0 or 1 respectively.)

  The phosphorus compound represented by the general formula (1) is a condensed phosphate ester having k of 1 to 5. For a mixture of condensed phosphate esters having different k, k is an average value of the mixture. X represents an arylene group and is a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone, bisphenol A, and the like.

  As a specific example of the phosphorus compound represented by the general formula (1), when resorcinol is used as a dihydroxy compound, phenyl resorcinol polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, Xylyl resorcin polyphosphate, phenyl-pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin polyphosphate Etc.

  The phosphorus compound represented by the general formula (2) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the phosphorus compound represented by the general formula (2) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, and phenylphosphonic acid. Examples include diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

  Further, the phosphorus-based flame retardant in the present invention may be a phosphazene compound. Such a compound is at least one selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound.

  The content of the phosphorus-based flame retardant is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and preferably 20 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A). When the blending amount of the phosphorus-based flame retardant is less than 5 parts by mass, the expression of the flame retardant effect tends to be insufficient, and when it exceeds 20 parts by mass, a remarkable decrease in heat resistance and mechanical properties are likely to occur.

[7-2. Metal salt flame retardant]
It is also preferable to mix a metal salt flame retardant as the flame retardant in the resin composition of the present invention. As the metal salt flame retardant, an organic metal salt compound is more preferable, and an organic sulfonic acid metal salt compound is particularly preferable. By selecting an organic sulfonic acid metal salt compound, mechanical properties and thermal properties are improved.

・ Organic sulfonic acid metal salt Examples of the organic sulfonic acid metal salt include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. Among them, aromatic sulfonic acid metal salts and perfluoroalkane sulfonic acid metal salts are used. A perfluoroalkanesulfonic acid metal salt is particularly preferable.
The metal of the organic sulfonic acid metal salt is not particularly limited but preferably includes alkali metals such as sodium, lithium, potassium, rubidium and cesium, and alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium. It is done. Of these, potassium is preferred from the viewpoints of flame retardancy and hydrolysis resistance. These organic sulfonic acid metal salts may be used in combination of two or more.

The aromatic sulfonesulfonic acid metal salt is preferably an aromatic sulfonesulfonic acid alkali metal salt, an aromatic sulfonesulfonic acid alkaline earth metal salt, or the like. The acid alkaline earth metal salt may be a polymer.
Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium 4 / 4'-dibromodiphenyl-sulfone-3-sulfone Salt, potassium salt of 4,4′-dibromodiphenylsulfone-3-sulfone, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid di Examples thereof include sodium salts and dipotassium salts of diphenylsulfone-3,3′-disulfonic acid.

The perfluoroalkanesulfonic acid metal salt is preferably an alkali metal salt of perfluoroalkanesulfonic acid, an alkaline earth metal salt of perfluoroalkanesulfonic acid, or the like, more preferably a perfluoroalkane having 4 to 8 carbon atoms. Examples include sulfonic acid alkali metal salts having an alkane group and sulfonic acid alkaline earth metal salts having a C 4-8 perfluoroalkane group.
Specific examples of the perfluoroalkanesulfonic acid metal salt include sodium perfluorobutanesulfonate, potassium perfluorobutanesulfonate, sodium perfluoromethylbutanesulfonate, potassium perfluoromethylbutanesulfonate, sodium perfluorooctanesulfonate, Examples include potassium perfluorooctane sulfonate and tetraethylammonium salt of perfluorobutane sulfonic acid.
Among these, potassium perfluorobutanesulfonate is particularly preferable.

  Moreover, it is preferable to further contain an octafluorobutanesulfonic acid alkali metal salt as the organic sulfonic acid metal salt. By containing the octafluorobutanesulfonic acid alkali metal salt together with the perfluorobutanesulfonic acid alkali metal salt, more stable flame retardancy can be imparted.

Specific examples of the alkali metal of the octafluorobutanesulfonic acid alkali metal salt include sodium, lithium, potassium, rubidium, cesium, etc., preferably sodium, potassium, cesium, more preferably sodium or potassium. In particular, potassium salt is preferred.
As specific compounds, more preferred compounds are sodium octafluorobutane sulfonate and potassium octafluorobutane sulfonate. Of these, potassium octafluorobutane sulfonate is more preferred, and in particular, 1,1,2 2,3,3,4,4-octafluorobutanesulfonic acid potassium salt.
Further, the ratio of the alkali metal perfluorobutane sulfonate and the alkali metal octafluorobutane sulfonate is, by mass ratio, 100% alkali metal salt component of perfluorobutane sulfonic acid / metal salt component of octafluorobutane sulfonic acid. /0.001-5 is preferable, 100 / 0.005-4 is more preferable, and 100 / 0.01-3 is more preferable.

  The preferable content of the organic sulfonic acid metal salt is 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, particularly 0.1 to 0.1 part by mass with respect to 100 parts by mass of the thermoplastic resin (A). 0.3 parts by mass. When the content is less than 0.01 parts by mass, sufficient flame retardancy is difficult to obtain, and when it exceeds 1 part by mass, the thermal stability and hydrolysis resistance are likely to be lowered.

[8. Fluorine resin (G component)]
In this invention, it is preferable to mix | blend a fluororesin (G). The fluororesin is a fluororesin having a fibril forming ability, and is an anti-drip agent that easily disperses in a resin composition and exhibits a tendency to bond polymers to form a fibrous structure. The molecular weight of the fluororesin tree having the ability to form fibrils has a very high molecular weight of 1,000,000 to 10,000,000, and shows a tendency to bond the fluororesins to each other by an external action such as shearing force to form a fiber. As the fluororesin, tetrafluoroethylene (TFE) resin, perfluoroalkoxy (PFA) resin, and fluorinated ethylene propylene (FEP) resin are shown, and polytetrafluoroethylene is particularly preferable.

  Examples of the polytetrafluoroethylene having fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui / Dupont Fluorochemical Co., Ltd. and polyflon (trade name) manufactured by Daikin Chemical Industries, Ltd. The resin (G) is preferably used in the form of its aqueous dispersion. By mixing with the thermoplastic resin (A) in the presence of water, the aggregation of the fluororesin is suppressed, the dispersion of the fluororesin in the resin composition is improved, no lumps are generated, and the surface of the molded body has no flaws. No longer occurs.

This dispersion is an aqueous dispersion produced by adding a surfactant to a fluororesin latex usually obtained by emulsion polymerization, and concentrating and stabilizing the dispersion. The content of the fluororesin in the aqueous dispersion is preferably 20 to 80% by mass, particularly preferably 30 to 70% by mass. The fluororesin having fibril forming ability preferably has a primary particle size in the range of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm.
In the resin composition, the fluororesin is preferably in the form of a fibril having a thickness of 0.5 microns or less, and the fibril is preferably present in a network structure and / or in a branched form.
As an aqueous dispersion of polytetrafluoroethylene, Teflon (registered trademark) 30J, Teflon (registered trademark) 31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Fullon D-1 manufactured by Daikin Chemical Industries, Ltd., vinyl A polytetrafluoroethylene polymer having a multilayer structure obtained by polymerizing a monomer, for example, Metabrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd. can be mentioned.

  The blending amount of the fluororesin (G) is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the thermoplastic resin (A). When the amount of the resin composition exceeds 1 part by mass, the mechanical strength and processing fluidity of the resin composition are likely to deteriorate, and the appearance of the molded product tends to deteriorate, more preferably 0.03 to 0.8. Part by mass, particularly preferably 0.05 to 0.6 part by mass.

[9. UV absorber]
It is preferable to mix | blend a ultraviolet absorber with the composition of this invention.
Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, and hindered amine compounds. Examples include ultraviolet absorbers.
Of these, organic ultraviolet absorbers are preferred, and benzotriazole compounds are more preferred. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals , "Tinubin 326", "Tinubin 327", "Tinubin 328 Etc. The.

  The content of the ultraviolet absorber is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin (A), and the upper limit is preferably 1. It is 0.5 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

[10. Other additives]
The polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include heat stabilizers, antioxidants, release agents, dyes and pigments, fluorescent brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, A dispersing agent, an antibacterial agent, etc. are mentioned.

-Heat stabilizer As a heat stabilizer, a phosphorus compound is mentioned, for example. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

  The content of the heat stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin (A). Moreover, it is 1 mass part or less normally, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

-Antioxidant As an antioxidant, a hindered phenolic antioxidant is mentioned, for example.
Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable.

  The content of the antioxidant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 100 parts by mass of the thermoplastic resin (A). 0.5 parts by mass or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

-Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils. It is done.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid.
Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, a monovalent or polyvalent saturated alcohol having 30 or less carbon atoms is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

  The content of the release agent is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 100 parts by mass of the thermoplastic resin (A). 1 part by mass or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[11. Production method of thermoplastic resin composition]
There is no limitation on the method for producing the thermoplastic resin composition of the present invention, and a wide variety of known methods for producing thermoplastic resin compositions can be adopted. The thermoplastic resin (A) and each of the above components, and blended as necessary For example, after mixing in advance using other mixers such as a tumbler and a Henschel mixer, the components are mixed with a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, or the like. The method of melt-kneading is mentioned. The temperature for melt kneading is not particularly limited, but is usually in the range of 240 to 320 ° C.

  In addition, “high thermal conductivity” of the high thermal conductivity thermoplastic resin composition of the present invention is used in the sense that the thermal conductivity is increased by blending boron nitride (B) and boron oxide (C). Although it is not directly intended to include only those having a thermal conductivity higher than a certain value, it is usually about 0.5 W / m · K or higher in terms of thermal conductivity in the flow direction during molding. More preferably, it is 0.7 W / m · K or more, particularly 0.9 W / m · K or more.

[12. Molding]
The thermoplastic resin composition of the present invention can be produced by molding pelletized pellets by various molding methods. Further, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion-molded product, a blow-molded product, an injection-molded product or the like without going through pellets.
Examples of molding methods include injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, and rapid heating molds. Molding method used, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding Law. A molding method using a hot runner method can also be used. There is no limitation on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Since the resin composition of the present invention is a highly heat conductive resin composition excellent in whiteness, reflectivity, heat conductivity, and heat dissipation, a molded product obtained by molding the resin composition is an LED mounting substrate in LED lighting. Preferred examples include a reflective member for a light source such as an LED display, a mini projector, various illuminators, and a vehicle, and a backlight reflective member for a liquid crystal display.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

(Examples 1-3, Comparative Examples 1-5)
As the thermoplastic resin (A), an aromatic polycarbonate resin (trade name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight: 21,000) is used, and boron nitride (B) Boron oxide (C) and calcium oxide (D) were blended in the proportions (expressed in mass%) shown in Table 1 below, mixed uniformly with a tumbler mixer, and then twin screw extruder (Nippon Steel) Using a TEX30HSST), the cylinder temperature is 280 ° C., the screw rotation speed is 200 rpm, the discharge rate is 10 kg / hr, the feed from the barrel upstream of the extruder to the extruder, and melt-kneading to obtain a resin composition pellet. .
The following (1) to (3) were evaluated using the pellets of the resin composition, and the results are shown in Tables 2 and 3.
In addition, the average particle diameter of boron nitride in Tables 2 and 3 refers to D50 measured by a laser diffraction type particle size distribution measuring device, using “Laser diffraction type particle size distribution measuring device SALD-2100” manufactured by Shimadzu Corporation. Measurements were made.

(1) Flammability:
The pellets obtained by the above method were dried at 120 ° C. for 5 hours, and then injection molded at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. using a J50-EP type injection molding machine manufactured by Nippon Steel. Thus, a test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.58 mm was obtained. The flame retardancy is evaluated for 48 hours in a temperature-controlled room with a temperature of 23 ° C and a humidity of 50%, and the UL94 test (combustion of plastic materials for equipment parts) established by US Underwriters Laboratories (UL). Test). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

(2) YI value:
Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SH100, mold clamping force 100T) at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C., a mold: 100 mm long, 100 mm wide, 3 mm thick The product is injection-molded under the condition of injection pressure: 147 MPa, and the obtained molded product is measured with a color tester (SC-1-CH manufactured by Suga Test Instruments Co., Ltd.), and the tristimulus value XYZ, which is the absolute value of the color, is measured. The YI value, which is an index of yellowness, was calculated from the following relational expression.
YI = (100 / Y) × (1.28 × X−1.06 × Z)
The larger the YI value, the more yellow it is colored.

(3) Thermal conductivity From an injection molded product obtained by the same molding method as in (2), using a rapid thermal conductivity measuring device (Keotherm QTM-D3, manufactured by Kyoto Electronics Industry Co., Ltd.), the flow direction during molding The thermal conductivity of and the thermal conductivity in the thickness direction were measured. Three injection molded products are stacked, and the heat conductivity is measured by pressing the direction of the heating wire of the rapid thermal conductivity measuring device probe so as to match the flow direction of the uppermost molded product stacked. Let the value be λ _MD . Similarly, the thermal conductivity is measured by pressing so that the direction of the heating wire of the probe matches the direction perpendicular to the flow direction, and this value is set as λ _TD .
Next, the test piece was cut to a width of 2 cm in a direction perpendicular to the flow direction, and a laminate was prepared by laminating 35 sheets, and the thermal conductivity was measured by pressing the heating wire of the probe against the laminate surface. Is λ _T.
The thermal conductivity in the flow direction and the thickness direction was determined by the following formula.
Flow direction thermal conductivity = λ _TD × λ _T / λ _MD
Thickness direction thermal conductivity = λ _MD × λ _TD / λ _T

(Examples 4 to 10, Comparative Examples 6 to 8)
In addition to the components used above, the following components were used.
(E) Titanium oxide based additive and zinc oxide Titanium oxide surface-treated with the following siloxane was used as the titanium oxide based additive.
(E-1) Made by Ishihara Sangyo Co., Ltd., trade name “Taipek PC-3”
(E-2) Product name “Kronos 2233” manufactured by Kronos
(E-3) Product name “PC-5” manufactured by Resino Color Co., Ltd.

(F) Flame retardant (F-1) Phosphorus flame retardant (phosphate ester compound):
Resorcinol bis (dixylenyl phosphate)
Product name “PX200” manufactured by Daihachi Chemical Industry Co., Ltd.
(F-2) Metal salt flame retardant-1: potassium perfluorobutane sulfonate (F-3) Metal salt flame retardant-2: potassium octafluorobutane sulfonate (G) Fluororesin Daikin Industries, Ltd. Polyflon (trade name) F-201L "
(H) Release agent Pentaerythritol distearate, manufactured by NOF Corporation, trade name “Unistar H476D”

Each component was mix | blended in the ratio (displayed in the mass%) shown in following Table 3, and the pellet of the resin composition was obtained like the above. Evaluation similar to the above was performed using pellets of this resin composition.
The results are shown in Table 3.

As can be seen from the results of the examples, it can be seen that the high thermal conductivity thermoplastic resin composition of the present invention has a small YI value, excellent whiteness, and high thermal conductivity. Stable flammability can be obtained without deteriorating the flammability of the composition containing the flame retardant.
On the other hand, it can be seen that a composition not containing a predetermined amount of boron oxide has a high YI value and the molded piece is yellowish. In addition, it was confirmed that the composition containing titanium oxide and zinc oxide has improved light concealment and improved reflectance even in a thin molded product. In particular, the composition of the present invention having a small YI value has good light reflectivity.
Therefore, from the above Examples and Comparative Examples, the effect of being excellent in whiteness, reflectivity, thermal conductivity, and heat dissipation (combustibility for a composition containing a flame retardant) is obtained for the first time by the configuration of the present invention. It was confirmed to be a thing.

  According to the high thermal conductivity thermoplastic resin composition of the present invention, since a high thermal conductivity thermoplastic resin material excellent in whiteness, reflectivity, thermal conductivity and heat dissipation can be obtained, an LED mounting substrate in LED lighting, It can be used in a wide range of fields such as LED displays, mini projectors, various illuminators, reflecting members for light sources of vehicles, backlight reflecting members for liquid crystal displays, and the like, and has very high industrial applicability.

Claims (7)

A polycarbonate resin composition containing 1 to 70 parts by mass of boron nitride (B) , boron oxide (C) and calcium oxide (D) with respect to 100 parts by mass of an aromatic polycarbonate resin (A), and boron oxide (C ) Is in the range of 1 to 20% by mass with respect to the total of 100% by mass of (B) and (C), and the amount of calcium oxide (D) is the sum of (B), (C) and (D) A highly heat-conductive polycarbonate resin composition characterized by being in a range of 2 to 5% by mass with respect to 100% by mass . Furthermore, 0.1 to 20 parts by mass of one or more compounds (E) selected from titanium oxide, zinc oxide, and zinc sulfide are included with respect to 100 parts by mass of the aromatic polycarbonate resin (A). The highly heat-conductive polycarbonate resin composition according to claim 1. Furthermore, 3-20 mass parts of phosphorus flame retardants (F-1) are included with respect to 100 mass parts of aromatic polycarbonate resin (A), The high heat conductive polycarbonate resin of Claim 1 or 2 characterized by the above-mentioned. Composition. The highly heat-conductive polycarbonate resin composition according to claim 3 , wherein the phosphorus-based flame retardant (F-1) is a phosphate ester-based compound. Furthermore, 0.01-0.5 mass part is contained with respect to 100 mass parts of aromatic polycarbonate resin (A), metal salt flame retardant (F-2), The any one of Claims 1-4 characterized by the above-mentioned. 2. A highly heat-conductive polycarbonate resin composition according to item 1. Furthermore, 0.01-1 mass part of fluororesin (G) is included with respect to 100 mass parts of aromatic polycarbonate resin (A), The high heat conduction of any one of Claims 1-5 characterized by the above-mentioned. Polycarbonate resin composition. A molded product obtained by molding the highly heat-conductive polycarbonate resin composition according to any one of claims 1 to 6 .