JP2007231080A - Polycarbonate resin composition and molded body made therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thickening agent prevented from thermofusing and suppressed in powder blocking, and to provide a polycarbonate resin composition using the thickening agent. <P>SOLUTION: The polycarbonate resin composition comprises (A) 100 pts.wt. of a polycarbonate resin and (B) 0.1-50 pts.wt. of the thickening agent obtained by coating 100 pts.wt. of (B-1) polymer particles 60°C or higher in glass transition temperature and 50-500 μm in volume-average size with 0.5-30 pts.wt. of (B-2) polymer particles 0.01-0.5 μm in volume-average size. In this polycarbonate resin composition, the polymer particles(B-1) are such as to be obtained by copolymerization between (a) 70-95 wt.% of an aromatic vinyl monomer, (b) 5-30 wt.% of a 1-8C alkyl acrylate and (c) 0-10 wt.% of another vinyl monomer copolymerizable therewith. A molded product made from the polycarbonate resin composition is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition for obtaining a molded article excellent in molding processability in extrusion molding, injection molding, blow molding and the like of a polycarbonate resin, and excellent in transparency and gloss, and a molded article obtained therefrom. It is.

  Polycarbonate resins are excellent in physical properties such as transparency, heat resistance, dimensional stability, mechanical properties, and chemical properties such as water resistance and acid resistance. Electrical and electronic equipment, OA equipment, automobile parts, etc. It is used for interior materials of housings, vehicles, and aircraft.

  However, since the polycarbonate resin generally has a large temperature dependence of the melt viscosity, the melt viscosity is low and disadvantageous in melt processing such as injection molding, extrusion molding, and blow molding performed in a temperature region higher than the melting point. With respect to the regenerated polycarbonate resin, the tendency of the melt viscosity to become lower becomes more remarkable. For this reason, for the purpose of improving the moldability of polycarbonate resins, studies have been conventionally made on blending copolymers having compatibility with these resins as melt viscosity modifiers (thickeners).

  Further, although the impact resistance strength of polycarbonate resin is excellent in a thin-walled molded product, it is greatly reduced when thick-walled molding is performed, and the impact strength at low temperature is insufficient, and improvement is required.

  As a method for solving such a problem, a method of blending an epoxy group-containing polyolefin with a polycarbonate resin (see Patent Documents 1 to 3) is disclosed. However, in this document, both the increase in melt viscosity at a level sufficient to ensure stable moldability and surface properties in injection molding, extrusion molding, and blow molding, and maintaining high transparency and gloss of the molded body are achieved. It was difficult.

  For example, when a copolymer obtained by copolymerizing a monomer having reactivity with a thermoplastic polyester resin such as glycidyl methacrylate is blended as a thickener, the melt viscosity of the thermoplastic polyester resin increases. In some cases, the surface of the resulting molded product is whitened, and an undesirable tendency is observed in that the transparency and gloss are lowered.

  Therefore, in extrusion molding, injection molding, and blow molding, there has been a strong demand for a technique that achieves both stable molding processability, high transparency of molded products, and maintenance of gloss.

  In addition, since the polycarbonate resin is generally easily hydrolyzed to lower the molecular weight, the melt viscosity is further lowered, and the melt processing becomes more difficult. Since the hydrolysis reaction of the polycarbonate resin is easily accelerated by the influence of ionic impurities such as an emulsifier, a thickener used for the polycarbonate resin composition is prepared using an emulsion polymerization method in which a large amount of the emulsifier remains. Is disadvantageous.

  As a method for improving this problem, it is conceivable to select a polymerization method using almost no ionic impurities as a polymerization method for the thickener used in the polycarbonate resin composition. However, for example, in a polymerization method that hardly uses ionic impurities such as a suspension polymerization method, the average particle diameter of the particles obtained generally tends to be broad and tends to be broad. There is a problem that the solid-liquid separation property at the time deteriorates and fine powder flows out into the dewatered waste water.

Further, when a polymer having a relatively low molecular weight is produced in order to improve the dispersibility in the polycarbonate resin, there is a problem that the polymer is thermally fused in the drying step or the powder blocking property is deteriorated.
JP 57-125253 A JP-A-58-201842 Japanese Patent Laid-Open No. 9-255863

  The present invention efficiently increases the melt viscosity of a polycarbonate resin, exhibits a stable moldability in extrusion molding, injection molding, and blow molding, and has a molded article having good transparency and gloss. It is a problem to obtain.

  In addition, in the case of producing a low molecular weight polymer, there is a problem of heat fusion in the drying process, for example, in the suspension polymerization method, a problem that a lot of fine powder is generated and the filterability is poor at the time of dehydration, and when polycarbonate resin is molded It is an object to solve the problem of decrease in melt viscosity due to hydrolysis of polycarbonate resin.

  As a result of intensive studies based on the above situation, the present inventor has blended a polymer having a specific structure obtained by polymerizing a monomer mixture of a specific type and amount as a thickener for a polycarbonate resin. The polycarbonate resin composition expresses a tremendous thickening effect not seen in the prior art, and the molded product obtained therefrom can achieve both high transparency and gloss, and the above problems can be solved all at once. The headline and the present invention have been completed.

  That is, according to the first aspect of the present invention, 100 parts by weight of polymer particles (B-1) having a glass transition temperature of 60 ° C. or higher and a volume average particle diameter of 50 to 500 μm are added to 100 parts by weight of the polycarbonate resin (A). Polycarbonate resin composition containing 0.1 to 50 parts by weight of thickener (B) coated with 0.5 to 30 parts by weight of polymer particles (B-2) having an average particle size of 0.01 to 0.5 μm The polymer particles (B-1) are (a) 70 to 95% by weight of an aromatic vinyl monomer and (b) 5 to 30% by weight of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. And (c) 0 to 10% by weight of other vinyl monomers copolymerizable with these [100% by weight in combination of (a), (b) and (c)] The present invention relates to a polycarbonate resin composition.

  In a preferred embodiment, the monomer constituting the polymer particle (B-1) has an epoxy group, an isocyanate group, an oxazoline group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group, and an acid chloride group. It is a monomer which does not contain, It is related with the said polycarbonate resin composition characterized by the above-mentioned.

  In a preferred embodiment, any one of the above, wherein the alkyl acrylate (b) constituting the polymer particle (B-1) is an alkyl acrylate having an alkyl group having 1 to 4 carbon atoms. The present invention relates to a polycarbonate resin composition.

  In a preferred embodiment, the alkyl acrylate (b) constituting the polymer particle (B-1) is an alkyl acrylate having an alkyl group having 1 to 2 carbon atoms, according to any one of the above. The present invention relates to a polycarbonate resin composition.

  A preferred embodiment relates to the polycarbonate resin composition according to any one of the above, wherein the polymer particles (B-1) have a weight average molecular weight of 10,000 to 4,000,000.

  A preferred embodiment relates to the polycarbonate resin composition according to any one of the above, wherein the polymer particles (B-1) have a weight average molecular weight of 10,000 to 400,000.

  A preferred embodiment relates to the polycarbonate resin composition according to any one of the above, wherein the polymer particles (B-1) have a refractive index of 1.56 to 1.59.

  A preferred embodiment relates to the polycarbonate resin composition according to any one of the above, wherein the polymer particles (B-2) have a Vicat softening temperature of 80 ° C. or higher.

  In a preferred embodiment, the polymer particles (B-2) are 50 to 95% by weight of methyl methacrylate, 5 to 50% by weight of alkyl methacrylate having an alkyl group having 2 to 8 carbon atoms, and others copolymerizable therewith. 60 to 95 parts by weight of a mixture of 0 to 20% by weight of a vinyl monomer, and in the presence of the resulting polymer latex, one or more monomers selected from alkyl methacrylates excluding alkyl acrylate and methyl methacrylate 5 to 40 parts by weight of a mixture of 20 to 80% by weight of the body, 20 to 80% by weight of methyl methacrylate, and 0 to 20% by weight of other vinyl monomers copolymerizable therewith so that the total amount becomes 100 parts by weight. The polycarbonate resin composition according to any one of the above, wherein the polycarbonate resin composition is obtained by polymerization by adding to To.

  In a preferred embodiment, in the presence of a polymer obtained by polymerizing a mixture of methyl methacrylate, a copolymerizable monomer and a crosslinkable monomer, the polymer particle (B-2) is an alkyl acrylate, a copolymerizable monomer, and It has at least a three-layer structure obtained by polymerizing a monomer mixture comprising an alkyl (meth) acrylate and a copolymerizable monomer in the presence of a two-layer polymer obtained by polymerizing a mixture comprising a crosslinkable monomer. The polycarbonate resin composition according to any one of the above.

  In a preferred embodiment, the polymer particles (B-2) are (x) 30 to 100% by weight of butadiene monomer, 0 to 70% by weight of aromatic vinyl monomer, and other vinyl monomers 0 to 10 copolymerizable therewith. 40 to 90 parts by weight of a butadiene copolymer core obtained by polymerizing a monomer mixture containing 5% by weight and 0 to 5% by weight of a crosslinkable monomer, (y) 60 to 98% by weight of an aromatic vinyl monomer, and a hydroxy group Alternatively, 5 to 40 parts by weight of an inner shell formed by polymerizing a monomer mixture containing 2 to 40% by weight of an alkyl (meth) acrylate containing an alkoxy group and 0 to 20% by weight of another vinyl monomer copolymerizable therewith, (Z) 10 to 100% by weight of aromatic vinyl monomer, 0 to 90% by weight of alkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl group, and A core shell comprising 5 to 20 parts by weight of an outer shell formed by polymerizing a monomer mixture containing 0 to 50% by weight of another polymerizable vinyl monomer (100 parts by weight in total of (x), (y) and (z)) The polycarbonate resin composition according to any one of the above, which is a graft copolymer.

  A preferred embodiment contains 100 parts by weight of the polycarbonate resin (A), 0.1 to 50 parts by weight of the thickener (B), and 1 to 100 parts by weight of the thermoplastic resin (C) other than the polycarbonate resin. The present invention relates to a polycarbonate resin composition.

  A preferred embodiment relates to the polycarbonate resin composition described above, wherein the thermoplastic resin (C) other than the polycarbonate resin is a thermoplastic polyester resin, an ABS resin, or a polyolefin resin.

  2nd of this invention is related with the molded object obtained from the polycarbonate resin composition in any one of the said.

  A preferred embodiment relates to the above-mentioned molded product, which is obtained by injection molding.

  A preferred embodiment relates to the above-mentioned molded product, which is obtained by extrusion molding.

  A preferred embodiment relates to the above-mentioned molded product, which is obtained by blow molding.

  The polycarbonate resin composition of the present invention has an increased melt viscosity, enables stable processing in extrusion molding, injection molding and blow molding, and improves the transparency and gloss of the resulting molded product.

  Further, the thickener for polycarbonate resin used in the present invention has a low glass transition temperature because of its low molecular weight, for example, when produced by a suspension polymerization method. Although problems such as problems and deterioration of powder blocking properties are likely to occur, the surface is coated with polymer particles having an average particle diameter of 0.01 to 0.5 μm obtained by, for example, an emulsion polymerization method. Wearability can be greatly improved.

  In the present invention, 100 parts by weight of the polymer particles (B-1) having a glass transition temperature of 60 ° C. or higher and a volume average particle diameter of 50 to 500 μm are added to a polymer having a volume average particle diameter of 0.01 to 0.5 μm. It is characterized by using the thickener (B) coated with 0.5 to 30 parts by weight of the particles (B-2).

  The thickener (B) used in the present invention is excellent in physical properties that the polycarbonate resin originally has, for example, by blending 0.1 to 50 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). Without impairing the chemical characteristics, the melt viscosity at the time of melt processing in extrusion molding, injection molding, blow molding or the like can be drastically improved, and the expected effect can be remarkably exhibited.

  Although there is no restriction | limiting in particular as an aromatic vinyl monomer used for preparation of the polymer particle (B-1) in the thickener (B) of this invention, For example, styrene, (alpha) -methylstyrene, chlorostyrene etc. are illustrated. sell. These may be used alone or in combination of two or more. These are contained in the polymer particles (B-1) in an amount of 70 to 95% by weight, preferably 70 to 90% by weight, and more preferably 75 to 90% by weight, which stabilizes the melt viscosity of the polycarbonate resin. This is preferable from the viewpoint of improving the extrusion molding, injection molding, and blow molding to a possible level.

  The alkyl acrylate having 1 to 8 carbon atoms in the alkyl group used for the preparation of the polymer particles (B-1) is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2- Preferred examples include ethylhexyl acrylate, more preferably alkyl acrylates having 1 to 4 carbon atoms such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate, and particularly preferably 1 to 1 carbon atoms such as methyl acrylate and ethyl acrylate. An alkyl acrylate that is 2 may be exemplified. These may be used alone or in combination of two or more. These are contained in the polymer particles (B-1) in an amount of 5 to 30% by weight, preferably 10 to 30% by weight, and more preferably 10 to 25% by weight, thereby stabilizing the melt viscosity of the polycarbonate resin. This is preferable from the viewpoint of improving the extrusion molding, injection molding, and blow molding to a possible level.

  As a copolymerizable vinyl monomer used for the preparation of the polymer particles (B-1), an aromatic vinyl monomer, an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms, and the like can be used. Although not limited, for example, alkyl methacrylate and vinyl cyanide monomer can be exemplified. Examples of the alkyl methacrylate include alkyl methacrylates having 1 to 8 carbon atoms in the alkyl group such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more. These are contained in the polymer particles (B-1) in an amount of 0 to 10% by weight, preferably 0 to 8% by weight, and more preferably 0 to 5% by weight, which stabilizes the melt viscosity of the polycarbonate resin. This is preferable from the viewpoint that the extrusion molding, injection molding, and blow molding can be improved.

  As the monomer used for the production of the polymer particles (B-1) in the present invention, it is preferable to use a monomer that does not contain a functional group having reactivity with the polycarbonate resin (A), specifically, an epoxy group, an isocyanate. It is preferable to use a monomer that does not contain a reactive group such as a group, an oxazoline group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group, and an acid chloride group. When the polymer particles (B-1) are produced using the monomer having the reactive group, the surface of the resulting molded body is whitened, although the effect of thickening the melt viscosity of the polycarbonate resin composition is excellent. There is a case where transparency and gloss tend to decrease.

  The weight average molecular weight of the polymer particles (B-1) in the present invention is not particularly limited. From the point that the melt viscosity of the polycarbonate resin can be improved to a level at which stable extrusion molding, injection molding, and blow molding are possible. It is preferable that it is 10,000 to 4,000,000. More preferably, it is 10,000-2,500,000, More preferably, it is 10,000-400,000, Especially preferably, it is 10,000-300,000. The weight average molecular weight is obtained by, for example, dissolving a sample in tetrahydrofuran (THF) and using gel permeation chromatography (manufactured by WATERS, 510 type pump 410RI486UV) based on polystyrene as a soluble component. (Sample solution: sample 20 mg / THF 10 mL, measurement temperature: 25 ° C., detector: differential refraction system, injection amount: 1 mL).

  Although there is no limitation in particular about the refractive index of the polymer particle (B-1) in this invention, when aiming at maintaining the outstanding transparency of polycarbonate resin, it is the range of 1.56-1.59. It is preferable to adjust to. In addition, although the refractive index in this invention is a value measured with the Abbe refractometer at 20 degreeC, it can also calculate and obtain | require based on literature values (Polymer Handbook 4th edition, JOHN WILEY & SONS, etc.).

  Although the manufacturing method of the polymer particle (B-1) in this invention is not specifically limited, Manufacturing by a suspension polymerization method is especially preferable. Compared with the polymer particles produced by the emulsion polymerization method, the polymer particles produced by the suspension polymerization method can reduce ionic impurities remaining in the obtained polymer. The total amount of ionic impurities remaining in the adhesive (B) can be reduced. By reducing the amount of ionic impurities, hydrolysis of the polycarbonate resin is suppressed, and a decrease in melt viscosity can be suppressed.

  For example, when the polymer particles (B-1) are produced by a suspension polymerization method, the monomer mixture is mixed with an appropriate medium, a dispersion stabilizer, a polymerization initiator, and, if necessary, a chain transfer agent according to a known method. Etc. can be performed in the presence of. The medium used in the suspension polymerization method is usually water.

  As the dispersion stabilizer, known inorganic dispersants and organic dispersants can be used. Examples of inorganic dispersants include magnesium carbonate and tricalcium phosphate, and examples of organic dispersants include starch, gelatin, acrylamide, partially saponified polyvinyl alcohol, partially saponified polymethyl methacrylate, and polyacrylic acid. And natural salts such as cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyalkylene oxide, polyvinyl pyrrolidone, polyvinyl imidazole, sulfonated polystyrene, and synthetic polymer dispersants, as well as alkylbenzene sulfonates, fatty acid salts, etc. A low molecular dispersant or an emulsifier may be exemplified.

  The polymerization initiator is not particularly limited, and known oil-soluble polymerization initiators can be used. For example, ordinary organic peroxides, azo compounds, etc. may be used alone. Examples of preferable organic peroxides include benzoyl peroxide and lauroyl peroxide. Preferred examples of the azo compound include azobisisobutyronitrile, azobis (2-methylbutyronitrile), azobis-2,4-dimethylvaleronitrile, and the like.

  The chain transfer agent is not particularly limited, and examples thereof include alkyl mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, t-decyl mercaptan, n-decyl mercaptan, n-octyl mercaptan, and 2-ethylhexyl thioglycolate. Alkyl ester mercaptans and the like can be used. Of these, alkyl ester mercaptans such as 2-ethylhexyl thioglycolate are preferred because no odor is generated during molding.

  The temperature and time during the polymerization reaction are not particularly limited, and may be adjusted as appropriate according to the purpose.

  As a production method by suspension polymerization, a method in which a monomer or a monomer mixture is suspended in water and then a polymerization reaction is started, or a part of the monomer or monomer mixture is suspended in water. Start the polymerization reaction by turbidity, and with the progress of the polymerization reaction, the remaining monomer or monomer mixture aqueous suspension is added to the polymerization reactor in one or several stages or continuously. A known method such as a method for carrying out the polymerization reaction can be used.

  In the present invention, the polymer particles (B-1) preferably have a volume average particle diameter in the range of 50 to 500 μm. When the volume average particle diameter is smaller than 50 μm, (B-2) per unit volume of (B-1) required for coating the polymer particles (B-1) with the polymer particles (B-2) The amount tends to increase too much, which is disadvantageous from the viewpoint of ionic impurities, the filterability deteriorates during dehydration after polymerization, and the moisture content in the resin after dehydration increases and the drying efficiency decreases. is there. Conversely, when the volume average particle diameter is larger than 500 μm, it tends to be difficult to control the weight average molecular weight of the polymer particles. For example, the volume average particle diameter of the polymer particles obtained by suspension polymerization can be measured using, for example, a particle size analyzer Microtrac FRA manufactured by Nikkiso Co., Ltd.

  In the present invention, the polymer particles (B-1) preferably have a glass transition temperature of 60 ° C. or higher, more preferably 70 ° C. or higher, from the viewpoints of heat-fusibility and powder blocking properties in the drying step and the like. More preferably. The glass transition temperature can be determined by, for example, a differential scanning calorimetry method.

  In the present invention, it is possible to coat the obtained polymer particles (B-1) with polymer particles (B-2) separately produced by, for example, emulsion polymerization or the like of the thickener (B) in the present invention. This is an essential condition for improving the powder blocking property. The Vicat softening temperature of the polymer particles (B-2) is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, particularly 90 ° C. or higher, from the viewpoint of improving powder blocking properties. The Vicat softening temperature means a temperature at which a plastic specimen is subjected to a load and heated at a constant speed and the specimen starts to deform. For example, JIS K-7206, A50 method (test load 10 N, The initial temperature is 50 ° C. and the heating rate is 50 ° C./hr).

  Below, the polymer particle (B-2) for coat | covering the polymer particle (B-1) in the thickener (B) used by this invention is demonstrated. The polymer particles (B-2) are not particularly limited as long as the volume average particle diameter is in the range of 0.01 to 0.5 μm, but among them, those that are widely used as quality improvers for polycarbonate resins, Even when recovered as the thickener (B) of the present invention, it is possible from the viewpoint that various quality improvement effects possessed by them can be expressed and productivity can be improved. Specifically, an emulsion polymer obtained by emulsion polymerization of a vinyl monomer is preferable.

  Examples of the polymer particles (B-2) include (1) 50 to 95% by weight of methyl methacrylate, 5 to 50% by weight of alkyl methacrylate having an alkyl group having 2 to 8 carbon atoms, and vinyl copolymerizable therewith. 60 to 95 parts by weight of a mixture of 0 to 20% by weight of monomers and one or more monomers 20 selected from alkyl methacrylates excluding alkyl acrylate and methyl methacrylate in the presence of the resulting polymer latex -80 wt%, methyl methacrylate 20-80 wt%, and a mixture of vinyl monomers 0-20 wt% copolymerizable therewith, 5-40 parts by weight, so that the total amount is 100 parts by weight, An emulsion polymer obtained by polymerization, (2) a mixture comprising methyl methacrylate, a copolymerizable monomer and a crosslinkable monomer; In the presence of a two-layer polymer obtained by polymerizing a mixture of an alkyl acrylate, a copolymerizable monomer, and a crosslinkable monomer in the presence of the polymer formed by the polymerization, further alkyl (meth) An emulsion polymer having at least a three-layer structure obtained by polymerizing a monomer mixture comprising an acrylate and a copolymerizable monomer, (3) (x) 30-100% by weight of butadiene, aromatic vinyl monomer 0 Butadiene copolymer core 40 obtained by polymerizing a monomer mixture containing ˜70 wt%, copolymerizable vinyl monomer 0-10 wt%, and crosslinkable monomer 0-5 wt% -90 parts by weight, (y) 60-98% by weight of an aromatic vinyl monomer, 2-40% by weight of an alkyl (meth) acrylate containing a hydroxy group or an alkoxy group, and a vinyl monomer copolymerizable therewith 0-20 5 to 40 parts by weight of an inner shell formed by polymerizing a monomer mixture containing 2% by weight, (z) 10 to 100% by weight of an aromatic vinyl monomer, and an alkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl group 5 to 20 parts by weight of an outer shell formed by polymerizing a monomer mixture containing 0 to 90% by weight and 0 to 50% by weight of a vinyl monomer copolymerizable therewith [(x), (y), ( An emulsion polymer which is a core-shell type graft copolymer consisting of 100 parts by weight of z) and the like can be preferably used. The general method for producing the emulsion polymer described in the above (1) to (3) is described in detail in, for example, JP-A-2-269755, but is not limited thereto.

  The volume average particle diameter of the polymer particles (B-2) is preferably in a range of volume average particle diameter of 0.01 to 0.5 μm, more preferably in a range of 0.05 to 0.5 μm from the viewpoint of coating efficiency. . The volume average particle diameter of the polymer particles (B-2) can be measured, for example, using light scattering at a wavelength of 546 nm using a U-2000 spectrophotometer manufactured by Hitachi.

  Although there is no restriction | limiting in particular about the manufacturing method of the thickener (B) used by this invention, For example, suspension of the polymer particle (B-1) with a volume average particle diameter manufactured by suspension polymerization of 50-500 micrometers The liquid and a latex of polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm produced by emulsion polymerization are mixed, and an aqueous electrolyte solution is brought into contact with the mixture, whereby polymer particles ( B-1) can be efficiently coated with the polymer particles (B-2). Here, the term “coating” refers to covering the surface of the polymer particles with another polymer particle. For example, by coating softer polymer particles with harder polymer particles, adhesion or powder in the dryer can be achieved. Fusion between each other can be prevented.

  Regarding a method of mixing a suspension of polymer particles (B-1) having a volume average particle size of 50 to 500 μm and latex of polymer particles (B-2) having a volume average particle size of 0.01 to 0.5 μm Although there is no particular limitation, the latex of the polymer particles (B-2) is added while stirring the suspension of the polymer particles (B-1), or the latex of the polymer particles (B-2) is stirred. It is preferable to carry out by adding a suspension of polymer particles (B-1). The solid content concentration of the latex of the polymer particles (B-2) and the suspension of the polymer particles (B-1) at the time of mixing is not particularly limited, but the polymer latex obtained by a normal polymerization operation or It is most convenient in production to use the polymer suspension as it is. Usually, it is preferably 25 to 45% by weight for a polymer latex obtained by an emulsion polymerization method and 33 to 45% by weight for a polymer suspension obtained by a suspension polymerization method. The temperature at the time of mixing is preferably 5 ° C. or higher in consideration of the utility usage of the subsequent heat treatment operation.

  Next, in producing the thickener (B) used in the present invention, as described above, an electrolyte is added to the mixture of the polymer particle (B-1) suspension and the polymer particle (B-2) latex. The contact of the aqueous solution will be described. The contact with the aqueous electrolyte solution is preferably carried out by adding the aqueous electrolyte solution to the mixture of the polymer suspension and the polymer latex with stirring. By this operation, for example, the polymer fine particles formed as a by-product when the polymer particles (B-1) are produced by the suspension polymerization method are polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm. ) And the surface of the polymer particles (B-1) having a volume average particle diameter of 50 to 500 μm can be coagulated. As a result, for example, polymer fine particles (fine powder) generated in the suspension polymerization method and the like can be removed, so that problems with deterioration of solid-liquid separation during dehydration and outflow of polymer fine particles (fine powder) into dewatered wastewater can be solved. Can be improved.

  The electrolyte aqueous solution is not particularly limited, and may be an aqueous solution of an organic acid (or a salt thereof) or an inorganic acid (or a salt thereof) having a property capable of coagulating or coagulating a polymer latex. Sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, potassium iodide, sodium iodide, potassium sulfate, sodium sulfate, ammonium sulfate, ammonium chloride, sodium nitrate, potassium nitrate, calcium chloride , Aqueous solutions of inorganic salts such as ferrous sulfate, magnesium sulfate, zinc sulfate, copper sulfate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulfate, aluminum sulfate, potassium alum, iron alum , Aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, Organic acids and their aqueous solutions such as acid, sodium acetate, calcium acetate, sodium formate, aqueous solution of organic acid salts such as calcium formate can be used alone or in combination of two or more. In particular, sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, ferrous chloride, aluminum sulfate, potassium alum, iron alum, hydrochloric acid, sulfuric acid, nitric acid, acetic acid aqueous solution It can be used suitably.

  The concentration of the aqueous electrolyte solution is not limited, but is usually 0.001% by weight or more, preferably 0.1% by weight or more, and more preferably 1% by weight or more. When the concentration of the aqueous electrolyte solution is 0.001% by weight or less, it is necessary to add a large amount of the aqueous electrolyte solution in order to coagulate the polymer particles, and the amount of utility used during the subsequent heat treatment operation may increase. .

  The addition of the aqueous electrolyte solution to the mixture of the suspension of the polymer particles (B-1) and the latex of the polymer particles (B-2) is performed at a temperature lower than the Vicat softening temperature of the polymer particles (B-2). It is preferable to do this. When the temperature of the mixture at the time of adding the aqueous electrolyte solution exceeds the Vicat softening temperature of the polymer particles (B-2), for example, the shape of the thickener (B) to be produced becomes distorted and the water content after dehydration is high. There may be a problem that the polymer particles (B-2) that are not yet solidified are increased and the solid-liquid separation property is deteriorated, or the aggregation between the thickeners (B) frequently occurs.

  When the electrolyte aqueous solution is added to the mixture of the suspension of polymer particles (B-1) and the latex of polymer particles (B-2), the solid content concentration of the mixture is adjusted to 20 to 50% by weight. It is preferable to carry out. When the solid content concentration is less than 20% by weight, polymer fine particles may remain in the system even after addition of the aqueous electrolyte solution. On the other hand, when the solid content concentration is higher than 50% by weight, polymer particles ( Secondary aggregated particles may be generated via B-2), and the water content after dehydration tends to increase.

  The solid content weight ratio of the polymer particles (B-1) and the polymer particles (B-2) in the thickener (B) used in the present invention is preferably 100 parts by weight of the polymer particles (B-1). On the other hand, the polymer particles (B-2) are 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, particularly preferably 3 to 10 parts by weight. . When the polymer particles (B-2) are less than 0.5 parts by weight with respect to 100 parts by weight of the polymer particles (B-1), the polymer fine particles remain in the system even after addition of the aqueous electrolyte solution. Solid-liquid separability tends to deteriorate, and when the resulting thickener (B) is dried, it tends to increase adhesion to the inner wall surface of the dryer, which is not preferable. Moreover, when the polymer particles (B-2) exceed 30 parts by weight with respect to 100 parts by weight of the polymer particles (B-1), secondary aggregated particles via the polymer particles (B-2) Since it tends to be generated and the amount of the remaining emulsifier tends to increase, hydrolysis of the polycarbonate resin tends to be promoted, and the thickening effect tends to decrease.

  In producing the thickener (B) used in the present invention, polymer particles (B-2) in a mixture of a suspension of polymer particles (B-1) and a latex of polymer particles (B-2). When the ratio of the latex is high, the addition rate of the aqueous electrolyte solution is extremely high, or the concentration of the aqueous electrolyte solution is extremely high, a significant increase in viscosity may be observed when the aqueous electrolyte solution is added. In such a case, an operation for reducing the viscosity of the system to such an extent that a normal stirring state can be maintained, such as adding water appropriately to the system, may be performed. The amount of the aqueous electrolyte solution varies depending on the ratio of the polymer particles (B-2) in the mixture of the suspension of polymer particles (B-1) and the latex of the polymer particles (B-2). What is necessary is just to add more than the quantity from which an uncoagulated polymer particle (B-2) does not exist.

  For example, when the electrolyte aqueous solution is an acidic aqueous solution and the suspension after granulation is acidic, after neutralizing with an alkali such as sodium hydroxide, and when the electrolyte aqueous solution is a neutral aqueous solution, Heat treatment is preferably performed at 50 to 120 ° C. Thereby, the aggregate of the polymer particle (B-2) covering the surface of the polymer particle (B-1) is densified, and the moisture content of the resulting thickener (B) can be reduced.

  Then, the thickener (B) in this invention can be obtained by performing dehydration and drying by a normal method.

  Although the compounding ratio of the polycarbonate resin (A) and the thickener (B) in the polycarbonate resin composition of the present invention can be widely adopted as necessary, the thickener is preferably based on 100 parts by weight of the polycarbonate resin (A). (B) 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight of thickener (B), more preferably 0.5 to 10 parts by weight, still more preferably 0.5 to 7 parts by weight Part. If the blending amount of the thickener (B) is less than 0.1 parts by weight, the melt viscosity cannot be increased sufficiently and stable workability may not be realized. On the other hand, if it exceeds 50 parts by weight, the melt viscosity Is too high, the resulting molded product may shrink, or its gloss and transparency may be lost.

  The polycarbonate resin (A) used in the present invention is not particularly limited as long as it is used for molding. Specific examples thereof include aromatic polycarbonate resins, aliphatic polycarbonate resins, and aliphatic-aromatics. An aromatic polycarbonate resin is preferably used among them. The aromatic polycarbonate resin is generally produced by reacting an aromatic dihydroxy compound and a carbonate precursor.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2- (4-hydroxy-3,5-dimethylphenyl) propane, Bisphenols such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) ether, bis Dihydric phenol ethers such as (3,5-dichloro-4-hydroxyphenyl) ether, dihydroxydiphenyls such as p, p′-dihydroxydiphenyl, 3,3′-dichloro-4,4′-dihydroxydiphenyl, bis (4-Hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxypheny) ) Substitution with dihydroxyarylsulfones such as sulfone, dihydroxybenzenes such as resorcinol and hydroquinone, halogens or alkyl groups such as 1,4-dihydroxy-2,5-dichlorobenzene and 1,4-dihydroxy-3-methylbenzene Dihydroxybenzenes, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyl sulfides such as bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, and dihydroxydiphenyl sulfoxide Examples of such compounds include side compounds, and these may be used alone or in combination of two or more. Among these, 2,2-bis (4-hydroxyphenyl) propane can be preferably used.

  Examples of the carbonate precursor include carbonyl halides typified by phosgene, carbonyl esters typified by diphenyl carbonate, or haloholates, and these can be used alone or in combination of two or more. .

  The polycarbonate resin used in the present invention may be partially branched, for example, a thermoplastic random branched polycarbonate resin obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor, Furthermore, a mixture of a linear polycarbonate resin and a branched polycarbonate resin may be used.

  Examples of the polyfunctional aromatic compound include 1,1,1-tri (4-hydroxyphenyl) ethane, trimellitic anhydride, trimellitic acid, trimellitoyl trichloride, and 4-chloroformylphthalic anhydride. , Pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic acid anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic acid anhydride, etc., which are used alone or in combination of two or more. It is done.

  In this invention, thermoplastic resins (C) other than polycarbonate resin can be contained with respect to the composition containing polycarbonate resin (A) and a thickener (B).

  Examples of the thermoplastic resin (C) other than the polycarbonate resin used in the present invention include thermoplastic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, poly (1,4-cyclohexanedimethylene terephthalate), ABS resin ( And so-called acrylonitrile-butadiene-styrene resin), polyolefin resins such as polyethylene and polypropylene, and the like.

  The blending amount of the thermoplastic resin (C) other than the polycarbonate resin is not particularly limited, but is preferably contained in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). 30-100 weight part is more preferable.

  There is no limitation in particular as a method of manufacturing the resin composition of this invention, A well-known method is employable. For example, after a polycarbonate resin (A), a thickener (B) and, if necessary, a thermoplastic resin (C) other than the polycarbonate resin are mixed in advance using a Henschel mixer, a tumbler, etc., a single screw extruder, twin screw A method of obtaining a resin composition by melt kneading using an extruder, a Banbury mixer, a heating roll, or the like can be employed.

  Furthermore, for example, a high-concentration master batch in which the thickener (B) is mixed in a range exceeding 50 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A) is manufactured in advance, The master batch may be mixed with a polycarbonate resin and diluted so that the thickener (B) is added in a desired amount in the range of 0.1 to 50 parts by weight.

  In the polycarbonate resin composition of the present invention, if necessary, a compatibilizer, a flame retardant, an impact resistance enhancer, a spreading agent, a lubricant, a plasticizer, a colorant, a filler, a foaming agent, an antibacterial / antifungal agent Other additives such as may be added alone or in combination of two or more.

  A method for obtaining a molded body from the polycarbonate resin composition of the present invention is not particularly limited, and a generally used molding method can be applied. For example, an extrusion molding method, an injection molding method, a blow molding method and the like are preferable. Applicable. According to the present invention, at the time of melt processing, stable processability is exhibited even in an extrusion molding method or a blow molding method that requires a higher melt viscosity, and transparency and gloss are good and excellent in impact resistance. A molded product can be obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to these. In the following, “part” means “part by weight”. Styrene is ST, methyl acrylate is MA, butyl acrylate is BA, methyl methacrylate is MMA, allyl methacrylate is ALMA, potassium persulfate is KPS, 2-ethylhexyl thioglycolate is abbreviated as 2EHTG, lauroyl peroxide is abbreviated as LPO. There is a case.

  The evaluation methods used in the following examples and comparative examples are summarized below.

(Measurement of polymerization conversion)
The polymerization conversion was calculated by the following formula.
Polymerization conversion rate (%) = (polymer production amount / monomer charge amount) × 100

(Measurement of weight average molecular weight)
The weight average molecular weight of the polymer particles is obtained by dissolving a sample in tetrahydrofuran (THF), and using a gel permeation chromatography (manufactured by WATERS, 510 type pump 410RI486UV) based on polystyrene as a soluble component. (Sample solution: sample 20 mg / THF 10 mL, measurement temperature: 25 ° C., detector: differential refraction system, injection amount: 1 mL).

(Measurement of refractive index)
The refractive index of the polymer sample is a value at 20 ° C., and was determined using an Abbe refractometer 2T manufactured by Atago Co., Ltd.

(Measurement of volume average particle diameter of polymer particles)
The volume average particle size of the polymer particles of 50 to 500 μm was measured using a particle size analyzer (Microtrac FRA) manufactured by Nikkiso Co., Ltd.

(Measurement of volume average particle diameter of polymer particles)
The volume average particle diameter of the polymer particles of 0.01 to 0.5 μm was measured using light scattering at a wavelength of 546 nm using a Hitachi U-2000 spectrophotometer.

(Measurement of glass transition temperature)
The glass transition temperature of the polymer particles was determined by differential scanning calorimetry (temperature increase rate: 10 ° C./min) after the sample was heated to 100 ° C. and melt quenched.

(Measurement of Vicat softening temperature)
The Vicat softening temperature of the polymer particles was determined by JIS K-7206, A50 method (test load 10 N, heating rate 50 ° C./hr).

(Pellet production conditions)
A mixture of 100 parts of polycarbonate resin (Iupilon S-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 5 parts of a thickener sample dried at 80 ° C. for 5 hours was mixed with a 44 mm twin-screw extruder (TEX44) manufactured by Nippon Steel. Was melt-kneaded under the following conditions (molding temperature, screw rotation speed, discharge amount, die diameter) to produce pellets.
Cylinder temperature: C1 = 240 ° C., C2 = 250 ° C., C3 = 250 ° C., C4 = 260 ° C., C5 = 270 ° C., C6 = 270 ° C., Die = 280 ° C.
Screw rotation speed: 100rpm
Discharge rate: 20kg / hr
Die diameter: 3mmφ

(Injection molding conditions)
The pellet produced by the method as described above was injection molded under the following conditions using a 160MSP injection molding machine manufactured by Mitsubishi Heavy Industries, Ltd. to obtain a molded article for evaluating physical properties.
Cylinder temperature: C1 = 280 ° C., C2 = 280 ° C., C3 = 280 ° C., nozzle = 280 ° C., mold = 80 ° C.

(Evaluation of melt viscosity)
The melt flow index (hereinafter abbreviated as MFI) of the above pellets was used as an index of melt viscosity. A smaller MFI indicates a higher melt viscosity. The MFI of the above pellets was measured using a melt indexer (P-101, manufactured by Toyo Seiki Co., Ltd.) under conditions of cylinder temperature: 280 ° C. and load: 2.16 kg.

(Evaluation of heat fusion of powder)
A 0.5 g thick sample powder was spread thinly on the bottom of a 3 cm diameter aluminum container, and the temperature at which the powder melted and adhered to the metal wall surface when heated in an oven for 1 hour was measured and compared.

(Evaluation of gloss on the surface of the molded product)
The gloss of the surface of the molded body was measured using a gloss meter (manufactured by Gardner, Micro Gloss 60 °) on the surface of the flat molded body obtained by the extrusion molding.

(Transparency evaluation)
For the total light transmittance and haze value, a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., Σ80-VG-1D) was used, using a 7.5 cm × 5 cm × 2 mm plate-shaped molded body obtained by the extrusion molding. And measured according to ASTM-D-1003. It shows that transparency is so good that the number of total light transmittance is large and the haze value is small.

(Synthesis example)
Synthesis Example 1 of Suspension of Polymer Particles (B-1) for Production of Thickener (B) in the Present Invention, Polymer Particles Used for Coating the Polymer Particles (B-1) ( Synthetic examples 2, 3 and 4 of latex of B-2), Synthetic example 5 of thickener (B) in which polymer particles (B-2) are coated on the surface of polymer particles (B-1), polycarbonate resin Synthesis Example 6 of the thickener for emulsion by emulsion polymerization is shown below.

(Synthesis Example 1) Preparation of Suspension of Polymer Particles (B-1) In a reactor equipped with a stirrer and a cooler, 200 parts of distilled water, 0.6 part of tribasic calcium phosphate, 0.005 sodium α-olefin sulfonate Department was put in. Next, after the inside of the vessel was replaced with nitrogen, the reactor was heated to 40 ° C. while stirring. Next, 1.0 part of LPO was added and stirred for 15 minutes, and then a monomer mixture of ST89 part, MA part 9 and MMA part 2 was added, and the rotation speed of the stirrer was adjusted so that the dispersed particle size of the monomer was about 200 μm Adjusted. Thereafter, the temperature of the reaction vessel was raised to 60 ° C., polymerization was performed for 3 hours, the temperature was further raised to 80 ° C. and stirred for 2 hours to complete the polymerization, and a polymer suspension having a polymer solid content concentration of 35% by weight was obtained. Got. The polymerization conversion was 99.9%, and the volume average particle size was 195 μm. The suspension polymer particles had a glass transition temperature of 76 ° C. and a weight average molecular weight of 205,000.

(Synthesis example 2) Preparation of latex of polymer particles (B-2) 220 parts of distilled water, 0.3 part of boric acid, 0.03 part of sodium carbonate, N-lauroylsarcosine acid in a reactor equipped with a stirrer and a cooler 0.09 part of sodium, 0.09 part of sodium formaldehydesulfoxylate, 0.006 part of sodium ethylenediaminetetraacetate and 0.002 part of ferrous sulfate heptahydrate were charged, and the temperature was raised to 80 ° C. after nitrogen substitution. . 25% by weight of a monomer mixture consisting of 25 parts of MMA, 0.1 part of ALMA and 0.1 part of t-butyl hydroperoxide was charged all at once, and polymerization was carried out for 45 minutes. Subsequently, the remaining 75% by weight of the mixture was continuously added over 1 hour. After completion of the addition, the polymerization was completed by maintaining at the same temperature for 2 hours. During this period, 0.2 part of sodium N-lauroyl sarcosinate was added. The volume average particle diameter of the polymer particles in the obtained innermost layer crosslinked methacrylic polymer latex was 0.16 μm, and the polymerization conversion rate was 98.0%. Subsequently, the obtained crosslinked methacrylic polymer latex was kept at 80 ° C. in a nitrogen stream, and after adding 0.1 part of potassium persulfate, a monomer mixture of 41 parts of BA, 9 parts of ST and 1 part of ALMA was added to 5 parts. Added continuously over time. During this time, 0.1 part of potassium oleate was added in three portions. After completion of the addition of the monomer mixture, 0.05 part of potassium persulfate was further added and held for 2 hours in order to complete the polymerization. The resulting rubbery polymer had a volume average particle size of 0.23 μm and a polymerization conversion rate of 99.0%. Subsequently, the rubbery polymer latex obtained was kept at 80 ° C., 0.02 part of potassium persulfate was added, and then a mixed solution of 24 parts of MMA, 1 part of BA and 0.1 part of t-dodecyl mercaptan was added for 1 hour. Added continuously. After completion of the addition of the monomer mixture, the mixture was held for 1 hour to obtain an emulsion polymerization graft copolymer latex (X) having a multilayer structure with a volume average particle size of 0.25 μm. The Vicat softening temperature of the emulsion polymerization graft copolymer latex (X) was 88 ° C.

Synthesis Example 3 Preparation of Latex of Polymer Particles (B-2) A reactor equipped with a stirrer and a cooler was charged with 200 parts of distilled water, 1 part of sodium dioctylsulfosuccinate, and 0.03 part of potassium persulfate, and nitrogen. After the replacement, the temperature was raised to 65 ° C. A monomer mixture consisting of 84 parts of MMA and 16 parts of BA was added to this over 4 hours, followed by heating and stirring for 1 hour to complete the polymerization reaction. Thereafter, a monomer mixture consisting of 11 parts of BA and 9 parts of MMA was added over 1 hour, followed by further polymerization for 1.5 hours at 65 ° C., a volume average particle size of 0.08 μm, and a Vicat softening temperature of 93 ° C. An emulsion polymer latex (Y) was obtained.

(Synthesis example 4) Preparation of latex of polymer particles (B-2) In a reactor equipped with a stirrer and a cooler, 200 parts of distilled water, 1.5 parts of sodium oleate, 0.002 part of ferrous sulfate, ethylenediamine tetra 0.005 part of sodium acetate, 0.2 part of sodium formaldehyde sulfoxylate, 0.2 part of tricalcium phosphate, 76 parts of butadiene, 24 parts of styrene, 1.0 part of divinylbenzene and 0.1 part of diisopropylbenzene hydroperoxide Was polymerized at 50 ° C. for 15 hours to prepare a rubber latex (a) having a polymerization conversion rate of 99% and a volume average particle size of 0.07 μm. 180 parts of the rubber latex (a) (solid content 60 parts), 200 parts of distilled water, 0.002 part of ferrous sulfate, 0.004 part of sodium ethylenediaminetetraacetate and 0.1 part of sodium formaldehydesulfoxylate are mixed. At 60 ° C., a mixed solution of 30 parts of styrene, 3 parts of hydroxyethyl methacrylate and 0.2 part of cumene hydroperoxide was continuously added to prepare an inner layer shell. After completion of inner shell polymerization, a mixture of 5 parts of styrene, 2 parts of methyl methacrylate and 0.2 part of cumene hydroperoxide was added continuously at 60 ° C. to prepare an outer shell, volume average particle diameter was 0.16 μm, Vicat An emulsion polymerization graft copolymer latex (Z) having a softening temperature of 81 ° C. was prepared.

(Synthesis Example 5) Thickener (B): Preparation of Coated Polymer Sample 300 parts (100 parts solids) of the polymer suspension obtained in Synthesis Example 1 were adjusted to 80 ° C. and then stirred. The emulsion polymerization graft copolymer latex (X) obtained in Synthesis Example 2 was added dropwise in the order of 16 parts (solid content 5 parts) and 2 parts of a 15 wt% aqueous sodium sulfate solution. Then, it heated up to 95 degreeC under stirring and implemented heat processing operation.

  Filtration was performed using a centrifugal dehydrator, and the resulting polymer particles were washed with water and dried at 50 ° C. for 1 hour using a fluid dryer to obtain a thickener sample (1) in the form of a white powder.

Synthesis Example 6 Preparation of Thickener by Emulsion Polymerization 200 parts of distilled water and 0.5 part of dioctyl sulfosuccinate soda were placed in a reactor equipped with a stirrer and a cooler. Next, after the inside of the vessel was replaced with nitrogen, the temperature of the reactor was raised to 70 ° C. while stirring. Next, 0.2 part of potassium persulfate was added and stirred for 15 minutes, and then a mixture of ST89 part, 9 parts of MA, 2 parts of MMA, and 0.7 part of 2EHTG was continuously added over 4 hours. After completion of the addition, the mixture was further stirred for 1 hour and then cooled to obtain an emulsion polymer latex. The polymerization conversion rate was 99.7%. The obtained emulsion polymer latex was salted out and coagulated with an aqueous calcium chloride solution, heated to 90 ° C., and filtered using a centrifugal dehydrator. The resulting emulsion polymer dehydrated cake was washed with water and parallel. A thickener sample (14) having a weight average molecular weight of 52,000 and a volume average particle size of 0.08 μm was obtained by drying for 15 hours at 50 ° C. using a flow dryer.

Example 1
3 parts of the thickener sample (1) obtained in Synthesis Example 5 was blended in 100 parts of the polycarbonate resin, and MFI, the surface gloss of the molded article, and transparency were evaluated according to the above-described methods. The results are shown in Table 1.

(Examples 2 and 3 and Comparative Examples 1 to 3)
As shown in Table 1, as the thickener (B), the weight average molecular weight of the polymer particles (B-1) was adjusted to about 200,000 with the addition amount of LPO as a polymerization initiator being 1.0 part. Thickener samples (2) to (6) were obtained in the same manner as in Synthesis Example 5 except that the polymer particles (B-1) were produced by changing the composition ratio of the monomers. 3 parts of the obtained thickener sample was blended in 100 parts of polycarbonate resin, and MFI, surface gloss of the molded product, and transparency were evaluated in the same manner as in Example 1. The results are shown in Table 1.

  From the results of Table 1, in Examples 1 to 3 in which the composition ratio of the polymer particles (B-1) is within the preferable range of the present invention, the composition has good MFI, surface gloss of the molded product, and transparency. It can be seen that In Comparative Examples 1 to 3 in which the monomer composition ratio is out of the scope of the present invention, it can be seen that the balance between MFI, the surface gloss of the molded article and transparency is inferior to the others.

(Examples 4 to 8)
As the thickener (B), the addition amount of LPO which is a polymerization initiator and the addition amount of 2EHTG which is a chain transfer agent are changed as shown in Table 2, and the weight average molecular weight is about 50,000 to 3 million. Thickener samples (7) to (11) were obtained by the same method as in Synthesis Example 5 except that the polymer particles (B-1) were prepared by adjusting. 3 parts of the obtained thickener sample was blended with 100 parts of a polycarbonate resin, and MFI, the surface gloss of the molded product and the transparency were evaluated in the same manner as in Example 1. The results are shown in Table 2.

  From the results in Table 2, it can be seen that in Examples 1 and 4 to 8, compositions having a good balance of MFI, surface gloss of the molded article, and transparency can be obtained. Moreover, the tendency for molding processability to become favorable was seen, so that the value of a weight average molecular weight was small.

(Example 9 and Comparative Example 4)
Thickener samples (12) and (13) were obtained by the same method as in Synthesis Example 5 except that the glass transition temperature of the polymer particles (B-1) was changed as shown in Table 3. Using the resulting thickener sample, MFI and heat-fusibility were evaluated in the same manner as in Example 4. The results are shown in Table 3.

  From the results of Table 3, as in Examples 4 and 9, when the glass transition temperature of the polymer particles (B-1) is within the scope of the present invention, good moldability and heat fusion of the powder. It can be seen that On the other hand, when the thickener sample (13) in which the glass transition temperature of the polymer particles (B-1) is lower than the range of the present invention is used as in Comparative Example 4, the MFI is good, but the powder It can be seen that the heat-fusibility of the is reduced.

(Examples 10 to 12 and Comparative Example 5)
The same polymer particles (B-1) as those used in Synthesis Example 1 were used, and the polymer particles (B-2) covering the surfaces of the polymer particles (B-1) as shown in Table 4 MFI and heat when the thickener sample was prepared by changing the type of the thickener, and when the thickener sample (14) prepared by emulsion polymerization as shown in Synthesis Example 6 was used as the thickener component Evaluation of fusing property was performed by the same method as in Example 4. The results are shown in Table 4.

  From the results of Table 4, as in Examples 10 to 12, when the type of polymer particles (B-2) covering the polymer particles (B-1) is within the preferred range of the present invention, it is good. It can be seen that the MFI and the powder have heat fusion properties. On the other hand, when the thickener sample (14) prepared by emulsion polymerization of the thickener component as in Comparative Example 5 is used, the MFI is further deteriorated compared to Comparative Example 1, and the heat-fusibility is also reduced. I understand that. This further deterioration of MFI is thought to be due to hydrolysis of the polycarbonate resin. Moreover, when the surface is not coat | covered, it turns out that the heat-fusion property of powder falls.

(Examples 13 to 18 and Comparative Examples 6 to 8)
Using the same resin as that used in Example 4 as a sample in which a polycarbonate resin was used and the thickener component was prepared by suspension polymerization, the surfaces of the polymer particles (B-1) as shown in Table 5 were used. Evaluation of MFI and heat-fusibility when the amount of the polymer particles (B-2) to be coated was changed was carried out in the same manner as in Example 4. The results are shown in Table 5.

  From the results of Table 5, as in Examples 13 to 18, the amount of the polymer particles (B-2) covering the surface of the polymer particles (B-1) which is a component of the thickener (B) is When it is within the scope of the invention, it can be seen that good MFI and powder heat fusibility are exhibited. On the other hand, when the amount of the polymer particles (B-2) to be coated is small outside the scope of the present invention as in Comparative Examples 6 and 7, it can be seen that the heat fusion property of the powder is lowered. Moreover, it turns out that MFI falls when the quantity of the polymer particle (B-2) to coat | cover is large exceeding the range of this invention like the comparative example 8. This decrease in MFI is believed to be due to hydrolysis of the polycarbonate resin.

(Examples 19 to 22, Comparative Examples 9, 10 and Reference Example 1)
The thickener sample (1) obtained in Synthesis Example 5 was blended with a polycarbonate resin at the blending ratio shown in Table 6, and MFI, surface gloss and transparency of the molded product were evaluated in the same manner as in Example 1. Went. The results are shown in Table 6.

  From the results of Table 6, it can be seen that in Examples 19 to 22 in which the blending ratio of the thickener sample is within the range of the present invention, a composition having good MFI, molded product surface gloss and transparency can be obtained. . On the other hand, in Comparative Example 9 where the blending ratio of the thickener sample is less than the range of the present invention, sufficient MFI cannot be obtained, and a sample capable of evaluating the surface gloss and transparency of the molded product cannot be obtained. It was. Moreover, it turns out that the surface gloss and transparency of a molded object deteriorate in the comparative example 10 with more compounding ratios of a thickener sample than the range of this invention. As Reference Example 1, evaluation was also performed when no thickener sample was added.

(Examples 23 to 26 and Reference Example 2)
MFI and molded product when 100 parts of polycarbonate resin and 100 parts of polybutylene terephthalate resin (Mitsubishi Chemical Co., Ltd., Novador 5010) are blended with the thickener sample (1) at the blending ratio shown in Table 7. The surface property was evaluated. The results are shown in Table 7.

  From the results of Table 7, it can be seen that in Examples 23 to 26 in which the blending amount of the thickener sample is within the preferable range of the present invention, a composition having good MFI and molded product surface gloss can be obtained. As Reference Example 2, evaluation was also performed when no thickener sample was added.

Claims (17)

  With respect to 100 parts by weight of the polycarbonate resin (A), 100 parts by weight of the polymer particles (B-1) having a glass transition temperature of 60 ° C. or higher and a volume average particle diameter of 50 to 500 μm is 0.01 to A polycarbonate resin composition containing 0.1 to 50 parts by weight of a thickener (B) coated with 0.5 to 30 parts by weight of 0.5 μm polymer particles (B-2), wherein the polymer particles (B-1) includes (a) 70 to 95% by weight of an aromatic vinyl monomer, (b) 5 to 30% by weight of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and (c) A polycarbonate resin composition obtained by polymerizing 0 to 10% by weight of another polymerizable vinyl monomer (100% by weight in combination of (a), (b) and (c)).   The monomer constituting the polymer particle (B-1) is a monomer that does not contain an epoxy group, an isocyanate group, an oxazoline group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group, and an acid chloride group. The polycarbonate resin composition according to claim 1, wherein:   The polycarbonate resin composition according to claim 1 or 2, wherein the alkyl acrylate (b) constituting the polymer particles (B-1) is an alkyl acrylate having an alkyl group having 1 to 4 carbon atoms. object.   The polycarbonate resin composition according to claim 1 or 2, wherein the alkyl acrylate (b) constituting the polymer particles (B-1) is an alkyl acrylate having an alkyl group having 1 to 2 carbon atoms. object.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polymer particles (B-1) have a weight average molecular weight of 10,000 to 4,000,000.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polymer particles (B-1) have a weight average molecular weight of 10,000 to 400,000.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polymer particles (B-1) have a refractive index of 1.56 to 1.59.   The polycarbonate resin composition according to any one of claims 1 to 7, wherein the polymer particles (B-2) have a Vicat softening temperature of 80 ° C or higher.   The polymer particles (B-2) contain 50 to 95% by weight of methyl methacrylate, 5 to 50% by weight of alkyl methacrylate having an alkyl group having 2 to 8 carbon atoms, and other vinyl monomers 0 to copolymerizable therewith. 60 to 95 parts by weight of a mixture with 20% by weight is emulsion-polymerized, and in the presence of the resulting polymer latex, 20 to 80% by weight of one or more monomers selected from alkyl methacrylate excluding alkyl acrylate and methyl methacrylate , 20 to 80% by weight of methyl methacrylate, and 5 to 40 parts by weight of a mixture of 0 to 20% by weight of other vinyl monomers copolymerizable therewith are added so that the total amount becomes 100 parts by weight. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is obtained.   The polymer particle (B-2) comprises an alkyl acrylate, a copolymerizable monomer and a crosslinkable monomer in the presence of a polymer obtained by polymerizing a mixture of methyl methacrylate, a copolymerizable monomer and a crosslinkable monomer. It has at least a three-layer structure obtained by polymerizing a monomer mixture comprising an alkyl (meth) acrylate and a copolymerizable monomer in the presence of a two-layer polymer obtained by polymerizing the mixture. The polycarbonate resin composition according to any one of 1 to 8.   The polymer particles (B-2) are (x) 30 to 100% by weight of butadiene monomer, 0 to 70% by weight of aromatic vinyl monomer, 0 to 10% by weight of other vinyl monomers copolymerizable therewith, and cross-linking Containing 40 to 90 parts by weight of a butadiene-based copolymer obtained by polymerizing a monomer mixture containing 0 to 5% by weight of a functional monomer, (y) 60 to 98% by weight of an aromatic vinyl monomer, and containing a hydroxy group or an alkoxy group 5 to 40 parts by weight of an inner shell formed by polymerizing a monomer mixture containing 2 to 40% by weight of alkyl (meth) acrylate and 0 to 20% by weight of other vinyl monomers copolymerizable therewith, (z) aromatic 10 to 100% by weight of vinyl monomer, 0 to 90% by weight of alkyl (meth) acrylate having 1 to 8 carbon atoms in the alkyl group, and other vinyl resins copolymerizable therewith A core-shell graft copolymer comprising 5 to 20 parts by weight of an outer shell formed by polymerizing a monomer mixture containing 0 to 50% by weight of monomers [100 parts by weight in total of (x), (y) and (z)]. The polycarbonate resin composition according to any one of claims 1 to 8, wherein the composition is a polycarbonate resin composition.   Any one of Claims 1 thru | or 11 containing 100 weight part of polycarbonate resin (A), 0.1-50 weight part of thickener (B), and thermoplastic resin (C) other than polycarbonate resin. A polycarbonate resin composition according to claim 1.   The polycarbonate resin composition according to claim 12, wherein the thermoplastic resin (C) other than the polycarbonate resin is a thermoplastic polyester resin, an ABS resin, or a polyolefin resin.   The molded object obtained from the polycarbonate resin composition in any one of Claims 1 thru | or 13.   The molded article according to claim 14, which is obtained by injection molding.   The molded body according to claim 14, which is obtained by extrusion molding.   The molded article according to claim 14, which is obtained by blow molding.