JP5950627B2 - Rubber-reinforced thermoplastic resin composition and resin molded product - Google Patents

Description

  The present invention relates to a rubber-reinforced thermoplastic resin composition excellent not only in color developability and scratch resistance but also in mold contamination, impact resistance and fluidity balance.

  Conventionally, styrenic resins have a good balance of molding processability and mechanical properties, and are excellent in electrical insulation, so they have been used in a wide range of fields such as the electrical / electronic equipment field and OA equipment field. Yes. However, at the stage of commercialization, when the molded product obtained by molding the resin is transported to the assembly line, for example, when the molded product is packed one by one with a soft nonwoven fabric or the like for the purpose of preventing fine scratches Therefore, a great deal of labor and cost are required.

  In addition, in order to give various designs to the resin product and to prevent the product from being damaged during use, the product may be fully or partially coated. However, the coating process has a problem that the production yield is likely to decrease due to poor coating. In addition, from the recent trend of suppressing VOC emissions, the design can be colored with a vivid color or deep color, or have a metallic or pearly appearance, etc., with as little coating as possible. Resins that are easy to impart properties and are not easily damaged are desired.

  A method for improving scratch resistance by adding an appropriate amount of polyethylene wax or silicone oil to a styrene resin having a specific structure is known (Patent Document 1). However, in recent years, the color developability is not suitable for applications requiring a high-quality appearance. Furthermore, there is a problem that silicone oil bleeds out and is inferior in mold contamination. In addition, a method is disclosed in which the scratch resistance can be improved by adding a specific nitrogen-containing compound to a rubber-reinforced styrene resin having a specific particle size distribution (Patent Document 2). However, there is a problem that the scratch resistance is still insufficient.

JP 2000-119477 A

JP 2000-191866 A

  An object of the present invention is to provide a rubber-reinforced thermoplastic resin composition excellent not only in color developability and scratch resistance, but also in mold contamination, impact resistance and fluidity balance.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have used a graft copolymer in which the rubber particle diameter and graft ratio of the rubber-like polymer are limited to a specific range, and further have a specific structure. The present inventors have found that the above object can be achieved by using a rubber-reinforced thermoplastic resin composition using a silicone-based compound.

That is, the present invention is a rubber-reinforced thermoplastic resin composition comprising a graft copolymer (A), a (co) polymer (B) and a silicon-containing compound (C), wherein the graft copolymer (A) is The presence of a rubbery polymer (a) having a weight fraction in which particles having a particle size of 0.05 μm or more and less than 0.2 μm are 50 to 90% by weight, and particles having a particle size of 0.2 μm or more are 10 to 50% by weight Underneath, at least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid ester monomers and other copolymerizable monomers It is a graft copolymer obtained by graft copolymerization of (b) and having a graft ratio of 70 to 150%. (Co) polymer (B) is an aromatic vinyl monomer, vinyl cyanide monomer Monomer, (meth) acrylic acid ester monomer and other A (co) polymer obtained by (co) polymerizing at least one monomer (b) selected from the group consisting of polymerizable monomers, and the silicon-containing compound (C) is obtained by converting a silicone compound into silica powder. The supported silicon-containing compound has a volume average particle diameter of 5 to 250 μm, a bulk specific gravity of 0.1 to 0.7, and 100 parts by weight of a rubber-reinforced thermoplastic resin composition containing a rubber-like polymer (a 5 to 24 parts by weight, and 0.01 to 10 parts by weight of the silicon-containing compound (C) is used with respect to 100 parts by weight in total of the graft copolymer (A) and the (co) polymer (B). The present invention relates to a rubber-reinforced thermoplastic resin composition, and a resin molded product obtained from the rubber-reinforced thermoplastic resin composition.

  According to the present invention, it is possible to obtain a rubber-reinforced thermoplastic resin composition excellent not only in color developability and scratch resistance but also in mold property contamination, impact resistance and fluidity balance.

The present invention will be described in detail below.
The rubber-reinforced thermoplastic resin composition of the present invention is a rubber-reinforced thermoplastic resin composition comprising a graft copolymer (A), a (co) polymer (B) and a silicon-containing compound (C). is there.

  The graft copolymer (A) used in the present invention is an aromatic vinyl monomer, vinyl cyanide monomer, (meth) acrylic acid ester monomer in the presence of the rubbery polymer (a). And at least one monomer (b) selected from the group consisting of other copolymerizable monomers.

  The rubbery polymer (a) used for the graft copolymer (A) is not particularly limited, but polybutadiene rubber, styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS) block copolymer, styrene- (Ethylene-butadiene) -styrene (SEBS) block copolymer, acrylonitrile-butadiene rubber (NBR), diene rubber such as butyl acrylate-butadiene, butyl acrylate rubber, butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber Acrylic rubber such as 2-ethylhexyl methacrylate-butyl acrylate rubber, stearyl acrylate-butyl acrylate rubber, polyorganosiloxane-butyl acrylate composite rubber, ethylene-propylene rubber, Len - propylene - polyolefin rubber polymer such as diene rubber, silicone rubber polymers such as polyorganosiloxane rubber and the like, which may be used singly or in combination. In particular, polybutadiene rubber, styrene-butadiene rubber, butyl acrylate rubber, and ethylene-propylene-diene rubber are preferable.

  The rubber-like polymer (a) used for the graft copolymer (A) has a particle size of 50 to 90% by weight of particles having a particle size of 0.05 μm or more and less than 0.2 μm, and 10 to 50 particles having a particle size of 0.2 μm or more. It is necessary to have a weight fraction of particles that would be weight percent. When the particle size is 0.05 μm or more and less than 0.2 μm is less than 50% by weight, the color developability is inferior. It is preferable that the particle | grains of 0.05 micrometer or more and less than 0.2 micrometer are 55 to 85 weight%, and it is more preferable that it is 60 to 80 weight%. When the amount of particles of 0.2 μm or more is less than 10% by weight, the impact resistance is inferior. From the viewpoint of the balance between color developability and impact resistance, the particle size of 0.2 μm or more is preferably 15 to 45% by weight, and more preferably 20 to 40% by weight. Further, with respect to particles having a particle diameter of 0.2 μm or more, from the viewpoint of scratch resistance, the particles having a particle diameter of 0.2 μm or more and less than 0.4 μm are preferably 10 to 50% by weight, and 15 to 45% by weight. Is more preferable, and it is especially preferable that it is 20 to 40 weight%.

  The weight fraction of the rubber-like polymer (a) particles was determined by dyeing the rubber-like polymer with osmium tetroxide or the like, taking a transmission photograph using a transmission electron microscope, and measuring 500 to 1,000 rubber-like dispersed particles. It can be determined by measuring the particles.

  Rubbery weight having a particle weight fraction such that particles having a particle size of 0.05 μm or more and less than 0.2 μm are 50 to 90% by weight, and particles having a particle size of 0.2 μm or more are 10 to 50% by weight. The coalescence (a) can be obtained by appropriately adjusting the polymerization conditions and the like, but by mixing rubber-like polymers having different particle weight fractions, the desired particle weight fraction is obtained. An adjusted rubber-like polymer may be used.

  Examples of the aromatic vinyl monomer used in the graft copolymer (A) include styrene, α-methyl styrene, p-methyl styrene, t-butyl styrene, and dimethyl styrene. Can be used. Styrene is particularly preferable as the aromatic vinyl monomer.

  Examples of the vinyl cyanide monomer used in the graft copolymer (A) include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and one or more of them can be used. As the vinyl cyanide monomer, acrylonitrile is particularly preferable.

  Examples of the (meth) acrylic acid ester monomer used in the graft copolymer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl. Acrylate, phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl ( A meth) acrylate, a dichlorophenyl (meth) acrylate, a trichlorophenyl (meth) acrylate etc. can be illustrated and it can use 1 type (s) or 2 or more types. As the (meth) acrylic acid ester monomer, methyl methacrylate is particularly preferable.

  Examples of other copolymerizable monomers used in the graft copolymer (A) include maleimide monomers (for example, N-phenylmaleimide, N-cyclohexylmaleimide, etc.), unsaturated carboxylic acids or the like. Anhydrides (for example, acrylic acid, methacrylic acid and maleic acid anhydride), amide monomers (for example, acrylamide and methacrylamide) and the like can be used, and one or a combination of two or more can be used. Can be used.

  The graft copolymer (A) is obtained by graft copolymerization of the monomer (b) in the presence of the rubber-like polymer (a). The graft ratio of the graft copolymer (A) is 70 to It is necessary to be 150%. When the graft ratio is less than 70%, the color developability and scratch resistance are poor, and when it exceeds 150%, the impact resistance and fluidity are poor. The graft ratio of the graft copolymer (A) is preferably 80 to 130%, and more preferably 90 to 110%.

The graft ratio of the graft copolymer (A) can be determined by measuring the infrared absorption spectrum of the graft copolymer. Specifically, removing the acetone-soluble content of the graft copolymer, creating a film composed of the insoluble content of the graft copolymer, and measuring the infrared absorption spectrum of the film using an infrared spectrometer Thus, the constituent material and the constituent ratio of the graft copolymer can be obtained. When the composition ratio of the graft copolymer is obtained, the graft ratio can be obtained by calculating with the following formula.
Graft rate (%) = (component (% by weight) relating to monomer (b) / component (% by weight) relating to rubbery polymer (a)) × 100
However, the total of the component relating to the monomer (b) and the component relating to the rubber-like polymer (a) is 100% by weight.

  When determining the graft ratio of the graft copolymer in the rubber-reinforced thermoplastic resin composition for the measurement of the graft ratio of the graft copolymer, the acetone-insoluble content of the rubber-reinforced thermoplastic resin composition corresponds to the graft copolymer. Therefore, by measuring the infrared absorption spectrum of the acetone-insoluble matter, the graft ratio of the graft copolymer (A) present in the rubber-reinforced thermoplastic resin can be determined by the same method as described above.

  There is no restriction | limiting in particular about the polymerization method of a graft copolymer (A), Although it can manufacture by emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, or these combination, It is preferable to manufacture by emulsion polymerization.

  The (co) polymer (B) used in the present invention comprises an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylic acid ester monomer, and other copolymerizable monomers. The (co) polymer obtained by polymerizing one or more monomers (b) selected from the group containing the body is used in the graft copolymer (A). The thing similar to each monomer described as an example can be used. What is necessary is just to adjust suitably according to the physical property requested | required regarding the kind and usage ratio of the monomer to be used. The (co) polymer (B) is a monomer (co) polymer that was not (co) polymerized with the rubbery polymer (a) during the graft copolymerization of the graft copolymer (A). May be included.

  There is no restriction | limiting in particular about the polymerization method of (co) polymer (B), It can manufacture by well-known emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, or these combination.

  The rubber-reinforced thermoplastic resin composition of the present invention contains a graft copolymer (A) and a (co) polymer (B), but the rubber-like polymer (a) in 100 parts by weight of the rubber-reinforced thermoplastic resin composition. As long as 5 to 24 parts by weight is contained, there is no limitation on the use ratio of the graft copolymer (A) and the (co) polymer (B). That is, when the (co) polymer by-produced in the graft copolymerization of the graft copolymer (A) has the same role as the (co) polymer (B), the (co) polymer (B) May not be used. When the amount of the rubbery polymer (a) is less than 5 parts by weight, the impact resistance is inferior, and when it exceeds 24 parts by weight, the color developability, scratch resistance and fluidity are inferior. From the viewpoint of balance of physical properties, the rubber-like polymer (a) is preferably contained in an amount of 7 to 20 parts by weight, and more preferably 10 to 17 parts by weight.

  Further, the rubber-reinforced thermoplastic resin composition of the present invention is prepared by graft-polymerizing two or more kinds of rubber-like polymers having different weight fractions to produce two or more kinds of graft copolymers. It may be a rubber-reinforced thermoplastic resin composition obtained by melt-mixing the graft copolymer and the (co) polymer (B).

  There is no particular limitation on the reduced viscosity of the acetone soluble part of the rubber-reinforced thermoplastic resin composition of the present invention (0.4 g / 100 cc, measured at 30 ° C. as an N, N dimethylformamide solution). Although a thing can be used, it is preferable that it is 0.2-2.0 dl / g from a viewpoint of a physical-property balance, and it is more preferable that it is 0.3-1.5 dl / g.

  The silicon-containing compound (C) used in the present invention is a compound in which a silicone compound is supported on silica powder. Specifically, it is a silicon-containing compound in which a silicone compound is supported on the surface of silica powder.

  Examples of the silicone compound used for the silicon-containing compound (C) include silicone oil, silicone rubber or an intermediate thereof, silicone resin or an intermediate thereof.

  As the silicone compound, those containing, for example, an epoxy group, an acryloxy group, a methacryloxy group, a vinyl group, a phenyl group, or a hydroxyl group as a reactive functional group in the molecule or at the molecular end can be used. Among these, those containing a methacryloxy group can be preferably used.

The silica powder used for the silicon-containing compound (C) functions to support (absorb, adsorb or hold) the silicone compound, and fumed silica, precipitated silica, finely pulverized silica, or the like is used. The surface area of these silicas is preferably in the range of 50 to 400 m ² / g. When the surface area is in this range, it becomes easy to support the silicone compound.

  Although there is no restriction | limiting in particular in content of the silicone type compound of a silicon containing compound (C), 40-80 weight part is contained in 100 weight part of silicon containing compound (C) from a viewpoint of scratch resistance and color development. Is preferred. Moreover, it is preferable that the volume average particle diameter of a silicon-containing compound (C) exists in the range of 5-250 micrometers from the ease of dispersion | distribution to a resin composition. The bulk specific gravity of the silicon-containing compound (C) is preferably in the range of 0.1 to 0.7.

  The usage-amount of a silicon containing compound (C) is 0.1-10 weight part with respect to a total of 100 weight part of a graft copolymer (A) and a (co) polymer (B). If it is less than 0.1 part by weight, the scratch resistance is insufficient, and if it exceeds 10 parts by weight, the color developability is poor. Preferably it is 0.1-3 weight part.

  The rubber-reinforced thermoplastic resin composition of the present invention may contain various additives as necessary, for example, known antioxidants, light stabilizers, lubricants, plasticizers, antistatic agents, colorants, flame retardants, matting agents, A filler, glass fiber, etc. can be added suitably.

  The rubber-reinforced thermoplastic resin composition of the present invention can be used alone, but can also be used by mixing with other thermoplastic resins as necessary. Examples of such other thermoplastic resins that can be used include acrylic resins such as polymethyl methacrylate, polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyamide resins, and polylactic acid resins.

  The rubber-reinforced thermoplastic resin composition of the present invention can be obtained by mixing the above-described components. In order to mix, well-known kneading apparatuses, such as an extruder, a roll, a Banbury mixer, a kneader, can be used, for example. Moreover, there is no restriction | limiting in particular in the mixing method and order of the above-mentioned component, The silicon-containing compound (C) is added to the resin composition obtained by melt-kneading the graft copolymer (A) and the (co) polymer (B). May be obtained by mixing the graft copolymer (A), (co) polymer (B), and silicon-containing compound (C), and then melt-kneaded to obtain the resin composition. You can get things.

  Furthermore, the rubber-reinforced thermoplastic resin composition of the present invention can be molded by known molding methods such as extrusion molding, injection molding, blow molding and press molding, and various molded products can be produced.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” are based on weight.

<Test example>
For the graft copolymer (A), copolymer (B), and silicon-containing compound (C) having the composition ratios shown in Tables 3 and 4, Sumiplast Black HB (manufactured by Sumitomo Chemical Co., Ltd.) is used as a colorant. 0.0 parts mixed. Using a vented 50 mm single-screw extruder (manufactured by ON Machinery), the mixture was melt-mixed at a cylinder temperature of 210 ° C. and pelletized to obtain black colored pellets. In addition, each component shown in Table 1 and Table 2 is as follows.

Production of rubber polymer (a) Rubber polymer (a-1): 93 parts 1,3-butadiene, 7 parts styrene, 0.5 parts n-dodecyl mercaptan, 0.24 potassium persulfate in a pressure vessel Part, sodium rosinate 1.5 parts, sodium hydroxide 0.1 part and deionized water 150 parts, reacted at 70 ° C. for 15 hours, then cooled to terminate the reaction, thereby styrene-butadiene rubber Latex (a-1) was obtained. The obtained styrene-butadiene rubber latex (a-1) was dyed with osmium tetroxide (OsO ₄ ), and after drying, photographed with a transmission electron microscope. Using an image analysis processor (apparatus name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.), the area of 1000 rubber particles was measured, the circle equivalent diameter (diameter) was determined, and the weight average particle diameter of styrene-butadiene rubber And the weight fraction was calculated. Table 1 shows the weight average particle diameter and the weight fraction.

  Rubbery polymers (a-2) to (a-4): The styrene-butadiene rubber latex (a-1) obtained above was subjected to agglomeration and enlargement treatment of rubber particles. 270 parts of styrene-butadiene rubber latex (a-1) was added to a stirring tank and 0.09 part of a 10% aqueous sodium dodecylbenzenesulfonate solution was added and stirred for 10 minutes. Then, 0.8 part of a 5% aqueous phosphoric acid solution was added for 10 minutes. Was added over a period of time. Thereafter, a rubbery polymer (a-2) having a weight average particle diameter of 0.25 μm was obtained by adding 1 part of a 10% aqueous potassium hydroxide solution. Styrene-butadiene rubber latexes (a-3) to (a-4) were obtained by adjusting the amount of sodium dodecylbenzenesulfonate. By the above-mentioned method, the weight average particle diameter and weight fraction of the obtained styrene-butadiene rubber latex were measured. The measurement results are shown in Table 1.

  Rubbery polymers (a-5) to (a-9): By mixing the styrene-butadiene rubber latexes (a-1) to (a-4) in the composition ratios shown in Table 1, rubbery polymers ( a-5) to (a-9) were obtained.

Production of Graft Copolymer (A) Graft Copolymer (A-1): 30 parts (solid content) of styrene-butadiene rubber latex (a-5), 160 parts of water, ethylenediaminetetraacetic acid diacetylate in a nitrogen-substituted reactor. Sodium salt 0.1 part, ferrous sulfate 0.001 part, sodium formaldehyde sulfoxylate 0.3 part, heated to 60 ° C., 49 parts styrene, 21 parts acrylonitrile, 0.3 part t-dodecyl mercaptan And a mixture consisting of 0.2 parts of cumene hydroperoxide and a mixture consisting of 1.5 parts of potassium oleate and 15 parts of water was continuously added over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-1) was obtained by salting out, dehydrating and drying.

A certain amount of the graft copolymer (A-1) was put into acetone, shaken with a shaker for 2 hours, and the graft copolymer was immersed. This solution was centrifuged at 15,000 rpm for 30 minutes using a centrifuge, and then dried at room temperature for a whole day and night by vacuum drying to obtain an acetone insoluble matter. The obtained acetone-insoluble matter was formed into a film, and the weight ratio of styrene-butadiene rubber, styrene, and acrylonitrile was identified from the infrared absorption spectrum using an infrared spectroscopic analyzer (device name: Spectrum One Perkin Elmer). The graft ratio was calculated from the weight ratio of each component.
Moreover, after drying the acetone soluble part obtained above, it melt | dissolves in N, N- dimethylformamide, and after making it a solution of the density | concentration of 0.4 g / 100cc, it flows down at 30 degreeC using a Cannon Fenceke type | mold viscosity pipe | tube. The reduced viscosity was determined by measuring the time.
The graft ratio of the obtained graft copolymer (A-1) and the reduced viscosity of the acetone-soluble component were 91% and 0.40 dl / g, respectively.

  Graft copolymer (A-2): 30 parts (solid content) of styrene-butadiene rubber latex (a-6), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-2) was obtained by salting out, dehydrating, and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-2) and the reduced viscosity of the acetone-soluble component by the above-described method, the graft ratio was 89% and the reduced viscosity was 0.39 dl / g. .

  Graft copolymer (A-3): 30 parts (solid content) of styrene-butadiene rubber latex (a-5), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 iron 0.001 part, sodium formaldehyde sulfoxylate 0.3 part, and after heating to 60 ° C., a mixture of 49 parts of styrene, 21 parts of acrylonitrile and 0.2 part of cumene hydroperoxide and potassium oleate 1 A mixture consisting of .5 parts and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-3) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-3) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 130% and the reduced viscosity was 0.39 dl / g. .

  Graft copolymer (A-4): 30 parts (solid content) of styrene-butadiene rubber latex (a-5), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron and 0.3 part of sodium formaldehyde sulfoxylate are added, heated to 60 ° C., 21 parts of styrene, 49 parts of methyl methacrylate, 0.3 part of t-dodecyl mercaptan and 0. cumene hydroperoxide. A mixture consisting of 2 parts and a mixture consisting of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-4) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-4) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 81% and the reduced viscosity was 0.37 dl / g. .

  Graft copolymer (A-5): 20 parts (solid content) of styrene-butadiene rubber latex (a-5), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 56 parts of styrene, 24 parts of acrylonitrile, 0.4 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-5) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-5) and the reduced viscosity of the acetone-soluble component by the above-described method, the graft ratio was 75% and the reduced viscosity was 0.36 dl / g. .

  Graft copolymer (A-6): 48 parts (solid content) of styrene-butadiene rubber latex (a-5) in a nitrogen-substituted reactor, 140 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehydesulfoxylate are added, and after heating to 60 ° C., 39 parts of styrene, 13 parts of acrylonitrile, 0.6 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-6) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-6) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 40% and the reduced viscosity was 0.39 dl / g. .

  Graft copolymer (A-7): 20 parts (solid content) of styrene-butadiene rubber latex (a-5), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 iron 0.001 part, sodium formaldehyde sulfoxylate 0.3 part, heated to 60 ° C., mixture of styrene 56 parts, acrylonitrile 24 parts, cumene hydroperoxide 0.2 parts and potassium oleate 1 A mixture consisting of .5 parts and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-7) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-7) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 170% and the reduced viscosity was 0.44 dl / g. .

  Graft copolymer (A-8): 30 parts (solid content) of styrene-butadiene rubber latex (a-7), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-8) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-8) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 95% and the reduced viscosity was 0.41 dl / g. .

  Graft copolymer (A-9): 30 parts (solid content) of styrene-butadiene rubber latex (a-8), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-9) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-9) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 87% and the reduced viscosity was 0.38 dl / g. .

  Graft copolymer (A-10): 30 parts (solid content) of styrene-butadiene rubber latex (a-9) in a nitrogen-substituted reactor, 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And a mixture of 1.5 parts of potassium oleate and 15 parts of water was added continuously over 4 hours. After completion of the addition, polymerization was further performed at 60 ° C. for 2 hours. Then, the graft copolymer (A-10) was obtained by salting out, dehydrating and drying. As a result of measuring the graft ratio of the obtained graft copolymer (A-10) and the reduced viscosity of the acetone-soluble component by the above method, the graft ratio was 98% and the reduced viscosity was 0.41 dl / g. .

  Graft copolymer (A-11): 30 parts (solid content) of styrene-butadiene rubber latex (a-1), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehydesulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And 1.5 parts of potassium oleate were continuously added over 4 hours and further polymerized at 60 ° C. for 2 hours. Thereafter, after salting out, dehydration and drying, a graft copolymer (A-11) was obtained. As a result of measuring the graft ratio of the obtained graft copolymer (A-11) and the reduced viscosity of the acetone-soluble component, the graft ratio was 93% and the reduced viscosity was 0.40 dl / g.

  Graft copolymer (A-12): 30 parts (solid content) of styrene-butadiene rubber latex (a-2), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehyde sulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.28 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And 1.5 parts of potassium oleate were continuously added over 4 hours and further polymerized at 60 ° C. for 2 hours. Thereafter, after salting out, dehydration and drying, a graft copolymer (A-12) was obtained. As a result of measuring the graft ratio of the obtained graft copolymer (A-12) and the reduced viscosity of the acetone-soluble component, the graft ratio was 89% and the reduced viscosity was 0.39 dl / g.

  Graft copolymer (A-13): 30 parts (solid content) of styrene-butadiene rubber latex (a-2), 160 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid 1 part 0.001 part of iron, 0.3 part of sodium formaldehydesulfoxylate are added, and after heating to 60 ° C., 49 parts of styrene, 21 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan and 0.2 part of cumene hydroperoxide And 1.5 parts of potassium oleate were continuously added over 4 hours and further polymerized at 60 ° C. for 2 hours. Thereafter, after salting out, dehydration and drying, a graft copolymer (A-13) was obtained. As a result of measuring the graft ratio of the obtained graft copolymer (A-13) and the reduced viscosity of the acetone-soluble component, the graft ratio was 93% and the reduced viscosity was 0.40 dl / g.

Production of copolymer (B) Copolymer (B-1): A copolymer (B-1) comprising 70 parts by weight of styrene and 30 parts by weight of acrylonitrile was obtained by a known bulk polymerization method. As a result of measuring the reduced viscosity of the obtained copolymer (B-1) by the above method, the reduced viscosity was 0.60 dl / g.
Copolymer (B-2): A copolymer (B-2) comprising 30 parts by weight of styrene and 70 parts by weight of methyl methacrylate was obtained by a known bulk polymerization method. As a result of measuring the reduced viscosity of the obtained copolymer (B-2) by the above method, the reduced viscosity was 0.58 dl / g.

Silicon-containing compound (C)
Silicon-containing compound (C-1): DC4-7081 (manufactured by Toray Dow Corning Co., Ltd.)
A silicon-containing compound in which 60 parts of a silicone compound containing a methacryloxy functional group is supported on 40 parts of silica powder. Bulk specific gravity: 0.3 to 0.5, particle size: 10 to 200 μm
Silicon-containing compound (C-2): SH200-100CS (manufactured by Toray Dow Corning Co., Ltd.)
Dimethyl silicone oil. Viscosity: 100 mm ² / s
Silicon-containing compound (C-3): BY27-007 (manufactured by Dow Corning Toray)
Pellets made by melt-kneading ultrahigh molecular weight dimethyl silicone polymer and ABS resin (silicone content 50%).

(1) Color developability The lightness (L *) of the molded product was measured by hue measurement based on JIS-Z8729 and used as a measure of color developability. (Since the lightness (L *) of the molded product is smaller, the jetness of the molded product is better, and as a result, the color develops when the same colorant is added in the same amount.) And using the colored pellets obtained in the comparative example, a molded product (150 mm × 120 mm × 3 mm) molded by an injection molding machine (J-150EP manufactured by Nippon Steel Works, cylinder temperature: 200 ° C., mold temperature: 80 ° C.) Using. The spectrophotometer used was CMS-35SP manufactured by Murakami Color Research Co., Ltd.

(2) Scratch resistance reciprocating wear tester (product name: Tribogear TYPE: 30S, manufactured by Shinto Kagaku Co., Ltd.), set a Kankin No. 3 cotton cloth on an indenter with a tip of 27 mm in diameter, and a constant load of 1 kg Below, the surface of the molded product was rubbed 50 times (speed: 600 mm / min). As the molded product, the same molded product as used in (1) was used. After the test, scratches on the surface of the molded product were visually confirmed, and scratch resistance was evaluated by the following judgment.
No scratches are seen: ◎
Scratches are hardly seen: ○
Scratches are slightly visible:
Scratches are clearly seen: ×

(3) Mold fouling property Using colored pellets obtained in each of the examples and comparative examples, using J-150EP manufactured by Nippon Steel Works, cylinder set temperature 240 ° C, mold temperature 50 ° C, molding cycle 30 seconds A flat plate test piece (length 150 mm, width 150 mm, thickness 3 mm) was subjected to 1000 shot injection molding, and the mold contamination was evaluated by the following judgment.
No change on mold surface: ○
The mold surface is cloudy: △
The mold surface is extremely dirty and the appearance of the molded product is poor: ×

(4) Impact resistance Various test pieces were molded in accordance with ISO test method 294 using the colored pellets obtained in each of the examples and comparative examples, and the impact resistance was measured.
The impact resistance was in conformity with ISO 179, and a Charpy impact value with a notch was measured at a thickness of 4 mm. Unit: kJ / m ²

(5) Fluidity Using the colored pellets obtained in each Example and Comparative Example, melt volume flow rate was measured under the conditions of 220 ° C. and 10 kg load according to ISO1133. Unit; ^cm 3/10 minutes

  As shown in Table 3, it can be seen that the rubber-reinforced thermoplastic resin composition of the present invention not only has excellent scratch resistance and color developability, but also has excellent balance between physical properties of mold contamination, impact resistance and fluidity. . Regarding the weight fraction of the rubber-like polymer, when the particle size is 0.2 μm or more and less than 0.4 μm is in the range of 10 to 50% by weight, the result is particularly excellent in scratch resistance. Further, as shown in Examples 9 and 10, even when two or more kinds of rubber-like polymers are separately graft-polymerized and two or more kinds of graft copolymers are used, the graft ratio and particles defined in the present invention are used. As long as the weight fraction is satisfied, the object of the present application can be achieved.

  As shown in Table 4, Comparative Example 1 in which no silicon-containing compound was used resulted in poor scratch resistance. Comparative Example 2 in which the rubber content in the rubber-reinforced thermoplastic resin composition was less than 5 parts by weight resulted in poor impact resistance. Comparative Example 3 having a rubber content greater than 24 parts by weight resulted in poor color development, scratch resistance, and fluidity. Comparative Example 4 using the graft copolymer (A-6) having a graft ratio of less than 70% resulted in poor color development and scratch resistance. Comparative Example 5 using the graft copolymer (A-7) having a graft ratio exceeding 150% resulted in inferior impact resistance and fluidity. Comparison using rubbery polymers (a-8) and (a-9) in which particles of 0.05 μm or more and less than 0.2 μm are less than 50% by weight and particles of 0.2 μm or more are 50% by weight or more Examples 6 and 7 were inferior in color developability and scratch resistance. Comparative Example 8 using silicone oil resulted in poor scratch resistance and mold contamination. Comparative Example 9 using a silicon-containing compound in which a silicone compound was not supported on silica powder resulted in inferior color developability, scratch resistance, and mold contamination.

  The rubber-reinforced thermoplastic resin composition of the present invention can be used in a wide range of fields including the electric / electronic equipment field, the OA equipment field and the like by utilizing the above-described excellent characteristics. It is particularly suitable for applications in which both excellent physical property balance, color developability and scratch resistance are achieved.

Claims (3)

A rubber-reinforced thermoplastic resin composition comprising a graft copolymer (A), a (co) polymer (B) and a silicon-containing compound (C), the graft copolymer (A) having a particle size of 0.05 μm In the presence of the rubbery polymer (a) having a weight fraction of 50 to 90% by weight of particles having a particle size of less than 0.2 μm and 10 to 50% by weight of particles having a particle size of 0.2 μm or more At least one monomer (b) selected from the group consisting of a monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and other copolymerizable monomers is grafted. A graft copolymer obtained by polymerization and having a graft ratio of 70 to 150%. (Co) polymer (B) is an aromatic vinyl monomer, vinyl cyanide monomer, (meth) Acrylic ester monomers and other copolymerizable monomers In consisting at least one monomer of (b) were (co) polymerizing (co) polymer selected from the group, silicon-containing compound (C) is a silicon-containing compound obtained by supporting the silicone compound to the silica powder The volume average particle diameter is 5 to 250 μm, the bulk specific gravity is 0.1 to 0.7, and 5 to 24 parts by weight of the rubber-like polymer (a) in 100 parts by weight of the rubber-reinforced thermoplastic resin composition. A rubber reinforcement comprising 0.01 to 10 parts by weight of a silicon-containing compound (C) based on 100 parts by weight of the total of the graft copolymer (A) and the (co) polymer (B). Thermoplastic resin composition. Silicone compounds contained in the silicon-containing compound (C) comprises a methacryloxy group or a molecular terminal in the molecule, to claim 1 where the silicone compound to the silicon-containing compound in 100 parts by weight, characterized in that it comprises 40 to 80 parts by weight The rubber-reinforced thermoplastic resin composition described. Claim 1 resin molded article characterized in that it is obtained from a rubber-reinforced thermoplastic resin composition according to any one of 2.