JP6520491B2 - Thermoplastic resin composition and resin molded article thereof - Google Patents

Description

  The present invention relates to a thermoplastic composition containing a surface physical property modifier composition, and a resin molded article thereof.

  Polycarbonate resin (PC) is a thermoplastic resin excellent in impact resistance, processability and flame retardancy. Therefore, it is widely applied to large-sized injections that generate a large amount of heat, such as automobile parts, computers, office equipment, housings of electric appliances, etc., and its use area has recently been increased. On the other hand, there is a problem that the scratch resistance is low, and when it rubs against other members, it is easy to generate a stagnant noise.

  Patent Document 1 discloses a technique for improving the scratch resistance of PP by adding a composition of hydrocarbon wax and a vinyl copolymer containing a polyorganosiloxane group to polypropylene (PP). There is.

JP, 2013-53306, A

  Although the composition described in Patent Document 1 has a description regarding the improvement of the abrasion resistance of PP, there is no description regarding the effect on polycarbonate resins, and no description regarding the reduction of itching noise.

  Then, this invention solves the said subject, and it aims at providing the thermoplastic resin composition which is excellent in abrasion resistance improvement and a stagnant sound reduction effect, and its resin molded product.

（Ｒ^１：ＨまたはＣＨ_３、Ｒ^２：炭素数１〜４の直鎖または分岐炭化水素基） As means for that purpose, the present invention is a thermoplastic resin composition containing 0.1 to 20 parts by mass of a surface physical property improving agent composition with respect to 100 parts by mass of a polycarbonate resin. The surface property improver composition comprises (A) a wax, (B) a vinyl (co) polymer, and (C) an aliphatic hydrocarbon having 5 to 14 carbon atoms, and the (A) component comprises Or (a1) paraffin wax, (a2) microcrystalline wax, (a3) Fischer-Tropsch wax, and (a4) polyethylene wax, at least one wax selected from the group consisting of (B) components, (b1) (Meth) acrylonitrile, (b2) (meth) acrylic acid, (b3) hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, (b4) styrene, and (b5) represented by the following formula (1) Vinyl (co) polymerization obtained by radical polymerization of at least one vinyl monomer selected from (meth) acrylic acid alkyl esters 50 to 98 parts by mass of the component (A) in a total of 100 parts by mass of the component (A) and the component (B), and the amount of the component (C) relative to the total amount of the component (A) Component contains 0.001 to 1.0% by mass.

(R ¹ : H or CH ₃ , R ² : C 1-4 linear or branched hydrocarbon group)

（Ｒ^１：ＨまたはＣＨ_３、Ｒ^２：炭素数１〜４の直鎖または分岐炭化水素基） As still another means, the present invention is a thermoplastic resin composition containing 0.1 to 20 parts by mass of a different surface physical property improving agent composition with respect to 100 parts by mass of a polycarbonate resin. The surface property improver composition comprises (A) a wax, (B) a vinyl (co) polymer, and (C) an aliphatic hydrocarbon having 5 to 14 carbon atoms, and the (A) component comprises Or (a1) paraffin wax, (a2) microcrystalline wax, (a3) Fischer-Tropsch wax, and (a4) polyethylene wax, at least one wax selected from the group consisting of (B) components, (b1) (Meth) acrylonitrile, (b2) (meth) acrylic acid, (b3) hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, (b4) styrene, and (b5) represented by the following formula (1) (Meth) acrylic acid alkyl esters, at least one vinyl monomer selected from (meth) acrylic acid alkyl esters; A vinyl copolymer obtained by radical polymerization of a vinyl monomer having an amino group, and 50 of the (A) component in 100 parts by mass in total of the (A) component and the (B) component. It is -98 mass parts, and 0.001 to 1.0 mass% of the component (C) is contained with respect to the total amount of the component (A), and the vinyl monomer (b6) in the component (B) The composition ratio of is 1 to 30% by mass.

(R ¹ : H or CH ₃ , R ² : C 1-4 linear or branched hydrocarbon group)

  The thermoplastic resin composition according to the above two means can be molded into a predetermined shape to be a resin molded article.

  In the present invention, "○ to xx" indicating a numerical range means "○ or more and xx or less" unless otherwise specified. In addition, “(A) wax” in the present invention is a concept including “wax mixture” which contains some of component (C) as a minor component. Therefore, the content of the component (C) also includes the amount originally contained in the component (A). Moreover, "(co) polymer" is a concept including the polymer which consists of a single vinyl monomer, and the copolymer which consists of 2 or more types of vinyl monomers. Moreover, "(meth) acrylic acid" is a concept including both methacrylic acid and acrylic acid. Similarly, “(meth) acrylonitrile” is a concept including both methacrylonitrile and acrylonitrile.

  According to the thermoplastic resin composition of the present invention, it is possible to achieve high scratch resistance performance and stagnant noise reduction performance as compared to conventional PC. Generally, when a lubricant is added to PC, the molded appearance of the obtained polycarbonate resin molded article tends to be deteriorated or the surface is sticky. However, despite the fact that the polycarbonate resin molded article comprising the thermoplastic resin composition of the present invention contains the surface physical property improving agent composition as a lubricant, it has good scratch resistance and performance without reducing its molding appearance and Damping sound reduction performance can be achieved. In particular, the component (C) in the surface physical property improving agent composition has a function to further improve the lubricity of the (A) wax, whereby the smoothness of the surface of the polycarbonate resin molded article can be improved. Thus, it is possible to obtain a resin molded article which is excellent in the appearance of the molded article and is excellent in the abrasion resistance improvement and the stagnant sound reduction effect.

  In addition, since the vinyl monomer (b6) has surface orientation and lubricity, if the surface physical property modifier composition also contains the vinyl monomer (b6), the surface physical property modifier composition The product can be finely dispersed on the surface of a polycarbonate resin molded article, and the smoothness of the surface of the polycarbonate resin molded article can be further improved.

«Thermoplastic resin composition»
The thermoplastic resin composition of the present invention is obtained by adding a surface physical property improving agent composition described later as an additive (slidant) to a polycarbonate resin, and can be obtained by melt-kneading these.

<Polycarbonate resin (PC)>
The polycarbonate resin may be an aromatic polycarbonate produced by a known phosgene method, a melting method or the like. The specific manufacturing method is described, for example, in Japanese Patent Application Laid-Open Nos. 63-215763 and 2-124934. Typical diphenols used as raw materials include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A). Moreover, as a precursor for introduce | transducing carbonate, a phosgene, diphenyl carbonate, etc. are mentioned. As the polycarbonate resin produced, either one having a terminal OH group sealed or one having a terminal OH group not sealed can be used.

  In the present invention, the polycarbonate resin is preferably colored rather than non-colored. When a non-colored polycarbonate resin is used, the transparency is reduced.

<Surface physical property modifier composition>
The surface property improver composition contained in the thermoplastic resin composition of the present invention comprises (A) a wax, (B) a vinyl (co) polymer, and (C) an aliphatic hydrocarbon having 5 to 14 carbon atoms. And.

[(A) wax]
The wax (A) is a compound capable of developing properties such as low friction, and has a function mainly to improve the surface smoothness of the polycarbonate resin molded article. As the wax, a hydrocarbon component having 20 to 80 carbon atoms which is solid at 25 ° C. and 1 atm can be used. Specifically, from among (a1) paraffin wax and (a2) microcrystalline wax purified from petroleum, (a3) Fischer-Tropsch wax synthesized from natural gas, and (a4) polyethylene wax synthesized from ethylene At least one selected, or two or more can be used.

  In addition, (a1) paraffin wax, (a2) microcrystalline wax, and (a3) Fischer-Tropsch wax are a wax mixture and contain these wax components as main components, and some (C) components described below as minor components. (About 0.01 to 0.9 mass%) is contained. On the other hand, (a4) polyethylene wax is a pure wax and consists only of the polyethylene wax.

（Ｒ^１：ＨまたはＣＨ_３、Ｒ^２：炭素数１〜４の直鎖または分岐炭化水素基） [(B) vinyl (co) polymer]
(B) The vinyl (co) polymer has the function of compatibilizing (A) wax and PC and (A) finely dispersing the wax in PC. The (B) vinyl (co) polymer is (b1) (meth) acrylonitrile, (b2) (meth) acrylic acid, (b3) hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, (b4) ) Styrene, and (b5) obtained by radical polymerization of at least one, or two or more vinyl monomers selected from (meth) acrylic acid alkyl esters represented by the following formula (1) (co ) It is a polymer. Among them, a copolymer of (b1) (meth) acrylonitrile and (b4) styrene is preferable from the viewpoint of scratch resistance.

(R ¹ : H or CH ₃ , R ² : C 1-4 linear or branched hydrocarbon group)

  Further, as the (B) vinyl (co) polymer, a vinyl single monomer having a polyorganosiloxane group in one molecule of (b6) together with at least one selected from the above vinyl monomers (b1) to (b5) It is preferable to use a copolymer obtained by radical polymerization of a monomer (a monomer having a vinyl group at at least one end) as well. Such a vinyl monomer (b6) can significantly improve the surface orientation of the (B) vinyl copolymer by having a polyorganosiloxane group. Therefore, since the (A) wax compatibilized with the (B) vinyl copolymer is also oriented on the surface, the lubricity of the polycarbonate resin molded article surface can be improved. Furthermore, since the polyorganosiloxane itself also has lubricity, the (B) vinyl copolymer copolymerized with the vinyl monomer (b6) is lubricated, and therefore the surface of the polycarbonate resin molded article Smoothness can be significantly improved.

  As a vinyl monomer (b6), the product name of Shin-Etsu Chemical Co., Ltd. product: X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, for example , X-22-164E, X-22-2445, X-22-1602, X-22-174 ASX, X-22-174 BX, X-22-2426, X-22-2475, KF-2012, JNC (strains The product name of): Silaplain FM-0711, Silaplain FM-0721, Silaplain FM-0725, and the like. Among them, only one end is (meth) acrylic modified, X-22-174 ASX, X-22-174 BX, X-22-2426, X-22-2475, KF-2012, SYRAPURE FM-0711, SILAPURE FM- 0721, Thyraplane FM-0725 are preferred. These vinyl monomers (b6) may be used alone or in combination of two or more.

<Radical polymerization initiator>
The vinyl monomers (b1) to (b6) are radically polymerized by a radical polymerization initiator. As the radical polymerization initiator, an azo polymerization initiator, an organic peroxide, a persulfate, hydrogen peroxide water, a redox polymerization initiator (a polymerization initiator in which an oxidizing agent and a reducing agent are combined), and the like can be used.

  Examples of azo polymerization initiators include azobisisobutyronitrile, azobisisovaleronitrile, azobisdimethylvaleronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), 1-phenylethylazodiphenylmethane, and the like. Can be mentioned.

  Examples of organic peroxides include peroxyketals such as 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane and 1,1-di (t-hexylperoxy) cyclohexane. hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, etc., di (3, Examples include diacyl peroxides such as 5,5-trimethylhexanoyl peroxide and dibenzoyl peroxide; and peroxy esters such as cumylperoxyl neodecanoate and t-butylperoxyl neodecanoate.

  As an oxidizing agent used for a redox polymerization initiator, hydroperoxides or persulfate can be used. Examples of hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Be Examples of the persulfate include potassium persulfate, ammonium persulfate and the like. Examples of the reducing agent include glucose, dextrose, formaldehyde sodium sulfoxylate (long gallite), sodium thiosulfate, ferrous sulfate, copper sulfate and potassium hexacyanoferrate (III).

  Among the radical polymerization initiators exemplified above, di (3,5,5-trimethylhexanoyl) peroxide or potassium persulfate is preferable from the viewpoint of ease of handling and ease of control of the polymerization reaction.

<(B) Method for producing vinyl (co) polymer>
The vinyl (co) polymer (B) can be synthesized by a known suspension polymerization method or emulsion polymerization method using a radical polymerization initiator. At this time, when the vinyl monomer of (b6) is also used together with at least one selected from vinyl monomers (b1) to (b5), the total amount of (B) vinyl (co) polymer ( It mixes so that content of a vinyl monomer (b6) may be 1-30 mass% on the basis of 100 mass%). When the blend ratio (content) of the vinyl monomer (b6) is 31% by mass or more, the surface physical properties of the obtained polycarbonate resin molded product are degraded.

  Moreover, the compounding quantity (content) of a radical polymerization initiator shall be 0.001-10 mass parts preferably with respect to 100 mass parts of total amounts of each monomer. When the content of the radical polymerization initiator is less than 0.001 parts by mass, not only the reaction for a long time is required to complete the polymerization, but also the reaction is not completed, which is not preferable. On the other hand, if it exceeds 10 parts by mass, heat generation tends to be large, and control of the polymerization reaction tends to be difficult.

  When it synthesize | combines by the emulsion polymerization method, surfactant is also mixed with each monomer. As surfactant used for the said emulsion polymerization, well-known nonionic, anionic, or cationic surfactant can be used. When the polymer is taken out by salting out, an anionic surfactant is preferred. As an anionic surfactant, for example, fatty acid salt, sodium alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinic acid ester salt, alkyl phosphoric acid ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfuric acid ester salt, etc. Can be mentioned. These surfactants may be blended at a ratio of about 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomers (b1) to (b6).

  In the case of emulsion polymerization, if necessary, known pH adjusters, chelating agents, polymerization (viscosity) adjusters, polymerization stabilizers and the like can be added. As a pH regulator, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium hydrogencarbonate, sodium carbonate, disodium hydrogenphosphate and the like can be mentioned. Examples of the chelating agent include sodium ethylenediaminetetraacetate, sodium pyrophosphate and the like. As a viscosity regulator or a polymerization stabilizer, an inorganic electrolyte, an organic electrolyte, a polymer electrolyte, etc. are mentioned. Furthermore, in order to control the degree of polymerization, it is also possible to add known crosslinking agents, chain transfer agents, polymerization inhibitors and the like.

  After the polymerization is completed, the emulsion obtained by the emulsion polymerization may be, for example, acids such as hydrochloric acid, sulfuric acid and nitric acid, sodium chloride, potassium chloride, sodium sulfate, calcium chloride, magnesium sulfate, copper sulfate, calcium nitrate and other electrolytes After salting out using the above, filtration and drying are performed to obtain a (co) polymer.

  Moreover, when synthesize | combining by suspension polymerization method, a dispersing agent is also mixed with each monomer. As a dispersant, for example, as inorganic compounds, calcium triphosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid Calcium, barium sulfate, bentonite, silica, alumina, magnetic substances, ferrite and the like can be mentioned. Also, examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. The compounding amount of the dispersant may be about 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of each monomer. Then, after the suspension polymerization is completed, the (co) polymer is obtained by filtration and drying.

  The number average molecular weight (Mn) of the (B) vinyl (co) polymer synthesized by radical polymerization of each monomer is usually 1,000 to 6,000,000. When the number average molecular weight is less than 1,000, the heat resistance of the vinyl (co) polymer tends to decrease, and when the number average molecular weight exceeds 6,000,000, the vinyl (co) polymer is melted. When the flowability is deteriorated, the formability tends to be lowered.

  Therefore, it is also preferable to add a molecular weight modifier to the surface physical property modifier composition as required. Examples of the molecular weight modifier include alkyl mercaptans such as N-dodecyl mercaptan and phenyl mercaptan, α-methylstyrene dimers, halogenated alkyls such as carbon tetrachloride, alcohols such as isopropyl alcohol, and the like.

[(C) aliphatic hydrocarbon having 5 to 14 carbon atoms]
(C) The aliphatic hydrocarbon having 5 to 14 carbon atoms is a hydrocarbon component which is liquid at 25 ° C. and 1 atm, and has a function of further improving the lubricity of the (A) wax. (C) Specific examples of the aliphatic hydrocarbon having 5 to 14 carbon atoms include pentane, isopentane, hexane, isohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane and the like. These (C) aliphatic hydrocarbons having 5 to 14 carbon atoms may be used alone or in combination of two or more.

  The content of the component (C) is 0.001 to 1.0 mass% with respect to the total amount (100 mass%) of the wax (mixture). Outside this range, the surface properties of the obtained polycarbonate resin molded article are degraded. The amount originally contained in the wax (A) is also added to the content of the component (C).

  The surface property improver composition can be obtained by mixing the (A) wax and the (B) vinyl (co) polymer at a temperature equal to or higher than the melting point of the (A) wax. At this time, the (B) vinyl (co) polymer may be produced and then mixed with the (A) wax, or the (A) wax and each vinyl monomer (b1) to (b6) may be contained in the same container. And (B) vinyl (co) polymer may be produced in the presence of (A) wax. Also, in the surface physical property modifier composition, (A) wax and (B) vinyl (co) polymer are bonded by covalent bond, and they take the form of graft copolymer and / or block copolymer. Good. In this graft copolymer and / or block copolymer, (A) wax and each vinyl monomer (b1) to (b6) are charged in the same container, and in the presence of (A) wax (B) It is obtained by producing a vinyl (co) polymer.

  The blending ratio (content) of the (A) wax and the (B) vinyl (co) polymer is 50 to 98 parts by mass of the (A) wax (in other words, in (A) + (B) = 100 parts by mass) And (B) vinyl (co) polymer is 50 to 2 parts by mass). If the amount of the wax (A) is less than 50 parts by mass, the amount of lubricant decreases, so that the surface smoothness of the obtained polycarbonate resin molded product is deteriorated.

<Blending ratio>
The thermoplastic resin composition of the present invention contains the surface physical property improving agent composition in an amount of 0.1 to 20 parts by mass, preferably 1 to 20 parts by mass, with respect to 100 parts by mass of the polycarbonate resin. When the surface physical property improving agent composition is less than 0.1 parts by mass with respect to 100 parts by mass of the polycarbonate resin, it is impossible to obtain a sufficient scratch resistance and a stagnant noise reduction effect. On the other hand, when the surface physical property improving agent composition is more than 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin, the molding appearance of the obtained thermoplastic resin molded article is deteriorated.

  In the thermoplastic resin composition of the present invention, an antioxidant, an ultraviolet light absorber, a flame retardant, a mold release agent, a surfactant, a lubricant, a plasticizer, a coloring agent, an antibacterial agent, as long as the effects of the present invention are not impaired. Additives for resins such as nucleating agents, dispersing agents, fillers, glass fibers etc. can be added. These may use only 1 type and may use 2 or more types together.

<Method of producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention can be obtained by simultaneously melt-kneading a polycarbonate resin and a surface physical property improving agent composition. Polycarbonate resins are commercially available, and include Makrolon 2407 manufactured by Bayer, Lexan 241R manufactured by SABIC, Caliber 301-30 manufactured by Sumika Styron, and the like. As the melt-kneading method, known melt-kneading methods such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, and a roll are adopted.

«Resin molded products»
The resin molded article of the present invention is obtained by molding the thermoplastic resin composition into a predetermined shape, and the effect of the surface physical property improving agent composition contained in the thermoplastic resin composition is exhibited. As a form of a resin molded product, a sheet | seat, a film, a hollow body, a block body, a plate-like body, a cylinder, a complex shape body, etc. are not specifically limited. The molding method is not particularly limited as long as it is a general molding method of thermoplastic resin, and extrusion molding method, injection molding method, blow molding method, foam molding method, calendar molding method, pressure forming method, thermoforming method, A vacuum forming method, a powder slush molding method and the like can be mentioned. Resin molded articles can be used for various products and semi-finished products in a wide range of fields such as automobile parts, home electric appliance parts, sundries and the like due to the excellent surface physical property improvement effect.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

(Surface physical property modifier composition)
In the reaction vessel having a volume of 0.5 L, the proportions shown in Table 3 of (A) wax (mixture) of (a1) to (a4) shown in Table 1 and vinyl monomers (b1) to (b6 shown in Table 2) ), And (C) hydrocarbons shown in Table 3 are introduced in the types and ratios shown in Table 3, respectively, into which 280 g of water, 1.6 g of calcium phosphate tribasic as a dispersant and 0. Mixing 4 g of hydroxypropyl methylcellulose, 0.02 g of α-methylstyrene dimer as a molecular weight modifier and 0.66 g of di (3,5,5-trimethylhexanoyl) peroxide as a radical polymerization initiator The reaction vessel was charged and reacted while stirring at 70 ° C. for 3 hours. Next, 0.1 g of potassium persulfate as a radical polymerization initiator was dissolved in 0.5 g of water, charged into a reaction tank, and reacted at 70 ° C. for 1 hour. Then, it cooled to 40 degrees C or less, passed through the filtration and the drying process, and obtained the surface physical property improving agent composition.

(Polycarbonate resin molded product)
The surface physical property modifier composition obtained above is compounded at a ratio shown in Table 4 to 100 parts by mass of Macrolon 2407 (manufactured by Bayer) as PC, and extruded by a twin-screw extruder (PCM-30, manufactured by Ikegai) It melt-kneaded at the temperature of 240 degreeC, and obtained the pellet of the thermoplastic resin composition. Then, the pellets were injection-molded at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare JIS K 7113 type 1 test pieces and plate-shaped test pieces of 55 mm × 80 mm × t2 mm.

  For each of the obtained test pieces, the molded appearance, the scratch resistance, the scratch resistance, and the stagnation noise were evaluated by the following method. The results are also shown in Table 4.

<Molded appearance>
About the appearance of the injection molded article evaluated in the present Example and the comparative example, it judged on the following references | standards visually.
○: white, no injection unevenness such as flow marks on the surface of the molded article ×: non-white, or injection unevenness such as flow marks on the surface of the molded article

<Scratch resistance>
The apparatus uses Kato Tech's Scratch Tester KK-01, and the test piece is a JIS No. 1 test piece of JIS K 7113. Scratch load: 1 to 30 N according to ISO 19252, Scratch distance: 100 mm, Scratch speed The test was carried out with 100 mm / sec and tip: stainless steel φ = 1.0 mm. The load at which whitening scratches began to occur was taken as an evaluation point for scratch resistance. Those with an evaluation score of 10N or more were accepted.

<Scratch resistance>
The apparatus used Yasuda Seiki Mfg. Co., Ltd. make NO416-TMI CROCK METER, and the test piece used the plate-shaped test piece of 55 mm x 80 mm x t2 mm. Test load: 1 kg, number of tests: 100 reciprocations, test speed: 1 reciprocation / sec, counterpart material: cotton cloth (Kanakin No. 3). The evaluation was carried out using GLOSS CHECKER IG-330 manufactured by HORIBA, the gloss on the surface of the test piece before and after the test was measured (60 °), and the gloss retention was calculated from the formula (2) shown below. A gross retention of 90% or higher was considered to pass.
Gross retention rate = post test gloss / pre test gloss × 100 (%) ... (2)

<Sudden sound>
For the evaluation of the squeaky sound, for example, the method shown in Japanese Patent No. 5425535 can be adopted. The apparatus used Ziegler stick-slip measurement apparatus SSP-02, and the test piece used the plate-shaped test piece of 55 mm x 80 mm x t2 mm. Moreover, PC was injection-molded as a mating material, and the test piece of 55 mm x 80 mm x t2 mm was prepared. The test piece was fixed to the apparatus, and was rubbed against the mating material three times each under the conditions of load 5N, 10N, 40N, speed 1 mm / sec, 4 mm / sec, 10 mm / sec to measure a squeak noise risk value. In addition, in the said measuring apparatus, it is displayed on ten steps of lingering sound risk values 1-10.

  From the results of Table 4, it can be seen that the polycarbonate resin molded product blended with the surface physical property improving agent composition of each example exhibited a good scratch resistance improvement and a stagnant sound reduction effect. Among them, as in Example 2-1 to Example 2-11, a polycarbonate resin molded product blended with a surface physical property improving agent composition obtained by copolymerizing a vinyl monomer (b6) shows particularly good effect. The Moreover, when the compounding ratio of the surface physical property improving agent composition is compared with Example 1-1 to Example 1-11, the compounding ratio of the surface physical property improving agent composition is 1 to 20 parts by mass with respect to 100 parts by mass of PC. In Example 1-2-Example 1-11, the improvement effect of abrasion resistance became a favorable result. Similarly, when Example 2-1 to Example 2-11 are compared, Example 2-2 to Example 2-11 in which the compounding ratio of the surface physical property improving agent composition is 1 to 20 parts by mass with respect to 100 parts by mass of PC. In the above, the effect of improving the scratch resistance was a good result.

On the other hand, in Comparative Example 1-1, the surface physical property improving agent composition was not used, so the scratch resistance and the stagnation noise were bad. In Comparative Example 1-2 and Comparative Example 2-1, since the content of the surface physical property improving agent composition is too small, the scratch resistance and the stagnation noise were bad. On the contrary, since the content of the surface physical property improving agent composition is excessive in Comparative Example 1-3 and Comparative Example 2-2, the molding appearance is bad. In Comparative Example 3-1, since the comparative production example 1-1 in which the component (B) was not added to the surface physical property modifier composition was used, the molding appearance was bad. In Comparative Example 3-2, since the content of the component (A) in the surface physical property improving agent composition was too small in Comparative Production Example 1-2, the scratch resistance and the stagnation noise were bad. In Comparative Example 3-3, since the comparative production example 1-3 in which the component (C) was not added to the surface physical property improving agent composition was used, the stagnation noise was bad. On the contrary, in Comparative Example 3-4, since the comparative production example 1-4 in which the content of the component (C) in the surface physical property improving agent composition is too large was used, the molding appearance and the stagnant sound were bad. In Comparative Example 4-1, since the comparative production example 2-1 in which the component (A) was not added to the surface physical property improving agent composition was used, the scratch resistance and the stagnant noise were bad. On the other hand, in Comparative Example 4-2, since the comparative production example 2-2 in which the content of the component (A) in the surface physical property improving agent composition is too large was used, the molding appearance was bad. On the other hand, in Comparative Example 4-3, the use of Comparative Production Example 2-3 in which the content of the component (A) in the surface physical property improving agent composition is too small, the scratch resistance and the stagnation noise were bad. In Comparative Example 4-4, since the comparative production example 2-4 in which the composition ratio of (b6) in the component (B) is too large was used, the molding appearance was bad.

Claims (3)

0.1 to 20 parts by mass of a surface physical property improving agent composition is contained with respect to 100 parts by mass of a polycarbonate resin,
The surface property improver composition comprises (A) a wax, (B) a vinyl (co) polymer, and (C) an aliphatic hydrocarbon having 5 to 14 carbon atoms,
The component (A) is at least one wax selected from (a1) paraffin wax, (a2) microcrystalline wax, (a3) Fischer-Tropsch wax, and (a4) polyethylene wax.
The component (B) is (b1) (meth) acrylonitrile, (b 2) (meth) acrylic acid, (b 3) hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, (b 4) styrene, and b5) a vinyl (co) polymer obtained by radical polymerization of at least one vinyl monomer selected from (meth) acrylic acid alkyl esters represented by the following formula (1),
50 to 98 parts by mass of the component (A) is contained in 100 parts by mass of the total of the component (A) and the component (B),
The thermoplastic resin composition which contains the said (C) component 0.001-1.0 mass% with respect to the whole quantity of the said (A) component.

(R ¹ : H or CH ₃ , R ² : C 1-4 linear or branched hydrocarbon group) 0.1 to 20 parts by mass of a surface physical property improving agent composition is contained with respect to 100 parts by mass of a polycarbonate resin,
The surface property improver composition comprises (A) a wax, (B) a vinyl (co) polymer, and (C) an aliphatic hydrocarbon having 5 to 14 carbon atoms,
The component (A) is at least one wax selected from (a1) paraffin wax, (a2) microcrystalline wax, (a3) Fischer-Tropsch wax, and (a4) polyethylene wax.
The component (B) is (b1) (meth) acrylonitrile, (b 2) (meth) acrylic acid, (b 3) hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, (b 4) styrene, and b5) At least one vinyl monomer selected from (meth) acrylic acid alkyl esters represented by the following formula (1), and (b6) a vinyl monomer having a polyorganosiloxane group in one molecule A vinyl copolymer obtained by radical polymerization of
50 to 98 parts by mass of the component (A) is contained in 100 parts by mass of the total of the component (A) and the component (B),
0.001 to 1.0 mass% of the component (C) is contained with respect to the total amount of the component (A),
The thermoplastic resin composition whose composition ratio of the said vinyl monomer (b6) in the said (B) component is 1-30 mass%.

(R ¹ : H or CH ₃ , R ² : C 1-4 linear or branched hydrocarbon group)   A resin molded article obtained by molding the thermoplastic resin composition according to claim 1 into a predetermined shape.