JP2016125006A - Powder containing composite rubber-based graft copolymer, coagulation containing composite rubber-based graft copolymer, thermoplastic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in fluidity, impact resistance and molding appearance.SOLUTION: There is provided a powder containing a composite rubber-based graft copolymer (C) obtained by recovering from a mixture solution which is produced by mixing 100 pts.mass (solid content) of a composite ruber-based graft copolymer (A) in a slurry or latex state and 15 to 45 pts.mass of a hard copolymer (B) in a latex state which satisfies the following (1) and (2). There is provided a thermoplastic resin composition comprising the powder containing a composite rubber-based graft copolymer (C). (1) The ratio of the vinyl cyanide monomer unit in the whole monomer units constituting the hard copolymer (B) is 10 to 60 mass%, (2) The reduced viscosity measured at 25°C of a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide is 0.3 to 2.0 dl/g.SELECTED DRAWING: None

Description

  The present invention relates to a composite rubber-based graft copolymer-containing powder and a composite rubber-based graft copolymer-containing coagulated product that can provide a thermoplastic resin composition excellent in impact resistance, fluidity, and molding appearance. The present invention relates to a thermoplastic resin composition having excellent impact resistance, fluidity and molded appearance, and a molded product formed by molding this thermoplastic resin composition.

  In recent years, socialization of information has rapidly spread, and the demand for OA devices such as computers, printers, and copiers has increased, and the demand for portable information devices such as mobile computers has increased. For this reason, there are increasing demands for thinner and lighter molded articles made of thermoplastic resins such as housings and parts used in the information equipment and the like, and for improving the molded appearance.

  Conventionally, in order to satisfy such required characteristics, attempts have been made to improve impact resistance of molded products by blending specific rubbers such as silicone acrylic rubber and core-shell type rubber, or by increasing the rubber content. Has been made. For example, Patent Document 1, Patent Document 2, and Patent Document 3 disclose improvement in impact strength by blending a silicone / acrylic composite rubber. However, in these methods, by blending a specific composite rubber, the fluidity of the resulting thermoplastic resin composition is lowered, so that it is difficult to produce a thin and lightweight molded product, and the obtained molded product is obtained. There was a problem that the luster of the material was lowered.

  Patent Document 4 discloses that in a thermoplastic resin composition containing the above-described specific composite rubber, the fluidity is improved by controlling the molecular weight of the material resin within a specific range. However, even this method cannot sufficiently improve both the fluidity and impact resistance. Therefore, it is a highly fluid resin composition excellent in thin moldability and excellent in appearance such as gloss. The present situation is that a thermoplastic resin composition excellent in impact resistance has not been realized.

Japanese Patent Laid-Open No. 6-1897 JP-A-7-207085 JP-A-6-240127 JP-A-8-127686

An object of the present invention is to provide a thermoplastic resin composition excellent in fluidity, impact resistance, and molded appearance.
In the present invention, the “molded appearance” refers not only to the appearance of the molded product itself but also to a broadly defined molded appearance such as a metal vapor deposition appearance and a painted appearance, as in the evaluation items in the Examples section below. .

  As a result of intensive studies, the present inventors have found that a composite rubber-based graft copolymer (A) in a slurry or latex state and a low-viscosity hard copolymer (B) containing a vinyl cyanide monomer unit as an essential component (B) ) Was mixed in a latex state and coagulated to obtain a composite rubber-based graft copolymer-containing powder or a composite rubber-based graft copolymer-containing coagulated product. .

  That is, this invention makes the following a summary.

[1] 100 parts by mass (solid content) of a composite rubber-based graft copolymer (A) in a slurry or latex state and a hard copolymer (B) in a latex state that satisfies the following (1) to (2) 15 to 45 parts by mass (in terms of solid content) and a composite rubber-based graft copolymer-containing powder (C) that is recovered from the resulting mixture.
(1) The proportion of vinyl cyanide monomer units in all monomer units constituting the hard copolymer (B) is 10 to 60% by mass.
(2) The reduced viscosity measured at 25 ° C. of a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide is 0.3 to 2.0 dl / g.

[2] A composite rubber-based graft copolymer obtained by solid-liquid separation of the composite rubber-based graft copolymer-containing solidified product (D) obtained by coagulating the mixed solution in [1] Containing powder (C).

[3] Composite rubber-based graft copolymer-containing powder, wherein the composite rubber of the composite rubber-based graft copolymer (A) is a polyorganosiloxane / alkyl (meth) acrylate-based composite rubber in [1] or [2] (C).

[4] In any one of [1] to [3], the composite rubber-based graft copolymer (A) is a monomer containing an aromatic alkenyl compound and a vinyl cyanide compound in 10-80% by mass of the composite rubber. Composite rubber-based graft copolymer-containing powder (C) obtained by emulsion graft polymerization of 90 to 20% by mass of components (however, the total of the composite rubber and monomer components is 100% by mass) .

[5] 100 parts by mass (solid content) of a composite rubber-based graft copolymer (A) in a slurry or latex state, and a latex state hard copolymer (B) 15 to 45 satisfying the following (1) and (2) A composite rubber-based graft copolymer-containing coagulum (D) obtained through a process of mixing with a mass part (in terms of solid content).
(1) The proportion of vinyl cyanide monomer units in all monomer units constituting the hard copolymer (B) is 10 to 60% by mass.
(2) The reduced viscosity measured at 25 ° C. of a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide is 0.3 to 2.0 dl / g.

[6] In [5], a step of mixing the composite rubber graft copolymer (A) in a slurry or latex state and a hard copolymer (B) in a latex state, and a step of solidifying the obtained mixed solution A composite rubber-based graft copolymer-containing coagulum (D) obtained through

[7] A composite rubber-based graft copolymer-containing coagulum in which the composite rubber-based graft copolymer (A) is a polyorganosiloxane / alkyl (meth) acrylate composite rubber in [5] or [6] (D).

[8] In any one of [5] to [7], the composite rubber-based graft copolymer (A) is a monomer containing an aromatic alkenyl compound and a vinyl cyanide compound in 10 to 80% by mass of the composite rubber. Composite rubber graft copolymer-containing coagulum (D) obtained by emulsion graft polymerization of 90 to 20% by mass of the component (however, the total of the composite rubber and the monomer component is 100% by mass) .

[9] A thermoplastic resin composition comprising the composite rubber-based graft copolymer-containing powder (C) according to any one of [1] to [4].

[10] A thermoplastic resin composition comprising the composite rubber-based graft copolymer-containing coagulum (D) according to any one of [5] to [8].

[11] A molded product obtained by molding the thermoplastic resin composition according to [9] or [10].

According to the composite rubber-based graft copolymer-containing powder and the composite rubber-based graft copolymer-containing coagulated product of the present invention, it is possible to provide a thermoplastic resin composition excellent in impact resistance, fluidity and molded appearance. it can.
According to the thermoplastic resin composition of the present invention, a molded product having a complex deformed shape, a thin-walled product, or a small-sized molded product can be molded with a good yield with good moldability and excellent shape accuracy. In addition to being excellent in impact resistance and mechanical durability, it is possible to obtain a molded product having excellent molded appearance and high commercial value.

  Hereinafter, the present invention will be described in detail.

The composite rubber-based graft copolymer-containing powder (C) and the composite rubber-based graft copolymer-containing coagulum (D) of the present invention include a composite rubber-based graft copolymer (A) in a slurry or latex state, cyan A step of mixing the latex of the low-viscosity hard copolymer (B) containing a vinyl fluoride monomer unit as an essential component together in a liquid state at a predetermined ratio (hereinafter referred to as “latex mixing”). It is obtained through the process.
Thus, by mixing the composite rubber-based graft copolymer (A) and the hard copolymer (B) in latex, the composite rubber-based graft copolymer (A) particles and the hard copolymer (B) particles are mixed. Is uniformly mixed at a fine single particle level and solidified in the subsequent solidification process in the uniform mixed state. As a result, the composite rubber-based graft copolymer (A) has an original impact resistance and a hard copolymer. (B) It is possible to obtain a composite rubber-based graft copolymer-containing powder (C) or a composite rubber-based graft copolymer-containing coagulum (D) capable of exhibiting a good balance with the original fluidity. It becomes.
Further, since the composite rubber-based graft copolymer (A) is obtained by using a composite rubber as a rubber-like polymer and graft polymerizing a graft monomer component to the composite rubber, a good molded appearance can be obtained. Can do.
On the other hand, even if the graft copolymer and the hard copolymer (B) are mixed in latex, the rubber component of the graft copolymer is not a composite rubber but a single rubber such as polybutadiene. When combined, as shown in Comparative Example 8 described later, the molded appearance is inferior.
Further, the composite rubber graft copolymer (A) powder obtained by coagulating and recovering the composite rubber graft copolymer (A) from the latex of the composite rubber graft copolymer (A), and the hard copolymer Even if the powder of the hard copolymer (B) recovered from the latex of the polymer (B) is mixed in the powder state (hereinafter referred to as “powder mixing”), the composite rubber-based graft copolymer The coalescence (A) and the hard copolymer (B) are merely mixed as aggregated particles aggregated to a certain size, and they are mixed in a state of being uniformly dispersed at the level of fine particles. Therefore, it is not possible to obtain a graft copolymer-containing powder capable of exerting a good balance between impact resistance, fluidity, and molded appearance improvement, and the impact resistance is particularly poor.

<Composite rubber-based graft copolymer (A)>
The slurry or latex composite rubber-based graft copolymer (A) used in the present invention can be produced by emulsion graft polymerization of a copolymerizable monomer component in the presence of composite rubber particles.

The composite rubber used in the production of the composite rubber-based graft copolymer (A) is a diene / alkyl (compound) obtained by combining a diene rubber such as polybutadiene and an alkyl (meth) acrylate rubber such as butyl acrylic rubber. (Meth) acrylate composite rubber, polyorganosiloxysan / alkyl (meth) acrylate composite rubber, and the like. In terms of molding appearance and impact resistance, polyorganosiloxane / alkyl (meth) acrylate composite rubber is used. preferable.
In addition, a composite rubber can be used individually by 1 type or in combination of 2 or more types.
Hereinafter, the composite rubber-based graft copolymer (A) using a polyorganosiloxane / alkyl (meth) acrylate-based composite rubber as the composite rubber will be mainly described. However, the composite rubber-based graft copolymer according to the present invention ( The composite rubber A) is not limited to polyorganosiloxane / alkyl (meth) acrylate composite rubber.

  The polyorganosiloxane / alkyl (meth) acrylate composite rubber is prepared by, for example, adding an alkyl (meth) acrylate to the latex of the polyorganosiloxane rubber and causing a normal radical polymerization initiator to act on it. A polyorganosiloxane / alkyl (meth) acrylate composite with a structure in which polyalkyl (meth) acrylate particles are dispersed and polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber are alternately intertwined to form a reintegration Manufactured as rubber particles.

Specifically, in the present invention, a radical initiator is previously added to the polyorganosiloxane rubber latex, and an alkyl (meth) acrylate monomer is added dropwise thereto to initiate polymerization of the alkyl (meth) acrylate. That is, the dropped alkyl (meth) acrylate is impregnated in the polyorganosiloxane, and the polyorganosiloxane is swollen. In this state, the alkyl (meth) acrylate undergoes polymerization and becomes composite rubber particles. Thus, the composite rubber particle prepared by emulsion polymerization can be graft-polymerized with a vinyl monomer.
The alkyl (meth) acrylate may be added all at once to the latex polyorganosiloxane, or may be added continuously or intermittently. The polyalkyl acrylate rubber preferably has a crosslinked structure.

(Polyorganosiloxane)
The polyorganosiloxane constituting the composite rubber is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. The polyorganosiloxane having a vinyl polymerizable functional group can be obtained by polymerizing dimethyl polysiloxane, a siloxane having a vinyl polymerizable functional group, and, if necessary, a siloxane-based crosslinking agent.

  Examples of the dimethylpolysiloxane used for the production of the polyorganosiloxane include a trimer or higher cyclic dimethylpolysiloxane, which is not particularly limited, but a 3- to 7-mer is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used individually by 1 type or in mixture of 2 or more types. From the viewpoint of easy control of the particle size distribution, it is preferable to use octamethylcyclotetrasiloxane as the main component.

  The siloxane having a vinyl polymerizable functional group has a vinyl polymerizable functional group and has a reactive group that can be bonded to the dimethylpolysiloxane via a siloxane bond. In consideration of reactivity, it is preferable to use various alkoxysilane compounds containing a vinyl polymerizable functional group. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropylethoxydiethoxymethylsilane, methacryloyloxysilane such as δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane, vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane Further, mercapts such as γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. Siloxane, and the like. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

  The ratio of the above-mentioned dimethylpolysiloxane used in the production of the polyorganosiloxane having a vinyl polymerizable functional group and the above siloxane having a vinyl polymerizable functional group is dimethylpolysiloxane with respect to 100 parts by mass in total. 97 to 99.8 parts by mass, siloxane having a vinyl polymerizable functional group is 0.2 to 3 parts by mass, in particular, dimethylpolysiloxane is 99 to 99.7 parts by mass, and siloxane having a vinyl polymerizable functional group is 0. The proportion is preferably 3 to 1 part by mass, and if the amount of dimethylpolysiloxane is larger than this range and the amount of siloxane having a vinyl polymerizable functional group is small, the molded appearance is inferior. On the other hand, when the amount of dimethylpolysiloxane is small and the amount of siloxane having a vinyl polymerizable functional group is large, the impact resistance is poor.

Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane. A siloxane type crosslinking agent can be used individually by 1 type or in mixture of 2 or more types. A siloxane-based crosslinking agent is not necessarily required, but when a polyorganosiloxane is produced, it is preferable to use a siloxane-based crosslinking agent. The siloxane-based crosslinking agent is preferably used in a proportion of 0.2 to 3% by mass, particularly 0.3 to 1% by mass with respect to the polyorganosiloxane, from the viewpoint of molding appearance and impact balance.

  The production method of the polyorganosiloxane having a vinyl polymerizable functional group is not particularly limited, but dimethylpolysiloxane and a vinyl polymerizable functional group-containing siloxane, or a siloxane mixture containing a siloxane-based crosslinking agent as the emulsifier is used as an emulsifier. The emulsion emulsified with water is made into fine particles using a homomixer that makes fine particles by shearing force generated by high-speed rotation or a homogenizer that makes fine particles by jet output from a high-pressure generator, and then at high temperature using an acid catalyst. There is a method of polymerizing and then neutralizing the acid with an alkaline substance. In this case, examples of the method for adding the acid catalyst used for the polymerization include a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping an emulsion in which the siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate. .

  The emulsifier used in producing the polyorganosiloxane is not particularly limited, but an anionic emulsifier and a nonionic emulsifier are preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium diphenyl ether disulfonate, sodium alkyl sulfate, polyoxyethylene alkyl sodium sulfate, polyoxyethylene nonyl phenyl ether sodium sulfate, polyoxyethylene alkyl sodium phosphate, polyoxyethylene alkyl phosphoric acid. Calcium is mentioned. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene distyrenated phenyl ether, and polyoxyethylene tribenzyl phenyl ether. These emulsifiers can be used individually by 1 type or in mixture of 2 or more types.

  The method of mixing the siloxane mixture, emulsifier and water includes mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, etc., but the method using a homogenizer narrows the distribution of the particle size of the polyorganosiloxane latex. This is the preferred method.

  Examples of the acid catalyst used for the polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts can be used alone or in combination of two or more.

  The polymerization temperature for obtaining the polyorganosiloxane is not particularly limited, but is preferably 50 ° C or higher, more preferably 70 ° C or higher, for example, 75 to 80 ° C. The polymerization time for obtaining the polyorganosiloxane is not particularly limited, but is preferably 2 hours or longer, more preferably 5 hours or longer, for example 7 to 10 hours. The polymerization can be stopped by cooling the reaction solution and neutralizing the latex to pH 6 to 8 with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, aqueous ammonia solution or the like.

  The particle diameter of the polyorganosiloxane used for the production of the composite rubber is 0.03 to 0.2 μm, particularly 0.04 to 0.04 in weight average particle diameter in order to obtain composite rubber particles having a suitable composite ratio and particle diameter described later. It is preferably 0.1 μm. The weight average particle diameter of the polyorganosiloxane is measured by the method described in the Examples section below.

(Alkyl (meth) acrylate)
Examples of the alkyl (meth) acrylate constituting the composite rubber include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; hexyl methacrylate, 2-ethylhexyl methacrylate, and n- Examples thereof include alkyl methacrylates having 6 or more carbon atoms in the alkyl group such as dodecyl methacrylate. Among the alkyl (meth) acrylates, n-butyl acrylate is preferable because the impact resistance and gloss of the molded product obtained from the thermoplastic resin composition are improved. These alkyl (meth) acrylates may be used individually by 1 type, and may use 2 or more types together.

  In the production of the composite rubber, the ratio of the alkyl (meth) acrylate is preferably 50 to 97% by mass when the total of the polyorganosiloxane and the alkyl (meth) acrylate polymer is 100% by mass. . In particular, it is preferably used at a ratio of 80 to 94% by mass. If the amount of alkyl (meth) acrylate used is less than this range, the color developability will be inferior, and if it is greater, the impact resistance will be inferior.

(Crosslinking agent)
In producing the composite rubber, it is preferable to add a crosslinking agent and polymerize it in order to introduce a crosslinked structure into the polyalkyl (meth) acrylate component obtained from the above alkyl (meth) acrylate. The polymerized crosslinking agent contained in the composite rubber also functions as a graft crossing point for the vinyl monomer to be graft-bonded during the production of the composite rubber-based graft copolymer (A). Examples of the crosslinking agent include allyl (meth) acrylate, butylene di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4. -Butylene glycol di (meth) acrylate, triallyl cyanurate, triallyl isocyanurate. These may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the usage-amount of a crosslinking agent, It is preferable that it is the quantity used as 0.1-5.0 mass parts with respect to 100 mass parts in total of a crosslinking agent and an alkyl (meth) acrylate.

(Manufacture of composite rubber)
As a method for producing a composite rubber, for example, an alkyl (meth) acrylate and a crosslinking agent used as necessary are added to a polyorganosiloxane latex, polymerized using a known radical polymerization initiator, and combined. A method for obtaining rubber latex is mentioned. As a method of adding an alkyl (meth) acrylate and a crosslinking agent used as needed to the polyorganosiloxane latex, for example, an alkyl (meth) acrylate and a crosslinking agent used as needed are added to the polyorganosiloxane latex, respectively. Examples thereof include a method of adding all at once, and a method of dropping an alkyl (meth) acrylate and a cross-linking agent used as needed into a polyorganosiloxane latex at a constant rate.

In producing the latex of the composite rubber, an emulsifier can be added to stabilize the latex and control the average particle size of the composite rubber. Examples of the emulsifier used when producing the composite rubber latex include the same emulsifiers as used when producing the above-mentioned polyorganosiloxane latex, and anionic emulsifiers and nonionic emulsifiers are preferred.

  Although it does not specifically limit as a polymerization initiator, For example, the redox initiator which combined the peroxide, the azo initiator, or the oxidizing agent and the reducing agent is mentioned. Among these, it is preferable to use a redox initiator, particularly a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, a reducing agent and a peroxide.

Examples of the peroxide include organic peroxides such as diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide. These can be used alone or in combination of two or more. Examples of the reducing agent include sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, and inositol. These may be used alone or in combination of two or more.

  The polymerization temperature for obtaining the composite rubber is not particularly limited, but is preferably 50 ° C or higher, more preferably 60 ° C or higher, for example, 60 to 80 ° C. The polymerization time for obtaining the composite rubber is not particularly limited, but is preferably 30 minutes or longer, more preferably 1 hour or longer, for example 1 to 2 hours.

  The composite rubber latex used for the production of the composite rubber-based graft copolymer (A) is produced as described above. The gel content of the composite rubber in the latex is preferably 50 to 99% by mass, more preferably Is 60 to 95% by mass, particularly preferably 70 to 85% by mass. When the gel content is within this range, the properties of the resulting thermoplastic resin composition, particularly the impact strength, can be improved.

  In order to measure the gel content of the composite rubber, specifically, the weighed composite rubber was dissolved in a suitable solvent at room temperature (23 ° C.) for 20 hours, and then fractionated with a 100 mesh wire mesh. The insoluble matter remaining on the wire mesh is weighed after drying at 60 ° C. for 24 hours. The ratio (mass%) of the insoluble content with respect to the composite rubber before fractionation is determined and used as the gel content of the composite rubber. As the solvent used for dissolving the composite rubber, acetone is used for easy measurement.

  The particle diameter of the composite rubber particles is not particularly limited, but is preferably a volume average particle diameter of 0.1 to 1 μm, and more preferably 0.2 to 0.5 μm. In addition, the volume average particle diameter of the composite rubber particles can be measured by an optical method before graft polymerization. Further, after graft polymerization, the composite rubber particles are dyed with a dyeing agent, and then the average particle diameter can be calculated using a transmission electron microscope (TEM).

(Production of composite rubber-based graft copolymer (A))
In the presence of the composite rubber as described above, the latex composite rubber-based graft copolymer (A) is obtained by emulsion graft polymerization in which a graft monomer component composed of one or more vinyl monomers is radically polymerized. Can be obtained. The vinyl monomer is not particularly limited. For example, aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl methacrylate; methyl acrylate And acrylic acid esters such as ethyl acrylate and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These vinyl monomers can be used alone or in combination of two or more. Further, various chain transfer agents and graft crossing agents for adjusting the molecular weight and grafting rate of the graft polymer can be added to the vinyl monomer used in the graft polymerization.

  Of these graft monomer components, when a mixture of an aromatic alkenyl compound, preferably styrene, and a vinyl cyanide compound, preferably acrylonitrile, is used, the thermal stability of the composite rubber-based graft copolymer (A) is excellent. Therefore, it is preferable. In this case, the ratio of the aromatic alkenyl compound such as styrene and the vinyl cyanide compound such as acrylonitrile is preferably 10 to 50% by mass of the vinyl cyanide compound with respect to 50 to 90% by mass of the aromatic alkenyl compound ( However, the total of the aromatic alkenyl compound and the vinyl cyanide compound is 100% by mass.)

  The composite rubber-based graft copolymer (A) is obtained by emulsion graft polymerization of 90-20% by mass of the graft monomer component with respect to 10-80% by mass of the composite rubber. 100 mass% in total with the body components) is preferable because the appearance of the obtained molded product is excellent. More preferably, in the composite rubber-based graft copolymer (A), the composite rubber is 30 to 70% by mass, and the graft monomer component is 70 to 30% by mass.

Examples of the graft polymerization method of the graft monomer component onto the composite rubber include a method in which the graft monomer component is added to the latex of the composite rubber and polymerized in one or more stages. When polymerizing in multiple stages, it is preferable to polymerize by adding the graft monomer component in portions or continuously in the presence of a latex of a composite rubber. By such a polymerization method, good polymerization stability can be obtained, and a latex having a desired particle size and particle size distribution can be stably obtained. Examples of the polymerization initiator used for the polymerization of the graft monomer component include the same polymerization initiators used for the polymerization of the alkyl (meth) acrylate described above.

  When polymerizing the graft monomer component, an emulsifier can be added to stabilize the latex and control the average particle size of the resulting composite rubber-based graft copolymer (A). The emulsifier used when polymerizing the graft monomer component is not particularly limited, and examples thereof include those similar to the emulsifiers used for producing the aforementioned polyorganosiloxane latex. Anionic emulsifiers and nonionic emulsifiers are preferred. . The amount of the emulsifier used when polymerizing the graft monomer component is not particularly limited, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resulting composite rubber-based graft copolymer (A). 2 to 5 parts by mass is more preferable.

  In the production of a general graft copolymer, a latex of a graft copolymer is obtained by graft polymerization of a monomer component to a rubbery polymer by emulsion polymerization, and the resulting latex of the graft copolymer is obtained. In the present invention, the latex of the composite rubber-based graft copolymer (A) is left as it is or coagulated. The slurry is used for the next mixing step.

  When the composite rubber-based graft copolymer (A) is coagulated from the latex of the composite rubber-based graft copolymer (A) to form a slurry, for example, the composite rubber-based graft copolymer (A) latex is used as a coagulant. A wet method of coagulating in a slurry state can be adopted by putting it in hot water in which is dissolved. Here, examples of the coagulant used include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, and are selected according to the emulsifier used in the polymerization. The That is, when only a carboxylic acid soap such as fatty acid soap or rosin acid soap is used as an emulsifier, the composite rubber-based graft copolymer (A) can be coagulated and precipitated using any coagulant. From the standpoint of residence heat stability, it is preferable to coagulate and precipitate the composite rubber-based graft copolymer (A) using an inorganic acid. When an emulsifier exhibiting stable emulsifying power is contained even in an acidic region such as sodium alkylbenzene sulfonate, the recovered liquid becomes turbid with the inorganic acid, and it is difficult to precipitate the composite rubber-based graft copolymer (A). Therefore, it is necessary to use a metal salt as a coagulant.

Graft rate of the composite rubber-based graft copolymer (A) thus obtained (the amount of acetone soluble and insoluble in the composite rubber-based graft copolymer (A) and the rubber quality in the graft copolymer (A)) There is no particular limitation on the reduced viscosity (measured at 25 ° C. as an N, N-dimethylformamide solution at 0.2 g / dL, N, N-dimethylformamide solution) of acetone-soluble matter, which is determined from the weight of the polymer. Although a thing can be used, it is preferable that a graft rate is 5-150% and a reduced viscosity is 0.2-2.0 g / dL from a viewpoint of a physical-property balance.
In addition, the graft ratio of the composite rubber-based graft copolymer (A) and the reduced viscosity of the acetone-soluble component are specifically determined by the method described in the section of Examples described later.

  Moreover, about the latex of a composite rubber-type graft copolymer (A), the volume average particle diameter of the composite rubber-type graft copolymer (A) calculated | required by microtrack method should be 0.1-0.5 micrometer. It is preferable in terms of the balance between the molded appearance and the impact resistance. Moreover, it is preferable that the solid content density | concentration of a composite rubber type | system | group graft copolymer (A) latex or slurry is about 10-50 mass% from the surface of workability | operativity and productivity in the following mixing process.

<Hard copolymer (B)>
The hard copolymer (B) used in the present invention is an essential component in a proportion of 10 to 60% by mass of vinyl cyanide monomer units in all monomer units constituting the hard copolymer (B). As other components, it contains 40 to 90% by mass of at least one selected from the group consisting of aromatic alkenyl monomer units, (meth) acrylic acid ester monomer units, etc. 100% by mass in total of vinyl monomer units and other monomer units). The content of the vinyl cyanide monomer unit in the hard copolymer (B) is preferably 15 to 55% by mass, more preferably 20 to 50% by mass. When this proportion is less than 10% by mass, the resulting thermoplastic resin composition has poor impact resistance, and when it exceeds 60% by mass, the fluidity and the molded appearance deteriorate, The problem of thermal coloring of the thermoplastic resin composition becomes significant.

  Vinyl cyanide compound constituting vinyl cyanide monomer that can be used for production of hard copolymer (B), aromatic alkenyl compound constituting aromatic alkenyl monomer unit, and (meth) acrylic acid As an example of the (meth) acrylic acid ester which comprises an ester monomer unit, what was illustrated as a monomer component used for manufacture of the said composite rubber-type graft copolymer (A) can be used.

  By producing the hard heavy copolymer (B) by an emulsion polymerization method, it is possible to obtain a hard copolymer (B) in a latex state, which can be used for the next mixing step as it is, which is preferable. About the emulsifier and initiator used in that case, the thing similar to what was illustrated as what is used for manufacture of a composite rubber-type graft copolymer (A) can be used.

  The hard copolymer (B) has a reduced viscosity (hereinafter simply referred to as “reduced viscosity”) of 0.3 to 2.0 dl measured at 25 ° C. with respect to a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide. / G. This reduced viscosity is preferably 0.35 to 1.0 dl / g, more preferably 0.4 to 0.6 dl / g. When the reduced viscosity of the hard copolymer (B) is less than 0.3 dl / g, the impact resistance of the resulting thermoplastic resin composition is inferior, whereas it exceeds 2.0 dl / g. In the case, the fluidity of the thermoplastic resin composition and the deterioration of the molding appearance become remarkable.

  Any method may be used to adjust the reduced viscosity of the hard copolymer (B). However, a method of changing or using the chain transfer agent, a method of changing the amount of initiator used, a polymerization temperature, And a method of changing a method for supplying a monomer as a raw material.

  The solid content concentration of the hard copolymer (B) latex used in the present invention is preferably about 20 to 50% by mass from the viewpoint of workability and productivity in the next mixing step.

<Mixing process>
There is no particular limitation on the method of mixing the composite rubber-based graft copolymer (A) in the slurry or latex state and the hard copolymer (B) in the latex state, and the composite rubber-based graft copolymer in the slurry or latex state. The latex hard copolymer (B) may be added to and mixed with (A), and the slurry or latex hard copolymer (B) may be added to the latex hard copolymer (B). May be mixed. Although mixing time is not specifically limited, 3 minutes or more are preferable, and it is preferable to make mixing time into the range for 5 to 30 minutes from the surface of uniform mixing property and productivity. The mixing time is measured from the time when the hard rubber (B) starts to be mixed with the composite rubber-based graft copolymer (A).

  The hard copolymer (B) is 15 to 45 parts by mass (as solid content), preferably 20 to 40 parts by mass with respect to 100 parts by mass (as solid content) of the composite rubber-based graft copolymer (A). More preferably, it mixes so that it may become 25-35 mass parts. When the mixing ratio of the hard copolymer (B) is less than 15 parts by mass, the effect of improving the fluidity is small, and when it exceeds 45 parts by mass, the impact property of the obtained thermoplastic resin composition is lowered.

<Coagulation process>
As a method of precipitating the composite rubber-based graft copolymer-containing coagulum (D) from the mixed liquid of the composite rubber-based graft copolymer (A) and the hard copolymer (B) obtained in the above mixing step, There is a wet method in which a latex of a mixed solution is coagulated in a slurry state in hot water in which a coagulant is dissolved.

  Examples of the coagulant used in the wet coagulation method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, and metal salts such as calcium chloride, calcium acetate, and aluminum sulfate. A composite rubber-based graft copolymer (A ) And the emulsifier used in the polymerization of the hard copolymer (B) (in the case of mixing the composite rubber-based graft copolymer (A) in the slurry state and the hard copolymer (B) in the latex state, the hard copolymer It is selected according to the emulsifier used in the polymerization of (B). That is, when only a carboxylic acid soap such as a fatty acid soap or a rosin acid soap is used as an emulsifier, the coagulated product (D) containing the composite rubber graft copolymer can be precipitated using any coagulant. However, when an emulsifier exhibiting stable emulsifying power is contained in an acidic region such as sodium alkylbenzene sulfonate, the inorganic acid is insufficient, and a metal salt needs to be used as a coagulant.

  When wet coagulation is performed using a coagulant such as sulfuric acid, the concentration of the coagulant in hot water is preferably 1 to 10% by mass, and the temperature of the hot water is preferably about 50 to 100 ° C. When the composite rubber-based graft copolymer (A) and the hard copolymer (B) are mixed in an amount of about 10 to 150 parts by mass, the coagulation and recovery can be efficiently performed. .

  The composite rubber graft copolymer-containing coagulum (D) obtained by the above wet coagulation method is recovered by solid-liquid separation from the slurry and washed to elute and remove the remaining emulsifier residue in water. To do.

  The washing conditions are not particularly limited, but the amount of the emulsifier residue contained in 100% by mass of the composite rubber-based graft copolymer-containing powder (C) after drying described later is in the range of 0.5 to 2% by mass. It is preferable to wash under conditions. If the emulsifier residue in the composite rubber-based graft copolymer-containing powder (C) is 0.5% by mass or more, the resulting composite rubber-based graft copolymer-containing powder (C) and a resin composition containing the same There is a tendency for the fluidity of the to improve. On the other hand, if the emulsifier residue in the composite rubber-based graft copolymer-containing powder (C) is 2% by mass or less, gas generation can be suppressed when the resin composition is molded at a high temperature. Hereinafter, the content of the emulsifier residue in the dried composite rubber graft copolymer-containing powder (C) is simply referred to as “emulsifier residue content”.

<Drying process>
As a method of obtaining a composite rubber-based graft copolymer-containing powder (C) in a dry state after solid-liquid separation and washing of the solid-graft (D) containing the composite rubber-based graft copolymer as described above, washing is performed as a method. A method of drying the slurry of the coagulated product (D) containing the composite rubber-based graft copolymer later by centrifugation or a press dehydrator and the like, followed by drying with an air dryer or the like, and dehydration and drying by a press dehydrator or an extruder The method etc. which are implemented simultaneously are mentioned. By this method, a powder (C) containing a powder or particulate dry composite rubber-based graft copolymer is obtained.

  In addition, the composite rubber-based graft copolymer-containing powder (C) discharged from the press dehydrator or the extruder is not collected, but directly sent to an extruder or a molding machine for producing the resin composition to obtain a molded product. It is also possible.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains the composite rubber-based graft copolymer-containing powder (C) and / or the composite rubber-based graft copolymer-containing coagulum (D) of the present invention described above, and if necessary. And a thermoplastic resin component other than the composite rubber-based graft copolymer-containing powder (C) and / or the composite rubber-based graft copolymer-containing coagulum (D). Examples of other thermoplastic resins that can be contained in the thermoplastic resin composition of the present invention include diene rubber, alkyl (meth) acrylate rubber, ethylene-propylene copolymer rubber, polyorganosiloxane rubber, diene / Alkyl (meth) acrylate composite rubber, polyorganosiloxane / alkyl (meth) acrylate composite rubber, acrylonitrile-styrene copolymer, acrylonitrile-styrene-methyl methacrylate terpolymer, styrene-methyl methacrylate copolymer , Polycarbonate, polyester, polyamide, polyphenylene ether and the like.
Only 1 type of these resin components may be contained in the thermoplastic resin composition of this invention, and 2 or more types may be contained.

  The thermoplastic resin composition of the present invention contains other resin components other than the composite rubber-based graft copolymer-containing powder (C) and / or the composite rubber-based graft copolymer-containing coagulum (D) of the present invention. In the case of effectively obtaining excellent fluidity and impact resistance by the composite rubber-based graft copolymer-containing powder (C) and / or the composite rubber-based graft copolymer-containing coagulum (D) of the present invention, It is preferable that the ratio of the other resin component in 100 mass parts of all the resin components contained in the thermoplastic resin composition of this invention is 80 mass parts or less.

  The thermoplastic resin composition of the present invention may also contain additives such as dyes, pigments, stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, lubricants, and plasticizers as necessary.

<Molded product>
The thermoplastic resin composition of the present invention is made a desired molded article by various molding methods such as injection molding, extrusion molding, blow molding, compression molding, calendar molding, inflation molding and the like.

  Industrial examples of the molded product of the present invention formed by molding the thermoplastic resin composition of the present invention include vehicle parts, especially various exterior / interior parts used without painting, building materials such as wall materials and window frames. Examples include home appliance parts such as parts, tableware, toys, vacuum cleaner housings, television housings, and air conditioner housings, interior members, ship members, and communication equipment housings.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

  In the following, “part” means “part by mass” and “%” means “mass%”.

[Manufacture of composite rubber]
<Synthesis Example 1: Production of polyorganosiloxane (L-1)>
98 parts of octamethylcyclotetrasiloxane and 2 parts of γ-methacryloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 300 parts of distilled water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred for 2 minutes at 10000 rpm with a homomixer, and then passed once through the homogenizer at a pressure of 300 kg / cm ^2. A stable premixed organosiloxane was obtained. On the other hand, 10 parts of dodecylbenzenesulfonic acid and 90 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer to produce a 10% by weight aqueous solution of dodecylbenzenesulfonic acid. did. While this aqueous solution was heated to 85 ° C., the premixed organosiloxane latex was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the addition, followed by cooling. The reaction was then neutralized with aqueous sodium hydroxide. The polyorganosiloxane latex (L-1) thus obtained was dried at 170 ° C. for 30 minutes and the solid content was determined to be 17.7%. The weight average particle size of the polyorganosiloxane in the latex was 0.05 μm.
The mass average particle diameter of the polyorganosiloxane was determined by the following method.
Using a latex diluted with deionized water to a concentration of about 3% as a sample, the weight average particle size was measured using a CHDF2000 type particle size distribution meter manufactured by MATEC USA.
The measurement was performed under the following standard conditions recommended by MATEC.
Cartridge: Capillary cartridge for particle separation (trade name; C-202)
Carrier liquid: Dedicated carrier liquid (trade name: 2XGR500)
Carrier liquid: neutral Carrier liquid flow rate: 1.4 ml / min Carrier liquid pressure: about 4,000 psi (2,600 kPa)
Measurement temperature: 35 ° C
Sample usage: 0.1 ml
Further, as the standard particle size substance, monodisperse polystyrene with a known particle size manufactured by DUKE of the United States having a particle size of 12 points in the range of 40 to 800 nm was used.

[Production of graft copolymer]
The graft ratio of the graft copolymer produced in Synthesis Examples 2 and 3 below and the reduced viscosity of the acetone-soluble component were measured by the following methods.

<Graft ratio of graft copolymer>
80 mL of acetone was added to 2.5 g of the graft copolymer, and the mixture was refluxed in a 65 ° C. water bath for 3 hours to extract acetone-soluble components. The remaining acetone insolubles were separated by centrifugation, the weight after drying was measured, and the weight ratio of acetone insolubles in the graft copolymer was calculated. The graft ratio was calculated from the weight ratio of acetone insolubles in the obtained graft copolymer using the following formula.

<Reduced viscosity of acetone-soluble matter of graft copolymer>
About the N, N-dimethylformamide solution produced so that the concentration of the acetone soluble part of the graft copolymer is 0.2 dL / g, the reduced viscosity at 25 ° C. using an Ubbelohde viscometer: η _sp / C ( Unit: dL / g) was measured.

<Synthesis Example 2: Production of composite rubber-based graft copolymer (A-1)>
6.25 parts of the polyorganosiloxane latex (L-1) obtained in Synthesis Example 1 in terms of solid content and distilled water 182 are placed in a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device. Parts, butyl acrylate 56.25 parts, alkenyl succinate 0.7 parts, allyl methacrylate 0.2 parts, butylene dimethacrylate 0.08 parts and t-butyl hydroperoxide 0.1 parts. , Mixed. By passing a nitrogen stream through the reactor, the atmosphere was replaced with nitrogen, and then the temperature was raised to 60 ° C. Subsequently, an aqueous solution in which 0.00008 parts of ferrous sulfate, 0.0002 parts of ethylenediaminetetraacetic acid disodium salt and 0.17 parts of sodium formaldehyde sulfoxylate were dissolved in 10 parts of distilled water was added to initiate radical polymerization. . The liquid temperature rose to 78 ° C. due to the polymerization of the acrylate component. Thereafter, the mixture was maintained at 70 ° C. for 30 minutes to complete the polymerization of the acrylate component, and a composite rubber of a branched polyorganosiloxane rubber and a butyl acrylate rubber (polyorganosiloxane / butyl acrylate composite ratio = 6.25 / 56.25). ) Latex was obtained. The volume average particle diameter of the composite rubber was measured using a microtrack (manufactured by Nikkiso Co., Ltd., “Nanotrack 150”). The measured volume average particle diameter was 0.17 μm. Moreover, the gel content measured by the above-mentioned method was 85%.

The liquid temperature inside the reactor containing the composite rubber latex remained at 70 ° C., 0.2 parts of dipotassium alkenyl succinate, 0.001 part of ferrous sulfate, 0.003 part of disodium ethylenediaminetetraacetate and An aqueous solution in which 0.3 part of sodium formaldehyde sulfoxylate was dissolved in 10 parts of distilled water was added, and then a mixture of 9.4 parts of acrylonitrile, 28.1 parts of styrene and 0.225 parts of t-butyl hydroperoxide was added to 100 parts. Polymerized dropwise over a period of minutes. After completion of the dropping, the temperature is maintained at 75 ° C. for 20 minutes, 0.048 parts of cumene hydroperoxide is added, and the mixture is maintained at 75 ° C. for 30 minutes and then cooled to obtain a composite rubber composed of polyorganosiloxane and butyl acrylate rubber. A latex (solid content: 29.0%) of a composite rubber-based graft copolymer (A-1) obtained by graft polymerization of acrylonitrile-styrene copolymer was obtained.
This composite rubber graft copolymer (A-1) is obtained by grafting 50% composite rubber with 50% acrylonitrile and styrene as graft monomer components. The composite rubber graft in latex determined by the μ track method. The volume average particle diameter of the copolymer (A-1) was 0.17 μm, the graft ratio was 51.2%, and the reduced viscosity of the acetone-soluble component was 0.52 g / dL.

<Synthesis Example 3: Production of butadiene rubber-based graft copolymer (A-2)>
Polymerization was conducted in the same manner as in Synthesis Example 2 except that the composite rubber latex was changed to polybutadiene latex (gel content: 85%, average particle size: 0.29 μm, solid content: 34.0%). A latex (solid content: 28.9%) of the union (A-2) was obtained. The volume average particle size of the graft copolymer in the latex determined by the μ track method was 0.18 μm, the graft ratio was 61.4%, and the reduced viscosity of the acetone soluble component was 0.49 g / dL.

[Manufacture of hard copolymer]
The reduced viscosity of the hard copolymer produced in the following synthesis example was measured at 25 ° C. using an Ubbelohde viscometer after dissolving 0.2 g of the powdery copolymer recovered from the latex in 100 ml of dimethylformamide. .

<Synthesis Example 4: Production of Rigid Copolymer (B-1)>
In a 5 L glass reactor equipped with a stirrer, a thermometer, and a jacket type temperature controller, 335.7 parts of water, 2.0 parts of dipotassium alkenyl succinate, 25 parts of acrylonitrile (AN), 75 parts of styrene (ST), 0.4 part of t-dodecyl mercaptan was added, and the internal temperature was raised to 70 ° C. with stirring. To this was added an aqueous solution consisting of 0.25 parts of sodium persulfate and 15.3 parts of water to initiate radical polymerization. When the jacket temperature was maintained at that temperature, heat was rapidly generated after 30 minutes, and the internal temperature rose to 85 ° C. After the heat generation had stopped, the internal temperature was maintained at 70 ° C. for 1 hour and then cooled to obtain a latex of hard copolymer (B-1) having a solid content of 21.9% and a reduced viscosity of 0.59 dl / g.

<Synthesis Example 5: Production of hard copolymer (B-2)>
Polymerization was carried out in the same manner as in Synthesis Example 4 except that t-dodecyl mercaptan was changed to 0.8 part, and a hard copolymer having a solid content of 22.0% and a reduced viscosity of 0.41 dl / g (B-2 ) Latex was obtained.

<Synthesis Example 6: Production of hard copolymer (B-3)>
Polymerization was conducted in the same manner as in Synthesis Example 4 except that t-dodecyl mercaptan was changed to 1.2 parts, and a hard copolymer (B-3 having a solid content of 21.5% and a reduced viscosity of 0.32 dl / g) was obtained. ) Latex was obtained.

<Synthesis Example 7: Production of hard copolymer (b-1)>
Polymerization was conducted in the same manner as in Synthesis Example 4 except that t-dodecyl mercaptan was not added, and the hard copolymer (b-1) having a solid content of 21.7% and a reduced viscosity of 4.31 dl / g was obtained. Latex was obtained.

<Synthesis Example 8: Production of hard copolymer (b-2)>
Polymerization was conducted in the same manner as in Synthesis Example 4 except that t-dodecyl mercaptan was changed to 1.6 parts, and a hard copolymer (b-2) having a solid content of 21.6% and a reduced viscosity of 0.26 dl / g Latex was obtained.

<Synthesis Example 9: Production of hard copolymer (b-3)>
Polymerization was carried out in the same manner as in Synthesis Example 4 except that 9 parts of acrylonitrile and 91 parts of styrene were changed to a hard copolymer (b-3 having a solid content of 21.6% and a reduced viscosity of 0.27 dl / g). ) Latex was obtained.

<Synthesis Example 10: Production of hard copolymer (b-4)>
Polymerization was conducted in the same manner as in Synthesis Example 4 except that 65 parts of acrylonitrile and 35 parts of styrene were changed to a hard copolymer (b-4 having a solid content of 21.6% and a reduced viscosity of 0.71 dl / g). ) Latex was obtained.

[Production and Evaluation of Graft Copolymer-Containing Powder]
[Example 1]
<Production of Composite Rubber Graft Copolymer-Containing Powder (C-1)>
In a coagulator having a thermometer, a stirrer, and a steam blowing type temperature controller, 80 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% was heated to 75 ° C. and stirred.
100 parts of latex of the composite rubber-based graft copolymer (A-1) obtained in Synthesis Example 2 (in terms of solid content) and 25 parts of latex of the hard copolymer (B-1) obtained in Synthesis Example 3 ( Solid conversion) was mixed for 5 minutes, and this mixed solution was gradually dropped into the heated aqueous calcium acetate solution to be solidified. Subsequently, the precipitate was separated, washed so that the emulsifier residue content was 1% or less, and then dried to obtain a composite rubber-based graft copolymer-containing powder (C-1).

<Manufacture of thermoplastic resin composition>
70 parts of composite rubber-based graft copolymer-containing powder (C-1) and 30 parts of acrylonitrile-styrene copolymer produced by suspension polymerization method (“UMG AXS Resin S102N” manufactured by UMG ABS Co., Ltd.) Were mixed using a Henschel mixer, and this mixture was supplied to an extruder heated to 260 ° C. and kneaded to obtain pellets.

<Preparation of test piece>
Using the above pellets, a 4 ounce injection molding machine (manufactured by Nippon Steel Co., Ltd.) was molded under conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. A test piece 1 was obtained.
Similarly, a plate-like molded body 2 having a length of 100 mm, a width of 100 mm, and a thickness of 2 mm was obtained under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 60 ° C., and an injection rate of 5 g / second.

<Evaluation>
(Measure Charpy impact strength)
In accordance with ISO 179, Charpy impact strength was measured with the test piece 1 in an atmosphere of 23 ° C.

(Measurement of melt volume rate (MVR))
According to ISO 1133 standard, MVR of the thermoplastic resin composition pellets was measured under the condition of 220 ° C.-98N. In addition, MVR becomes a standard of the fluidity | liquidity of a thermoplastic resin composition.

(Measurement of diffuse reflectance)
An aluminum film having a thickness of 50 nm is formed on the surface of the molded body 2 by a vacuum deposition method (VPC-1100 manufactured by ULVAC) under conditions of a degree of vacuum of 6.0 × 10 ⁻³ Pa and a deposition rate of 10 Å / second (direct deposition). )did. About the film-forming surface of the obtained molded object 2, the diffuse reflectance (%) was measured with the reflectance meter (TR-1100AD made from Tokyo Denshoku). The diffuse reflectance indicates that the lower the value, the more excellent the surface of the molded product.

  The above evaluation results are shown in Table 1-A.

[Examples 2-3, Comparative Examples 1-6, 8]
As graft copolymers and hard copolymers, those shown in Table 1-A and Table 1-B were used in the proportions shown in Table 1-A and Table 1-B, and mixed and coagulated in the same manner as in Example 1. And drying to obtain graft copolymer-containing powders (C-2) to (C-3), (c-1) to (c-6), and (c-8), respectively. Similarly, the obtained graft copolymer-containing powder and acrylonitrile-styrene copolymer were mixed to produce a thermoplastic resin composition, which was similarly evaluated. The results are shown in Table 1-A and Table 1-B.

[Example 4]
<Production of Composite Rubber Graft Copolymer-Containing Powder (C-4)>
80 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 75 ° C. and stirred. Into this, 100 parts of latex of the composite rubber graft copolymer (A-1) obtained in Synthesis Example 2 (in terms of solid content) was dropped and solidified. The obtained slurry and 25 parts of latex of the hard copolymer (B-2) obtained in Synthesis Example 5 (in terms of solid content) were mixed for 5 minutes, and this mixture was heated to 75 ° C. with 5% calcium acetate. The solution was gradually dropped into 80 parts of the aqueous solution to solidify. Next, the precipitate was separated, washed so that the emulsifier residue content was 1% or less, and then dried to obtain a composite rubber-based graft copolymer-containing powder (C-4).

<Manufacture and evaluation of thermoplastic resin composition>
In the same manner as in Example 1, the obtained composite rubber-based graft copolymer-containing powder (C-4) and acrylonitrile-styrene copolymer were mixed to produce a thermoplastic resin composition, which was similarly evaluated. The results are shown in Table 1-A.

[Comparative Example 7]
<Production of Graft Copolymer-Containing Powder (c-7)>
80 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 75 ° C. and stirred. Into this, 100 parts of latex of the composite rubber graft copolymer (A-1) obtained in Synthesis Example 2 (in terms of solid content) was dropped and solidified.
Similarly, 25 parts (in terms of solid content) of the hard copolymer (B-2) obtained in Synthesis Example 5 was dropped into 20 parts of a 5% calcium acetate aqueous solution heated to 75 ° C. to be solidified. These precipitates were separated, washed, dried and then mixed to obtain a graft copolymer-containing powder (c-7).

<Manufacture and evaluation of thermoplastic resin composition>
In the same manner as in Example 1, the obtained graft copolymer-containing powder (c-7) and acrylonitrile-styrene copolymer were mixed to produce a thermoplastic resin composition, which was similarly evaluated. The results are shown in Table 1-B.

As described above, the following has been clarified from the results of Examples and Comparative Examples.
The thermoplastic resin compositions of Examples 1 to 4 exhibit excellent melt fluidity and molded appearance while maintaining Charpy impact strength.

  On the other hand, the thermoplastic resin compositions of Comparative Examples 1 to 8 were inferior in any of the items of Charpy impact strength, fluidity, and molded appearance. Specifically, the thermoplastic resin composition of Comparative Example 1 is inferior in fluidity and molded appearance because the reduced viscosity of the hard copolymer is too high. The thermoplastic resin composition of Comparative Example 2 had a reduced Charpy impact strength because the reduced viscosity of the hard copolymer was too low. In Comparative Example 3, the flowability is inferior because the amount of the hard copolymer added is small. In Comparative Example 4, since the amount of the hard copolymer added was excessive, the Charpy impact strength was lowered. In Comparative Example 5, the Charpy impact strength was lowered because the content of the acrylonitrile unit in the hard copolymer was small. In Comparative Example 6, the flowability and the molded appearance deteriorated because the content of the acrylonitrile unit in the hard copolymer was too large. Since the thermoplastic resin composition of Comparative Example 7 was powder-mixed with a hard copolymer, the Charpy impact strength was reduced. The thermoplastic resin composition of Comparative Example 8 is inferior in molding appearance because the graft copolymer rubber is not a composite rubber.

  The thermoplastic resin composition of the present invention using the composite rubber-based graft copolymer-containing powder (C) and / or the composite rubber-based graft copolymer-containing solidified product (D) retains impact resistance. However, it exhibits high fluidity and exhibits a good molded appearance. Since the balance of impact resistance, fluidity, and molding appearance is very excellent as compared with conventional thermoplastic resin compositions, the utility value as various industrial materials is extremely high.

Claims (11)

100 parts by mass (solid content) of a composite rubber-based graft copolymer (A) in a slurry or latex state and 15 to 45 parts by mass of a latex state hard copolymer (B) satisfying the following (1) to (2) A composite rubber-based graft copolymer-containing powder (C) obtained by mixing (solid content conversion).
(1) The proportion of vinyl cyanide monomer units in all monomer units constituting the hard copolymer (B) is 10 to 60% by mass.
(2) The reduced viscosity measured at 25 ° C. of a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide is 0.3 to 2.0 dl / g.   The composite rubber-based graft copolymer-containing powder obtained by solid-liquid separation of the composite rubber-based graft copolymer-containing solidified product (D) obtained by coagulating the mixed solution according to claim 1 (C).   The composite rubber graft copolymer-containing powder (C) according to claim 1 or 2, wherein the composite rubber of the composite rubber graft copolymer (A) is a polyorganosiloxane / alkyl (meth) acrylate composite rubber.   The composite rubber-based graft copolymer (A) according to any one of claims 1 to 3, wherein the composite rubber-based graft copolymer (A) includes a monomer component 90 to 90% by weight of the composite rubber containing an aromatic alkenyl compound and a vinyl cyanide compound. A composite rubber-based graft copolymer-containing powder (C) obtained by emulsion graft polymerization of 20% by mass (however, the total of the composite rubber and the monomer component is 100% by mass). 100 parts by mass (solid content) of a composite rubber-based graft copolymer (A) in a slurry or latex state, and 15 to 45 parts by mass of a latex state hard copolymer (B) that satisfies the following (1) and (2) ( A composite rubber-based graft copolymer-containing coagulum (D) obtained through a process of mixing (solid content conversion).
(1) The proportion of vinyl cyanide monomer units in all monomer units constituting the hard copolymer (B) is 10 to 60% by mass.
(2) The reduced viscosity measured at 25 ° C. of a solution obtained by dissolving 0.2 g of the hard copolymer (B) in 100 ml of dimethylformamide is 0.3 to 2.0 dl / g.   In Claim 5, It obtains through the process of mixing the composite rubber graft copolymer (A) of a slurry or a latex state, and the hard copolymer (B) of a latex state, and the process of coagulating the obtained liquid mixture. A composite rubber-based graft copolymer-containing coagulum (D).   The composite rubber-based graft copolymer-containing coagulum (D) according to claim 5 or 6, wherein the composite rubber-based graft copolymer (A) is a polyorganosiloxane / alkyl (meth) acrylate composite rubber.   The composite rubber-based graft copolymer (A) according to any one of claims 5 to 7, wherein the composite rubber-based graft copolymer (A) includes a monomer component 90 to 90% by weight of the composite rubber containing an aromatic alkenyl compound and a vinyl cyanide compound. A composite rubber-based graft copolymer-containing coagulum (D) obtained by emulsion graft polymerization of 20% by mass (however, the total of the composite rubber and the monomer component is 100% by mass).   A thermoplastic resin composition comprising the composite rubber-based graft copolymer-containing powder (C) according to any one of claims 1 to 4.   A thermoplastic resin composition comprising the composite rubber-based graft copolymer-containing coagulum (D) according to any one of claims 5 to 8.   A molded product formed by molding the thermoplastic resin composition according to claim 9.