JP2007031542A - Polycarbonate resin composition and molded article obtained from the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which contains a thickener for greatly increasing the melt viscosity of a polycarbonate resin and making it possible to stably extrusion-mold or injection-mold the resin to obtain the molded article having a good surface property and excellent impact resistance, and solves a heat fusion problem in a drying process on the production of the low mol.wt. polymer, a filterability problem on dehydration, and a melt-viscosity lowering problem on the molding of the polycarbonate resin. <P>SOLUTION: This polycarbonate resin composition comprises 100 pts.wt. of a polycarbonate resin (A) and 0.1 to 50 pts.wt. of a thickener (B) prepared by coating 100 pts.wt. of polymer particles (B-1) having a glass transition temperature of ≥60°C, a volume-average particle diameter of 50 to 500 μm and a reaction property with the polycarbonate resin with 0.5 to 30 pts.wt. of polymer particles (B-2) having a volume-average particle diameter of 0.01 to 0.5 μm. A molded article is obtained from the polycarbonate resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition excellent in moldability in extrusion molding, injection molding and the like of a polycarbonate resin, and a molded body obtained therefrom.

  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, polycarbonate resin generally has a large temperature dependence of melt viscosity, and therefore melts in injection molding and extrusion molding performed in a temperature range above the melting point, particularly in melt processing such as extrusion molding of atypical shapes, pipes, boards, etc. Viscosity is low and disadvantageous. 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, this document does not describe an increase in melt viscosity at a level sufficient to ensure stable moldability and surface properties in injection molding and extrusion molding, particularly extrusion molding of atypical shapes, pipes, boards and the like. Therefore, in extrusion molding, there has been a strong demand for improvement of molding processability for dimensional accuracy defects such as defective take-up and thickness non-uniformity, and improvement of surface properties for shrinkage of molded products, lack of gloss, surface roughness, and the like.

  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 dramatically increases the melt viscosity of polycarbonate resin, enables stable molding in extrusion molding and injection molding, especially extrusion molding of atypical shapes, pipes, boards, etc., and has good surface properties and impact resistance. It is an object to obtain a polycarbonate resin composition containing a thickener for obtaining an excellent molded body.

  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 inventors polymerized a monomer mixture of a specific type and amount by, for example, a suspension polymerization method, and the surface of the polymer particles was subjected to a specific weight. By using the polymer obtained by coating with coalesced particles as a thickener for polycarbonate resin, a dramatic thickening effect not found in the prior art can be obtained, and a specific type and amount of single amount By blending a core-shell type graft copolymer obtained by polymerizing a body mixture into a polycarbonate resin, a dramatic thickening effect and impact strength not found in the prior art can be obtained. The inventors have found that the problem can be solved at once, and have completed the present invention.

  That is, the first of the present invention is a polymer having a glass transition temperature of 60 ° C. or higher and a volume average particle diameter of 50 to 500 μm and a reactivity with the polycarbonate resin with respect to 100 parts by weight of the polycarbonate resin (A). Thickener (B) 0.1 having 100 parts by weight of particles (B-1) coated with 0.5 to 30 parts by weight of polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm It is related with polycarbonate resin composition characterized by containing -50 weight part.

  In a preferred embodiment, the polymer particle (B-1) having reactivity with the polycarbonate resin is selected from an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an isocyanate group, an acid anhydride group, and an acid chloride group. It is related with the said polycarbonate resin composition characterized by containing the 1 type, or 2 or more types of reactive group.

  In a preferred embodiment, the polymer particles (B-1) having reactivity with the polycarbonate resin are (a) 15 to 100% by weight of an epoxy group-containing (meth) acrylate, and (b) a vinyl monomer copolymerizable therewith. It is obtained by polymerizing 0 to 85% by weight of the body [100% by weight of (a) and (b) together], and has a weight average molecular weight of 1,000 to 400,000, To a polycarbonate resin composition.

  In a preferred embodiment, the polymer particles (B-1) having reactivity with the polycarbonate resin are (a) 15 to 95% by weight of (meth) acrylate containing an epoxy group, (b) (meth) acrylates other than (a). 5 to 85% by weight, and (c) 0 to 80% by weight of a vinyl monomer copolymerizable therewith (100% by weight in combination of (a), (b) and (c)). The polycarbonate resin composition according to any one of the above, wherein the weight average molecular weight is 40,000 to 150,000.

  In a preferred embodiment, the polymer particles (B-1) having reactivity with the polycarbonate resin are (a) 15 to 95% by weight of (meth) acrylate containing an epoxy group, and (b) 5 to 85 aromatic vinyl monomer. % By weight, and (c) 0 to 80% by weight of other monomers copolymerizable therewith (100% by weight in combination of (a), (b) and (c)), The polycarbonate resin composition according to any one of the above, wherein the weight average molecular weight is 40,000 to 150,000.

  In a preferred embodiment, the Vicat softening temperature of the polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm is 80 ° C. or higher, and the polycarbonate resin according to any one of the above Relates to the composition.

  In a preferred embodiment, the polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm have an alkyl methacrylate 5 to 50% by weight of methyl methacrylate and an alkyl group having 2 to 8 carbon atoms. Alkyl methacrylate excluding alkyl acrylate and methyl methacrylate by polymerizing 60 to 95 parts by weight of a mixture of 50% by weight and 0 to 20% by weight of vinyl monomers copolymerizable therewith, and in the presence of the resulting polymer latex 5 to 40 parts by weight of a mixture of 20 to 80% by weight of one or more selected monomers, 20 to 80% by weight of methyl methacrylate, and 0 to 20% by weight of a vinyl monomer copolymerizable therewith The polycarbonate according to any one of the above, which is obtained by adding and polymerizing so that the total amount becomes 100 parts by weight. Fat compositions relating.

  In a preferred embodiment, a polymer particle (B-2) having a volume average particle size of 0.01 to 0.5 μm is composed of methyl methacrylate, a monomer copolymerizable therewith, and a crosslinkable monomer. In the presence of a polymer obtained by polymerization, in the presence of a two-layer polymer obtained by polymerizing a mixture of an alkyl acrylate, a monomer copolymerizable therewith and a crosslinkable monomer, an alkyl ( The polycarbonate resin composition according to any one of the above, which has at least a three-layer structure obtained by polymerizing a monomer mixture containing (meth) acrylate and a monomer copolymerizable therewith.

  In a preferred embodiment, the polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm are (a) butadiene 30 to 100% by weight, aromatic vinyl monomer 0 to 70% by weight, 40 to 90 weight percent of butadiene-based copolymer core obtained by polymerizing a monomer mixture containing 0 to 10 weight percent of vinyl monomer copolymerizable with these and 0 to 5 weight percent of crosslinkable monomer Part (b) 60 to 98% by weight of an aromatic vinyl monomer, 2 to 40% by weight of an alkyl (meth) acrylate containing a hydroxy group or an alkoxy group, and vinyl monomers 0 to 20 copolymerizable therewith 5 to 40 parts by weight of an inner shell formed by polymerizing a monomer mixture containing 5% by weight, (c) 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 0 to 90% by weight, and these 5 to 20 parts by weight of outer shell formed by polymerizing a monomer mixture containing 0 to 50% by weight of copolymerizable vinyl monomer [100 parts by weight in total of (a), (b) and (c)] The polycarbonate resin composition according to any one of the above, wherein the polycarbonate resin composition is a core-shell type 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, wherein the thermoplastic resin (C) other than the polycarbonate resin is a thermoplastic polyester resin or an ABS resin.

  Preferred embodiments are: 100 parts by weight of polycarbonate resin (A), 0.1 to 50 parts by weight of thickener (B), 1 to 100 parts by weight of thermoplastic resin (C) other than polycarbonate resin, and core-shell type graft It is related with the said polycarbonate resin composition containing 1-50 weight part of copolymers (D).

  In a preferred embodiment, the core-shell type graft copolymer (D) comprises (d-1) 35 to 100% by weight of butadiene and / or alkyl acrylate monomer, and (d-2) aromatic vinyl monomer 0. A monomer mixture containing ˜65 wt%, (d-3) 0-20 wt% vinyl monomer copolymerizable with these, and (d-4) 0-5 wt% polyfunctional monomer 50 to 95 parts by weight of a rubbery polymer (d ′) consisting of (d) and having a glass transition temperature of 0 ° C. or less is contained as a core layer, (e-1) 10 to 100% by weight of an alkyl methacrylate monomer, (E-2) 0 to 60% by weight of alkyl acrylate monomer, (e-3) 0 to 90% by weight of aromatic vinyl monomer, (e-4) 0 to 25% by weight of vinyl cyanide monomer, And (e-5) 0 to 20 vinyl monomers copolymerizable therewith Percent wherein the polymer comprising monomer mixture (e) a (e ') 5 to 50 parts by weight containing as a shell layer containing, related to the polycarbonate resin composition.

  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.

  The polycarbonate resin composition of the present invention has an increased melt viscosity, enables stable processing in extrusion molding and injection molding, and improves the surface properties 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 addition, it is difficult to achieve with the prior art by blending the thickener and a core-shell type graft copolymer obtained by polymerizing a monomer mixture of a specific kind and amount into a polycarbonate resin composition. The dramatic thickening effect and impact strength can be exhibited.

  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 size of 50 to 500 μm and reactivity with the polycarbonate resin are used. It is characterized by using a thickener (B) coated with 0.5 to 30 parts by weight of polymer particles (B-2) of 01 to 0.5 μm.

  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 or the like can be dramatically improved, and the expected effect can be remarkably exhibited.

  From the viewpoint of reactivity with the polycarbonate resin, the polymer particles (B-1) having reactivity with the polycarbonate resin used for the preparation of the thickener (B) in the present invention are epoxy groups, hydroxy groups, carboxy groups, It is preferable to contain one or more reactive groups selected from an alkoxy group, an isocyanate group, an acid anhydride group, and an acid chloride group. Among these, an epoxy group, a hydroxy group, a carboxy group, and an alkoxy group are more preferable, and an epoxy group is particularly preferable.

  The preparation of the polymer particles (B-1) having reactivity with the polycarbonate resin is not particularly limited, but as a monomer component constituting the polymer particles (B-1), an epoxy group-containing (meta ) (Meth) acrylates having functional groups such as acrylate, hydroxy group-containing alkyl (meth) acrylate, carboxy group-containing (meth) acrylate, alkoxy group-containing alkyl (meth) acrylate, isocyanate groups, acid anhydride groups, acids It is preferable to contain a monomer having reactivity with a polycarbonate resin exemplified by a monomer having a functional group such as a chloride group. Among these, from the viewpoint of good reactivity, it is preferable to contain an epoxy group-containing (meth) acrylate. In the present invention, unless otherwise specified, for example, (meth) acrylate means acrylate and / or methacrylate.

  Specific examples of the epoxy group-containing (meth) acrylate include an epoxy group-containing acrylate such as glycidyl acrylate, and an epoxy group-containing methacrylate such as glycidyl methacrylate. These may be used alone or in combination of two or more. It is stable extrusion molding and injection that these are contained in the polymer particles (B-1) having reactivity in an amount of 15 to 100% by weight, preferably 15 to 95% by weight, more preferably 20 to 95% by weight. This is preferable from the viewpoint of improving the melt viscosity of the polycarbonate resin composition to a level where molding or the like is possible.

  Examples of the hydroxy group-containing (meth) acrylate include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, and hydroxypropyl acrylate. Examples of the carboxy group-containing (meth) acrylate include methacrylic acid and acrylic acid. Examples of the alkoxy group-containing (meth) acrylate include ethoxy methacrylate, ethoxy acrylate, methoxy methacrylate, and methoxy acrylate.

  In the present invention, the polymer particles (B-1) having reactivity with the polycarbonate resin are (a) 15 to 100% by weight of an epoxy group-containing (meth) acrylate, and (b) a vinyl monomer copolymerizable therewith. It is preferably obtained by polymerizing 0 to 85% by weight of the body [100% by weight of (a) and (b) in total], and further (a) 15 to 95% by weight of (meth) acrylate containing epoxy group, (B) 5 to 85% by weight of (meth) acrylate other than (a), and (c) 0 to 80% by weight of vinyl monomer copolymerizable therewith [(a), (b), (c) More preferably, it is obtained by polymerizing a total of 100% by weight].

  For example, the (meth) acrylate other than (a) serving as the component (b) is not particularly limited. For example, the alkyl group having 1 to 8 carbon atoms such as 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, and methyl acrylate. Preferred examples include alkyl methacrylates having 1 to 8 carbon atoms in the alkyl group such as alkyl acrylate, 2-ethylhexyl methacrylate, butyl methacrylate, ethyl methacrylate, and methyl methacrylate. These may be used alone or in combination of two or more. These are contained in the polymer particles (B-1) having reactivity with the polycarbonate resin in an amount of 0 to 85% by weight, preferably 5 to 85% by weight, more preferably 5 to 80% by weight. This is preferable from the viewpoint of improving the melt viscosity to a level at which stable extrusion molding and injection molding are possible.

  The vinyl monomer copolymerizable with these is not particularly limited as long as it is copolymerizable with (a) epoxy group-containing (meth) acrylate, (b) (meth) acrylate other than (a), and the like. However, for example, an aromatic vinyl monomer or a vinyl cyanide monomer can be exemplified. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, chlorostyrene, and the like. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more. These are preferably contained in the polymer particles (B-1) having reactivity with the polycarbonate resin in an amount of 0 to 80% by weight, more preferably 0 to 75% by weight, thereby stabilizing the melt viscosity of the polycarbonate resin. This is preferable from the viewpoint that extrusion molding, injection molding, and the like can be improved.

  The weight average molecular weight of the polymer particles (B-1) having reactivity with the polycarbonate resin used in the present invention is not particularly limited, but the melt viscosity of the polycarbonate resin is to a level that enables stable extrusion molding and injection molding. It is preferable that it is 1000-400,000 from the point which can improve efficiently. More preferably, it is 40,000-300,000, More preferably, it is 40,000-200,000, Especially preferably, it is 40,000-150,000. 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).

  The polymer particles (B-1) having reactivity with the polycarbonate resin used in the present invention are produced by suspension polymerization from the viewpoint of improving the effect of suppressing the decrease in melt viscosity due to hydrolysis of the polycarbonate resin. Is particularly preferred. Moreover, it is the powder blocking property of the thickener (B) in this invention to coat | cover the obtained polymer particle (B-1) with the polymer particle (B-2) separately manufactured, for example by emulsion polymerization etc. It is an indispensable condition for improving. 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).

  For example, when the polymer particles (B-1) having reactivity with the polycarbonate resin are produced by suspension polymerization, the monomer mixture is mixed with an appropriate medium, dispersion stabilizer, polymerization initiator and If necessary, it can be carried out in the presence of a chain transfer agent or the like. 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, and alkylbenzene sulfonates, fatty acid salts, etc. Examples thereof include a low molecular dispersant or an emulsifier.

  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) having reactivity with the polycarbonate resin 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) having reactivity with the polycarbonate resin preferably have a glass transition temperature of 60 ° C. or higher from the viewpoints of heat-fusibility and powder blocking properties in the drying step and the like. Furthermore, it is more preferable that it is 70 degreeC or more. The glass transition temperature can be determined by, for example, a differential scanning calorimetry method.

  The production method of the polymer particles (B-1) having reactivity with the polycarbonate resin in the present invention is not particularly limited, but it is particularly preferred to produce the polymer particles by a suspension polymerization method. 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.

  Next, the polymer particle (B-2) for coating the polymer particle (B-1) in the thickener (B) used in the present invention will be described. 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) (a) 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, (b) 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, (c) 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 [(a), (b), ( An emulsion polymer that is a core-shell type graft copolymer consisting of 100 parts by weight of c) 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 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 electrolyte aqueous solution is 0.001% by weight or less, it is necessary to add a large amount of the electrolyte aqueous solution in order to coagulate the polymer particles, which is not preferable because the amount of utility used during the subsequent heat treatment operation increases. .

  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. Since the unsolidified polymer particles (B-2) remain high, resulting in deterioration of solid-liquid separation, or problems such as frequent aggregation between thickeners (B) may occur. It is not preferable.

  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 ( In some cases, secondary agglomerated particles may be generated via B-2), and the moisture content after dehydration tends to increase, which is not preferable.

  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 the like. Is mentioned.

  In the present invention, a core-shell type graft copolymer (D) is further added to the composition containing the polycarbonate resin (A), the thickener (B), and the thermoplastic resin (C) other than the polycarbonate resin. can do. The core-shell type graft copolymer (D) used in the present invention comprises a polymer obtained by polymerizing a specific monomer mixture, and is used in combination with the thickener (B) to produce a polycarbonate. The melt viscosity and impact strength at the time of melt processing such as extrusion molding and injection molding can be effectively improved without deteriorating the physical and chemical properties of the resin.

  The core-shell type graft copolymer (D) used in the present invention contains a rubber-like polymer (d ′) having a glass transition temperature of 0 ° C. or less as a core layer, and the copolymer (e ′) is a shell layer. The core-shell type graft copolymer contained as is preferable. The rubbery polymer (d ′) forming the core layer of the graft copolymer may have a single layer structure, or may have a multilayer structure of two or more layers. Good. Similarly, the polymer (e ′) forming the shell layer may have a single layer structure, or may have a multilayer structure of two or more layers. Usually, the core-shell type graft copolymer (D) is obtained by graft copolymerization of the rubber-like polymer (d ′) and the monomer mixture (e). The monomer mixture (e) can be obtained by graft polymerization in the presence of a rubber latex (d ″) containing a solid polymer (d ′) as a solid content.

  The rubbery polymer (d ′) as the core layer is composed of 35-100% by weight of butadiene and / or acrylic acid alkyl ester monomer (d-1), aromatic vinyl monomer (d-2) 0-65. Monomer mixture (d) containing 0 to 20% by weight of vinyl monomer (d-3) copolymerizable with these and 0 to 5% by weight of polyfunctional monomer (d-4) ). A rubber latex (d ″) containing a rubbery polymer (d ′) can be obtained by, for example, emulsion polymerization of the monomer mixture (d). When the rubbery polymer (d ′) is obtained by the emulsion polymerization method, the rubbery polymer (d ′) remains in the state of the rubber latex (d ″) dispersed in the aqueous medium. It can be used for graft copolymerization with the monomer mixture (e).

  As the butadiene in the butadiene and / or acrylic acid alkyl ester monomer (d-1), 1,3-butadiene can be usually used. The alkyl acrylate ester is a component for improving the impact resistance improvement effect without impairing the weather resistance of the molded article finally obtained from the polycarbonate resin composition of the present invention. Specific examples of the acrylic acid alkyl ester include, for example, acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Is not to be done. These may be used alone or in combination of two or more.

  The amount of butadiene and / or alkyl acrylate monomer (d-1) used is preferably 35 to 100% by weight, more preferably 60 to 95% by weight, and particularly preferably 65 to 95% by weight. . When the amount of butadiene and / or alkyl acrylate monomer (d-1) used is less than 35% by weight, the impact resistance of the finally obtained molded article may not be sufficiently improved.

  The ratio of butadiene and alkyl acrylate contained in butadiene and / or alkyl acrylate monomer (d-1) is not particularly limited. However, when high weather resistance is imparted to the finally obtained molded body, the total amount of butadiene and alkyl acrylate is 100% by weight, and butadiene 0-25% by weight, acrylic acid alkyl ester 75-100. It is preferable to set it as weight%, It is more preferable to set it as 0-12 weight% of butadiene, and 88-100 weight% of acrylic acid alkylesters, It is further more preferable to set it as 0 weight% of butadiene and 100 weight% of acrylic acid alkylesters.

  The aromatic vinyl monomer (d-2) mainly has an action of improving the transparency of the molded product finally obtained from the polycarbonate resin composition of the present invention, and the refraction of the graft copolymer (D). It is a component for adjusting the difference between the refractive index and the refractive index of the polycarbonate resin (A) to be as small as possible. Specific examples of the aromatic vinyl monomer (d-2) include, for example, styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, but are not limited thereto. . These may be used alone or in combination of two or more.

  The amount of the aromatic vinyl monomer (d-2) used is 0 to 65% by weight. When the amount of the aromatic vinyl monomer (d-2) used exceeds 65% by weight, the amount of the butadiene and / or acrylic acid alkyl ester monomer (d-1) used is relatively reduced, and the impact resistance is increased. It tends to be difficult to obtain a rubbery polymer (d ′) having excellent properties. However, when transparency is not required or when importance is given to impact strength, the content is preferably 0 to 25% by weight, and more preferably 0% by weight.

  The vinyl monomer (d-3) copolymerizable with these is a component mainly for finely adjusting the compatibility between the graft polymer (D) and the polycarbonate resin (A). Specific examples of vinyl monomers (d-3) copolymerizable with these include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and 4-hydroxybutyl acrylate. It is not limited to these. These may be used alone or in combination of two or more.

  The usage-amount of the vinyl monomer (d-3) copolymerizable with these is 0-20 weight%, Preferably it is 0-10 weight%, More preferably, it is 0 weight%. When the amount of the vinyl monomer (d-3) copolymerizable with these exceeds 20% by weight, the amount of the butadiene and / or acrylic acid alkyl ester monomer (d-1) used is relatively small. The rubbery polymer (d ′) having excellent impact resistance is less likely to be obtained.

  The polyfunctional monomer (d-4) is a component for forming a crosslinked structure in the resulting rubbery polymer (d ′). Specific examples of the polyfunctional monomer (d-4) include, but are not limited to, divinylbenzene, allyl acrylate, allyl methacrylate, and the like. In addition, as the polyfunctional monomer (d-4), a molecule called a macromer having functional groups capable of radical polymerization at both ends, such as α, ω-dimethacryloyloxypolyoxyethylene, can also be used. These may be used alone or in combination of two or more.

  The usage-amount of a polyfunctional monomer (d-4) is 0 to 5 weight%, Preferably it is 0.1 to 3 weight%. When the usage-amount of a polyfunctional monomer (d-4) exceeds 5 weight%, a crosslinking degree will become high too much and impact resistance may fall.

  The method for obtaining the rubbery polymer (d ′) is not particularly limited, and butadiene and / or an acrylic acid alkyl ester monomer (d-1), an aromatic vinyl monomer (d-2), An aqueous medium, a polymerization initiator, an emulsifier and the like are added to a monomer mixture (d) containing a desired amount of each of a polymerizable vinyl monomer (d-3) and a polyfunctional monomer (d-4). For example, a method of obtaining a rubber latex (d ″) by polymerization by a usual emulsion polymerization method can be employed.

  There is no particular limitation on the polymerization method of the monomer mixture (d) for obtaining the rubber-like polymer (d ′). For example, the polymerization may be performed in one step or in multiple steps. In addition, the monomer mixture (d) may be added all at once, may be added continuously, may be added in two or more stages, and combinations thereof may be performed. There is no limitation.

  Monomer mixture (d) is a monomer of butadiene and / or alkyl acrylate ester (d-1) and aromatic vinyl monomer in a reaction vessel in which an aqueous medium, an initiator, an emulsifier and the like are previously introduced. (D-2), vinyl monomer (d-3) and polyfunctional monomer (d-4) copolymerizable therewith are introduced separately or in some combination thereof. It can also be obtained in the form of an emulsion by stirring and mixing in a reaction vessel. In this case, the monomer mixture (d) is polymerized by, for example, a usual emulsion polymerization method by shifting to a condition in which the inside of the reaction vessel can start polymerization, and the rubber is emulsified and dispersed in the rubber latex (d ″). A shaped polymer (d ′) can be obtained.

  The rubbery polymer (d ′) thus obtained preferably has a glass transition temperature of 0 ° C. or lower, more preferably −30 ° C. or lower. If the glass transition temperature exceeds 0 ° C., impact may not be absorbed when a large deformation rate is finally applied to the molded product obtained from the composition according to the present invention.

  The monomer mixture (e) constituting the shell layer is 10 to 100% by weight of the methacrylic acid alkyl ester monomer (e-1), 0 to 60% by weight of the acrylic acid alkyl ester monomer (e-2), Aromatic vinyl monomer (e-3) 0 to 90% by weight, vinyl cyanide monomer (e-4) 0 to 25% by weight, and vinyl monomer copolymerizable therewith (e-5) It is preferably composed of 0 to 20% by weight.

  The alkyl methacrylate ester monomer (e-1) mainly improves the adhesion between the graft copolymer (D) and the polycarbonate resin (A), and is finally obtained from the polycarbonate resin composition of the present invention. It is a component for improving the impact strength of the molded body. Specific examples of the methacrylic acid alkyl ester monomer (e-1) include methacrylic acid alkyl esters having an alkyl group having 1 to 5 carbon atoms such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. It is not limited. These may be used alone or in combination of two or more.

  The usage-amount of a methacrylic acid alkylester monomer (e-1) is 10-100 weight%, Preferably it is 20-100 weight%, More preferably, it is 30-100 weight%. If it is less than 10% by weight, the impact strength of the finally obtained molded article may not be sufficiently improved. Further, by containing 60 to 100% by weight, more preferably 80 to 100% by weight of methyl methacrylate in the methacrylic acid alkyl ester monomer (e-1), the molded article finally obtained can be obtained. Impact strength can be dramatically improved.

  The acrylic acid alkyl ester monomer (e-2) is obtained by adjusting the softening temperature of the shell layer of the graft copolymer (D) mainly, so that the graft copolymer (D ) Is promoted in the polycarbonate resin (A) and the impact strength of the molded article is improved. Specific examples of the acrylic acid alkyl ester monomer (e-2) include, for example, acrylic acid alkyl esters having an alkyl group having 2 to 12 carbon atoms such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. However, it is not limited to these. These may be used alone or in combination of two or more.

  The usage-amount of an acrylic acid alkylester monomer (e-2) is 0 to 60 weight%, Preferably it is 0 to 50 weight%, More preferably, it is 0 to 40 weight%. If it exceeds 60% by weight, the amount of the methacrylic acid alkyl ester monomer (e-1) used is relatively small, and the impact strength of the finally obtained molded article may not be sufficiently improved.

  While maintaining sufficient adhesion between the graft copolymer (D) and the polycarbonate resin (A), the graft copolymer (D) in the molded product finally obtained is excellent in the polycarbonate resin (A). In order to achieve satisfactory dispersion, the total amount of the methacrylic acid alkyl ester monomer (e-1) and the acrylic acid alkyl ester monomer (e-2) contained in the monomer mixture (e) is 100% by weight. (E-1) 60 to 100% by weight, (e-2) preferably 0 to 40% by weight, (e-1) 70 to 100% by weight, (e-2) 0 to 30% by weight More preferably, (e-1) is 80 to 100% by weight, and (e-2) is 0 to 20% by weight.

  The aromatic vinyl monomer (e-3) mainly has an action of improving the transparency of the finally obtained molded article, and the refractive index of the graft copolymer (D) and the polycarbonate resin (A). This is a component for adjusting the difference from the refractive index to be as small as possible. Specific examples of the aromatic vinyl monomer (e-3) include, but are not limited to, monomers exemplified as specific examples of the aromatic vinyl monomer (d-2). It is not a thing. These may be used alone or in combination of two or more.

  The usage-amount of an aromatic vinyl monomer (e-3) is 0 to 90 weight%, Preferably it is 0 to 50 weight%, More preferably, it is 0 to 30 weight%. If it exceeds 90% by weight, the amount of the methacrylic acid alkyl ester monomer (e-1) used is relatively small, and the impact strength of the finally obtained molded article may not be sufficiently improved.

  The vinyl cyanide monomer (e-4) is a component mainly for finely adjusting the compatibility between the graft copolymer (D) and the polycarbonate resin (A). Specific examples of the vinyl cyanide monomer (e-4) include, but are not limited to, acrylonitrile, methacrylonitrile and the like. These may be used alone or in combination of two or more.

  The usage-amount of a vinyl cyanide monomer (e-4) is 0 to 25 weight%, More preferably, it is 0 weight%. When it exceeds 25% by weight, the amount of the methacrylic acid alkyl ester monomer (e-1) used is relatively small, and the impact strength of the finally obtained molded article may not be sufficiently improved. .

  The vinyl monomer (e-5) copolymerizable with these is a component mainly for improving processability at the time of molding of the polycarbonate resin composition. Specific examples of the vinyl monomer (e-5) include, but are not limited to, methyl acrylate, 4-hydroxybutyl acrylate, glycidyl methacrylate, and the like. These may be used alone or in combination of two or more.

  The amount of vinyl monomer (e-5) copolymerizable with these is 0 to 20% by weight, preferably 0 to 10% by weight, more preferably 0% by weight. When the amount of the copolymerizable vinyl monomer (e-5) used exceeds 20% by weight, the amount of the methacrylic acid alkyl ester monomer (e-1) used is relatively small, and finally The impact strength of the resulting molded article may not be sufficiently improved.

  The core-shell type graft copolymer (D) used in the present invention can be obtained by graft copolymerization of the rubbery polymer (d ′) and the monomer mixture (e). Monomer mixture (e) gives polymer (e ') as a result of graft copolymerization.

  The ratio of the rubber-like polymer (d ′) which is the core layer of the core-shell type graft copolymer (D) and the polymer (e ′) which is the shell layer used in the present invention is (d ′) 50 to 95 parts by weight, preferably (e ′) 50 to 5 parts by weight, more preferably (d ′) 60 to 95 parts by weight, (e ′) 40 to 5 parts by weight (provided that (d ′) And (e ') is 100 parts by weight). When the rubbery polymer (d ′) is less than 50 parts by weight and the polymer (e ′) is more than 50 parts by weight, the impact strength of the molded product finally obtained from the polycarbonate resin composition of the present invention is sufficient. This is not preferable because it cannot be improved. If the rubbery polymer (d ′) is more than 95 parts by weight and the polymer (e ′) is less than 5 parts by weight, the adhesion between the graft copolymer (D) and the polycarbonate resin (A) is lost. It is not preferable because the impact strength of the molded article finally obtained from the polycarbonate resin composition of the present invention is not sufficiently improved.

  The method for obtaining the core-shell type graft copolymer (D) used in the present invention is not particularly limited, and the rubber containing the rubbery polymer (d ′) having a glass transition temperature of 0 ° C. or less prepared as described above. Latex (d ″) is mixed with methacrylic acid alkyl ester monomer (e-1), acrylic acid alkyl ester monomer (e-2), aromatic vinyl monomer (e-3), vinyl cyanide monomer Monomer (e-4) and monomer mixture (e-5) to monomer mixture (e-5) copolymerizable with monomer (e-4), respectively. e) is added, a polymerization initiator is blended and polymerized by an ordinary polymerization method, and a method of obtaining a powdered graft copolymer (D) from the obtained graft copolymer latex may be employed. it can.

  The polymerization of the monomer mixture (e) may be performed in one stage or in multiple stages, and there is no particular limitation. The monomer mixture (e) may be added all at once, may be added continuously, or may be added in a combination of two or more stages, with particular limitations. Absent.

  The particles in the core-shell type graft copolymer latex thus obtained are taken out from the latex by salting out by adding an ordinary electrolyte, coagulation, or spraying in hot air and drying. Moreover, washing, dehydration, drying, etc. are performed by a normal method as needed.

  Although the blending ratio of the polycarbonate resin (A) and the core-shell type graft copolymer (D) can be widely adopted, the core-shell type graft copolymer (D) is used with respect to 100 parts by weight of the polycarbonate resin (A). 1 to 50 parts by weight, preferably 5 to 40 parts by weight, and more preferably 8 to 30 parts by weight. If the amount is less than 1 part by weight, the effect of improving the impact resistance strength cannot be sufficiently exhibited. If the amount exceeds 50 parts by weight, the melt viscosity becomes too high, so that the resulting molded product shrinks or loses its gloss. A phenomenon appears.

  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 the polycarbonate resin (A), the thickener (B) and the core-shell type graft copolymer (D) are mixed in advance using a Henschel mixer, a tumbler, etc., a single screw extruder, a twin screw extruder, A method of obtaining a resin composition by melt kneading using 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 and diluted with a polycarbonate resin so that a desired addition amount is in the range of 0.1 to 50 parts by weight.

  In the polycarbonate resin composition of the present invention, other additives such as spreading agents, lubricants, plasticizers, colorants, fillers, foaming agents, antibacterial / antifungal agents and the like are used alone or in combination as necessary. May be added in combination.

  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, particularly a variant, a pipe, a board, etc. The extrusion molding method such as can be preferably applied. According to the present invention, at the time of melt processing, it is possible to obtain a molded product that exhibits stable workability even in an extrusion molding method that requires a higher melt viscosity, and has good surface properties and excellent impact resistance. it can.

  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”. Also, glycidyl methacrylate is abbreviated as GMA, methyl methacrylate as MMA, butyl acrylate as BA, styrene as ST, lauroyl peroxide as LPO, and 2-ethylhexyl thioglycolate as 2EHTG. The evaluation methods used in the 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 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.

(Izod impact strength)
The Izod impact strength was measured in accordance with ASTM D-256 using a flat molded body obtained by the injection molding (test piece shape: 1/8 inch, notched, measurement temperature: 23 ° C., −30 ° C, average value of 5 samples, unit: kJ / m ² ).

(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 for emulsion thickeners by emulsion polymerization method, Synthesis Examples 7 and 8 for core-shell type graft copolymer (D) are 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, after adding 1.0 part of LPO and stirring for 15 minutes, a monomer mixture of 40 parts of GMA, 45 parts of MMA, 15 parts of BA, 0.7 part of 2EHTG is added so that the dispersed particle size of the monomer becomes about 200 μm. The rotation speed of the stirrer was 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 99.6%, and the volume average particle size was 200 μm. The suspension polymer particles had a glass transition temperature of 74 ° C. and a weight average molecular weight of 52,000.

(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 40 parts of GMA, 45 parts of MMA, 15 parts of BA, 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 99.6%. 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. The emulsion polymer sample (5) 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.

(Synthesis example 7) Preparation of core-shell type graft copolymer (D) 200 parts of water, 1.5 parts of sodium oleate, 0.002 part of ferrous sulfate (FeSO ₄ .7H ₂ O), EDTA 2Na 0.005 parts of salt, 0.2 parts of sodium formaldehydesulfoxylate, 0.2 parts of tripotassium phosphate, 100 parts of butadiene, 0.5 part of divinylbenzene and 0.1 part of diisopropylbenzene hydroperoxide, with a stirrer A pressure-resistant polymerization vessel was charged and polymerized at 50 ° C. for 15 hours to obtain a rubber latex (R1-1) having a polymerization conversion rate of 99%, a volume average particle size of 0.08 μm, and a glass transition temperature of −90 ° C.

Next, 7 parts (solid content) of the rubber latex (R1-1), 200 parts of water, 0.0017 part of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.004 part of EDTA · 2Na salt, formaldehyde sulfone 0.17 part of sodium xylate, 0.17 part of tripotassium phosphate, 93 parts of butadiene, 0.45 part of divinylbenzene and 0.085 part of diisopropylbenzene hydroperoxide were charged into a pressure-resistant polymerization vessel equipped with a stirrer at 50 ° C. After 6 hours, 12 hours, 18 hours, and 24 hours from the start of polymerization, 0.3 part of sodium oleate was added, and after 30 hours, the polymerization conversion was 99%, the volume average particle size was 0. A rubber latex (R1-2) having 21 μm and a glass transition temperature of −90 ° C. was obtained.

Furthermore, 210 parts of rubber latex (R1-2) (solid content 70 parts), water 200 parts, ferrous sulfate (FeSO ₄ · 7H ₂ O) 0.002 parts, EDTA · 2Na salt 0.004 parts, formaldehyde After mixing 0.1 part of sodium sulfoxylate, the temperature was raised to 70 ° C. Thereafter, a mixed solution of 27 parts of MMA, 3 parts of ST and 0.1 part of cumene hydroperoxide was continuously added over 4 hours, followed by post-polymerization for 1 hour to obtain a graft copolymer latex having a volume average particle diameter of 0.23 μm ( G1-1) was obtained.

  The obtained graft copolymer latex (G1-1) was coagulated with sulfuric acid and subjected to heat treatment, dehydration treatment and drying treatment to obtain a powdered graft copolymer (I).

(Synthesis Example 8) Preparation of core-shell type graft copolymer (D) 200 parts of water, 0.5 part of sodium oleate, 0.002 part of ferrous sulfate (FeSO ₄ .7H ₂ O), EDTA · 2Na 0.005 part of salt, 0.2 part of sodium formaldehyde sulfonate and 0.2 part of tripotassium phosphate are charged into a polymerization vessel equipped with a stirrer, 99 parts of BA, 1 part of divinylbenzene and 0.1 part of diisopropylbenzene hydroperoxide. Part of the mixture was continuously added at 50 ° C. over 10 hours, and after 2.5 hours, 5 hours, and 7.5 hours from the start of polymerization, 0.5 parts of sodium oleate was added, and post-polymerization was performed for 1 hour. Thereafter, a rubber latex (R2-1) containing a rubbery polymer having a polymerization conversion rate of 99%, a volume average particle size of 0.08 μm, and a glass transition temperature of −43 ° C. was obtained.

Next, 5 parts (solid content) of the rubber latex (R2-1), 190 parts of water, 0.0019 parts of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.0048 parts of EDTA · 2Na salt, formaldehyde sulfone 0.19 parts of sodium xylate and 0.19 parts of tripotassium phosphate are charged into a polymerization vessel equipped with a stirrer, and a mixed solution of 94.05 parts of BA, 0.95 parts of divinylbenzene and 0.095 parts of diisopropylbenzene hydroperoxide is added. Continuously added at 50 ° C. over 9.5 hours. After 2.5 hours, 5 hours, and 7.5 hours from the start of polymerization, 0.2 parts of sodium oleate was added, and after 1 hour of post-polymerization, A rubber latex (R2-2) having a polymerization conversion rate of 99%, a volume average particle size of 0.22 μm, and a glass transition temperature of −43 ° C. was obtained.

240 parts of the rubber latex (R2-2) (80 parts of solid content), 200 parts of water, 0.002 part of ferrous sulfate (FeSO ₄ .7H ₂ O), 0.004 part of EDTA · 2Na salt, formaldehyde sulfone After 0.1 parts of sodium xylate was charged in a polymerization vessel equipped with a stirrer and mixed, the temperature was raised to 70 ° C. Thereafter, a mixed solution of 18 parts of MMA, 2 parts of EA and 0.1 part of cumene hydroperoxide was continuously added over 2 hours and 30 minutes, followed by post-polymerization for 1 hour, and a graft copolymer latex having a volume average particle size of 0.24 μm. (G2-1) was obtained.

  The obtained graft copolymer latex (G2-1) was coagulated with sulfuric acid and subjected to heat treatment, dehydration treatment and drying treatment to obtain a powdered graft copolymer (II).

Example 1
3 parts of the thickener sample (1) obtained in Synthesis Example 5 was blended with 100 parts of a polycarbonate resin, and MFI was evaluated according to the method described above. The results are shown in Table 1.

(Example 2 and Comparative Examples 1 and 2)
As the thickener (B), the addition amount of LPO which is a polymerization initiator is 1.0 part, the addition amount of 2EHTG which is a chain transfer agent is 0.7 part, and the obtained weight average molecular weight is about 50,000 to 70000. The thickener sample (2) was prepared by the same method as in Synthesis Example 5 except that the suspension polymer particles were produced by changing the composition ratio of GMA, MMA, BA and ST as shown in Table 1. ) 3 parts of the obtained thickener sample was blended with 100 parts of polycarbonate resin, and MFI was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  From the results in Table 1, it can be seen that in Examples 1 and 2, compositions having good MFI can be obtained. On the other hand, as in Comparative Examples 1 and 2, commercially available ethylene 88%, GMA 12% copolymer (Sumitomo Chemical Co., Ltd., BF-E), ethylene 83%, GMA 12%, vinyl acetate 5% copolymer (Sumitomo). It can be seen that the MFI is not improved so much when BF-7B) manufactured by Kagaku Corporation is used.

(Examples 3 and 4 and Comparative Example 3)
Thickener sample (3) with the glass transition temperature changed by the same method as in Synthesis Example 5 except that the glass transition temperature of the suspension polymer particles was changed as shown in Table 2 and fixed to 40 parts of GMA. (4) was obtained. Using the obtained thickener sample, MFI was evaluated in the same manner as in Example 1, and further heat fusion property was evaluated according to the evaluation method. The results are shown in Table 2.

  From the results in Table 2, it can be seen that, as in Examples 3 and 4, when the glass transition temperature of the suspended polymer particles is within the range of the present invention, good MFI and powder heat fusion properties are exhibited. . On the other hand, when the thickener sample (4) having a glass transition temperature of the suspension polymer particles lower than the range of the present invention is used as in Comparative Example 1, the MFI is good, but the heat melting of the powder. It can be seen that the wearability decreases.

(Examples 5 to 7 and Comparative Example 4)
Using the same suspension polymer particles as those used in Synthesis Example 1 and changing the type of the emulsion polymer sample covering the surface of the suspension polymer particles as shown in Table 3, a thickener sample is obtained. Evaluation of MFI and heat-fusibility is the same as in Example 3 when prepared and when a thickener sample (5) prepared by emulsion polymerization as shown in Synthesis Example 6 is used. The method was performed. The results are shown in Table 3.

  From the results of Table 3, as in Examples 5 to 7, when the type of the emulsion polymer particles covering the suspension polymer particles is within the preferred range of the present invention, good MFI and powder heat fusion It turns out that it shows sex. On the other hand, when the thickener sample (5) produced by the emulsion polymerization method as in Comparative Example 2 is used, it can be seen that the MFI and heat-fusibility are lowered. This decrease in MFI is believed 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 8 to 10 and Comparative Examples 5 and 6)
Thickener sample (1) obtained in Synthesis Example 5 was blended with 100 parts of polycarbonate resin at the blending ratio shown in Table 4, and MFI and evaluation of the surface property of the molded product were conducted in the same manner as in Example 1. Went. The results are shown in Table 4.

表４の結果より、増粘剤試料の配合比率が本発明の範囲内である実施例８〜１０では、良好なＭＦＩおよび成形体の表面性を有する組成物が得られることがわかる。一方、増粘剤試料を配合していない比較例３では、ＭＦＩが充分ではなく、成形体の表面性の評価を実施できるサンプルを得ることもできなかった。また、配合比率が本発明の範囲よりも多い比較例４では、成形体の表面光沢が悪化することがわかる。

From the results of Table 4, it can be seen that in Examples 8 to 10 in which the blending ratio of the thickener sample is within the range of the present invention, a composition having good MFI and surface properties of the molded body can be obtained. On the other hand, in Comparative Example 3 in which no thickener sample was blended, the MFI was not sufficient, and a sample capable of evaluating the surface property of the molded article could not be obtained. Moreover, it turns out that the surface gloss of a molded object deteriorates in the comparative example 4 with a compounding ratio larger than the range of this invention.

(Examples 11-14 and Comparative Example 7)
100 parts of polycarbonate resin, 100 parts of polybutylene terephthalate resin (manufactured by Mitsubishi Chemical Co., Ltd., Novador 5010), 3 parts of thickener sample (1), and a sample of the amount shown in Table 5 as a core-shell type graft copolymer ( When I) and (II) were used, MFI, surface properties of the molded body, and Izod impact strength were evaluated. The results are shown in Table 5.

  From the results of Table 5, in Examples 11 to 14 in which the blending amount of the core-shell type graft copolymer is within the preferable range of the present invention, a composition having good MFI, surface property of the molded product, and Izod impact strength. It turns out that a thing is obtained.

Claims (16)

  100 weight parts of the polymer resin (B-1) having a glass transition temperature of 60 ° C. or higher and a volume average particle diameter of 50 to 500 μm and having reactivity with the polycarbonate resin with respect to 100 weight parts of the polycarbonate resin (A). Containing 0.1 to 50 parts by weight of the thickener (B) coated with 0.5 to 30 parts by weight of polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm. A polycarbonate resin composition characterized by the above.   The polymer particle (B-1) having reactivity with the polycarbonate resin is one or two selected from an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an isocyanate group, an acid anhydride group, and an acid chloride group. The polycarbonate resin composition according to claim 1, comprising at least one kind of reactive group.   Polymer particles (B-1) having reactivity with polycarbonate resin are (a) 15 to 100% by weight of epoxy group-containing (meth) acrylate, (b) 0 to 85% of vinyl monomer copolymerizable therewith. % [100% by weight combining (a) and (b)], and having a weight average molecular weight of 1,000 to 400,000, The polycarbonate resin according to claim 1 or 2 Composition.   Polymer particles (B-1) having reactivity with polycarbonate resin are (a) 15 to 95% by weight of (meth) acrylate containing epoxy group, and (b) 5 to 85% by weight of (meth) acrylate other than (a). And (c) 0 to 80% by weight of a vinyl monomer copolymerizable therewith [100% by weight in combination of (a), (b) and (c)], and a weight average molecular weight. The polycarbonate resin composition according to any one of claims 1 to 3, wherein is from 40,000 to 150,000.   The polymer particles (B-1) having reactivity with the polycarbonate resin are (a) 15 to 95% by weight of an epoxy group-containing (meth) acrylate, (b) 5 to 85% by weight of an aromatic vinyl monomer, and ( c) obtained by polymerizing 0 to 80% by weight of other monomers copolymerizable with these [100% by weight of (a), (b) and (c) together], and having a weight average molecular weight of 4 The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate resin composition is 10,000 to 150,000.   The polycarbonate resin according to any one of claims 1 to 5, wherein the Vicat softening temperature of the polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 µm is 80 ° C or higher. Composition.   Polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm are 50 to 95% by weight of methyl methacrylate, 5 to 50% by weight of alkyl methacrylate having 2 to 8 carbon atoms, and A polymer selected from 60 to 95 parts by weight of a copolymer of 0 to 20% by weight of a vinyl monomer copolymerizable therewith and selected from alkyl methacrylates excluding alkyl acrylate and methyl methacrylate in the presence of the resulting polymer latex A total amount of 100 to 40 wt.% Of a mixture of 20 to 80 wt.% Of the monomer or more, 20 to 80 wt.% Of methyl methacrylate, and 0 to 20 wt.% Of the vinyl monomer copolymerizable therewith. The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin composition is obtained by addition and polymerization so as to be a part. .   Polymer particles (B-2) having a volume average particle diameter of 0.01 to 0.5 μm are polymerized by polymerizing a mixture of methyl methacrylate, a monomer copolymerizable therewith and a crosslinkable monomer. In the presence of a two-layer polymer obtained by polymerizing a mixture of an alkyl acrylate, a monomer copolymerizable therewith and a crosslinkable monomer in the presence of a polymer, an alkyl (meth) acrylate and The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin composition has at least a three-layer structure obtained by polymerizing a monomer mixture containing a monomer copolymerizable therewith.   Polymer particles (B-2) having a volume average particle size of 0.01 to 0.5 μm are copolymerizable with (a) butadiene 30 to 100% by weight, aromatic vinyl monomer 0 to 70% by weight. 40 to 90 parts by weight of a butadiene copolymer core obtained by polymerizing a monomer mixture containing 0 to 10% by weight of a vinyl monomer and 0 to 5% by weight of a crosslinkable monomer, (b) A monomer comprising 60 to 98% by weight of an aromatic vinyl monomer, 2 to 40% by weight of an alkyl (meth) acrylate containing a hydroxy group or an alkoxy group, and 0 to 20% by weight of a vinyl monomer copolymerizable therewith. 5 to 40 parts by weight of inner shell formed by polymerizing the monomer mixture, (c) 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 vinyl copolymerizable therewith A core-shell type comprising 5 to 20 parts by weight of an outer shell formed by polymerizing a monomer mixture containing 0 to 50% by weight of a monomer [100 parts by weight in combination of (a), (b) and (c)] The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition is a graft copolymer.   Any one of Claims 1 thru | or 9 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 any one of the above.   11. The polycarbonate resin composition according to claim 10, wherein the thermoplastic resin (C) other than the polycarbonate resin is a thermoplastic polyester resin or an ABS resin.   100 parts by weight of polycarbonate resin (A), 0.1 to 50 parts by weight of thickener (B), 1 to 100 parts by weight of thermoplastic resin (C) other than polycarbonate resin, and core-shell type graft copolymer (D The polycarbonate resin composition according to any one of claims 1 to 11, comprising 1 to 50 parts by weight.   The core-shell type graft copolymer (D) is (d-1) butadiene and / or alkyl acrylate monomer 35 to 100% by weight, (d-2) aromatic vinyl monomer 0 to 65% by weight, (D-3) a monomer mixture (d) containing 0 to 20% by weight of a vinyl monomer copolymerizable with these, and (d-4) 0 to 5% by weight of a polyfunctional monomer. 50 to 95 parts by weight of a rubbery polymer (d ′) having a glass transition temperature of 0 ° C. or less is contained as a core layer, (e-1) 10 to 100% by weight of an alkyl methacrylate monomer, (e-2) 0 to 60% by weight of alkyl acrylate monomer, (e-3) 0 to 90% by weight of aromatic vinyl monomer, (e-4) 0 to 25% by weight of vinyl cyanide monomer, and (e-5) ) Monomers containing 0-20% by weight of vinyl monomers copolymerizable with these Characterized in that it contains a polymer consisting of compound (e) a (e ') 5 to 50 parts by weight of the shell layer, polycarbonate resin composition according to claim 12.   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.