TW201339233A - Rubber-reinforced thermoplastic resin composition and resin molded article - Google Patents

Abstract

A rubber-reinforced thermoplastic resin composition having: a dispersed phase that is composed of a graft copolymer (A) produced by the graft copolymerization of at least one monomer (b) selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth)acrylic acid ester monomer and other copolymerizable monomers in the presence of a rubbery polymer (a); and a continuous phase that is composed of a (co)polymer (B) produced by the (co)polymerization of at least one monomer (b) selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth)acrylic acid ester monomer and other copolymerizable monomers. The rubber-reinforced thermoplastic resin composition is characterized in that the rubbery polymer (a) has such weight fractions that particles each having a particle diameter of 0.05 mum or more and less than 0.2 mum are contained in an amount of 50 to 90 wt% and particles each having a particle diameter of 0.2 mum or more are contained in an amount of 10 to 50 wt%, the graft rate of the graft copolymer (A) is 70 to 150%, and the rubbery polymer (a) is contained in an amount of 5 to 24 parts by weight relative to 100 parts by weight of the rubber-reinforced thermoplastic resin composition.

Description

Rubber-reinforced thermoplastic resin composition and resin molded article

The present invention relates to a rubber-reinforced thermoplastic resin composition and a resin molded article.

Since styrene-based resins have excellent balance between moldability and mechanical properties and excellent electrical insulation properties, they have been used in a wide range of fields such as electrical, electronic equipment, and OA equipment. However, in the stage of productization, when the molded article obtained by molding the resin is transported to, for example, an assembly line, it is necessary to pack the molded articles one by one with a soft non-woven fabric or the like in order to prevent minute scratches. Therefore, it takes a lot of work. With cost.

Further, in order to impart various designs to the resin product or to prevent damage to the product, there is a case where the product is entirely coated or partially coated. However, the coating treatment has a problem that the production yield due to poor coating is likely to be lowered. In addition, in recent years, it is expected that the trend of suppressing VOC discharge can be colored into a bright color or a deep color or an appearance having a metallic color or a pearl color without performing a coating process, and it is easy to impart design and is not easily damaged. Resin.

A method of improving the scratch resistance by adding an appropriate amount of a polyethylene wax or a polyoxygenated oil to a styrene resin having a specific structure is known (Patent Document 1). However, in recent years, color development is seriously inappropriate in applications requiring a high-grade appearance. Further, there is a problem that the polyphthalic acid oil oozes and the mold contamination is poor. Also, it is revealed that it has a specific particle size distribution A method of adding a specific nitrogen-containing compound to a rubber-reinforced styrene-based resin to improve damage (Patent Document 2). However, there is a problem that the damage resistance is still insufficient.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2000-119477

Patent Document 2: Japanese Laid-Open Patent Publication No. 2000-191866

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

The inventors of the present invention conducted intensive studies to solve the problems of the prior art, and as a result, found that by limiting the rubber particle diameter and the graft ratio of the rubber-like polymer constituting the graft copolymer to a specific range, it is not necessary to use it as a polyfluorene. The above object is attained by an additive of an oxygen-based compound or the like, thereby completing the present invention.

The invention of one aspect of the invention relates to a rubber-reinforced thermoplastic resin composition and a resin molded article obtained from the rubber-reinforced thermoplastic resin composition, the following graft copolymer (A) The (co)polymer (B) constitutes a continuous phase, and the graft copolymer (A) is in the presence of the rubbery polymer (a) and is selected from an aromatic vinyl group. a graft copolymerization of at least one monomer (b) of a monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and another copolymerizable monomer group, the (co) The polymer (B) is at least one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth)acrylate monomer, and other copolymerizable monomers. (b) (co)polymerized; characterized in that the rubbery polymer (a) has a particle diameter of 0.05 μm or more and less than 0.2 μm, and has a weight fraction of 50 to 90% by weight, and a particle diameter of 0.2 μm. The above particles have a weight fraction of 10 to 50% by weight, and the graft ratio of the graft copolymer (A) is 70. ~150%, 5 to 24 parts by weight of the rubber-like polymer (a) is contained in 100 parts by weight of the rubber-reinforced thermoplastic resin composition.

Moreover, the inventors of the present invention conducted intensive studies to solve the problems of the prior art, and as a result, found that by using a graft copolymer in which the rubber particle diameter and the graft ratio of the rubber-like polymer are limited to a specific range, Further, the above object can be attained by using a rubber-reinforced thermoplastic resin composition having a polyoxynitride-based compound having a specific structure, thereby completing the present invention.

That is, the invention according to another aspect of the invention relates to a rubber-reinforced thermoplastic resin composition containing a graft copolymer (A) and a resin molded article obtained from the rubber-reinforced thermoplastic resin composition. (co)polymer (B) and cerium-containing compound (C), characterized in that the graft copolymer (A) is a weight of 50 to 90% by weight of particles having a particle diameter of 0.05 μm or more and less than 0.2 μm. In the presence of a rubbery polymer (a) having a particle fraction of 0.2 μm or more and a particle weight of 10 to 50% by weight, the aromatic vinyl monomer and the vinyl cyanide monomer are selected from the group consisting of aromatic vinyl monomers and vinyl cyanide monomers. a graft copolymer obtained by graft copolymerization of at least one monomer (b) of a (meth) acrylate monomer and other copolymerizable monomer groups, and a graft copolymer having a graft ratio of 70 to 150%. The (co)polymer (B) is at least selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and other copolymerizable monomers. a monomer (b) (co)polymerized, the cerium-containing compound (C) is supported on a cerium oxide powder The cerium-containing compound contains 5 to 24 parts by weight of the rubbery polymer (a) in 100 parts by weight of the rubber-reinforced thermoplastic resin composition, based on the total of the graft copolymer (A) and the (co)polymer (B). 100 parts by weight of the cerium-containing compound (C) is used in an amount of 0.01 to 10 parts by weight.

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

Hereinafter, the present invention will be described in detail.

The rubber-reinforced thermoplastic resin composition according to the first embodiment of the present invention is characterized in that the graft copolymer (A) constitutes a dispersed phase, and the (co)polymer (B) constitutes a continuous phase.

The rubber-reinforced thermoplastic resin composition according to the second embodiment of the present invention is characterized by comprising a graft copolymer (A), a (co)polymer (B), and a ruthenium-containing compound (C).

The graft copolymer (A) used in the present invention is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth) acrylate in the presence of a rubbery polymer (a). It is obtained by graft copolymerization of at least one monomer (b) of a group of monomers and other copolymerizable monomers.

The rubbery polymer (a) used in the graft copolymer (A) is not particularly limited, and examples thereof include polybutadiene rubber, styrene-butadiene rubber (SBR), and styrene-butylene. Alkene-styrene (SBS) block copolymer, styrene-(ethylene-butadiene)-styrene (SEBS) block copolymer, acrylonitrile-butadiene rubber (NBR), butyl acrylate-butyl Diene rubber such as olefin, butyl acrylate rubber, butadiene butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, 2-ethylhexyl methacrylate-butyl acrylate rubber, acrylic acid Acrylic rubber such as stearyl acrylate-butyl acrylate rubber, polyorganosiloxane or butyl acrylate composite rubber, polyolefin rubber polymer such as ethylene-propylene rubber or ethylene-propylene-diene rubber, polyorganosiloxane The ruthenium-based rubber polymer such as rubber may be used alone or in combination of two or more. Particularly preferred are polybutadiene rubber, styrene-butadiene rubber, butyl acrylate rubber, and ethylene-propylene-diene rubber.

The rubbery polymer (a) used in the graft copolymer (A) must have a particle diameter of 0.05 μm or more and less than 0.2 μm to be 50 to 90% by weight and a particle diameter of 0.2 μm. The above particles are a weight fraction of particles of 10 to 50% by weight. When the particles of 0.05 μm or more and less than 0.2 μm are less than 50% by weight, the color rendering property is inferior, and if it exceeds 90% by weight, the impact resistance is inferior. The particles of 0.05 μm or more and less than 0.2 μm are preferably 55 to 85% by weight, more preferably 60 to 80% by weight. When the particle of 0.2 μm or more is less than 10% by weight, the impact resistance is inferior, and when it is 50% by weight or more, the scratch resistance and the color rendering property are inferior. From the viewpoint of the balance between color rendering properties and impact resistance, particles of 0.2 μm or more are preferably 15 to 45% by weight, more preferably 20 to 40% by weight. Further, in the case of particles having a particle diameter of 0.2 μm or more, particles having a particle diameter of 0.2 μm or more and less than 0.4 μm are preferably 10 to 50% by weight, more preferably 15 to 45% by weight, particularly from the viewpoint of scratch resistance. Good is 20~40% by weight.

The weight fraction of the particles of the rubbery polymer (a) can be determined by dyeing the rubbery polymer by osmium tetroxide or the like, and photographing the penetrating image using a transmission electron microscope to measure the rubbery dispersion. Particles of 500~1000 particles.

The rubbery polymer (a) having a particle diameter of a particle having a particle diameter of 0.05 μm or more and a particle size of not more than 0.2 μm of 50 to 90% by weight and a particle diameter of 0.2 μm or more is 10 to 50% by weight. It is obtained by appropriately adjusting the polymerization conditions and the like, and can also be adjusted to the target particle weight fraction by mixing rubbery polymers having different particle weight fractions.

The aromatic vinyl monomer used as the graft copolymer (A) is exemplified by styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and dimethylstyrene. Alternatively, one type or two or more types can be used. As the aromatic vinyl monomer, styrene is particularly preferred.

The vinyl cyanide monomer to be used for the graft copolymer (A) may, for example, be acrylonitrile, methacrylonitrile, ethacrylonitrile or fumaronitrile, and one type or two or more types may be used. . As the vinyl cyanide monomer, acrylonitrile is particularly preferable.

The (meth) acrylate type monomer used for the graft copolymer (A) may, for example, be methyl (meth) acrylate, ethyl (meth) acrylate or propyl (meth) acrylate. Base) Butyl olefinate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, 4-tert-butyl phenyl (meth) acrylate, bromophenyl (meth) acrylate, (meth) acrylate Bromophenyl ester, 2,4,6-tribromophenyl (meth)acrylate, monochlorophenyl (meth)acrylate, dichlorophenyl (meth)acrylate, trichlorophenyl (meth)acrylate, etc. One type or two or more types can be used. As the (meth) acrylate monomer, methyl methacrylate is particularly preferred.

As the other copolymerizable monomer used for the graft copolymer (A), for example, a maleimide-based monomer (for example, N-phenylbutyleneimine, N-ring) can be used. Hexylm-butyleneimine or the like), an unsaturated carboxylic acid or an anhydride thereof (for example, acrylic acid, methacrylic acid, maleic anhydride, etc.), and a guanamine-based monomer (for example, acrylamide and methyl group) One type of the acrylamide or the like may be used alone or two or more types may be used in combination.

The graft copolymer (A) can be obtained by graft copolymerization of the monomer (b) in the presence of the rubbery polymer (a), and the graft ratio of the graft copolymer (A) must be 70 to 150%. When the graft ratio is less than 70%, color rendering property and scratch resistance are inferior, and if it exceeds 150%, impact resistance and fluidity are inferior. The graft ratio of the graft copolymer (A) is preferably from 80 to 130%, more preferably from 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, the acetone-soluble component of the graft copolymer is removed to form a film composed of an insoluble component of the graft copolymer, and the infrared absorption spectrum of the film is measured by an infrared spectroscopic device, whereby the composition of the graft copolymer can be determined. Substance and composition ratio. When the composition ratio of the graft copolymer is obtained, the graft ratio can be determined by calculation using the following formula.

Graft ratio (%) = (component (% by weight) related to monomer (b) / component (% by weight) related to rubbery polymer (a)) × 100

In addition, the total of "components related to the monomer (b)" and "components related to the rubbery polymer (a)" was 100% by weight.

Determination of grafting ratio of graft copolymer for rubber-reinforced thermoplastic resin In the case of the graft ratio of the graft copolymer in the composition, since the acetone-insoluble component of the rubber-reinforced thermoplastic resin composition corresponds to the graft copolymer, the infrared absorption spectrum of the acetone-insoluble component can be measured and utilized. The graft ratio of the graft copolymer (A) present in the rubber-reinforced thermoplastic resin was determined by the same method.

The polymerization method of the graft copolymer (A) is not particularly limited, and it can be produced by emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization or a combination thereof, and is preferably produced by emulsion polymerization.

The (co)polymer (B) used in the present invention is selected from the group consisting of an aromatic vinyl-based monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and other copolymerizable ones. When the monomer (b) of the monomer group is obtained by polymerization, the monomer to be used may be the same as the monomer used as the graft copolymer (A). The type of the monomer to be used or the ratio of use may be appropriately adjusted depending on the desired physical properties. Further, the (co)polymer (B) may also contain a (co)polymer of a monomer which is not (co)polymerized with the rubbery polymer (a) during graft copolymerization of the graft copolymer (A).

The polymerization method of the (co)polymer (B) is not particularly limited, and it can be produced by a known emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof.

The rubber-reinforced thermoplastic resin composition according to the first embodiment of the present invention comprises a graft copolymer (A) as a dispersed phase and a (co)polymer (B) as a continuous phase, as long as the rubber-reinforced thermoplastic resin composition 100 is used. When the rubbery polymer (a) is contained in an amount of 5 to 24 parts by weight, the ratio of use of the graft copolymer (A) to the (co)polymer (B) is not limited. That is, in the case where the (co)polymer formed by the graft copolymerization of the graft copolymer (A) is a continuous phase, the (co)polymer (B) may not be used. When the rubbery polymer is less than 5 parts by weight, the impact resistance is inferior, and if it exceeds 24 parts by weight, color rendering properties, scratch resistance, and fluidity are inferior. From the viewpoint of the balance of physical properties, it is preferably 7 to 20 parts by weight, more preferably 10 to 17 parts by weight, based on the rubbery polymer.

In addition, the rubber-reinforced thermoplastic resin composition of the first embodiment may be obtained by graft-polymerizing two or more kinds of rubber-like polymers having different weight fractions to produce two or more kinds. The copolymer is grafted and the graft copolymer is melt-kneaded with the (co)polymer. However, in this case, the graft ratio of each graft copolymer must be 70 to 150%.

The reduction viscosity (0.4 g/100 cc, measured by N,N-dimethylformamide solution at 30 ° C) of the continuous phase (acetone soluble portion) of the rubber-reinforced thermoplastic resin composition of the first embodiment is not particularly limited. Any value may be used depending on the required performance. From the viewpoint of physical balance, it is preferably 0.2 to 2.0 dl/g, more preferably 0.3 to 1.5 dl/g.

Further, the rubber-reinforced thermoplastic resin composition of the second embodiment of the present invention contains the graft copolymer (A) and the (co)polymer (B), and rubbery polymerization is contained in 100 parts by weight of the rubber-reinforced thermoplastic resin composition. When the amount of the (a) is 5 to 24 parts by weight, the ratio of use of the graft copolymer (A) to the (co)polymer (B) is not limited. That is, when the (co)polymer which is produced by the graft copolymerization of the graft copolymer (A) has the same action as the (co)polymer (B), the (co)polymer may not be used ( B). When the rubbery polymer (a) is less than 5 parts by weight, the impact resistance is poor, and when it exceeds 24 parts by weight, color rendering properties, scratch resistance, and fluidity are inferior. From the viewpoint of the balance of physical properties, it is preferably 7 to 20 parts by weight, more preferably 10 to 17 parts by weight, based on the rubbery polymer (a).

In addition, the rubber-reinforced thermoplastic resin composition of the second embodiment may be obtained by graft-polymerizing two or more kinds of rubber-like polymers having different weight fractions to produce two or more kinds. The copolymer is grafted and the graft copolymer is melt-kneaded with the (co)polymer (B).

The reduction viscosity of the acetone-soluble portion of the rubber-reinforced thermoplastic resin composition of the second embodiment (0.4 g/100 cc, measured by N,N-dimethylformamide solution at 30 ° C) is not particularly limited, and may be as required. The performance of any value is preferably from 0.2 to 2.0 dl/g, more preferably from 0.3 to 1.5 dl/g, from the viewpoint of physical balance.

The ruthenium-containing compound (C) used in the present invention is a ruthenium-containing compound containing a polyfluorene-based compound in a cerium oxide powder. Specifically, it is a ruthenium-containing compound containing a polyfluorene-based compound on the surface of the cerium oxide powder.

The polyfluorene-based compound used in the cerium-containing compound (C) may, for example, be a polyoxyxylene oil, a polyoxyxylene rubber or an intermediate thereof, a polyoxyxylene resin or an intermediate thereof.

The polyoxygenated compound may further contain, as a reactive functional group, a molecule such as an epoxy group, a acryloxy group, a methacryloxy group, a vinyl group, a phenyl group or a hydroxyl group in the molecule or at the molecular terminal. Among them, those containing a methacryloxy group can be preferably used.

The cerium oxide powder used in the cerium-containing compound (C) functions as a polypyroxium-based compound (absorption, adsorption or retention), and can be used for smoking cerium oxide, precipitated cerium oxide or finely pulverizing cerium oxide. Wait. It is preferred that the surface area of the cerium oxide is in the range of 50 to 400 m ² /g. When the surface area is within this range, it becomes easy to carry a polyfluorene-based compound.

The content of the polyoxonium-containing compound containing the cerium compound (C) is not particularly limited, and from the viewpoint of scratch resistance and color rendering properties, it is preferably contained in the range of 40 to 80 in 100 parts by weight of the cerium-containing compound (C). Parts by weight. Further, the volume average particle diameter of the cerium-containing compound (C) is preferably in the range of 5 to 250 μm in terms of ease of dispersion in the resin composition. Further, the specific gravity of the cerium-containing compound (C) is preferably in the range of 0.1 to 0.7.

The amount of the ruthenium-containing compound (C) used is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the graft copolymer (A) and the (co)polymer (B). When 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. It is preferably 0.1 to 3 parts by weight.

The rubber-reinforced thermoplastic resin composition of the present invention may be appropriately added with various additives as needed, such as known antioxidants, light stabilizers, lubricants, plasticizers, antistatic agents, colorants, flame retardants, matting agents, fillers, Glass fiber, etc.

The rubber-reinforced thermoplastic resin composition of the present invention can be used alone or as needed It should be mixed with other thermoplastic resins. As such another thermoplastic resin, for example, an acrylic resin such as polymethyl methacrylate, a polycarbonate resin, a polybutylene terephthalate resin, a polyethylene terephthalate resin, or a polydecylamine can be used. Resin, polylactic acid resin, etc.

The rubber-reinforced thermoplastic resin composition of the present invention can be obtained by mixing the above components. For the mixing, for example, a known kneading device such as an extruder, a drum, a Banbury kneader, or a kneader can be used.

Further, the mixing method or the order of the above components is not particularly limited, and in the case of the rubber-reinforced thermoplastic resin composition of the second embodiment of the present invention, the graft copolymer (A) and the (co)polymer may be used. (B) The resin composition obtained by melt-kneading is mixed with the cerium-containing compound (C) to obtain a resin composition, and the graft copolymer (A), the (co)polymer (B), and the cerium-containing compound (C) may also be obtained. After premixing, melt kneading is carried out to obtain a resin composition.

Further, the rubber-reinforced thermoplastic resin composition of the present invention can be molded by a known molding method such as extrusion molding, injection molding, blow molding, press molding, or the like, and various molded articles can be produced.

Example

The invention is illustrated by the following examples, but the invention is not limited thereto. In addition, the "parts" and "%" shown in the examples are based on the weight.

<Test example> (Examples A1 to A10, and Comparative Examples A1 to A6)

The graft copolymer (A) and the copolymer (B) having a composition ratio shown in Tables 3 and 4 were mixed with Sumiplast Black HB (manufactured by Sumitomo Chemical Co., Ltd.) as a coloring agent. Using a 50 mm single-axis extruder (manufactured by O.N. Machinery) with a vent hole, melt mixing and granulation were carried out at a cylinder temperature of 210 ° C, whereby particles colored in black were obtained.

(Examples B1 to B12, and Comparative Examples B1 to B9)

Graft copolymer (A), copolymer (B) and composition ratios shown in Tables 5 and 6 The ruthenium-containing compound (C) was mixed with Sumiplast Black HB (manufactured by Sumitomo Chemical Co., Ltd.) as a coloring agent in 1.0 part. Using a 50 mm single-axis extruder (manufactured by O.N. Machinery) with a vent hole, melt mixing and granulation were carried out at a cylinder temperature of 210 ° C, whereby particles colored in black were obtained.

In addition, the components shown in Table 1 and Table 2 are as follows.

[Manufacture of rubbery polymer (a)]

Rubber-like polymer (a-1): 93 parts of 1,3-butadiene, 7 parts of styrene, 0.5 parts of n-dodecyl mercaptan, 0.24 parts of potassium persulfate, and 1.5 parts of sodium rosinate were added to the pressure vessel. 0.1 parts of sodium hydroxide and 150 parts of deionized water were reacted at 70 ° C for 15 hours, and then cooled and the reaction was terminated, whereby a styrene-butadiene rubber latex (a-1) was obtained. The obtained styrene-butadiene rubber latex (a-1) was dyed with osmium tetroxide (OsO ₄ ), dried, and photographed by a transmission electron microscope. The area of 1000 rubber particles was measured using an image analysis processing apparatus (device name: IP-1000PC manufactured by Asahi Kasei Co., Ltd.), and the projected area diameter (diameter) was determined to calculate the weight average particle size of the styrene-butadiene rubber. Diameter and weight fraction. The weight average particle diameter and the weight fraction are shown in Table 1.

Rubber-like polymer (a-2) to (a-4): Coagulation and agglomeration treatment of rubber particles was carried out using the styrene-butadiene rubber latex (a-1) obtained above. After adding 270 parts of styrene-butadiene rubber latex (a-1) and 0.09 parts of 10% sodium dodecylbenzenesulfonate aqueous solution to the stirring tank and stirring for 10 minutes, it took 10 minutes to add 0.8 parts of 5% phosphoric acid aqueous solution. . Thereafter, 1 part of a 10% potassium hydroxide aqueous solution was added, whereby a rubbery polymer (a-2) having a weight average particle diameter of 0.25 μm was obtained. The styrene-butadiene rubber latex (a-3) to (a-4) was obtained by adjusting the amount of sodium dodecylbenzenesulfonate used. The weight average particle diameter and the weight fraction of the obtained styrene-butadiene rubber latex were measured by the above method. The measurement results are shown in Table 1.

Rubber-like polymer (a-5) to (a-9): obtained by mixing styrene-butadiene rubber latex (a-1) to (a-4) at a composition ratio shown in Table 1. Rubbery polymerization (a-5)~(a-9).

[Manufacture of graft copolymer (A)]

Graft Copolymer (A-1): 30 parts of styrene-butadiene rubber latex (a-5) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.3 parts of third-dodecanethiol were continuously added for 4 hours. A mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-1) is obtained.

The fixed amount of the graft copolymer (A-1) was put into acetone, and the mixture was shaken for 2 hours with a shaker to impregnate the graft copolymer. The solution was centrifuged at 15,000 rpm for 30 minutes using a centrifugal separator, and dried by vacuum drying at normal temperature for a day and night to obtain an acetone-insoluble component. The obtained acetone-insoluble matter was film-formed, and the weight ratio of styrene-butadiene rubber, styrene, and acrylonitrile was identified by infrared absorption spectrum using an infrared spectroscopic analyzer (device name: Spectrum One, manufactured by Perkin Elmer Co., Ltd.). The graft ratio was calculated from the weight ratio of each component.

Further, the acetone-soluble component obtained above was dried and dissolved in N,N-dimethylformamide to prepare a solution having a concentration of 0.4 g/100 cc, followed by Cannon-Fenske. The viscosity was measured at 30 ° C to determine the reducing viscosity.

The graft ratio of the obtained graft copolymer (A-1) and the reduction viscosity of the acetone soluble component were 91% and 0.40 dl/g, respectively.

Graft Copolymer (A-2): 30 parts of styrene-butadiene rubber latex (a-6) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.3 parts of third-dodecanethiol were continuously added for 4 hours. a mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water Compound. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-2) is obtained. The graft ratio of the obtained graft copolymer (A-2) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 89%, and the reduction viscosity was 0.39 dl/g.

Graft Copolymer (A-3): 30 parts of styrene-butadiene rubber latex (a-5) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 part of sodium salt, 0.001 part of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, heated to 60 ° C, and then added for 4 hours, 49 parts of styrene, 21 parts of acrylonitrile, and 0.2 parts of cumene hydroperoxide. The mixture was a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-3) is obtained. The graft ratio of the obtained graft copolymer (A-3) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 130%, and the reduction viscosity was 0.39 dl/g.

Graft Copolymer (A-4): 30 parts of styrene-butadiene rubber latex (a-5) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, it took 4 hours to continuously add 21 parts of styrene, 49 parts of methyl methacrylate, and third-dodecyl mercaptan. A mixture of 0.3 parts and 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying were carried out, whereby a graft copolymer (A-4) was obtained. The graft ratio of the obtained graft copolymer (A-4) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 81%, and the reduction viscosity was 0.37 dl/g.

Graft Copolymer (A-5): 20 parts of styrene-butadiene rubber latex (a-5) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, it took 4 hours to continuously add 56 parts of styrene, 24 parts of acrylonitrile, and 0.4 parts of third-dodecanethiol. And a mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-5) is obtained. The graft ratio of the obtained graft copolymer (A-5) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 75%, and the reduction viscosity was 0.36 dl/g.

Graft Copolymer (A-6): 48 parts of styrene-butadiene rubber latex (a-5) (solid content), 140 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, it took 4 hours to continuously add 39 parts of styrene, 13 parts of acrylonitrile, and 0.6 parts of third-dodecanethiol. A mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-6) is obtained. The graft ratio of the obtained graft copolymer (A-6) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 40%, and the reduction viscosity was 0.39 dl/g.

Graft Copolymer (A-7): 20 parts of styrene-butadiene rubber latex (a-5) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 part of sodium salt, 0.001 part of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, it takes 4 hours to continuously add 56 parts of styrene, 24 parts of acrylonitrile, and 0.2 parts of cumene hydroperoxide. The mixture was a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-7) is obtained. The graft ratio of the obtained graft copolymer (A-7) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 170%, and the reduction viscosity was 0.44 dl/g.

Graft Copolymer (A-8): 30 parts of styrene-butadiene rubber latex (a-7) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 part of sodium salt, 0.001 part of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, heated to 60 ° C, A mixture of 49 parts of styrene, 21 parts of acrylonitrile, 0.3 parts of tri-dodecyl mercaptan and 0.2 parts of cumene hydroperoxide was added continuously for 4 hours, and consisted of 1.5 parts of potassium oleate and 15 parts of water. mixture. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-8) is obtained. The graft ratio of the obtained graft copolymer (A-8) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 95%, and the reduction viscosity was 0.41 dl/g.

Graft Copolymer (A-9): 30 parts of styrene-butadiene rubber latex (a-8) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.3 parts of third-dodecanethiol were continuously added for 4 hours. A mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying are carried out, whereby a graft copolymer (A-9) is obtained. The graft ratio of the obtained graft copolymer (A-9) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 87%, and the reduction viscosity was 0.38 dl/g.

Graft Copolymer (A-10): 30 parts of styrene-butadiene rubber latex (a-9) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.3 parts of third-dodecanethiol were continuously added for 4 hours. A mixture of 0.2 parts of cumene hydroperoxide and a mixture of 1.5 parts of potassium oleate and 15 parts of water. After the completion of the addition, the mixture was further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying were carried out, whereby a graft copolymer (A-10) was obtained. The graft ratio of the obtained graft copolymer (A-10) and the reduction viscosity of the acetone soluble component were measured by the above method, and as a result, the graft ratio was 98%, and the reduction viscosity was 0.41 dl/g.

Graft Copolymer (A-11): Adding Phenyl E to a Nitrogen Displacement Reactor 30 parts of ene-butadiene rubber latex (a-1) (solid content), 160 parts of water, 0.1 parts of disodium ethylenediaminetetraacetate, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, heated to After 60 ° C, it took 4 hours to continuously add a mixture of 49 parts of styrene, 21 parts of acrylonitrile, 0.3 parts of tri-dodecyl mercaptan and 0.2 parts of cumene hydroperoxide and 1.5 parts of potassium oleate, and further Polymerization was carried out at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying were carried out to obtain a graft copolymer (A-11). The graft ratio of the obtained graft copolymer (A-11) and the reduction viscosity of the acetone soluble component were measured, and as a result, the graft ratio was 93%, and the reduction viscosity was 0.40 dl/g.

Graft Copolymer (A-12): 30 parts of styrene-butadiene rubber latex (a-2) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.28 parts of third-dodecanethiol were continuously added for 4 hours. A mixture of 0.2 parts of cumene hydroperoxide and 1.5 parts of potassium oleate was further polymerized at 60 ° C for 2 hours, and then salted out, dehydrated, and dried to obtain a graft copolymer (A-12). The graft ratio of the obtained graft copolymer (A-12) and the reduction viscosity of the acetone soluble component were measured, and as a result, the graft ratio was 89%, and the reduction viscosity was 0.39 dl/g.

Graft Copolymer (A-13): 30 parts of styrene-butadiene rubber latex (a-2) (solid content), 160 parts of water, ethylenediaminetetraacetic acid in a reactor substituted with nitrogen 0.1 parts of sodium salt, 0.001 parts of ferrous sulfate, 0.3 parts of sodium formaldehyde sulfoxylate, and after heating to 60 ° C, 49 parts of styrene, 21 parts of acrylonitrile, and 0.3 parts of third-dodecanethiol were continuously added for 4 hours. A mixture of 0.2 parts of cumene hydroperoxide and 1.5 parts of potassium oleate were further polymerized at 60 ° C for 2 hours. Thereafter, salting out, dehydration, and drying were carried out to obtain a graft copolymer (A-13). The graft ratio of the obtained graft copolymer (A-13) and the reduction viscosity of the acetone soluble component were measured, and as a result, the graft ratio was 93%, and the reduction viscosity was 0.40 dl/g.

[Manufacture of Copolymer (B)]

Copolymer (B-1): 70 parts by weight of styrene obtained by a known block polymerization method 30 parts by weight of the acrylonitrile copolymer (B-1). The reduction viscosity of the obtained copolymer (B-1) was measured by the above method, and as a result, the reduction viscosity was 0.60 dl/g.

Copolymer (B-2): A copolymer (B-2) composed of 30 parts by weight of styrene and 70 parts by weight of methyl methacrylate was obtained by a known bulk polymerization method. The reduction viscosity of the obtained copolymer (B-2) was measured by the above method, and as a result, the reduction viscosity was 0.58 dl/g.

Antimony compound (C)

Antimony-containing compound (C-1): DC4-7081 (manufactured by Dow Corning Toray Co., Ltd.)

Forty parts of the cerium oxide powder contained 60 parts of a cerium-containing compound containing a methacryloxy group-containing functional group. Body specific gravity: 0.3~0.5, particle size: 10~200 μm

Antimony-containing compound (C-2): SH200-100CS (manufactured by Dow Corning Toray Co., Ltd.)

Dimethylpolyphthalic acid oil. Viscosity: 100 mm ² /s

Antimony-containing compound (C-3): BY27-007 (manufactured by Dow Corning Toray Co., Ltd.)

A pellet produced by melt-kneading an ultrahigh molecular weight dimethylpolyoxyl polymer with an ABS resin (polyoxyl content 50%).

(1) Color rendering

The brightness (L*) of the molded article was measured by the hue measurement according to JIS-Z8729 as a reference for color rendering. (When the brightness (L*) of the molded article is small, the molded article is excellent in the blackening property, and as a result, the coloring property is excellent when the same coloring agent is added in the same amount), and the molded article is obtained by using each of the examples and the comparative examples. The colored particles were molded into a molded article (150 mm × 120 mm × 3 mm) by an injection molding machine (J-150EP manufactured by Nippon Steel Co., Ltd., cylinder temperature: 200 ° C, mold temperature: 80 ° C). The spectrophotometer uses CMS-35SP manufactured by Murakami Color Research Co., Ltd.

(2) Damage resistance

Using a round-trip wear tester (manufactured by Shinto Scientific Co., Ltd., product name: Tribogear, model: 30S), a cotton cloth of cotton cloth No. 3 was placed at a tip end of 27 mm in diameter, for Examples A1 to A10 and Comparative Examples. A1~A6, 20 round trips (speed 600 mm/min) were applied to the surface of the molded article under a fixed load of 500 g. For Examples B1 to B12 and Comparative Examples B1 to B9, the molding was performed under a fixed load of 1 kg. The surface of the product was subjected to a friction of 50 round trips (speed 600 mm/min). As the molded article, the same one as the molded article used in the above (1) is used. After the test, the damage of the surface of the molded article was visually confirmed, and the damage resistance was evaluated by the following determination.

No damage at all: ◎

Almost no damage can be seen: ○

Slightly see the damage: △

Obviously see the damage: ×

(3) Impact resistance

The colored particles obtained in each of the examples and the comparative examples were used, and various test pieces were molded in accordance with ISO Test Method 294 and the impact resistance was measured.

The impact resistance is measured according to ISO 179 at a thickness of 4 mm. Unit: kJ/m ² .

(4) Liquidity

Using the colored particles obtained in each of the Examples and Comparative Examples, the melt volume flow rate was measured in accordance with ISO 1133 at 220 ° C under a load of 10 kg. Unit: cm ³ /10 min.

(5) mold contamination

Using the colored particles obtained in each of the examples and the comparative examples, using a J-150EP manufactured by Nippon Steel Co., Ltd., a flat test piece (length 150 mm, at a cylinder set temperature of 240 ° C, a mold temperature of 50 ° C, and a molding cycle of 30 seconds) After 150 shots and 150 mm wide and 3 mm thick) The evaluation of mold contamination was performed by the following determination.

No change in the surface of the mold: ○

Smudge on the surface of the mold: △

The surface of the mold is extremely dirty, and the appearance of the molded product is poor: ×

As shown in Table 3, it is understood that the rubber-reinforced thermoplastic resin composition of the present invention is excellent not only in damage resistance and color rendering properties but also in physical properties such as impact resistance and fluidity. In particular, when the weight fraction of the rubbery polymer is 0.2 μm or more and the particles of 0.4 μm or less are in the range of 10 to 50% by weight, the damage resistance is excellent. Further, as shown in Examples A9 and A10, even when two or more kinds of rubber-like polymers are graft-polymerized and two or more kinds of graft copolymers are used, the graft ratio and the weight of the particles are satisfied. The purpose of this application can be achieved by the provisions of the rate.

As shown in Table 4, the rubber content of the rubber-reinforced thermoplastic resin composition is less than The impact resistance of Comparative Example A1 of 5 parts by weight was poor. Comparative Example A2 having a rubber content of more than 24 parts by weight was inferior in color rendering property, scratch resistance, and fluidity. Comparative Example A3 using the graft copolymer (A-6) having a graft ratio of less than 70% was inferior in color rendering property and scratch resistance. Comparative Example A4 using a graft copolymer (A-7) having a graft ratio of more than 150% was inferior in impact resistance and fluidity. A rubber-like polymer (a-8) in which particles of 0.05 μm or more and less than 0.2 μm are less than 50% by weight, particles of 0.2 μm or more are 50% by weight or more, and Comparative Examples A5 and A6 of (a-9) are used. Poor color rendering.

As shown in Table 5, it is understood that the rubber-reinforced thermoplastic resin composition of the present invention is excellent not only in damage resistance and color rendering properties, but also in physical properties such as mold contamination, impact resistance and fluidity. When the weight fraction of the rubbery polymer is 0.2 μm or more and the particles of 0.4 μm or less are in the range of 10 to 50% by weight, the scratch resistance is particularly excellent. Again, such as In the case of using two or more types of graft copolymers by graft-polymerizing two or more kinds of rubber-like polymers, as shown in Examples B9 and B10, the graft ratio and the particles specified in the present invention are satisfied. The weight fraction can be used to achieve the purpose of this application.

As shown in Table 6, Comparative Example B1 in which no antimony-containing compound was used was a result of poor damage resistance. Comparative Example B2 in which the rubber content in the rubber-reinforced thermoplastic resin composition was less than 5 parts by weight was a result of poor impact resistance. Comparative Example B3 having a rubber content of more than 24 parts by weight was a result of poor color rendering properties, scratch resistance, and fluidity. Comparative Example B4 using a graft copolymer (A-6) having a graft ratio of less than 70% was a result of poor color rendering properties and poor damage resistance. Comparative Example B5 using a graft copolymer (A-7) having a graft ratio of more than 150% was a result of poor impact resistance and poor fluidity. The rubbery polymers (a-8) and (a-9) of Comparative Examples B6 and B7 in which the particles of 0.05 μm or more and less than 0.2 μm were less than 50% by weight and the particles of 0.2 μm or more were 50% by weight or more were used. The result of poor color rendering and damage resistance. Comparative Example B8 using polyoxygenated oil was the result of poor damage resistance and poor mold contamination. Comparative Example B9 using a ruthenium-containing compound which was not supported on the ruthenium dioxide powder was found to have poor color developability, scratch resistance, and mold contamination.

[Industrial availability]

The rubber-reinforced thermoplastic resin composition of the present invention can be effectively used in a wide range of fields including electric, electronic equipment, and OA machine fields, etc., by utilizing the above-described excellent characteristics. In particular, it is suitable for applications that have excellent physical balance, color rendering, and damage resistance.

Claims (5)

A rubber-reinforced thermoplastic resin composition in which the following graft copolymer (A) constitutes a dispersed phase, and the following (co)polymer (B) constitutes a continuous phase, the graft copolymer ( A) is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and others copolymerizable in the presence of a rubbery polymer (a). The at least one monomer (b) of the monomer composition is graft copolymerized, and the (co)polymer (B) is selected from the group consisting of an aromatic vinyl monomer and a vinyl cyanide monomer. And (co)polymerized at least one monomer (b) of a (meth) acrylate monomer and other copolymerizable monomer composition; characterized in that the rubbery polymer (a) is granulated Particles having a diameter of 0.05 μm or more and less than 0.2 μm have a weight fraction of 50 to 90% by weight, particles having a particle diameter of 0.2 μm or more have a weight fraction of 10 to 50% by weight, and grafting of the graft copolymer (A) The ratio is 70 to 150%, and the rubber-like polymer (a) is contained in an amount of 5 to 24 parts by weight based on 100 parts by weight of the rubber-reinforced thermoplastic resin composition. A rubber-reinforced thermoplastic resin composition comprising a graft copolymer (A), a (co)polymer (B), and a cerium-containing compound (C), characterized in that the graft copolymer (A) is in a particle size of 0.05 μm In the presence of a rubbery polymer (a) having a weight fraction of 50 to 90% by weight and a particle diameter of 0.2 μm or more and having a weight fraction of 10 to 50% by weight, the particles having a particle size of less than 0.2 μm are selected. Graft copolymerization of at least one monomer (b) of a free aromatic vinyl monomer, a vinyl cyanide monomer, a (meth) acrylate monomer, and other copolymerizable monomer groups And the graft ratio is 70 to 150%, and the (co)polymer (B) is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth) acrylate monomer. Any one of (b) (co)polymerized from at least one of the other copolymerizable monomer groups, the cerium-containing compound (C) is based on a cerium oxide powder containing a polyfluorene-based compound, in rubber 100 parts by weight of the reinforced thermoplastic resin composition contains 5 to 24 parts by weight of the rubbery polymer (a), and 100 parts by weight based on the total of the graft copolymer (A) and the (co)polymer (B). , The antimony-containing compound (C) is used in an amount of 0.01 to 10 parts by weight. The rubber-reinforced thermoplastic resin composition according to the second aspect of the invention, wherein the cerium-containing compound (C) has a volume average particle diameter of 5 to 250 μm and a bulk specific gravity of 0.1 to 0.7. The rubber-reinforced thermoplastic resin composition according to claim 2, wherein the polyfluorene-based compound contained in the cerium-containing compound (C) contains a methacryloxy group in a molecule or at a molecular end. The polyfluorene oxide compound is contained in an amount of 40 to 80 parts by weight based on 100 parts by weight of the cerium-containing compound. A resin molded article obtained by the rubber-reinforced thermoplastic resin composition according to any one of claims 1 to 4.