JP7128082B2 - Thermoplastic resin mixture, thermoplastic resin composition and molded article - Google Patents

Description

The present invention provides a thermoplastic resin mixture in which a coloring agent and an additive are uniformly mixed, a thermoplastic resin composition in which the thermoplastic resin mixture is contained in a thermoplastic resin, and a molded article formed from the thermoplastic resin composition. It is about. More specifically, by using a thermoplastic resin powder having a specific particle size distribution and mixing this powder with a coloring agent and an additive, a thermoplastic resin mixture is used as a molded product. The present invention relates to a resin material having stable hue and excellent optical properties.

In recent years, along with the improvement of design in automotive applications and electrical and electronic equipment applications and the enlargement of electronic equipment, in addition to the conventional opaque color tone, both color tone with light transmission and optical properties such as total light transmittance There is an increasing demand for resin materials with transparent, diffusive, and opalescent color tones that control the

In order to obtain a material having both stable color tone and optical properties, it is necessary to uniformly mix a thermoplastic resin as a base resin, a coloring agent, and an additive. For mixing, a mixer such as Nauta mixer, tumbler, or blender is used to mix uniformly. However, it was not possible to obtain a homogeneous mixture.

As a method to solve this problem, a machine such as a high-speed mixer that discharges the mixture while rotating blades can suppress the classification during discharge and obtain a uniform mixture. However, there are disadvantages such as deterioration of work efficiency due to increased cleaning time for color change of the high-speed mixer, and occurrence of aggregation and poor dispersion of coloring agents and additives due to shear heat generation during mixing.

In order to suppress this, a method of mixing coloring agents and additives with dispersants such as metal soaps is adopted, but dispersants have an adverse effect on thermoplastic resins in processes that generate heat such as extrusion and molding. , the molecular weight of the thermoplastic resin is lowered, and the original mechanical properties of the resin are impaired. Furthermore, a method is known in which the surface of resin particles is coated with a spreading agent and then mixed with a powdery additive (Patent Document 1). chemicals may adversely affect quality.

Japanese Patent Application Laid-Open No. 2001-302803

An object of the present invention is to provide a thermoplastic resin mixture in which a coloring agent and an additive are uniformly mixed, a thermoplastic resin composition in which the thermoplastic resin mixture is contained in a thermoplastic resin, and a stable hue and optical properties. To provide a molded product excellent in

As a result of intensive studies by the inventors of the present invention to solve the above problems, a molded product can be obtained by using a thermoplastic resin powder having a specific particle size distribution and mixing the powder with a coloring agent and an additive. As a result, the present inventors have completed the present invention.

That is, according to the present invention, the following (configuration 1) to (configuration 5) are provided.
(Configuration 1)
Polycarbonate resin powder obtained by a standard sieving method using a Tyler sieve containing 5% by weight or less of particles larger than 20 mesh and 30% by weight or less of particles smaller than 60 mesh, and a coloring agent or an additive. Polycarbonate resin mixture.
(Configuration 2)
2. The polycarbonate resin mixture according to the preceding item 1, wherein the polycarbonate resin powder contains 15% by weight or less of particles larger than 32 mesh.
(Composition 3)
3. The polycarbonate resin mixture according to item 1 or 2, wherein the polycarbonate resin powder contains 60% by weight or more of particles having a size larger than 60 mesh and smaller than 32 mesh.
(Composition 4)
A polycarbonate resin composition containing 1 to 100 parts by weight of the polycarbonate resin mixture according to any one of the preceding items 1 to 3 with respect to 100 parts by weight of the polycarbonate resin component.
(Composition 5)
5. A molded article molded from the polycarbonate resin composition according to 4 above.

In the thermoplastic resin mixture of the present invention, a coloring agent and additives are uniformly mixed, and a molded article molded from a thermoplastic resin composition containing the thermoplastic resin mixture in a thermoplastic resin has a stable hue and optical properties. Due to its excellent properties, it is suitable as a material for applications that require both color tone and optical properties, mainly in the fields of automobiles and electrical and electronic equipment.

The details of the present invention will be described below.
(Thermoplastic resin)
The thermoplastic resin to be used in the present invention is not basically limited, and thermoplastic resins that are preferably used for housings of electronic devices are preferably used. Examples of such thermoplastic resins include polypropylene resins, styrene resins, modified polyphenylene oxide resins, polyamide resins, polycarbonate resins, polyphenylene sulfide resins, and polyester resins. Particularly preferred resins include, for example, AS resins, ABS resins, polycarbonate resins, polyethylene terephthalate resins, polybutylene terephthalate resins, and mixtures of two or more of these. Polycarbonate resin is particularly preferred.

The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of reaction methods include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl ) propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)- 1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl) Pentane, 4,4'-(p-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane , bis(4-hydroxyphenyl) oxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) ketone, bis(4- hydroxyphenyl) ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. be done. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, of which bisphenol A is particularly preferred from the standpoint of impact resistance and is widely used.

Carbonate precursors include carbonyl halides, diesters of carbonic acid and haloformates, and specific examples include phosgene, diphenyl carbonate and dihaloformates of dihydric phenols.

In producing an aromatic polycarbonate resin by interfacial polymerization of the dihydric phenol and a carbonate precursor, if necessary, a catalyst, a terminal terminator, and an antioxidant to prevent oxidation of the dihydric phenol. etc. may be used. In addition, the aromatic polycarbonate resin of the present invention is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, a polyester obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid It includes carbonate resins, copolymerized polycarbonate resins copolymerized with difunctional alcohols (including alicyclic alcohols), and polyester carbonate resins copolymerized with such difunctional carboxylic acids and difunctional alcohols. Moreover, the mixture which mixed 2 or more types of obtained aromatic polycarbonate resin may be sufficient.

The branched polycarbonate resin can impart anti-drip performance and the like to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucine, phloroglucide, or 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2 ,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl) ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[ trisphenols such as 1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1, 4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among others, 1,1,1-tris(4-hydroxy Phenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

Structural units derived from a polyfunctional aromatic compound in the branched polycarbonate are preferably 0.01 to 1 mol %, more preferably 0.05 to 0.9 mol %, still more preferably 0.05 to 0.8 mol %.

Further, particularly in the case of the melt transesterification method, a branched structural unit may occur as a side reaction. It is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, still more preferably 0.01 to 0.8 mol %. The ratio of such branched structures can be calculated by 1H-NMR measurement.

Aliphatic bifunctional carboxylic acids are preferably α,ω-dicarboxylic acids. Examples of aliphatic bifunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, and cyclohexanedicarboxylic acid. Alicyclic dicarboxylic acids such as are preferably exemplified. Alicyclic diols are more suitable as bifunctional alcohols, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

Furthermore, a polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin.

Reaction formats such as the interfacial polymerization method, the melt transesterification method, the carbonate prepolymer solid phase transesterification method, and the ring-opening polymerization method of a cyclic carbonate compound, which are methods for producing the polycarbonate resin of the present invention, can be found in various literatures and patent publications. It is a well-known method in

In producing the polycarbonate resin mixture of the present invention, the viscosity-average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8×10 ⁴ to 4.0×10 ⁴ , more preferably 2.0×10 4 to 4.0×10 4 . 0×10 ⁴ to 3.5×10 ⁴ , more preferably 2.2×10 ⁴ to 3.0×10 ⁴ . Polycarbonate resins having a viscosity-average molecular weight of less than 1.8×10 ⁴ may not provide good mechanical properties. On the other hand, a resin mixture obtained from a polycarbonate resin having a viscosity-average molecular weight exceeding 4.0×10 ⁴ is inferior in versatility due to poor fluidity during injection molding.

The viscosity-average molecular weight of the polycarbonate resin in the polycarbonate resin mixture of the present invention is calculated in the following manner. That is, the mixture is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble matter in the mixture. Such soluble matter is collected by celite filtration. The solvent in the resulting solution is then removed. After removing the solvent, the solid is sufficiently dried to obtain a solid of the component soluble in methylene chloride. From a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride, the specific viscosity at 20° C. is obtained in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.
Specific viscosity (η _SP ) = (tt ₀ )/t ₀
[t ₀ is the number of seconds the methylene chloride falls, t is the number of seconds the sample solution falls]
The viscosity-average molecular weight M is calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[η]=1.23×10 ⁻⁴ M ^0.83
c=0.7

(Thermoplastic resin powder)
The thermoplastic resin powder of the present invention contains 5% by weight or less of particles larger than 20 mesh obtained by a standard sieving method using a Tyler sieve, and 30% by weight or less of particles smaller than 60 mesh. is satisfied. The content of particles larger than 20 mesh is preferably 4% by weight or less, more preferably 3% by weight or less, and even more preferably 2% by weight or less. The content of particles smaller than 60 mesh is preferably 27% by weight or less, more preferably 25% by weight or less, and even more preferably 23% by weight or less.

The thermoplastic resin powder preferably contains 15% by weight or less of particles larger than 32 mesh, more preferably 13% by weight or less, and even more preferably 12% by weight or less. Further, the thermoplastic resin powder preferably contains 60% by weight or more of particles larger than 60 mesh and smaller than 32 mesh, more preferably 63% by weight or more, and even more preferably 65% by weight or more.

By using a thermoplastic resin powder that satisfies the particle size range described above, it can be uniformly mixed with the coloring agent and additives described later, and the resulting molded article obtained by molding the mixture has stable hue and optical properties. It has the advantage of excellent properties.

Here, particles larger than 20 mesh are particles remaining on 20 mesh (840 μm opening) measured by a standard sieving method using a Tyler sieve. Particles larger than 32 mesh mean particles remaining on 32 mesh (500 μm opening) measured by the same method. On the other hand, particles smaller than 60 mesh are particles passing through 60 mesh (opening 250 μm) measured by the same method.

Examples of methods for obtaining the thermoplastic resin powder according to the present invention include 1) a method of classifying the powder, and 2) a method of pulverizing the powder.

(coloring agent)
Colorants that are preferably used in the present invention include dyes, organic pigments, inorganic pigments, etc., but are not particularly limited as long as they can be colored, and may be used singly or in combination of two or more. You may mix and use.

Dyes include anthraquinone dyes, perylene dyes, perinone dyes, quinoline dyes, nitro dyes, nitroso dyes, azo dyes, triphenyl dyes, thiazole dyes, methine dyes, oxazine dyes, India Examples include phenol dyes, ketone dyes, thiazine dyes, indigo dyes, and the like.

Examples of organic pigments include phthalocyanine pigments, condensed azo pigments, azo lake pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, and condensed polycyclic pigments.

Inorganic pigments include simple oxides such as zinc oxide, titanium dioxide, red iron oxide, chromium oxide and iron black, sulfides such as cadmium yellow, cadmium orange and cadmium red, and chromium such as yellow lead, zinc yellow and chrome vermilion. Inorganic coloring agents such as acid salts, ferrocyanides such as Prussian blue, silicates such as ultramarine blue, carbon black, and metal powders.

Examples of inorganic pigments include oxide pigments such as carbon black, titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black. is mentioned.

The mixing ratio of the colorant is preferably 0.0001 to 150 parts by weight, more preferably 0.0005 to 125 parts by weight, and even more preferably 0.001 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin powder. . When the blending ratio is within the above range, coloring is sufficiently recognized, and stable hue and excellent optical properties are obtained, which is preferable.

(Additive)
Additives suitably used in the present invention include light diffusing agents, fluorescent whitening agents, heat stabilizers, ultraviolet absorbers, release agents, etc., but are not particularly limited, and one type may be used alone. , may be used in combination of two or more.

(light diffusing agent)
The light diffusing agent suitably used as the additive in the present invention may be either organic fine particles represented by polymer fine particles or inorganic fine particles. Organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer are typically exemplified as polymer fine particles. In addition to such monomers, other copolymerizable monomers can also be used. Other organic crosslinked particles include silicone crosslinked particles typified by polyorganosilsesquioxane.

Among the light diffusing agents, polymer fine particles are preferable, and organic crosslinked particles can be particularly preferably used. Examples of monomers used as non-crosslinking monomers in such organic crosslinked particles include non-crosslinking vinyl-based monomers such as acrylic monomers, styrene-based monomers and acrylonitrile-based monomers, and olefin-based monomers.

Examples of acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate alone or in combination. can be used as Among these, methyl methacrylate is particularly preferred.

As the styrene-based monomer, styrene, alkylstyrene such as α-methylstyrene, methylstyrene (vinyltoluene) and ethylstyrene, and halogenated styrene such as brominated styrene can be used, and styrene is particularly preferred. .

Acrylonitrile and methacrylonitrile can be used as acrylonitrile-based monomers. Ethylene and various norbornene type compounds can be used as olefinic monomers.

Further, other copolymerizable monomers can be exemplified by glycidyl methacrylate, N-methylmaleimide, maleic anhydride, and the like. The organic crosslinked particles of the present invention can also have units such as N-methylglutarimide as a result.

On the other hand, crosslinkable monomers for such non-crosslinkable vinyl monomers include, for example, divinylbenzene, allyl methacrylate, triallyl cyanurate, triallyl isocyanate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol. (Meth)acrylates, 1,6-hexanediol di(meth)acrylate, trimethylolpropane (meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate, dicyclopentanyl di(meth)acrylate , dicyclopentenyl di(meth)acrylate, and N-methylol(meth)acrylamide.

The average particle size of the light diffusing agent used in the present invention is preferably 0.01 to 50 μm, more preferably 1 to 30 μm, still more preferably 2 to 30 μm. If the average particle size is less than 0.01 μm or more than 50 μm, light diffusibility may be insufficient. Such an average particle size is represented by the 50% value (D50) of the cumulative distribution of particle sizes determined by a laser diffraction/scattering method. The particle size distribution may be single or multiple. That is, it is possible to combine two or more light diffusing agents having different average particle diameters. However, more preferred light diffusing agents are those with a narrow particle size distribution. It is more preferable to have a distribution in which 70% by weight or more of the particles are contained in the range of 2 μm before and after the average particle diameter. The shape of the light diffusing agent is preferably nearly spherical from the viewpoint of light diffusion, and more preferably nearly spherical. Such spherical shapes include elliptical spheres.

The refractive index of the light diffusing agent used in the present invention is generally preferably in the range of 1.3 to 1.8, more preferably 1.33 to 1.70, and still more preferably 1.35 to 1.65. is. These exhibit a sufficient light diffusing function when blended in the resin composition.

The mixing ratio of the light diffusing agent is preferably 0.01 to 40 parts by weight, more preferably 0.05 to 35 parts by weight, and further 0.1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin powder. preferable. Light diffusibility is sufficient at 0.01 parts by weight or more, and light transmittance is excellent at 40 parts by weight or less.

(Fluorescent brightener)
The fluorescent brightening agent suitably used as an additive in the present invention is not particularly limited as long as it is used to improve the color tone of resins to white or bluish white. Benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds are included. Specific examples include CI Fluorescent Brightener 219:1 and EASTOBRITE OB-1 manufactured by Eastman Chemical Company. Here, the fluorescent whitening agent has the function of absorbing energy in the ultraviolet region of light and emitting this energy in the visible region.

The blending ratio of the fluorescent brightener is preferably 0.001 to 2.5 parts by weight, more preferably 0.005 to 2.0 parts by weight, and more preferably 0.01 to 2.0 parts by weight with respect to 100 parts by weight of the thermoplastic resin powder. 1.5 parts by weight is more preferred. Within the above range, an effect of improving color tone can be obtained.

(Heat stabilizer)
Heat stabilizers suitable for use as additives in the present invention include phosphorus stabilizers, hindered phenol stabilizers, and sulfur stabilizers.

(Phosphorus stabilizer)
Phosphorus-based stabilizers are already widely known as heat stabilizers for thermoplastic resins. Phosphorus-based stabilizers enhance the thermal stability of the resin composition to the extent that it can withstand extremely severe thermal loads. Phosphorus stabilizers mainly include phosphite compounds and phosphonite compounds.

Examples of phosphite compounds include triphenylphosphite, tris(nonylphenyl)phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, and dioctylmonophenylphosphite. , diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, tris(diethylphenyl ) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6- Di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4 -methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite Examples include phosphite, dicyclohexylpentaerythritol diphosphite, and the like.

Further, other phosphite compounds that react with dihydric phenols and have a cyclic structure can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2′-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite , 2,2′-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and the like.

Phosphonite compounds include, for example, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite night, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6- Di-n-butylphenyl)-3-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl) )-3-phenyl-phenylphosphonite and the like, preferably tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, tetrakis(2 ,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite are more preferred. Such a phosphonite compound can preferably be used in combination with a phosphite compound having an aryl group substituted with two or more alkyl groups.

The mixing ratio of the phosphorus stabilizer is preferably 0.001 to 7.0 parts by weight, more preferably 0.005 to 6.0 parts by weight, and more preferably 0.01 to 5.5 parts by weight per 100 parts by weight of the thermoplastic resin powder. Part by weight is more preferred, and 0.01 to 5.0 parts by weight is particularly preferred.

(Hindered phenol stabilizer)
Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4′-hydroxy-3′,5′-di-tert-butylfer) propionate, 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N ,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′- methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2, 2′-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 2,2′-butylidene-bis(4- methyl-6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3 -tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1 ,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4 , 4′-di-thiobis(2,6-di-tert-butylphenol), 4,4′-tri-thiobis(2,6-di-tert-butylphenol mol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4- Hydroxy-3′,5′-di-tert-butylanilino)-1,3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide) , N,N′-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert- Butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl- 4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethylisocyanurate, and tetrakis[methylene-3-(3′, 5′-di-tert-butyl-4-hydroxyphenyl)propionate]methane and the like are exemplified. All of these are readily available. The above hindered phenol stabilizers may be used alone or in combination of two or more.

The blending ratio of the hindered phenol stabilizer is preferably 0.001 to 14 parts by weight, more preferably 0.01 to 12 parts by weight, and further 0.05 to 10 parts by weight per 100 parts by weight of the thermoplastic resin powder. Preferably, 0.1 to 8 parts by weight is particularly preferred.

(Sulfur stabilizer)
Sulfur-based stabilizers include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), and pentaerythritol tetrakis. (3-dodecylthiopropionate), pentaerythritol tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol tetrakis (3-stearylthiopropionate), etc. mentioned. These may be used alone or in combination of two or more.

The mixing ratio of the sulfur-based stabilizer is preferably 0.001 to 7.0 parts by weight, more preferably 0.005 to 6.0 parts by weight, and more preferably 0.01 to 5.5 parts by weight per 100 parts by weight of the thermoplastic resin powder. Part by weight is more preferred, and 0.01 to 5.0 parts by weight is particularly preferred.

(Ultraviolet absorber)
Molded articles molded from the thermoplastic resin mixture of the present invention may be used without coating or the like. In such cases, good light resistance may be required, and the addition of an ultraviolet absorber is effective.

Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′,4,4′ -tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4- hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Benzotriazoles include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3, 5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2′-methylenebis[4-(1,1,3 ,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2- Hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5 -tert-octylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'- methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4, 5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole and 2-(2′-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with said monomers 2-hydroxyphenyl-2H such as copolymers with and copolymers of 2-(2′-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and a vinyl monomer copolymerizable with the monomer -A polymer having a benzotriazole skeleton is exemplified.

In the hydroxyphenyltriazine series, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5 -triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl -1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol, etc. exemplified. Furthermore, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc., in which the phenyl group of the above-exemplified compounds is 2,4-dimethylphenyl A compound having a phenyl group is exemplified.

Cyclic imino esters include, for example, 2,2′-p-phenylenebis(3,1-benzoxazin-4-one), 2,2′-m-phenylenebis(3,1-benzoxazin-4-one) , and 2,2′-p,p′-diphenylenebis(3,1-benzoxazin-4-one).

Cyanoacrylates include, for example, 1,3-bis-[(2′-cyano-3′,3′-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy ]methyl)propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

Furthermore, the above-mentioned ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet-absorbing monomer and/or photostable monomer and a monomer such as alkyl (meth)acrylate It may be a polymer-type UV absorber obtained by copolymerizing with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester. be.

The blending ratio of the ultraviolet absorber is preferably 0.01 to 40 parts by weight, more preferably 0.05 to 30 parts by weight, and further 0.1 to 25 parts by weight with respect to 100 parts by weight of the thermoplastic resin powder. preferable. When the blending amount of the ultraviolet absorber is within the above range, a sufficient weather resistance effect can be obtained, and defects in appearance, deterioration in physical properties, and deterioration in flame retardancy due to gas generation are less likely to occur, which is preferable.

(Release agent)
The thermoplastic resin mixture in the present invention may optionally contain a release agent. Known release agents can be used. For example, saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene waxes, 1-alkene polymers, etc., those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds. (fluorinated oil represented by polyfluoroalkyl ether), paraffin wax, beeswax, and the like.

Among them, fatty acid esters (component C-1) are preferred as release agents. Such fatty acid esters are esters of fatty alcohols and fatty carboxylic acids. Such fatty alcohols may be monohydric alcohols or polyhydric alcohols having a valence of 2 or more. The number of carbon atoms in the alcohol is in the range of 3-32, more preferably in the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol-hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, more preferably 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanic acid, icosanoic acid, and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, the aliphatic carboxylic acid preferably has 14 to 20 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

Since the above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (beef tallow, pork fat, etc.) and vegetable fats (palm oil, etc.), these aliphatic carboxylic acids Acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of component C-1 of the present invention, aliphatic carboxylic acids, especially stearic acid and palmitic acid, which are produced from such natural fats and oils and are in the form of mixtures containing other carboxylic acid components, are preferably used.

Fatty acid esters may be either partial esters or full esters. However, since partial esters usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures, full esters are more preferable. The acid value of component C of the present invention is preferably 20 or less (can be substantially 0). Further, the hydroxyl value of the C component is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less (can be substantially 0). These properties can be obtained by the method specified in JIS K 0070.

The mixing ratio of the release agent is preferably 0.001 to 20 parts by weight, more preferably 0.05 to 15 parts by weight, and even more preferably 0.1 to 10 parts by weight per 100 parts by weight of the thermoplastic resin powder. Within this range, the thermoplastic resin mixture has good releasability.

In the present invention, the thermoplastic resin may further contain other conventional additives such as reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons, milled fibers, glass flakes, Carbon fiber, carbon flake, carbon bead, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers, etc.), flame retardants (halogen-based, phosphate-based, metal salt-based, red phosphorus, silicon-based, fluorine-based, metal hydrate-based, etc.), flame-retardant aids (sodium antimonate, antimony trioxide), drip prevention agent (polytetrafluoroethylene), impact modifier represented by graft rubber, sliding agent (e.g. PTFE particles), phosphorescent pigment, fluorescent dye, antistatic agent, Fluidity modifiers, lubricants, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (microparticle titanium oxide, microparticle zinc oxide, etc.), infrared absorbers, and photochromic agents can be blended.

(Thermoplastic resin mixture, thermoplastic resin composition and molded article)
Any method can be used to mix the thermoplastic resin powder and the colorant or additive. For example, the thermoplastic resin granules and the colorant or additive can be sufficiently mixed using mixing means such as a V-type blender, Henschel mixer, super floater, and extrusion mixer.

The obtained thermoplastic resin mixture is melt-kneaded with a thermoplastic resin as it is or by a method such as melt-kneading with a melt-kneader typified by a vent-type twin-screw ruder, and then pelletized by a device such as a pelletizer to obtain a thermoplastic resin composition. can get things. At this time, it is preferable to add 1 to 100 parts by weight of the thermoplastic resin mixture, more preferably 2 to 90 parts by weight of the thermoplastic resin mixture, based on 100 parts by weight of the thermoplastic resin component.

The thermoplastic resin mixture or the thermoplastic resin composition in which the thermoplastic resin mixture is contained in the thermoplastic resin component can be used to obtain desired molded articles by various methods. As the molding method, various methods known as molding methods for ordinary thermoplastic resin mixtures can be used, such as extrusion molding, injection molding, compression molding, and the like.

The present invention will be further described with reference to the following examples. In addition, unless otherwise specified, parts in the examples are parts by weight, and %s are % by weight. In addition, evaluation was implemented by the following method.
(i) Hue Using the obtained pellets, a molded plate (length 90 mm × width 50 mm) having a thickness of 2 mm and an arithmetic mean roughness (Ra) of 0.03 µm was formed at a cylinder temperature of 290 ° C. and a mold temperature of 80. ° C., an injection speed of 70 mm / s, and the resulting molded plate is measured using a spectrophotometer (Macbeth Color-Eye 7000A) under a D65 light source (correlated color temperature 6504K). * (brightness) was measured, and the difference R between the maximum and minimum measured values was obtained. A smaller R indicates a more stable hue.
(ii) Optical properties Using a haze meter (NDH-2000 manufactured by Nippon Denshoku Co., Ltd.), the molded plate obtained by the method described in (i) under a D65 light source (correlated color temperature 6504K), Tt ( Total light transmittance) was measured, and the difference R between the maximum and minimum measured values was obtained. A smaller R indicates a more stable optical characteristic.

[Examples 1 to 10, Comparative Examples 1 to 5]
A mixture of components having the compositions shown in Tables 2-1 and 2-2 was added to 100 parts by weight of the polycarbonate resin powder, and mixed uniformly with a V-blender. The mixture and polycarbonate resin powder were supplied from the first supply port of the extruder with the compositions shown in Tables 3-1 and 3-2. Polycarbonate resin is extruded using a vented twin-screw extruder (Japan Steel Works, Ltd. TEX30α-38.5BW-3V) with a diameter of 30 mmφ, screw rotation speed 230 rpm, discharge rate 25 kg / h, vent vacuum degree 3 kPa Melt. The mixture was kneaded to obtain pellets. The extrusion temperature was 280° C. from the first supply port to the die. Some of the obtained pellets were dried at 120°C for 6 hours in a hot air circulating dryer, and then molded using an injection molding machine at a cylinder temperature of 290°C and a mold temperature of 80°C to form a molded plate having a thickness of 2 mm. (Length 90 mm x Width 50 mm) was molded.

In addition, each component represented by symbols in Tables 1, 2-1, 2-2, 3-1 and 3-2 is as follows.
(A component)
A-1-1: Aromatic polycarbonate resin powder obtained by pulverizing the polycarbonate resin powder shown in A-2 below (Polycarbonate resin powder A having a viscosity average molecular weight of 22,400 made by a conventional method from bisphenol A and phosgene -1-2: Aromatic polycarbonate resin powder obtained by pulverizing the polycarbonate resin powder shown in A-2 below (Polycarbonate resin powder having a viscosity average molecular weight of 22,400 made by a conventional method from bisphenol A and phosgene A- 2: Aromatic polycarbonate resin powder (polycarbonate resin powder having a viscosity average molecular weight of 22,400 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP (product name) manufactured by Teijin Limited)
The particle size distribution of the aromatic polycarbonate resin powder is shown in Table 1 below.

(B component)
B-1: Carbon black (#970 manufactured by Mitsubishi Chemical Corporation)
B-2: Green dye (Oil Green 5602 manufactured by Arimoto Chemical Industry Co., Ltd.)
B-3: Blue dye (MACROLEX Blue RR manufactured by Lanxess)
B-4: Yellow dye (Plast Yellow 8005 manufactured by Arimoto Chemical Industry Co., Ltd.)
B-5: Red dye (Plast Red 8370 manufactured by Arimoto Chemical Industry Co., Ltd.)
B-6: Titanium dioxide (Tipaque PC-3 manufactured by Ishihara Sangyo Co., Ltd.)
(C component)
C-1: Bead-shaped crosslinked silicon (TSR9002 manufactured by Momentive Performance Materials Japan, average particle size 2 μm)
C-2: Bead-shaped crosslinked acrylic particles (MBX-5 manufactured by Sekisui Plastics Co., Ltd., average particle size 5 μm)
(D component)
D: Fluorescent brightener (Hakkor PSR manufactured by Showa Chemical Industry Co., Ltd.)

In the thermoplastic resin mixture of the present invention, a coloring agent and additives are uniformly mixed, and a molded article molded from a thermoplastic resin composition containing the thermoplastic resin mixture in a thermoplastic resin has a stable hue and optical properties. Due to its excellent properties, it is useful as a material for applications that require both color tone and optical properties, mainly in the fields of automobiles and electrical and electronic equipment.

Claims (5)

Polycarbonate resin powder obtained by a standard sieving method using a Tyler sieve containing 5% by weight or less of particles larger than 20 mesh and 30% by weight or less of particles smaller than 60 mesh, and a coloring agent or an additive. Polycarbonate resin mixture. 2. The polycarbonate resin mixture according to claim 1, wherein the polycarbonate resin powder contains 15% by weight or less of particles larger than 32 mesh. 3. The polycarbonate resin mixture according to claim 1, wherein the polycarbonate resin powder contains 60% by weight or more of particles larger than 60 mesh and smaller than 32 mesh. A polycarbonate resin composition containing 1 to 100 parts by weight of the polycarbonate resin mixture according to any one of claims 1 to 3 with respect to 100 parts by weight of the polycarbonate resin component. A molded article molded from the polycarbonate resin composition according to claim 4 .