JP2017193659A - Thermoplastic resin composition and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which shows an appearance inherent to gold by bonding of a resin, and enables substitution for gold coating, and to provide a molded article of the same.SOLUTION: There are provided a thermoplastic resin composition that contains 0.1-5 pts.mass of a plate-like filler (B) on which a coating layer containing titanium oxide, iron oxide, silicon oxide and tin oxide is formed and 0.1-5 pts.mass of a plate-like filler (C) on which a coating filler containing titanium oxide, silicon oxide and tin oxide is formed with respect to 100 pts.mass of a thermoplastic resin (A), where the plate-like filler (B) and the plate-like filler (C) satisfy the following relationship: average particle diameter Dof plate-like filler (B)<average particle diameter Dof plate-like filler (C); and a molded article obtained by molding the thermoplastic resin composition.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition and a molded article thereof, and more specifically, a thermoplastic resin composition having an improved design so as to exhibit a gold-specific appearance by blending a bright pigment and a polarizing pigment into the thermoplastic resin. And a molded article formed by molding this thermoplastic resin composition.

In recent years, especially for home appliances, electronic devices, housings of image display devices and automobile interior parts, etc., while various design features are required, VOC problems, work environments, and cost-related painting “Paint-less decoration” as an alternative to decoration is drawing attention. For this reason, various proposals have been made for imparting design properties by resin original deposition in which a material for imparting design properties such as a colorant is blended with the raw material resin. For example, it is proposed that a polycarbonate resin is blended with a bright pigment such as a metal-coated flaky glass or a polarizing pigment to give a bright feeling (shiny feeling), a color change due to light interference, and further coloring (for example, Patent Documents 1, 2).
Patent Document 3 exemplifies metal oxide-coated plate-like fillers such as titanium oxide-coated glass flakes and titanium oxide-coated mica as bright pigments. Further, it is described that a phosphorus-based heat stabilizer such as a phosphite ester or a phosphate ester is blended as a heat stabilizer.

JP 2010-6862 A JP-A-4-359937 JP2015-96566A

  It is difficult to produce an appearance like gold only by blending a conventional bright pigment or polarizing pigment. In addition, when viewed from a certain direction, even if it has a glittering metallic appearance like gold, when viewed from a different angle, there is no metallic feeling, and there may be a matte plastic appearance. is there. For this reason, in the prior art, it is difficult to replace gold paint with resin resin.

  An object of the present invention is to provide a thermoplastic resin composition that exhibits an appearance unique to gold by resin deposition and can be used as a substitute for gold paint, and a molded product thereof.

  As a result of intensive studies to solve the above problems, the present inventor, by combining a specific bright pigment and a polarizing pigment in combination, has a metallic appearance that glitters like gold regardless of the angle to be observed. It was found that can be produced.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] 0.1 to 5 mass of plate filler (B) in which a coating layer containing titanium oxide, iron oxide, silicon oxide, and tin oxide is formed on a base material with respect to 100 mass parts of thermoplastic resin (A). And a plate-like filler (C) having a coating layer containing titanium oxide, silicon oxide, and tin oxide formed on the substrate, 0.1 to 5 mass, A thermoplastic resin composition, wherein the filler (B) and the plate-like filler (C) satisfy the following relationship.
The average particle diameter _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C)

[2] The thermoplastic resin composition according to [1], wherein the particle size of the plate filler (B) is 10 to 100 μm, and the base material is mica.

[3] The thermoplastic resin composition according to [1] or [2], wherein the particle size of the plate-like filler (C) is 20 to 200 μm, and the base material is glass.

[4] The thermoplastic resin (A) comprises 50 to 100 parts by mass of the polycarbonate resin (A-1) and 0 to 50 parts by mass of a thermoplastic resin other than the polycarbonate resin, and further includes alkyl acid phosphate, alkenyl acid phosphate, and these. 1 to 2 parts or more of a phosphate stabilizer (D) selected from metal salts of 0.01 to 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A-1) [1 ] To the thermoplastic resin composition according to any one of [3].

[5] The thermoplastic resin composition according to [4], wherein the alkyl acid phosphate or alkenyl acid phosphate is represented by the following formula (I).
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or an alkenyl group, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. .)

[6] The thermoplastic resin composition according to [5], wherein R in the formula (I) is an alkyl group or an alkenyl group having 9 to 30 carbon atoms.

[7] The thermoplastic resin composition according to [6], wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms.

[8] The phosphate stabilizer (D) is represented by the following formula (II), and is a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in the formula (II). The thermoplastic resin composition according to [4], which is characterized.
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II)

[9] The phosphate stabilizer (D) is a mixture of a distearyl acid phosphate zinc salt represented by the following formula (IIIa) and a monostearyl acid phosphate zinc salt represented by the following formula (IIIb) [4] The thermoplastic resin composition according to [4].

[10] Further, the hydrogensiloxane (E) is contained in an amount of 0.003 to 0.15 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A-1). The thermoplastic resin composition according to any one of the above.

[11] A molded product formed by molding the thermoplastic resin composition according to any one of [1] to [10].

  According to the present invention, by combining a specific luster pigment and a polarizing pigment in combination, it is possible to realize a highly-designed product that exhibits a sparkling metallic appearance like a gold product with a resin original. It is possible to improve production efficiency, reduce manufacturing costs, and reduce the thickness and weight of products by replacing gold paint.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. It can be implemented by changing.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention (hereinafter sometimes referred to as the “resin composition of the present invention”) is composed of titanium oxide, iron oxide, and oxide as a base material with respect to 100 parts by mass of the thermoplastic resin (A). 0.1 to 5 parts by mass of a plate-like filler (B) in which a coating layer containing silicon and tin oxide is formed, and a plate shape in which a coating layer containing titanium oxide, silicon oxide and tin oxide is formed on the base material A thermoplastic resin composition containing 0.1 to 5 mass of filler (C), wherein the plate-like filler (B) and plate-like filler (C) satisfy the following relationship.
The average particle diameter _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C)

In the present invention, the particle size of the plate-like fillers (B) and (C) is the distance between the plates when the plate-like fillers (B) and (C) are sandwiched between two parallel plates. The average particle diameter D ₅₀ in the present invention refers to the median diameter D ₅₀ measured by a laser diffraction particle size distribution measuring device, for example, “Laser diffraction particle size distribution manufactured by Shimadzu Corporation”. Although it is measured using “measurement apparatus SALD-2100”, catalog values can be adopted for commercially available products.
In addition, the content of each metal oxide contained in the base material or coating layer of the plate-like fillers (B) and (C) is determined from the metal content obtained by fluorescent X-ray analysis or energy dispersive X-ray spectroscopy. However, catalog values can be adopted for commercial products.
Furthermore, the pH of the plate-like fillers (B) and (C) is a value measured with a pH test paper or a pH measuring device for the filtrate or supernatant after boiling the filler in distilled water. The catalog value applies to.

[Action mechanism]
The plate-like filler (B) in which the coating layer containing titanium oxide, iron oxide, silicon oxide, and tin oxide is formed on the base material has a glittering appearance like gold because the coating layer contains iron oxide. It is possible to produce an effect, and it is possible to produce an excellent gloss feeling because the coating layer contains silicon oxide. On the other hand, the plate-like filler (C) in which the coating layer containing titanium oxide, silicon oxide, and tin oxide is formed on the base material provides a high glitter feeling because the coating layer contains titanium oxide.

By using such a plate-like filler (B) and a plate-like filler (C) in combination, it is possible to obtain a brilliant metallic appearance such as gold. In particular, the average particle size of the plate-like filler (B) Since the diameter D ₅₀ is smaller than the average particle diameter D ₅₀ of the plate-like filler (C), the effect of the plate-like filler (B) and the effect of the plate-like filler (C) act synergistically. From this angle, and under any light source, it is possible to realize a brilliant metallic appearance like gold.

  The plate-like filler (B) and the plate-like filler (C) used in the present invention are generally alkaline, and when blended with a thermoplastic resin (A) containing a polycarbonate resin, the polycarbonate resin is deteriorated during molding processing. In order to prevent deterioration of the polycarbonate resin due to these plate-like fillers (B) and (C), when the resin composition of the present invention contains a polycarbonate resin as the thermoplastic resin (A), It is preferable to blend a specific phosphate stabilizer (D) described later, and further hydrogen siloxane (E).

[Thermoplastic resin (A)]
The thermoplastic resin (A) used in the present invention is not particularly limited, and polycarbonate resin, polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, styrene-maleic anhydride copolymer, ABS resin. AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, (meth) acrylate copolymer, polymethacryl methacrylate resin, polyphenyl ether resin, amorphous polyalkylene terephthalate resin, polyester resin, polyacetal resin, Amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, styrene thermoplastic elastomer, olefin thermoplastic elastomer, poly Bromide-based thermoplastic elastomers, polyester thermoplastic elastomers, thermoplastic elastomers such as polyurethane-based thermoplastic elastomers Kyora. These may be used alone or in combination of two or more.

  In one aspect of the present invention, the thermoplastic resin (A) is excellent in transparency, excellent in the appearance imparting characteristics peculiar to gold by the combination of the plate filler (B) and the plate filler (C), Since it is excellent in impact resistance, heat resistance, and dimensional stability, it is preferable that it contains polycarbonate resin (A-1). In this case, the content of the polycarbonate resin (A-1) in 100 parts by mass of the thermoplastic resin (A) is 50 to 100 parts by mass in order to sufficiently obtain the above effect by using the polycarbonate resin (A-1). It is preferable that When the thermoplastic resin (A) includes a thermoplastic resin other than the polycarbonate resin (A-1), examples of other thermoplastic resins include ABS resins (A-2) and polyester resins such as polybutylene terephthalate (A-3). ). Further, the thermoplastic resin (A) used in the present invention may be a polyacetal resin (A-4).

<Polycarbonate resin (A-1)>
As polycarbonate resin (A-1) used by this invention, aromatic polycarbonate resin is preferable from surfaces, such as transparency, impact resistance, and heat resistance.
The aromatic polycarbonate resin is an optionally branched thermoplastic polymer or copolymer obtained by reacting an aromatic dihydroxy compound or a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Moreover, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with the following branching agents, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Tin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Dose, the aromatic dihydroxy compound is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As the aromatic polycarbonate resin, among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other aromatic dihydroxy Polycarbonate copolymers derived from the compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure.

  The aromatic polycarbonate resin mentioned above may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-. And propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is arbitrary depending on the application, and may be appropriately selected and determined. The viscosity average molecular weight (Mv) is preferably 20,000 to 50,000. When the viscosity average molecular weight is less than 20,000, the mechanical strength such as impact resistance of the obtained molded product is lowered. The viscosity average molecular weight of the aromatic polycarbonate resin is more preferably 20,000 to 40,000, and further preferably 21,000 to 30,000. Two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed. Good.

The viscosity average molecular weight (Mv) is obtained by using methylene chloride as a solvent and obtaining the intrinsic viscosity (η) (unit dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer, , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity (η) is a value calculated from the following equation by measuring the specific viscosity (η _sp ) at each solution concentration (C) (g / dl).

The viscosity characteristic of the aromatic polycarbonate resin can be expressed by MVR (melt volume rate) in addition to the above-mentioned viscosity average molecular weight (Mv). The MVR of the aromatic polycarbonate resin used in the present invention is arbitrary depending on the use and may be appropriately selected and determined, but is preferably ^{3 to 30} cm 3/10 minutes. MVR is larger than 30 cm ^3/10 min, mechanical strength such as impact resistance of the molded article obtained is reduced, and less than ^{3 cm} 3/10 min, fluidity is deteriorated, problems in moldability. More preferred MVR aromatic polycarbonate resin is 5~25cm ^3/10 min, more preferably from 8~20cm ^3/10 min, particularly preferably 10 to 15 cm ^3/10 min. Two or more types of aromatic polycarbonate resins having different MVRs may be mixed and used, and in this case, an aromatic polycarbonate resin having an MVR outside the above preferred range may be mixed. The MVR of the aromatic polycarbonate resin is a value measured under conditions of a measurement temperature of 300 ° C. and a measurement load of 1.2 kgf (11.8 N) in accordance with ISO 1133.

<ABS resin (A-2)>
ABS resin (A-2) is effective in improving the fluidity and impact resistance of polycarbonate resin (A-1).

  Examples of the ABS resin (A-2) include an acrylonitrile-butadiene-styrene copolymer (ABS resin), a resin in which styrene and / or acrylonitrile in the acrylonitrile-butadiene-styrene copolymer is substituted with another monomer, acrylonitrile-butadiene- Examples thereof include a resin obtained by replacing a rubber component mainly composed of butadiene of a styrene copolymer with another rubber component.

  The production method of the ABS resin (A-2) is arbitrary, and one produced by a known method such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method or a bulk polymerization method can be used.

  Other monomers in the resin in which styrene and / or acrylonitrile in the ABS resin (A-2) are substituted with other monomers include other styrene monomers, vinyl cyanide monomers, and (meth) acrylate monomers. It is done. Examples of the styrene monomer include α-methylstyrene, p-methylstyrene, o-ethylstyrene, vinyltoluene, and op-dichlorostyrene. Examples of the vinyl cyanide monomer include methacrylonitrile and ethacrylonitrile, and examples of the (meth) acrylic acid ester monomer include acrylic acid and methacrylic acid esters such as methyl, ethyl, propyl, n-butyl, and n-hexyl. Is mentioned. When styrene and / or acrylonitrile is substituted with another monomer, a part of styrene and / or acrylonitrile can be substituted with another monomer, or the entire amount can be substituted with another monomer.

  Further, it may be a copolymer of other vinyl monomers copolymerizable therewith. In this case, examples of other copolymerizable vinyl monomers include maleimide, N-methylmaleimide, N-cyclohexylmaleimide, N- Maleimide monomers such as phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, unsaturated acids such as acrylic acid and methacrylic acid, glycidyl acrylate, Examples include glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, and the like.

  Examples of the diene rubber component mainly composed of butadiene of the ABS resin (A-2) include polybutadiene, butadiene / styrene copolymer, polyisoprene, butadiene / (meth) acrylic acid lower alkyl ester copolymer, And a lower alkyl ester copolymer of butadiene / styrene / (meth) acrylic acid. Examples of the other rubber component in the resin in which the diene rubber component is replaced with another rubber component include ethylene-propylene rubber and acrylic rubber.

  The content of butadiene units in the ABS resin (A-2) is preferably 5 to 39% by mass, particularly preferably 10 to 30% by mass.

  Commercially available products can be widely used as the ABS resin (A-2).

<Polyester resin (A-3)>
The polyester resin (A-3) is effective in improving chemical resistance and thermal stability.

  As the polyester resin (A-3), any conventionally known polyester resin can be used, and among them, an aromatic polyester resin is preferable. Here, the aromatic polyester resin refers to a polyester resin having an aromatic ring in a polymer chain unit, and includes, for example, an aromatic dicarboxylic acid component and a diol (and / or its ester or halide) component as main components. These are polymers or copolymers obtained by polycondensation of these.

  Examples of the aromatic dicarboxylic acid component include phthalic acid, terephthalic acid, dimethyl terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Biphenyl-2,2′-dicarboxylic acid, biphenyl-3,3′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, Diphenylsulfone-4,4′-dicarboxylic acid, diphenylisopropylidene-4,4′-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4 ′ -Dicarboxylic acid, pyridine-2,5-dicarboxylic acid, succinic acid, adipic acid, seba Phosphate, suberic acid, azelaic acid, and dimer acid.

  Only 1 type may be used for these aromatic dicarboxylic acid components, and 2 or more types may be used together in arbitrary ratios. Of these aromatic dicarboxylic acids, terephthalic acid is preferred. As long as the effects of the present invention are not impaired, an alicyclic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid, sebacic acid, dimer acid or the like is used in combination with these aromatic dicarboxylic acids. May be.

  Examples of the diol component include aliphatic glycols, polyoxyalkylene glycols, alicyclic diols, and aromatic diols. Examples of the aliphatic glycols include ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol and the like having 2 to 2 carbon atoms. Among these, aliphatic glycols having 2 to 12 carbon atoms, particularly 2 to 10 carbon atoms are preferable.

  Examples of the polyoxyalkylene glycols include glycols having 2 to 4 carbon atoms in the alkylene group and having a plurality of oxyalkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, Examples include tritetramethylene glycol.

  Examples of alicyclic diols include 1,4-cyclohexanediol, 1,4-cyclohexanedimethylol, hydrogenated bisphenol A, and the like. Examples of aromatic diols include 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, xylylene glycol, and tetramethylcyclobutanediol.

  Examples of other diol components include esters of the diols described above, and halogenated diols such as halides such as adducts of tetrabromobisphenol A and alkylene oxide (such as ethylene oxide and propylene oxide) of tetrabromobisphenol A. These diol components may use only 1 type and may use 2 or more types together in arbitrary ratios. If the amount is small, long chain diols having a molecular weight of 400 to 6000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol may be used.

  As the aromatic polyester resin used in the present invention, polyalkylene terephthalate is preferable. Here, the polyalkylene terephthalate refers to a resin containing an alkylene terephthalate structural unit, and may be a copolymer of an alkylene terephthalate structural unit and another structural unit.

  Examples of the polyalkylene terephthalate used in the present invention include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and poly (cyclohexane-1,4). -Dimethylene-terephthalate), polytrimethylene terephthalate and the like.

  Further, as the polyalkylene terephthalate used in the present invention, in addition to the above, an alkylene terephthalate copolymer such as PETG, PCTG, PCTA, Tritan, etc., having an alkylene terephthalate structural unit as a main structural unit, or a polyalkylene terephthalate as a main component. Examples include polyalkylene terephthalate mixtures. Furthermore, what contains or copolymerized elastomer components, such as polyoxytetramethylene glycol (PTMG), can also be used.

  Examples of the alkylene terephthalate copolyester include a copolyester composed of two or more diol components and terephthalic acid, and a copolyester composed of a diol component, terephthalic acid, and a dicarboxylic acid other than terephthalic acid. When two or more diol components are used, they may be appropriately selected and determined from the diol components described above, but the monomer unit copolymerized with alkylene terephthalate, which is the main structural unit, is 25% by mass or less. It is preferable because the heat resistance becomes good.

  For example, ethylene glycol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polyethylene terephthalate), 1,4-butanediol / isophthalic acid / terephthalic acid copolymer (isophthalic acid copolymerized polybutylene terephthalate), In addition to the alkylene terephthalate copolyester having an alkylene terephthalate structural unit as a main structural unit, 1,4-butanediol / isophthalic acid / decanedicarboxylic acid copolymer and the like can be mentioned. Of these, an alkylene terephthalate copolyester is preferred.

  As the polyester resin (A-3) used in the present invention, when an alkylene terephthalate copolyester is used, the above-mentioned isophthalic acid copolymerized polybutylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate, and the like are preferable. From the viewpoint of heat resistance, those having an isophthalic acid component of 25% by mass or less are preferable.

(polyethylene terephthalate)
As the polyester resin (A-3), it is particularly preferable to use polyethylene terephthalate. Here, the polyethylene terephthalate is a ratio of oxyethyleneoxyterephthaloyl units (hereinafter sometimes referred to as “ET units”) composed of terephthalic acid and ethylene glycol to all the structural repeating units (hereinafter referred to as “ET ratio”). The polyethylene terephthalate resin is preferably 90 equivalent% or more, and the polyethylene terephthalate in the present invention may contain constituent repeating units other than ET units in a range of less than 10 equivalent%. The polyethylene terephthalate in the present invention is produced using terephthalic acid or its lower alkyl ester and ethylene glycol as main raw materials, but other acid components and / or other glycol components may be used together as raw materials.

  Acid components other than terephthalic acid include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3- Examples thereof include phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid or derivatives thereof.

  Examples of diol components other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, aliphatic glycols such as pentamethylene glycol, hexamethylene glycol, and neopentyl glycol, cyclohexane Examples include alicyclic glycols such as dimethanol, and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

  A raw material containing terephthalic acid or an ester-forming derivative thereof and ethylene glycol as described above is subjected to esterification or transesterification in the presence of an esterification catalyst or transesterification catalyst, and bis (β-hydroxyethyl) terephthalate and Then, an oligomer thereof is formed, and then a melt polycondensation is performed under high temperature and reduced pressure in the presence of a polycondensation catalyst and a stabilizer to obtain a polymer.

  The esterification catalyst is not particularly required because terephthalic acid serves as an autocatalyst for the esterification reaction. The esterification reaction can be carried out in the presence of an esterification catalyst and a polycondensation catalyst described later, and can be carried out in the presence of a small amount of an inorganic acid or the like. As the transesterification catalyst, alkali metal salts such as sodium and lithium, alkaline earth metal salts such as magnesium and calcium, and metal compounds such as zinc and manganese are preferably used. Compounds are particularly preferred.

  As the polycondensation catalyst, compounds soluble in a reaction system such as a germanium compound, an antimony compound, a titanium compound, a cobalt compound, and a tin compound are used alone or in combination. As the polycondensation catalyst, germanium dioxide is particularly preferable from the viewpoints of color tone and transparency. These polycondensation catalysts may be used in combination with a stabilizer in order to suppress the decomposition reaction during polymerization. Examples of the stabilizer include phosphate esters such as trimethyl phosphate, triethyl phosphate and triphenyl phosphate, and triphenyl phosphate. Phosphites such as phyto, trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl phosphate acidic phosphate, phosphorous compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid Or 2 or more types are preferable.

  The use ratio of the above catalyst is usually in the range of 1 to 2000 ppm, preferably 3 to 500 ppm as the weight of the metal in the catalyst in the total polymerization raw material, and the use ratio of the stabilizer is the stabilizer in the total polymerization raw material. The weight of the phosphorus atom is usually 10 to 1000 ppm, preferably 20 to 200 ppm. The catalyst and the stabilizer can be supplied at any stage of the esterification reaction or transesterification reaction in addition to the preparation of the raw slurry. Further, it can be supplied at the beginning of the polycondensation reaction step.

The reaction temperature during the esterification reaction or transesterification reaction is usually 240 to 280 ° C., and the reaction pressure is usually 0.2 to 3 kg / cm ² G (20 to 300 kPa) as a relative pressure to the atmosphere. The reaction temperature during polycondensation is usually 250 to 300 ° C., and the reaction pressure is usually 500 to 0.1 mmHg (67 to 0.013 kPa) as an absolute pressure. Such esterification or transesterification reaction and polycondensation reaction may be performed in one step or in multiple steps. The polyethylene terephthalate thus obtained has an intrinsic viscosity of usually 0.45 to 0.70 dl / g, and is chipped by a conventional method. The average particle diameter of this chip is usually in the range of 2.0 to 5.5 mm, preferably 2.2 to 4.0 mm.

  Next, the polymer obtained by melt polycondensation as described above is usually subjected to solid phase polymerization. A polymer chip subjected to solid phase polymerization may be subjected to solid phase polymerization after preliminarily crystallizing by heating to a temperature lower than the temperature at which solid phase polymerization is performed in advance. Such precrystallization includes (a) a method in which a dry polymer chip is heated at a temperature of usually 120 to 200 ° C., preferably 130 to 180 ° C. for 1 minute to 4 hours, and (b) a dry polymer chip. A method of heating the water in an atmosphere of water vapor or water vapor-containing inert gas at a temperature of usually 120 to 200 ° C. for 1 minute or longer, (c) a polymer chip that absorbs moisture in a water, water vapor or water vapor-containing inert gas atmosphere and adjusts the humidity Can be performed by a method of heating at a temperature of usually 120 to 200 ° C. for 1 minute or more. The humidity control of the polymer chip is carried out so that the moisture content is usually in the range of 100 to 10,000 ppm, preferably 1000 to 5000 ppm. By subjecting the conditioned polymer chip to crystallization or solid phase polymerization, it is possible to further reduce the amount of acetaldehyde contained in PET and impurities contained in a trace amount.

The solid phase polymerization step consists of at least one stage, and usually has a polymerization temperature of 190 to 230 ° C., preferably 195 to 225 ° C., usually 1 kg / cm ² G to 10 mmHg (absolute pressure 200 to 1.3 kPa), preferably 0. The reaction is carried out under a flow of inert gas such as nitrogen, argon, carbon dioxide or the like under conditions of a polymerization pressure of 5 kg / cm ² G to 100 mmHg (150 to 13 kPa as an absolute pressure). The solid phase polymerization time may be shorter as the temperature is higher, but is usually 1 to 50 hours, preferably 5 to 30 hours, and more preferably 10 to 25 hours. The intrinsic viscosity of the polymer obtained by solid phase polymerization is usually in the range of 0.70 to 0.90 dl / g.

  The intrinsic viscosity of the polyethylene terephthalate used in the present invention may be appropriately selected and determined, but is usually 0.5 to 2 dl / g, particularly 0.6 to 1.5 dl / g, particularly 0.7 to 1.0 dl. / G is preferable. An intrinsic viscosity of 0.5 dl / g or more, particularly 0.7 dl / g or more is preferred because mechanical properties, residence heat stability, chemical resistance, and moist heat resistance tend to be improved. On the other hand, the intrinsic viscosity is preferably 2 dl / g or less, and particularly preferably 1.0 dl / g or less because the workability tends to be improved.

  In the present invention, the intrinsic viscosity of polyethylene terephthalate is a value measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1).

  The density | concentration of the terminal carboxyl group of the polyethylene terephthalate used for this invention is 1-60microeq / g normally, and it is preferable that it is 3-50microeq / g especially 5-40microeq / g. When the terminal carboxyl group concentration is 60 μeq / g or less, heat resistance, residence heat stability and hue tend to be improved. Conversely, when the terminal carboxyl group concentration is 1 μeq / g or more, processability is improved. This is preferable.

  The terminal carboxyl group concentration of polyethylene terephthalate can be determined by dissolving 0.5 g of polyethylene terephthalate in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

By the way, the resin composition obtained by compounding the polyester resin with the polycarbonate resin has poor thermal stability, and causes a transesterification reaction between the polycarbonate resin and the polyester resin by being held at a high temperature in the cylinder in the molding process. The generation of decomposition gas due to the reaction causes the appearance of the molded product called foam and silver to deteriorate; the lowering of the molecular weight of the polycarbonate resin impairs the original impact resistance, heat distortion resistance, etc. of the polycarbonate resin; Due to the retention at the bottom, a change in viscosity of the polycarbonate resin composition occurs, so that molding stability at the time of injection molding is impaired, and short shots and burrs of the molded product are generated.
The problem of this residence heat deterioration is caused by the polycondensation catalyst contained in the polyethylene terephthalate used in the production process of polyethylene terephthalate and provided as a product.

In terms of relatively few problems due to this polycondensation catalyst, the polyethylene terephthalate used in the present invention is a polyethylene terephthalate produced using a germanium compound as the polycondensation catalyst, and the germanium compound content in the polyethylene terephthalate is The germanium atom is preferably 1 to 50 ppm, particularly preferably about 1 to 30 ppm. That is, the germanium compound is preferable in that it has little adverse effect on the polycarbonate resin and hardly deteriorates the polycarbonate resin. In addition, polyethylene terephthalate using a germanium compound as a polycondensation catalyst is preferable in that the hue of the resulting composition is good in the melt-kneading step.
For the same reason, the polyethylene terephthalate used in the present invention is a polyethylene terephthalate produced by using an antimony compound as a polycondensation catalyst, and the content of the antimony compound in the polyethylene terephthalate is 100 to 300 ppm as an antimony atom, particularly 150 to What is about 250 ppm is preferable.

In addition, it is preferable that the polyethylene terephthalate used in the present invention has been subjected to a deactivation treatment of the polycondensation catalyst in terms of more reliably suppressing the residence heat deterioration of the polycarbonate resin due to the polycondensation catalyst.
In addition, polyethylene terephthalate that has been subjected to the deactivation treatment of the polycondensation catalyst is also preferable in terms of excellent heat resistance during processing and good hue in the melt-kneading process.

  There is no restriction | limiting in particular as a deactivation processing method of the polycondensation catalyst of a polyethylene terephthalate resin, A conventionally well-known deactivation process can be given according to the polycondensation catalyst used. Examples of the deactivation treatment method include the following methods.

Deactivation treatment method of polycondensation catalyst 1: Hot water (steam) treatment of germanium catalyst A method of deactivating germanium catalyst in polyethylene terephthalate by treating polyethylene terephthalate with hot water (steam).
Specifically, the container is filled with polyethylene terephthalate, and steam at 70 to 150 ° C., for example, about 100 ° C., is steamed at a rate of 1 to 100 mass% per hour for 5 to 6000 minutes with respect to the polyethylene terephthalate. After done, dry.
Polyethylene terephthalate is dipped in 0.3 to 10 times the mass of polyethylene terephthalate in the container, and then the container containing polyethylene terephthalate and distilled water is heated from the outside to control the internal temperature to 70 to 110 ° C. Then, after holding for 3 to 3000 minutes and performing a hot water treatment, dehydration and drying.
The said drying is normally performed for 3 to 8 hours at 120-180 degreeC in inert gas, such as nitrogen.

Deactivation treatment method 2 of polycondensation catalyst: Addition of phosphorus compound to titanium catalyst A phosphorus compound is added to polyethylene terephthalate to deactivate the titanium catalyst in the polyethylene terephthalate. In this case, the amount of phosphorus atoms added is preferably in the range of 7 to 145 ppm based on the mass of polyethylene terephthalate. If the addition amount of the phosphorus compound is 7 ppm or more, the catalyst can be sufficiently deactivated to obtain the desired effect. If the addition amount of the phosphorus atom is 145 ppm or less, the phosphorus compound itself is coarsely aggregated. Particles are prevented from causing problems such as poor appearance and reduced impact resistance.

  In addition, as a phosphorus compound to add, conventionally well-known phosphate ester compounds, phosphite ester compounds, phosphonate compounds, etc. are mentioned. Among these, phosphonate compounds represented by the following general formula (2) are preferable.

R ¹ OC (O) XP (O) (OR ² ) ₂ (2)
Wherein R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, X is —CH ₂ — or —CH (Y) — (Y represents a phenyl group), and R ¹ and R ² are Each may be the same or different.)

  Among the phosphonate compounds represented by the above formula (2), alkyl phosphonate compounds are preferably exemplified, and among these, triethylphosphonoacetic acid is particularly preferable. These may be used alone or in combination of two or more.

  The deactivation treatment method for the polycondensation catalyst of polyethylene terephthalate is an example of the deactivation treatment that can be employed in the present invention, and the deactivation treatment according to the present invention is not limited to the above method.

  Hereinafter, polyethylene terephthalate subjected to the deactivation treatment of the polycondensation catalyst is referred to as “deactivated PET”, and untreated polyethylene terephthalate is referred to as “untreated PET”.

The deactivated PET used in the present invention is subjected to the deactivation treatment of the polycondensation catalyst in polyethylene terephthalate as described above, so that the solid phase polymerization rate Ks calculated by the following formula (3) is 0.006 (dl / G · hr) or less, in particular, 0.005 (dl / g · hr) or less, particularly about 0.001 to 0.004 (dl / g · hr).
Solid-phase polymerization rate Ks = ([η] s− [η] m) / T (3)
Here, [η] s is the intrinsic viscosity (dl / g) of the polyethylene terephthalate after the polyethylene terephthalate is held at 210 ° C. for 3 hours under a nitrogen stream, and [η] m is the polyethylene terephthalate converted to nitrogen. It is the intrinsic viscosity (dl / g) of the polyethylene terephthalate after being held at 210 ° C. for 2 hours under an air stream. T is 1 (hour). That is, in the present invention, the intrinsic viscosity after holding at 210 ° C. for 3 hours under a nitrogen stream is [η] s, and the intrinsic viscosity after holding for 2 hours under the same conditions is [η] m. The solid phase polymerization rate Ks calculated by the above-described equation (3) was used as the solid phase polymerization rate Ks. T is 1 hour.

  If the solid phase polymerization rate Ks of the deactivated PET is 0.006 (dl / g · hr) or less, the deactivation treatment of the polycondensation catalyst is sufficient, and the effect of suppressing the residence heat deterioration can be sufficiently obtained. . However, it is difficult to make the solid phase polymerization rate Ks excessively small, and it is usually 0.001 (dl / g · hr) or more.

(Polybutylene terephthalate)
As the polyester resin (A-3), polybutylene terephthalate may be used. Here, polybutylene terephthalate refers to a resin having a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded. In the present invention, it is preferable to use polybutylene terephthalate in which 50 mol% or more of dicarboxylic acid units are terephthalic acid units and 50 mol% or more of diol components are 1,4-butanediol units. The proportion of terephthalic acid units in all dicarboxylic acid units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. The proportion of 1,4-butanediol units in all diol units is preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 95 mol% or more, and optimally 98 mol% or more. If the terephthalic acid unit or the 1,4-butanediol unit is in the above range, the crystallization speed is in an appropriate range, and thus the moldability is good.

  As described above, the polybutylene terephthalate may contain dicarboxylic acid units other than terephthalic acid. The dicarboxylic acid other than terephthalic acid is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4, Aromatic dicarboxylic acids such as 4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 2,6-naphthalenedicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; . These dicarboxylic acid units can be introduced into the polymer skeleton by using a dicarboxylic acid or a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.

  As described above, polybutylene terephthalate may contain a diol unit other than 1,4-butanediol. Diols other than 1,4-butanediol are not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, and dibutylene. Aliphatic diols such as glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1- Cycloaliphatic diols such as cyclohexane dimethylol and 1,4-cyclohexane dimethylol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) Nyl) sulfone and other aromatic diols;

  Polybutylene terephthalate is further a hydroxycarboxylic acid such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid; Monofunctional compounds such as acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane , Trimethylolpropane, glycerol, pentaerythritol and the like trifunctional or higher polyfunctional compounds; and the like.

Although there is no restriction | limiting in particular about the intrinsic viscosity of the polybutylene terephthalate used for this invention, a lower limit may be determined from a viewpoint of mechanical properties, and an upper limit may be determined from a viewpoint of moldability. The intrinsic viscosity of polybutylene terephthalate is preferably 0.70 to 3.0 dl / g, more preferably 0.80 to 1.5 dl / g, and particularly preferably 0.80 to 1.2 dl / g. . When the intrinsic viscosity is within the above range, good mechanical properties can be exhibited and good moldability can be obtained. The intrinsic viscosity is a value measured at a temperature of 30 ° C. using a mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio).
In the present invention, two or more polybutylene terephthalates having different intrinsic viscosities may be used in combination.

  The terminal carboxyl group concentration of the polybutylene terephthalate used in the present invention is preferably 120 μeq / g or less, more preferably 2 to 80 μeq / g, and particularly preferably 5 to 60 μeq / g. When the terminal carboxyl group concentration is 120 μeq / g or less, hydrolysis resistance and fluidity are improved, and it is preferably 2 μeq / g or more from the viewpoint of productivity. The terminal carboxyl group concentration can be determined by dissolving polybutylene terephthalate in benzyl alcohol and titrating with an aqueous solution of 0.1N (mol / L) sodium hydroxide. The above value is equivalent to the carboxyl group equivalent per gram. It is.

  A polyester resin (A-3) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

<Polyacetal resin (A-4)>
Polyacetal resin (A-4) should just contain a bivalent oxymethylene group with a structural unit. Accordingly, the polyacetal resin (A-4) may be an acetal homopolymer containing only an oxymethylene group as a constituent unit, or a copolymer containing an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms as constituent units. It may be.

  Among these, a copolymer containing an oxymethylene group and an oxyalkylene group having 2 or more carbon atoms as constituent units is preferable.

  Examples of the oxyalkylene group having 2 or more carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, an oxyethylene group is preferable because the characteristics of the polyacetal resin (A-4) are more sufficiently suppressed.

  In the said polyacetal resin (A-4), as above-mentioned, it is preferable that the ratio of a C2 or more oxyalkylene group is a ratio of 0.5-10 mol per 100 mol of oxymethylene groups.

  In this case, compared with the case where the said ratio is less than the lower limit of the said range, polyacetal resin (A-4) has more sufficient thermal stability. On the other hand, when the said ratio is in the said range, compared with the case where the upper limit of the said range is exceeded, it becomes difficult to fall the crystallinity of a polyacetal resin (A-4), and the intensity | strength of a polyacetal resin composition falls large. Is more sufficiently suppressed.

  The ratio of the oxyalkylene group is more preferably 0.5 to 10 mol per 100 mol of the oxymethylene group. When the said ratio exists in the range of 0.5-10 mol, compared with the case where it remove | deviates from the said range, the thermal stability of polyacetal resin (A-4) improves more. The ratio is more preferably 0.8 to 9.0 mol, and further preferably 1.0 to 8.0 mol.

  In order to produce the polyacetal resin (A-4), trioxane is usually used as a main raw material. In order to introduce an oxyalkylene group having 2 or more carbon atoms into the polyacetal resin (A-4), for example, cyclic formal or cyclic ether can be used. Specific examples of cyclic formal include 1,3-dioxolane, 1,3-dioxane, 1,3-dioxepane, 1,3-dioxocane, 1,3,5-trioxepane, 1,3,6-trioxocane and the like. Can be mentioned. Specific examples of the cyclic ether include ethylene oxide, propylene oxide, butylene oxide and the like. In order to introduce an oxyethylene group into the polyacetal resin (A-4), for example, 1,3-dioxolane may be used. To introduce an oxypropylene group, 1,3-dioxane may be used, and oxybutylene. In order to introduce the group, 1,3-dioxepane may be introduced.

  The polyacetal resin (A-4) is, for example, a catalyst deactivation treatment, removal of unreacted monomers, washing, drying, and stabilization of unstable terminal portions of the crude polyacetal resin obtained by polymerizing the above raw materials. After carrying out the treatment, it can be obtained by further carrying out a stabilization treatment by blending various stabilizers. Typical stabilizers include hindered phenol compounds, nitrogen-containing compounds, alkali or alkaline earth metal hydroxides, inorganic salts, and carboxylates.

  The melt index of the polyacetal resin (A-4) is not particularly limited, but is preferably 0.5 to 100 g / 10 minutes, and more preferably 1.0 to 80 g / 10 minutes. Here, the melt index refers to a value measured in accordance with the ASTM-D1238 standard under the conditions of 190 ° C. and 2.16 kg.

[Plate-like filler (B)]
The plate-like filler (B) used in the present invention functions as a bright pigment, and is a substrate in which a coating layer containing titanium oxide, iron oxide, silicon oxide, and tin oxide is formed.

  Examples of the material of the flaky particles used as the base material of the plate filler (B) include mica (mica), silica, alumina, glass and the like (hereinafter, flaky mica, flaky silica, flaky alumina, The substrate may be flaky metal particles, but the substrate of the plate filler (B) is preferably made of mica.

  In the plate-like filler (B) used in the present invention, a coating layer containing titanium oxide, iron oxide, silicon oxide, and tin oxide is formed on the flaky particles, preferably flaky mica, as the base material. 30 to 40% by mass of the base material, 20 to 30% by mass of titanium oxide, 15 to 25% by mass of iron oxide, 15 to 25% by mass of silicon oxide, and 0.1 to 4.0 of tin oxide. It is preferable that it contains a mass%. When the content of the substrate, titanium oxide, iron oxide, silicon oxide and tin oxide is within the above range, the design properties as a bright pigment can be sufficiently obtained.

  As the plate-like filler (B), a metal oxide containing titanium oxide, iron oxide, silicon oxide and tin oxide is chemically or physically vapor-deposited on flake mica having an average thickness of about 0.1 to 10 μm. What formed the coating layer of the thickness of about 0.01-1 micrometer is preferable.

In the present invention, the particle diameter and average particle diameter _{D 50} of the plate-like filler (B) is the above-mentioned formula: average particle size _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C) However, the plate-like filler (B) has a particle size of 10 to 100 μm, particularly 10 to 80 μm, and the average particle size D ₅₀ is preferably 10 to 60 μm. The average particle diameter D ₅₀ of the plate-like filler (B) is less than 10 [mu] m, it may not be possible to obtain a bright imparting effect by blending platy filler (B) sufficiently. When the average particle diameter D ₅₀ of the plate-like filler (B) is more than 100 [mu] m, impact resistance of the molded article obtained tends to decrease. The average particle diameter D50 of the plate-like filler (B) is particularly preferably about 15 to 55 μm, particularly about 20 to ₅₀ μm.

  As the plate-like filler (B), a commercially available product can be used. For example, a trade name “Iriodin 305 Solar Gold” manufactured by MERCK, which is a mica pigment coated with titanium oxide, iron oxide, silicon oxide, and tin oxide. (Particle size of 10-60 μm) can be used.

As the plate-like filler (B), one kind may be used alone, or two or more kinds of the constituent materials or the particle diameters of the base material and the coating layer may be used in combination.
When two or more plate-like filler (B), it is preferable average particle diameter D ₅₀ of all of the plate-like filler was used (B) it is within the above range.

  In addition, in order to make adhesiveness with a thermoplastic resin (A) favorable, a plate-like filler (B) may be surface-treated with a surface treatment agent such as a silane coupling agent.

  In the resin composition of the present invention, the content of the plate filler (B) is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, with respect to 100 parts by mass of the thermoplastic resin (A). More preferably, it is 0.3-2 mass parts. If the amount of the plate-like filler (B) is less than the above lower limit, the above-mentioned effect due to the addition of the plate-like filler (B) cannot be sufficiently obtained, and if it is too much, the impact resistance of the molded product obtained is too high. It becomes inferior.

[Plate-like filler (C)]
The plate-like filler (C) used in the present invention functions as a polarizing pigment, and is a substrate in which a coating layer containing titanium oxide, silicon oxide, and tin oxide is formed.

  Examples of the material of the flaky particles used as the base material of the plate-like filler (C) include mica (silica), silica, alumina, and glass (hereinafter, flaky mica, flaky silica, flaky alumina, The substrate may be flaky metal particles, but the substrate of the plate filler (C) is preferably made of glass.

  The plate-like filler (C) used in the present invention is such that a coating layer containing titanium oxide, silicon oxide, and tin oxide is formed on such a flaky particle serving as a base material, preferably flaky glass. The substrate preferably contains 55 to 70% by mass, titanium oxide 10 to 25% by mass, silicon oxide 15 to 25% by mass, and tin oxide 0.1 to 4.0% by mass. When the content of the substrate, titanium oxide, silicon oxide, and tin oxide is within the above range, the design properties as a polarizing pigment can be sufficiently obtained.

  As the plate-like filler (C), in particular, a metal oxide containing titanium oxide, silicon oxide and tin oxide is subjected to chemical vapor deposition or physical vapor deposition on flaky glass having an average thickness of about 0.1 to 10 μm. What formed the coating layer of thickness about -1 micrometer is preferable.

In the present invention, the particle diameter and average particle diameter _{D 50} of the plate-like filler (C) is the aforementioned formula: average particle size _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C) However, the plate-like filler (C) preferably has a particle size of ₂₀ to 200 μm, particularly 30 to 180 μm, and an average particle size D ₅₀ of 40 to 160 μm. The average particle diameter D ₅₀ of the plate-like filler (C) is less than 20 [mu] m, it may not be possible to obtain a polarizing effect of imparting by blending a platy filler (C) sufficiently. When the average particle diameter D ₅₀ of the plate-like filler (C) is more than 200 [mu] m, impact resistance of the molded article obtained tends to decrease significantly. The average particle diameter _{D 50} of the plate-like filler (C) is particularly 25～180Myuemu, it is preferred that especially about 30～160Myuemu.

  As the plate-like filler (C), a commercially available product can be used. For example, a product “Miraval 5400 Luxwin Twink” manufactured by MERCK, which is an aluminoborosilicate glass pigment coated with titanium oxide, silicon oxide, and tin oxide ( A particle size of 20 to 200 μm) can be used.

As the plate filler (C), one kind may be used alone, or two or more kinds of materials constituting the base material and the coating layer or those having different particle diameters may be used in combination.
When two or more plate-like filler (C), it is preferable that all the average particle diameter D ₅₀ of the plate-like filler (C) was used in the range described above.

  In addition, in order to make adhesiveness with a thermoplastic resin (A) favorable, plate-shaped filler (C) may be surface-treated with surface treatment agents, such as a silane coupling agent.

  In the resin composition of the present invention, the content of the plate filler (C) is 0.1 to 5 parts by mass, preferably 0.2 to 3 parts by mass, with respect to 100 parts by mass of the thermoplastic resin (A). More preferably, it is 0.3-2 mass parts. If the amount of the plate-like filler (C) is less than the above lower limit, the above-mentioned effect due to the addition of the plate-like filler (C) cannot be obtained sufficiently, and if it is too much, the impact resistance of the molded product obtained is too high. It becomes inferior.

[Combination of plate filler (B) and plate filler (C)]
As described above, in the present invention, by using a plate-like filler (B) and a plate-like filler (C) that satisfy the following relationship, a molded product exhibiting a gold-specific appearance can be obtained.
The average particle diameter _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C)

The average particle diameter D ₅₀ of the plate-like filler (B) may be smaller than the average particle diameter D ₅₀ of the plate-like filler (C), to obtain the effects of the present invention more effectively, the plate-like filler (C the average particle diameter _{D 50} of) is, 10 [mu] m or more larger than the average particle diameter _{D 50} of the plate-like filler (B), it is preferable particularly 20μm or larger. Although no particular limitation on the upper limit of the difference in the average particle diameter D ₅₀ of the two, from the viewpoint of satisfying the suitable average particle size D ₅₀ of the aforementioned each of the plate-like filler, usually not more than 110 [mu] m.

  In addition, in the resin composition of the present invention, the resin composition of the present invention can be used to obtain a good balance between glitter and polarization by using the plate filler (B) and the plate filler (C) in combination. The content of the plate-like filler (B) and the content of the plate-like filler (C) are almost equal, and the content of the plate-like filler (B) is 0.5 of the content of the plate-like filler (C). It is preferably in the range of ~ 1.5 mass times, preferably in the range of 0.7 to 1.3 mass times, and the total content of the plate filler (B) and the plate filler (C) The amount is preferably 10 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A).

[Phosphate stabilizer (D)]
When the resin composition of the present invention contains the polycarbonate resin (A-1) as the thermoplastic resin (A), in order to suppress the deterioration of the polycarbonate resin (A-1) due to the plate fillers (B) and (C). It is preferable that 1 type, or 2 or more types of phosphate stabilizers (D) chosen from alkyl acid phosphate, alkenyl acid phosphate, and these metal salts are included.

The alkyl acid phosphate or alkenyl acid phosphate of the phosphate stabilizer (D) used in the present invention is preferably one represented by the following formula (I). That is, the alkyl acid phosphate or alkenyl acid phosphate is represented by the following formula (I), and the alkyl acid phosphate metal salt or the alkenyl acid phosphate metal salt is zinc of the alkyl acid phosphate or alkenyl acid phosphate represented by the following formula (I). A metal salt such as a salt or an aluminum salt is preferred.
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or an alkenyl group, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. .)

  The alkyl group represented by R in the above formula (I) may be a linear alkyl group and may have a branch, but preferably has 9 or more and 30 or less carbon atoms. Specifically, nonyl , Isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl (stearyl), eicosyl, tetracosyl group and the like. Also, the alkenyl group represented by R may be a straight chain alkenyl group or may be branched, but preferably has 9 to 30 carbon atoms, and specifically includes an oleyl group and the like. It is done. n is 1 or 2, and may be a mixture thereof.

The carbon number of the alkyl group or alkenyl group represented by R in the above formula (I) is more preferably any one of 13, 18, and 24. As the alkyl acid phosphate, in particular, in the following formula (II) Preferred is a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in formula (II).
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II)

  The metal salt of alkyl acid phosphate is preferably a mixture of a distearyl acid phosphate zinc salt represented by the following formula (IIIa) and a monostearyl acid phosphate zinc salt represented by the following formula (IIIb).

  These phosphate stabilizers (D) may be used alone or in combination of two or more.

  When the resin composition of the present invention contains a phosphate stabilizer (D), the content thereof is preferably 0.01 to 100 parts by mass of the polycarbonate resin (A-1) in the thermoplastic resin (A). 1 part by mass, more preferably 0.02 to 0.5 part by mass, still more preferably 0.03 to 0.1 part by mass. When the content of the phosphate stabilizer (D) is less than the above lower limit, the effect of suppressing the decomposition of the polycarbonate resin (A-1) due to the blending of the phosphate stabilizer (D) cannot be sufficiently obtained. When there is more content of a phosphate stabilizer (D) than the said upper limit, there exists a possibility that impact resistance may fall and the external appearance of a molded article may be impaired.

[Hydrogensiloxane (E)]
When the resin composition of the present invention contains the polycarbonate resin (A-1) as the thermoplastic resin (A), in order to further reliably prevent the polycarbonate resin (A-1) from being decomposed, hydrogensiloxane ( E) is preferably included.

  The molecular weight of the hydrogen siloxane (E) used in the present invention is not particularly limited, and may belong to any group of oligomers and polymers. More specifically, polyorganohydrogensiloxanes represented by the formulas (A) to (C) described in JP-B 63-26140 are preferable. As the hydrogen siloxane (E), for example, a polysiloxane having the following formula (d-1) as a repeating unit and a compound represented by the following formula (d-2) or (d-3) are preferably used.

(R ^a ) _α (H) _β SiO (d-1)
(In the above formula, R ^a is ^a linear or branched alkyl group having 1 to 10 carbon atoms, and the sum of α and β is 2.)

(In the above formula, A and B are each a group selected from the following group, and r is an integer of 1 to 500.)

(In said formula, A and B are synonymous with each in said Formula (d-2), and t is an integer of 1-50.)

  As the hydrogen siloxane (E), a commercially available silicone oil, for example, SH1107 (product of Toray Dow Corning Co., Ltd.) can be used.

  These hydrogen siloxanes (E) may be used individually by 1 type, and may use 2 or more types together.

  When the resin composition of the present invention contains hydrogen siloxane (E), the content thereof is preferably 0.003 to 100 parts by mass of the polycarbonate resin (A-1) in the thermoplastic resin (A). It is 0.15 mass part, More preferably, it is 0.005-0.12 mass part, More preferably, it is 0.01-0.1 mass part. If the content of the hydrogen siloxane (E) is less than the above lower limit, the effect of suppressing the decomposition of the polycarbonate resin (A-1) 1 due to the blending of the hydrogen siloxane (E) cannot be sufficiently obtained. When the content of gensiloxane (E) is larger than the above upper limit, gas is generated during melt-kneading, which tends to cause mold deposit. The hydrogen siloxane (E) may be blended into the resin composition after being previously treated with a filler.

[Other ingredients]
The resin composition of the present invention may contain one or more selected from various additives within a range not impairing the effects of the present invention. Examples of such additives include colorants, mold release agents, flame retardants, antioxidants, and ultraviolet absorbers.

<Colorant>
The resin composition of the present invention may contain various dyes and pigments as a colorant as desired. By containing the dye / pigment, the concealability and weather resistance of the resin composition of the present invention can be improved, and the design of a molded product obtained by molding the resin composition of the present invention can be improved.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.

  Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

  Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

As for said coloring agent, 1 type may contain and 2 or more types may contain it by arbitrary combinations and a ratio.
In addition, the colorant may be used as a masterbatch with the thermoplastic resin (A) for the purpose of improving the handleability during extrusion and improving the dispersibility in the resin composition.

  When the resin composition of the present invention contains a colorant, the content may be appropriately selected according to the required design properties, but is usually 0.001 with respect to 100 parts by mass of the thermoplastic resin (A). Part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less, even more preferably. Is 0.5 parts by mass or less. If the content of the colorant is less than the lower limit of the above range, the coloring effect may not be sufficiently obtained. If the content of the colorant exceeds the upper limit of the above range, a mold deposit or the like occurs. , May cause mold contamination.

<Release agent>
The resin composition of the present invention may contain a release agent in order to improve the release property and improve the surface smoothness of the molded product.
A preferable mold release agent is a compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, and an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000. Among these, compounds selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters are preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellic acid, and tetrariacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

  These release agents may be used alone or in combination of two or more.

  When the resin composition of this invention contains a mold release agent, it is preferable that the content is 0.01-1 mass part with respect to 100 mass parts of thermoplastic resins (A). It is preferable for the content of the release agent to be in the above range since there is no decrease in hydrolysis resistance and a release effect can be obtained.

<Flame Retardant>
The resin composition of the present invention may contain a flame retardant in order to obtain flame retardancy. The flame retardant is not particularly limited as long as it improves the flame retardancy of the thermoplastic resin (A), but organic sulfonic acid metal salts, silicone compounds, organic phosphate esters, and phosphazenes are suitable.

  The organic sulfonic acid metal salt for the flame retardant is preferably an aliphatic sulfonic acid metal salt or an aromatic sulfonic acid metal salt. These may be used alone or in combination of two or more. You may do it. The metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, an alkaline earth metal, etc., and the alkali metal and the alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium. , Calcium, strontium and barium.

  As the aliphatic sulfonate, a fluoroalkane-sulfonic acid metal salt is preferable, and a perfluoroalkane-sulfonic acid metal salt is more preferable. Preferred examples of the fluoroalkane-sulfonic acid metal salt include alkali metal salts and alkaline earth metal salts, and more preferred are alkali metal salts and alkaline earth metals of fluoroalkanesulfonic acid having 4 to 8 carbon atoms. Examples include salt. Specific examples of the fluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, potassium perfluorobutane-sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluorooctane. -Sodium sulfonate, perfluorooctane-potassium sulfonate, etc. are mentioned.

  Moreover, as an aromatic sulfonic acid metal salt, Preferably, an alkali metal salt, an alkaline-earth metal salt, etc. are mentioned. Specific examples of the aromatic sulfonesulfonic acid alkali metal salt and aromatic sulfonic acid metal salt include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, and benzenesulfonic acid sodium salt. Sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, 4,4′-dibromophenyl-sulfone -3- potassium salt of sulfonic acid, calcium salt of 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid, disodium salt of diphenylsulfone-3,3'-disulfonic acid, diphenylsulfone-3,3 ' -Dipotassium salt of disulfonic acid and the like.

  When the resin composition of this invention contains these organic sulfonic acid metal salts, it is preferable that the content is 0.01-3 mass parts with respect to 100 mass parts of thermoplastic resins (A), 0 0.02 to 2 parts by mass is more preferable, and 0.03 to 1 part by mass is even more preferable. It is preferable for the content of the organic sulfonic acid metal salt as the flame retardant to be in the above range because the resin composition has flame retardancy and good thermal stability. If the content of the organic sulfonic acid metal salt is more than the above range, the transparency of the resin composition may be impaired, and if it is less, sufficient flame retardancy cannot be obtained.

As the silicone compound for the flame retardant, polyorganosiloxane having a linear or branched structure described in JP-A No. 2006-169451 is preferable. The organic group of the polyorganosiloxane is a hydrocarbon such as an alkyl group having 1 to 20 carbon atoms and a substituted alkyl group, or a vinyl and alkenyl group, a cycloalkyl group, and an aromatic hydrocarbon group such as phenyl or benzyl. It is chosen from among them.
The polydiorganosiloxane may not contain a functional group or may contain a functional group. In the case of a polydiorganosiloxane containing a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.

  When the resin composition of this invention contains these silicone compounds for flame retardants, it is preferable that the content is 0.5-10 mass parts with respect to 100 mass parts of thermoplastic resins (A). It is preferable for the content of the silicone compound as a flame retardant to be in the above range because flame retardancy is improved without impairing transparency, appearance, elastic modulus, and the like.

  As the organic phosphate ester flame retardant, a condensed phosphate ester flame retardant is preferable from the viewpoint of thermal stability, and a phosphate ester compound represented by the following general formula (1) is particularly preferable.

(Wherein R ¹ , R ² , R ³ and R ⁴ 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 p, q , R and s are each 0 or 1, k is an integer of 1 to 5, and X ¹ represents an arylene group.)

  The phosphate ester compound represented by the above general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of phosphate esters having different k, k is a mixture of those compounds. Average value. In the case of a mixture of compounds having different k numbers, the average k number is preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.2, particularly preferably 1 to 1.15. It is a range.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Moreover, p, q, r, and s in General formula (1) represent 0 or 1, respectively, and it is preferable that it is 1 especially.

R ¹ , R ² , R ³ and R ⁴ 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. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

  Specific examples of the condensed phosphate ester flame retardant represented by the general formula (1) include phenyl resorcin / 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 acid value of the condensed phosphate ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, and further preferably 0.1 mgKOH / g or less. Yes, particularly preferably 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is preferably 1.5% by mass or less, more preferably 1.1% by mass or less, and further preferably 0.9% by mass or less. When the acid value exceeds 0.2 mgKOH / g, or when the half ester content exceeds 1.5% by mass, the thermal stability and hydrolysis resistance of the thermoplastic resin composition of the present invention are likely to be reduced.

  When the thermoplastic resin composition of the present invention contains such a condensed phosphate ester flame retardant, the content thereof is preferably 5 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). More preferably, it is 8-18 mass parts, More preferably, it is 10-16 mass parts. When the content of the condensed phosphate ester flame retardant is less than 5 parts by mass, the flame retardancy is insufficient, and when it exceeds 20 parts by mass, the heat resistance and the mechanical properties are significantly deteriorated.

  The phosphazene flame retardant is an organic compound having a —P═N— bond in the molecule, and preferably a cyclic phosphazene compound represented by the following general formula (2) and a chain represented by the following general formula (3). And at least one phosphazene compound selected from the group consisting of the following general formula (2) and the following general formula (3) is at least selected from the group consisting of a crosslinked phosphazene compound crosslinked by a crosslinking group One kind of compound. As the crosslinked phosphazene compound, those crosslinked by a crosslinking group represented by the following general formula (4) are preferable from the viewpoint of flame retardancy.

  The phosphazene-based flame retardant has a high flame retardant effect, and can suppress a decrease in mechanical strength and gas generation that may occur due to the blending of the flame retardant.

(In the formula (2), m is an integer of 3 to 25, and R ¹¹ may be the same or different and represents an aryl group or an alkylaryl group.)

(In the formula (3), u is an integer of 3 to 10,000, Z represents a —N═P (OR ¹¹ ) ₃ group or a —N═P (O) OR ¹¹ group, and Y represents a — P (OR ¹¹ ) ₄ group or —P (O) (OR ¹¹ ) ₂ group is shown, R ¹¹ may be the same or different and represents an aryl group or an alkylaryl group.

(In the formula (4), Q is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, l is 0 or 1.)

Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (2) and (3) include, for example, phenoxyphosphazene and (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene, etc. Cyclic and / or chain C _1-6 alkyl C _6-20 aryloxyphosphazenes and (poly) phenoxytolyloxyphosphazenes (eg, phenoxy o-tolyloxyphosphazenes, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxy) Hospha Phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene, preferably cyclic and / or chain phenoxy Phosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or chain tolyloxy) Phosphazene, cyclic and Is a or linear phenoxy tolyl phenoxyphosphazene etc.).

As the cyclic phosphazene compound represented by the general formula (2), cyclic phenoxyphosphazene in which R ¹¹ is a phenyl group is particularly preferable. Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (2) is 3 to 5, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less is preferable.

As the chain phosphazene compound represented by the general formula (3), chain phenoxyphosphazene in which R ¹¹ is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group. U in the general formula (3) of the linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

  Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned.

Moreover, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹¹ is a phenyl group in the general formula (2) with a crosslinking group represented by the general formula (4), or the above A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ¹¹ is a phenyl group in the general formula (3) with a crosslinking group represented by the general formula (4) is preferable from the viewpoint of flame retardancy, and cyclic A crosslinked phenoxyphosphazene compound obtained by crosslinking a phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  As the phosphazene-based flame retardant, the cyclic phenoxyphosphazene compound represented by the general formula (2) is preferable from the viewpoint of flame retardancy and mechanical properties.

  When the thermoplastic resin composition of the present invention contains such a phosphazene-based flame retardant, the content is preferably 10 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). More preferably, it is -25 mass parts, and it is further more preferable that it is 12-22 mass parts. By setting the content of the phosphazene-based flame retardant to 10 parts by mass or more, the flame retardancy can be sufficiently improved, and by setting it to 30 parts by mass or less, good thermal characteristics and mechanical strength can be maintained. Can do.

  In addition, you may use together 2 or more types of the said organic sulfonic acid metal salt, a silicone compound, an organic phosphate ester, and a phosphazene type flame retardant.

<Antioxidant>
The resin composition of the present invention may contain an antioxidant.
As the antioxidant, a phenolic antioxidant is preferable, and more specifically, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-). tert-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenyl), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) Propionate], and 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylpheny And l) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,6] undecane. Among these, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is preferable.
These antioxidants may be used alone or in combination of two or more.

  When the resin composition of this invention contains antioxidant, it is preferable that the content is 0.02-0.5 mass part with respect to 100 mass parts of thermoplastic resins (A). This range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.

<Ultraviolet absorber>
The resin composition of the present invention may contain an ultraviolet absorber. Resin molded products tend to become yellowish due to ultraviolet rays when exposed to light such as sunlight or fluorescent lamps for a long time, but the addition of UV absorbers prevents such yellowing. Or it can be delayed. Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and hindered amine.

  Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone. 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4 And '-tetrahydroxy-benzophenone.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylmethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl- 6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol, 2,2′-methylenebis [ 6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol] and the like.

Specific examples of the phenyl salicylate UV absorber include phenylsaltylate, 2,4-ditertiary-butylphenyl-3,5-ditertiary-butyl-4-hydroxybenzoate, and the like.
Specific examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

  These may be used alone or in combination of two or more.

  When the resin composition of this invention contains a ultraviolet absorber, it is preferable that the content is 0.001-1 mass part with respect to 100 mass parts of thermoplastic resins (A), 0.005- More preferably, it is 0.8 mass part, and it is still more preferable that it is 0.01-0.5 mass part. It is preferable for the content of the ultraviolet absorber to be in the above-mentioned range since the brightness and polarization properties are not lowered by light absorption, and the weather resistance can be improved without causing bleed out on the surface of the molded product.

<Others>
The resin composition of the present invention includes, in addition to the above components, an antistatic agent, an antifogging agent, a lubricant, an antiblocking agent, a fluidity improver, and a plasticizer, as long as the purpose of the present invention is not impaired as necessary. , Dispersants, antibacterial agents and the like can be blended.
These may be used alone or in combination of two or more.

[Production method]
The resin composition of the present invention can be produced by mixing each component by melt-kneading by a conventionally known method. Specific mixing methods include thermoplastic resin (A), plate-like filler (B), plate-like filler (C), and phosphate-based stabilizer (D) and hydrogen siloxane (E) blended as necessary. And other additive components are weighed and mixed using various mixers such as tumblers and Henschel mixers, and then banbury mixers, rolls, plastic penders, single-screw kneading extruders, twin-screw kneading extruders, kneaders, etc. And melt-kneading.

〔Molding〕
The molded article of the present invention is formed by molding the resin composition of the present invention as described above.

  As a molding method for producing the molded product of the present invention formed by molding the resin composition of the present invention, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general 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, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.

[Usage]
The molded product of the present invention formed by molding the resin composition of the present invention has a design appearance that exhibits a beautiful gold-coated product-like appearance by the combined use of a specific plate filler (B) and plate filler (C). Can be commercialized without painting, electrical / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building parts, various containers, playground equipment, toys, etc. It can be applied to various uses such as leisure goods / sports goods, cosmetics, accessories, stationery and other miscellaneous goods.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
In addition, the structural component of the resin composition used in the following Examples and Comparative Examples is as follows.

<Thermoplastic resin (A)>
A-1-1 (PC-1): Aromatic polycarbonate resin “Iupilon S-3000F” (Mitsubishi Engineering Plastics) (viscosity average molecular weight = 21500)
A-1-2 (PC-2): Aromatic polycarbonate resin “Iupilon E-2000F” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (viscosity average molecular weight = 28000)
A-1-3 (Si-PC) : manufactured by Idemitsu Kosan Co., Ltd., the siloxane copolycarbonate resin "Tafuron'neo AG1760", the high flow type (MVR = 13cm ^3/10 min (ISO1133,300 ℃, 1.2kgf))
A-2 (ABS): ABS resin “Santac UT-61” manufactured by A & L, Japan (butadiene unit content = 10% by mass)
A-3 (PBT): polybutylene terephthalate “Novaduran 5010L” manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity 1.00 dl / g, terminal carboxyl group concentration = 25 μeq / g)
A-4 (POM): Polyacetal resin “Iupital F20-03” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (melt index (ASTM-D1238 standard: 190 ° C., 2.16 kg) = 9.0 g / 10 min)

<Plate filler>
B-1 (305): MERCK Co. _{(TiO 2 / SnO 2 / SiO} 2 / Fe 2 O 3) coated mica "Iriodin305"
C-1 (5400): MERCK (TiO ₂ / SnO ₂ / SiO ₂ ) coated glass “Miraval 5400”
b-1 (306): MERCK (TiO ₂ / Fe ₂ O ₃ ) coated mica “Iriodin 306”

  The specifications of the plate fillers B-1, C-1, and b-1 are shown in Table 1 below.

<Stabilizer>
AX-71: “ADEKA STAB AX-71” manufactured by ADEKA (mixture of monostearyl acid phosphate and distearyl acid phosphate represented by the formula (II))
JP-513: “JP-513” (isotridecyl acid phosphate represented by the following formula (IV)) manufactured by Johoku Chemical Co., Ltd.

JP-518-O: “JP-518-O” manufactured by Johoku Chemical Co., Ltd. (oleyl acid phosphate represented by the following formula (V))

JP-524R: “JP-524R” manufactured by Johoku Chemical Co., Ltd. (tetracosyl acid phosphate represented by the following formula (VI))

  JP-518Zn: “JP-518Zn” manufactured by Johoku Chemical Co., Ltd. (mixture of distearyl acid phosphate zinc salt and monostearyl acid phosphate zinc salt represented by the above formulas (IIIa) and (IIIb))

ADK2112: “ADEKA STAB 2112” (Tris (2,4-di-tert-butylphenyl) phosphite) manufactured by ADEKA
SH1107: “DOW CORNING TORAY SH1107 FLUID” (methylhydrogensiloxane) manufactured by Toray Dow Corning

<Release agent>
VPG861: "Roxyol VPG861" (pentaerythritol tetrastearate) manufactured by Emery Oleochemicals Japan

[Examples 1 to 11 and Comparative Examples 1 to 6]
A thermoplastic resin and various additives are blended in the proportions shown in Tables 2 and 3, and mixed for 20 minutes with a tumbler. Then, a cylinder with a single-screw extruder with a screw diameter of 40 mm (“VS-40” manufactured by Tanabe Plastics) is used. The mixture was kneaded at a temperature of 280 ° C. and a screw rotation speed of 54 rpm, and the extruded strand was cut to produce pellets.
The obtained pellets were dried at 120 ° C. for 5 hours, and then injection-molded on an injection molding machine (“S-2000i150B” manufactured by FANUC) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The various test pieces were prepared.
The obtained pellets or test pieces were evaluated as follows, and the results are shown in Tables 2 and 3.

(1) Flow value (Q value)
The pellet flow value (Q value) was evaluated by the method described in JIS K7210 Appendix C. The measurement was performed using a “flow tester CFD500D” manufactured by Shimadzu Corporation, using a die having a hole diameter of 1.0 mmφ and a length of 10 mm, under conditions of a test temperature of 278 ° C., a test force of 160 kg / cm ² , and a preheating time of 420 sec. The amount of molten resin (unit: cc / sec) was measured.

(2) 320 ° C residence flow value (320 ° C residence Q value)
The obtained pellets were dried at 120 ° C. for 5 hours, and then the cylinder temperature was 320 ° C. (however, only in Example 8 was 240 ° C.) and the mold temperature was 80 ° C. with an injection molding machine (“S-2000i150B” manufactured by FANUC). The injection molding was performed under the condition of a molding cycle of 600 seconds. The molded product of the third shot was pulverized and the Q value was measured. The Q value was determined using the same method as in (1).

(3) Izod Impact Strength Izod impact strength (unit: J / m) was measured at a temperature of 23 ° C. for a notched Izod impact test piece (thickness: 3.2 mm) according to ASTM D256.

(4) Metallic appearance evaluation For the toning test piece (50 mm (width) x 90 mm (length), 3 mm plate with thickness of 1 mm, 2 mm, and 3 mm), the following conditions (1) to (6) Was observed, and it was confirmed whether or not it had a shining metallic appearance like gold, and evaluated as follows.
○: Good appearance with glittering metal like gold ×: No matte appearance, matte appearance
(1) North Sky Daylight 45 °: The appearance of the three-stage plate was observed from about 45 ° obliquely using light entering from the north window around 13:00 on a sunny day (natural light avoiding direct sunlight). .
(2) North Sky Daylight 90 °: The appearance of the three-stage plate was observed from almost directly above using light entering from the north window at around 13:00 on a sunny day (natural light avoiding direct sunlight).
(3) A light source 45 °: Using a “DAY-LIGHT KD-DL4” optical box manufactured by Tokiner, the appearance of the three-stage plate was observed from about 45 ° obliquely with an A light source.
(4) A light source 90 °: Using a “DAY-LIGHT KD-DL4” optical box manufactured by Tokiner Co., Ltd., the appearance of the three-stage plate was observed from directly above with an A light source.
(5) D65 45 °: Using a “DAY-LIGHT KD-DL4” optical box manufactured by Tokiner, the appearance of the three-stage plate was observed from about 45 ° obliquely with a D65 light source.
(6) D65 90 °: Using a “DAY-LIGHT KD-DL4” optical box manufactured by Tokiner, the appearance of the three-stage plate was observed from directly above with a D65 light source.

As is clear from the results of Tables 2 and 3, in Examples 1 to 11 in which the plate-like filler (B) and the plate-like filler (C) according to the present invention were combined and combined, gold was used at any angle. Such a metallic appearance can be obtained.
On the other hand, a plate-like filler having a coating layer different from that of Comparative Examples 1, 2, 4, 5 using only the plate-like filler (B) or only the plate-like filler (C) or the plate-like filler (B) In Comparative Examples 3 and 6 used in combination with the filler (C), a metal feeling cannot be obtained when observed from an oblique direction.

Claims (11)

For 100 parts by mass of the thermoplastic resin (A),
0.1-5 parts by mass of a plate-like filler (B) in which a coating layer containing titanium oxide, iron oxide, silicon oxide, and tin oxide is formed on a base material;
A thermoplastic resin composition containing 0.1 to 5 mass of a plate-like filler (C) in which a coating layer containing titanium oxide, silicon oxide, and tin oxide is formed on a base material,
A thermoplastic resin composition, wherein the plate-like filler (B) and the plate-like filler (C) satisfy the following relationship.
The average particle diameter _{D 50} of the plate-like filler (B) <mean particle diameter _{D 50} of the plate-like filler (C)   The thermoplastic resin composition according to claim 1, wherein the particle size of the plate filler (B) is 10 to 100 µm, and the base material is mica.   The thermoplastic resin composition according to claim 1 or 2, wherein the particle size of the plate-like filler (C) is 20 to 200 µm, and the substrate is glass. The thermoplastic resin (A) consists of 50 to 100 parts by mass of a polycarbonate resin (A-1) and 0 to 50 parts by mass of a thermoplastic resin other than the polycarbonate resin.
Further, one or more phosphate stabilizers (D) selected from alkyl acid phosphates, alkenyl acid phosphates and metal salts thereof are added in an amount of 0.01 to 1 with respect to 100 parts by mass of the polycarbonate resin (A-1). The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition is contained in parts by mass. The thermoplastic resin composition according to claim 4, wherein the alkyl acid phosphate or alkenyl acid phosphate is represented by the following formula (I).
O = P (OH) _n (OR) _3-n (I)
(In the formula (I), R represents an alkyl group or an alkenyl group, and n represents an integer of 1 or 2. When n is 1, two Rs may be the same or different. .)   R in said Formula (I) is a C9-C30 alkyl group or alkenyl group, The thermoplastic resin composition of Claim 5 characterized by the above-mentioned.   7. The thermoplastic resin composition according to claim 6, wherein R in the formula (I) is an alkyl group or an alkenyl group having any of 13, 18, and 24 carbon atoms. The phosphate stabilizer (D) is represented by the following formula (II), and is characterized in that it is a mixture of n = 1 distearyl acid phosphate and n = 2 monostearyl acid phosphate in the formula (II). The thermoplastic resin composition according to claim 4.
O = P (OH) _n (OC ₁₈ H ₃₇ ) _3-n (II) The phosphate stabilizer (D) is a mixture of a distearyl acid phosphate zinc salt represented by the following formula (IIIa) and a monostearyl acid phosphate zinc salt represented by the following formula (IIIb): The thermoplastic resin composition according to claim 4.

  Furthermore, 0.003-0.15 mass part of hydrogen siloxane (E) is contained with respect to 100 mass parts of polycarbonate resin (A-1), In any one of Claim 4 thru | or 9 characterized by the above-mentioned. The thermoplastic resin composition as described.   A molded article formed by molding the thermoplastic resin composition according to any one of claims 1 to 10.