JP7106880B2 - Thermoplastic resin composition and molded article thereof - Google Patents

Description

The present invention provides a thermoplastic resin molded article having good moldability, impact resistance, low-temperature impact resistance, color development, gloss, molded appearance, molding speed dependence of molded appearance, and weather resistance. The present invention relates to a plastic resin composition and a method for producing the same. The present invention also relates to a molded article using this thermoplastic resin composition and a method for producing the same.

Thermoplastic resins are used in many fields including automobile fields, electrical/electronic equipment fields, and OA equipment such as printers. Among them, styrene-acrylonitrile copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, styrene-acrylonitrile-phenylmaleimide copolymer resin, etc. are added with a monomer that imparts compatibility with these resins. Materials typified by ABS resins, ASA resins, etc. containing graft copolymers obtained by graft polymerization have been widely used because of their excellent impact resistance and fluidity.

Among these, ASA resins using components such as (meth)acrylic acid ester rubber, which is a saturated rubber, in a rubbery polymer have the characteristic of being able to impart good weather resistance.

However, ASA resin has the drawback of being inferior to ABS resin in impact resistance. Therefore, in order to improve the impact resistance, an ASA resin has been proposed in which (meth)acrylic acid ester rubbers having different particle sizes are used in combination (Patent Document 1).
However, even with this ASA resin, the effect of improving the impact resistance is not sufficient. However, it was not able to sufficiently meet the severe needs of recent years.

A method of coating (meth)acrylic acid ester rubber on butadiene rubber or silicone rubber, which has excellent impact resistance, has also been proposed (Patent Documents 2 and 3). However, the products obtained by these methods also include butadiene rubber and silicone rubber that are not coated with (meth)acrylic acid ester rubber. Butadiene rubber had insufficient weather resistance, and silicone rubber had insufficient molding appearance.

A method of improving impact resistance by using a (meth)acrylic acid ester rubber with a narrow particle size distribution has also been proposed (Patent Document 4). However, if the rubber is soft, it is likely to be deformed during molding, and the appearance of the molded product will vary greatly depending on the molding speed. On the other hand, when the rubber is hard, there is a drawback that impact resistance is insufficient, although the difference in molding appearance due to molding speed is small.

JP 2012-214734 A JP 2013-151654 A JP 2013-64048 A WO2017/073294

INDUSTRIAL APPLICABILITY The present invention can provide a thermoplastic resin molded article having good moldability, impact resistance, low-temperature impact resistance, molded appearance, molding speed dependence of molded appearance, weather resistance, color development, and gloss. An object of the present invention is to provide a thermoplastic resin composition and a molded article thereof.

As a result of intensive studies to solve the above problems, the present inventors have found a rubbery polymer (A) containing a (meth)acrylic acid ester having a specific degree of crosslinking and a particle size, a crosslinking agent, and a specific hydrophobic substance. using a graft copolymer (B), a graft copolymer (E) using a specific rubbery polymer (C) having a specific particle size, and another thermoplastic resin (E) By doing so, the inventors have found that the above object can be achieved.
That is, the gist of the present invention is as follows.

[1] A thermoplastic composition containing the following component (B), component (D), and component (E).
Component (B): Polymerization reaction of a raw material mixture containing a (meth)acrylic acid ester, a cross-linking agent, and a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group. A rubbery polymer (A) having an acetone swelling degree of 500 to 1500% and a volume average particle size of 200 to 800 nm, an aromatic vinyl, a (meth)acrylic acid ester and a vinyl cyanide. Graft copolymer (B) in which at least one selected is graft-polymerized
Component (D): A rubbery polymer (C) that is a silicone rubbery polymer (S) and/or a silicone-acrylic rubbery polymer (SA) having a volume average particle size of 50 to 190 nm, Graft copolymer (D) in which at least one selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide is graft-polymerized
Component (E): thermoplastic resin (E) other than graft copolymer (B) and graft copolymer (D)

[2] In [1], the hydrophobic substance is the logarithm [logP] of the partition coefficient [P] represented by the ratio [c1/c2] of the concentration [c1] for 1-octanol and the concentration [c2] for water. A thermoplastic resin composition that is a hydrophobic substance with a value of 6 or more.

[3] In [1] or [2], the component (B) and the component (D) are combined with the rubbery polymer (A) in the component (B) and the rubbery polymer in the component (D) A thermoplastic resin composition containing the rubbery polymer (A) in an amount of 10 to 95% by mass out of 100% by mass in total with (C).

[4] In any one of [1] to [3], the volume average particle size (X) of the rubbery polymer (A) is represented by X, and the cumulative value of the frequency from the upper limit of the particle size distribution curve is 10. % is represented by Y as the upper limit of frequency 10% volume particle size (Y), and the particle size when the cumulative value of the frequency from the lower limit in the particle size distribution curve reaches 10% is the lower limit of frequency 10 When represented by Z as % volume particle size (Z), the volume average particle size (X) of the rubbery polymer (A), the upper frequency limit of 10% volume particle size (Y) and the frequency lower limit of 10% volume particle size ( A thermoplastic resin composition in which Z) satisfies the following (1) or (2).
(1) The volume average particle diameter (X) is 200 ≤ X < 300 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.6X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0 .5X.
(2) The volume average particle diameter (X) is X = 300 to 800 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.8X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0. .4X.

[5] In any one of [1] to [4], the rubbery polymer (A) in the graft copolymer (B) and the rubbery polymer (C) in the graft copolymer (D) is 0.1 to 90% by mass in the total 100% by mass of the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E), and the graft copolymer The total content of the coalescence (B) and the graft copolymer (D) is 0 in the total 100% by mass of the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E) .2 to 99% by mass of a thermoplastic resin composition;

[6] A method for producing a thermoplastic resin composition according to any one of [1] to [5], comprising: (meth)acrylic acid ester, a crosslinking agent, an alkyl group having 12 or more carbon atoms, an alkenyl group and a A mixing step of mixing a hydrophobic substance having a hydrocarbon group selected from an alkyl group, an emulsifier, and water, a mini-emulsification step of mini-emulsifying the mixture (a) obtained in the mixing step, and the mini-emulsion The rubber-like polymer (A) is produced through a polymerization step of polymerizing the mini-emulsion obtained in the polymerization step, and the obtained rubber-like polymer (A) is added with an aromatic vinyl and a (meth)acrylic acid ester. and vinyl cyanide is graft-polymerized to produce the graft copolymer (B).

[7] A molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [5].

[8] A method for producing a molded article by molding the thermoplastic resin composition obtained by the production method according to [6].

According to the present invention, a thermoplastic resin molded article having excellent impact resistance, low-temperature impact resistance, color development, gloss, molded appearance, and weather resistance, and having a small molding speed dependency of the molded appearance can be produced with good moldability and productivity. It is possible to manufacture under

FIG. 3 is a schematic diagram showing a mold used for gas generation/adhesion tests in Examples.

Embodiments of the present invention will be described in detail below.
As used herein, "(meth)acrylic acid ester" means one or both of "acrylic acid ester" and "methacrylic acid ester". In addition, "(meth)acrylate" means one or both of "acrylate" and "methacrylate".

[1] Thermoplastic resin composition The thermoplastic resin composition of the present invention is characterized by containing the following component (B), component (D), and component (E).
Component (B): Polymerization reaction of a raw material mixture containing a (meth)acrylic acid ester, a cross-linking agent, and a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group. A rubbery polymer (A) having an acetone swelling degree of 500 to 1500% and a volume average particle diameter of 200 to 800 nm (hereinafter referred to as the "rubbery polymer (A) of the present invention ) is graft-polymerized with at least one selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide (B) (hereinafter referred to as the “graft copolymer of the present invention ( (Sometimes referred to as B).)
Component (D): A rubbery polymer (C) that is a silicone-based rubbery polymer (S) and/or a silicone-acrylic rubbery polymer (SA) having a volume average particle size of 50 to 190 nm (hereinafter referred to as A graft copolymer obtained by graft-polymerizing at least one selected from aromatic vinyl, (meth)acrylic acid ester, and vinyl cyanide to "the rubbery polymer (C) of the present invention." (D) (hereinafter sometimes referred to as "the graft copolymer (D) of the present invention")
Component (E): A thermoplastic resin (E) other than the graft copolymer (B) and the graft copolymer (D) (hereinafter sometimes referred to as "the thermoplastic resin (E) of the present invention.")

[1-1] Component (B)
[1-1-1] Rubbery polymer (A)
The rubbery polymer (A) of the present invention, which constitutes the graft copolymer (B) of the present invention, which is the component (B), will be described below according to its preferred production method.

The rubbery polymer (A) of the present invention comprises a (meth)acrylic acid ester, a cross-linking agent, and a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group. A polymerization reaction product of a raw material mixture containing acetone having a swelling degree of 500 to 1500% and a volume average particle size of 200 to 800 nm.

Although not particularly limited, the rubbery polymer (A) of the present invention is preferably selected from (meth)acrylic acid esters, cross-linking agents, alkyl groups having 12 or more carbon atoms, alkenyl groups and cycloalkyl groups. A mixing step of mixing a hydrophobic substance having a hydrocarbon group, an emulsifier, and water, a mini-emulsifying step of mini-emulsifying the mixture (a) obtained in the mixing step, and a mini-emulsifying step obtained in the mini-emulsifying step and a polymerization step of polymerizing the resulting miniemulsion.

In the method for producing the rubbery polymer (A), monomer oil droplets of about 70 to 1000 nm are prepared by applying a strong shearing force using, for example, an ultrasonic homogenizer or a pressure homogenizer in the mini-emulsion process. do. At this time, the emulsifier molecules are preferentially adsorbed on the surface of the monomer oil droplets, and almost no free emulsifier or micelles exist in the aqueous medium. Therefore, in an ideal mini-emulsion polymerization, the monomer radicals are not distributed between the aqueous phase and the oil phase, and the polymerization proceeds with the monomer oil droplets serving as the nuclei of the particles. As a result, the formed monomer oil droplets are directly converted into polymer particles, making it possible to obtain homogeneous polymer nanoparticles and to obtain sufficient impact resistance.

On the other hand, in polymer particles prepared by general emulsion polymerization, the reaction progresses by transferring monomers from monomer oil droplets to micelles. Inability to form heterogeneous polymers. Furthermore, in order to form particles of 200 nm or more, it is known to enlarge particles of about 100 nm by seeding with a monomer to increase the size, or by agglomeration of particles using an acid or the like. However, in seed polymerization, it is necessary to continue dripping for a long time in order to make the particles sufficiently large, resulting in poor productivity. and the impact resistance is inferior.

<Mini-emulsion polymerization>
As described above, the mini-emulsion polymerization for producing the rubbery polymer of the present invention includes, but is not limited to, (meth)acrylic acid esters, cross-linking agents, other vinyl A step of mixing a compound, an emulsifier, a specific hydrophobic substance, and water, preferably further a radical polymerization initiator, and applying a shearing force to the resulting mixture (a) with an ultrasonic homogenizer or a pressure homogenizer to form a miniemulsion ( a step of preparing a pre-emulsion), and a step of heating this mixture (a) to the polymerization initiation temperature to polymerize it. In the mini-emulsion polymerization, after the monomers for polymerization and the emulsifier are mixed, for example, by performing a shearing step using a pressure homogenizer, the monomers are torn off by the shearing force to form monomer micro oil droplets covered with the emulsifier. be done. After that, by heating to the polymerization initiation temperature of the radical polymerization initiator, the monomer micro-oil droplets are directly polymerized to obtain polymer microparticles.

Any known method of applying a shearing force to form a mini-emulsion can be used, and examples of high-shearing devices capable of forming a mini-emulsion include, but are not limited to, high-pressure pumps and There are emulsifying devices that consist of interaction chambers, and devices that form mini-emulsions using ultrasonic energy or high frequencies.
More specifically, as an ultrasonic homogenizer, for example, Fisher Scient's "Sonic Dismembrator" and Nippon Seiki Seisakusho's "ULTRASONIC HOMOGENIZER", etc., as a pressure homogenizer, Powrex Co., Ltd.'s "Microfluidizer ”, “Nanomizer” manufactured by Nanomizer, “Starburst” manufactured by Sugino Machine Co., Ltd., “Pressure Homogenizer” manufactured by SPX Corporation APV, “Homogenizer” manufactured by Sanwa Engineering Co., Ltd., manufactured by Sanmaru Machine Industry Co., Ltd. "High-pressure homogenizer", "Homogenizer" manufactured by Izumi Food Machinery Co., Ltd., and the like, and as a high-speed stirrer, "Clairmix" manufactured by M-Technique Co., Ltd., and the like can be mentioned.

<(Meth) acrylic acid ester>
(Meth)acrylic acid esters constituting the rubbery polymer (A) of the present invention include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid esters having an alkyl group of 1 to 22 carbon atoms such as benzyl acrylate; be done. Of the (meth)acrylic acid esters, n-butyl acrylate is preferred because it improves the impact resistance and gloss of molded articles obtained from the thermoplastic resin composition. These (meth)acrylic acid esters may be used alone or in combination of two or more.

The (meth)acrylic acid ester is such that the content of the (meth)acrylic acid ester in 100 parts by weight in total of the (meth)acrylic acid ester, the cross-linking agent described later, and the other vinyl compound used as necessary is 10 parts by mass. It is preferably used in an amount of up to 99.9 parts by weight, particularly 50 to 99.5 parts by weight, especially 70 to 99 parts by weight. If the amount of the (meth)acrylic acid ester used is within the above range, the thermoplastic resin composition obtained by blending the graft copolymer (B) using the obtained rubbery polymer (A) will have good impact resistance. and excellent weather resistance.

<Crosslinking agent>
In the production of the rubbery polymer (A) of the present invention, in order to introduce a crosslinked structure into the (meth)acrylic acid ester component obtained from the (meth)acrylic acid ester described above, the (meth)acrylic acid ester is crosslinked together with the (meth)acrylic acid ester. Use agents. In the case of a crosslinked rubbery polymer (A) obtained using a crosslinking agent, the crosslinked portion thereof is a (meth)acrylic acid ester, an aromatic It also functions as a graft crossing point for graft bonding with at least one vinyl monomer selected from vinyl and vinyl cyanide.

Examples of cross-linking agents include allyl (meth)acrylate, butylene di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1, 4-butylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, polyester di(meth)acrylate, polyurethane di(meth)acrylate, polybutadiene Di(meth)acrylate, divinylbenzene, trivinylbenzene, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, diallyldimethylammonium chloride, polyglycerin poly(meth)acrylate, and the like. be done. These may be used individually by 1 type, and may use 2 or more types together.

The amount of the cross-linking agent to be used is not particularly limited, but the ratio of the cross-linking agent to 100 parts by mass of the (meth)acrylic acid ester, the cross-linking agent and other vinyl compounds described later is from 0.1 to 6.0 parts by mass. It is preferably in an amount of 0 parts by weight, particularly 0.2 to 2.0 parts by weight.
If the ratio of the cross-linking agent is within the above range, the resulting thermoplastic resin composition obtained by blending the graft copolymer (B) using the rubbery polymer (A) will have excellent impact resistance and weather resistance. It becomes a thing.

<Other vinyl compounds>
Other vinyl compounds used as necessary are not particularly limited as long as they are copolymerizable with (meth)acrylic acid esters and cross-linking agents. For example, aromatic vinyl such as styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene; vinyl cyanide such as acrylonitrile, methacrylonitrile; -Cyclohexylmaleimide, N-phenylmaleimide and other maleimides, and maleic anhydride. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

When other vinyl compounds are used, the amount of the other vinyl compounds used is not particularly limited, but the ratio of the other vinyl compounds to 100 parts by mass of the total of the (meth)acrylic acid ester, the cross-linking agent and the other vinyl compounds is 0. It is preferably used in an amount of up to 90 parts by weight, particularly 0.1 to 50 parts by weight, especially 0.3 to 30 parts by weight.

<Hydrophobic substance>
In the present invention, a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group is used when forming a mini-emulsion. The production stability of the mini-emulsion can be improved by using the hydrophobic substance having this specific hydrophobic hydrocarbon group.

The degree of hydrophobicity of the hydrophobic substance used in the present invention is the logarithm [logP] of the partition coefficient [P] represented by the ratio [c1/c2] of the concentration [c1] for 1-octanol and the concentration [c2] for water. The logarithm [logP] of the partition coefficient [P] of the hydrophobic substance used in the present invention is preferably 6.0 or more, particularly preferably 7.0 or more.
Hydrophobic substances having a logarithm [log P] value of partition coefficient [P] of 6 or more include non-polymerizable hydrophobic compounds such as hydrocarbons having 12 or more carbon atoms, alcohols having 12 or more carbon atoms, hydrophobic Examples of monomers include vinyl esters of alcohols having 14 to 30 carbon atoms, vinyl ethers of alcohols having 14 to 30 carbon atoms, vinyl esters of carboxylic acids having 15 to 30 carbon atoms (preferably 15 to 22 carbon atoms), and 20 to 30 carbon atoms. 40 p-alkylstyrene, hydrophobic chain transfer agents, and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

Specific examples of the hydrophobic substance used in the present invention include tetradecane (logP: 6.3), pentadecane (logP: 7.7), hexadecane (logP: 8.3), and heptadecane (logP: 8.0). 8), octadecane (logP: 9.3), icosane (logP: 10.4), liquid paraffin (logP > 6.0), liquid isoparaffin (logP > 6.0), paraffin wax (logP > 6.0) , polyethylene wax (logP>6.0), olive oil (logP>6.0), cetyl alcohol (logP: 6.7), stearyl alcohol (logP: 8.2), stearyl acrylate (logP: 7.7) , stearyl methacrylate (logP: 9.6), and the like.
By using these hydrophobic substances, it becomes possible to suppress an increase in non-uniformity in particle size due to Ostwald ripening and to synthesize a monodisperse rubbery polymer (A).

The amount of the hydrophobic substance to be added is preferably 0.1 to 10 parts by mass, more preferably 1 to 3 parts by mass, per 100 parts by mass of the total of the (meth)acrylic acid ester, the cross-linking agent and other vinyl compounds. .

<Emulsifier>
Examples of emulsifiers used in producing the rubbery polymer (A) of the present invention include carboxylic acids such as oleic acid, palmitic acid, stearic acid, alkali metal salts of rosin acid, and alkali metal salts of alkenylsuccinic acid. system emulsifiers, alkyl sulfates, sodium alkylbenzene sulfonate, sodium alkyl sulfosuccinate, anionic emulsifiers selected from sodium polyoxyethylene nonylphenyl ether sulfate, etc., known emulsifiers alone or in combination of two or more Can be used in combination. Also, part of the emulsifier can be added as appropriate after mini-emulsification and/or during the polymerization reaction in order to stabilize the latex.

Excessive emulsifiers tend to cause gas to adhere to the mold during the production of molded products, which may reduce productivity. It is preferably 0.01 to 3.0 parts by mass, more preferably 0.03 to 1.0 parts by mass, still more preferably 0.05 to 0.5 parts by mass, based on 100 parts by mass of the total vinyl compound. Within the above range, the rubbery polymer (A) can be stably produced.

<Initiator>
The initiator is a radical polymerization initiator for radical polymerization of the above-described (meth)acrylic acid ester, a cross-linking agent, and other vinyl compounds that are optionally used. Examples include initiators, inorganic peroxides, organic peroxides, redox initiators in which organic peroxides are combined with transition metals and reducing agents, and the like. Among these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox initiators, which can initiate polymerization by heating, are preferred. These may be used alone or in combination of two or more.

Examples of azo polymerization initiators include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′- Azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo]formamide, 4,4'-azobis(4-cyanovaleric acid), dimethyl 2,2'-azobis(2-methylpropionate), dimethyl 1,1'-azobis(1-cyclohexanecarboxylate) ), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2′-azobis(N-butyl-2-methylpropionamide), 2,2′-azobis ( N-cyclohexyl-2-methylpropionamide), 2,2′-azobis[2-(2-imidazolin-2-yl)propane], 2,2′-azobis(2,4,4-trimethylpentane), etc. mentioned.

Examples of inorganic peroxides include potassium persulfate, sodium persulfate, ammonium persulfate, and hydrogen peroxide.

Examples of organic peroxides include peroxyester compounds, specific examples of which include α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3, 3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy 2-hexylhexanoate, t-butylperoxy 2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy ) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1 -bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t -butylperoxy)cyclododecane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t- Butylperoxycyclohexyl)propane, α,α'-bis(t-butylperoxide)diisopropylbenzene, dicumylperoxide, 2,5 -dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, dilauroyl peroxide, diisononanoyl peroxide, t -butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, dimethylbis(t-butylperoxy)-3-hexyne, bis(t-butylperoxyisopropyl)benzene, bis(t-butylperoxy)trimethylcyclohexane, butyl-bis(t- butylperoxy)valerate, t-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramenthane hydroperoxide and t-butylperoxybenzoate.

As the redox initiator, a combination of an organic peroxide, ferrous sulfate, a chelating agent and a reducing agent is preferred. For example, one consisting of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, or a combination of t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (Rongalite), ferrous sulfate, and disodium ethylenediaminetetraacetate. etc.

Among these, organic peroxides are particularly preferred as initiators.

The amount of the initiator to be added is usually 5 parts by mass or less, preferably 3 parts by mass or less, for example 0.001 to 3 parts by mass, per 100 parts by mass of the total of the (meth)acrylic acid ester, the cross-linking agent and the other vinyl compound. Department.

The initiator may be added before or after forming the pre-emulsion, and the addition method may be batch, divided or continuous.

<Water>
In the present invention, from the viewpoint of workability, stability, manufacturability, etc., the amount of the water solvent used during mini-emulsion is such that the solid content concentration of the reaction system after polymerization is about 5 to 58% by mass. , it is preferably about 75 to 1900 parts by weight per 100 parts by weight of the mixture (a) other than water. More preferably, it is about 80 to 1,000 parts by mass, and even more preferably about 90 to 500 parts by mass.

<Rubber component>
In the production of the rubbery polymer (A) of the present invention, other rubber components may be present in the step of preparing the pre-emulsion. In this case, other rubber components include diene rubber such as polybutadiene, polyorganosiloxane, and the like. Diene/(meth)acrylic acid compounded with (meth)acrylic acid ester rubber such as butyl acrylate rubber by mini-emulsion polymerization of (meth)acrylic acid ester and a cross-linking agent in the presence of these rubber components A composite rubbery polymer (A) having an ester-based composite rubber or a polyorganosiloxane/(meth)acrylic acid ester-based composite rubber as a rubber component is obtained. The composite rubbery polymer (A) according to the present invention is not limited to these, and the rubber components to be composited can be used singly or in combination of two or more.

<Additive>
In the production of the rubbery polymer (A) of the present invention, additives may be contained in the step of preparing the pre-emulsion, if necessary. In this case, additives include, for example, polystyrene, poly(meth)acrylic acid ester, inorganic substances (silica, zirconia, mica, wollastonite, talc, etc.), fillers (glass fiber, carbon fiber, etc.), lubricants, pigments, etc. (carbon black, titanium oxide, etc.), dyes, heat-resistant agents, antioxidants, weather-resistant agents, release agents, plasticizers, antistatic agents, flame retardants, etc., which impair the physical properties of resin compositions and molded products. can be blended within the range of

<Reaction conditions>
The process of preparing the pre-emulsion is usually carried out at normal temperature (about 10 to 50°C) for about 5 to 600 minutes, and the process of mini-emulsion polymerization is carried out at 40 to 100°C for about 30 to 600 minutes.

<Gel content>
The rubbery polymer (A) of the present invention preferably has a gel content of 80% or more, more preferably 85% or more, still more preferably 90 to 100%. Here, the gel content rate is a value obtained as follows.

That is, 200 mL of methanol and about 10 g of latex of rubbery polymer (A) are put into a 300 mL beaker, and about 1 mL of 5% calcium acetate aqueous solution is added dropwise to coagulate the latex. The coagulum of the rubbery polymer (A) is filtered through 200 mesh, washed again with methanol, and dried under reduced pressure at 60° C. for 24 hours to obtain a polymer. About 1 g of this polymer was precisely weighed (W ₀ ), immersed in about 50 g of acetone at a temperature of 23° C. for 48 hours to swell the polymer, and then centrifuged at 14000 rpm at 5° C. for 2 hours (Hitachi Kogyo Co., Ltd.). CR21E manufactured by Co., Ltd.), and acetone is removed by decantation. Here, after the swollen polymer was precisely weighed (W _s ), it was dried under reduced pressure at 60° C. for 24 hours to evaporate and remove the acetone absorbed by the polymer, and again accurately weighed (W _d ), and the following formula Calculate the gel content.
Gel content (%) = W _d /W ₀ ×100
where W _d is the weight of the dry polymer and W ₀ is the weight of the polymer before immersion in acetone.

If the rubbery polymer (A) has a gel content of 80% or more, the impact resistance of the thermoplastic resin composition containing the graft copolymer (B) using this rubbery polymer (A) is improved. will be excellent.

<Particle size>
The particle size of the rubbery polymer (A) of the present invention is 200 to 800 nm, preferably 250 to 600 nm, more preferably 300 to 500 nm in terms of volume average particle size. If the volume average particle size is less than 200 nm, the fluidity of the thermoplastic resin composition of the present invention, which is obtained by blending the obtained graft copolymer (B) and the later-described graft copolymer (D), and the resistance of the obtained molded article. The impact resistance becomes inferior, and if it exceeds 800 nm, the production stability of the graft copolymer (B) of the present invention becomes inferior. Molded articles obtained from the blended thermoplastic resin composition of the present invention are inferior in molding appearance.

Furthermore, regarding the particle size of the rubbery polymer (A) of the present invention, the volume average particle size (X) is represented by X, and the cumulative value of the frequency from the upper limit of the particle size distribution curve is 10%. The particle diameter is represented by Y as the upper frequency limit 10% volume particle diameter (Y), and the particle diameter at which the cumulative value of the frequency from the lower limit in the particle diameter distribution curve reaches 10% is the lower frequency 10% volume particle diameter (Z ), the flow of a thermoplastic resin composition containing a graft copolymer (B) using this rubbery polymer (A) by satisfying the following (1) or (2) It is preferable because the properties, the impact resistance of the obtained molded article, the molded appearance and the surface gloss are improved.
(1) The volume average particle diameter (X) is X ≤ 300 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.60X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0.50X. is. More preferably, Y≦1.50X and Z≧0.60X, and even more preferably Y≦1.40X and Z≧0.65X.
(2) The volume average particle diameter (X) is X = 300 to 1000 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.8X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0. .4X. More preferably, Y≦1.75X and Z≧0.55X, and even more preferably Y≦1.60X and Z≧0.60X.

Furthermore, when the particle size of the rubbery polymer (A) of the present invention is represented by the above X, Y, and Z, the standard deviation (SD) shown below can be used as a measure of the particle size distribution. The smaller the SD, the narrower the particle size distribution. Good properties, molded appearance, and surface gloss. From this point of view, the SD of the rubbery polymer (A) of the present invention is preferably 250 nm or less, more preferably 180 nm or less, still more preferably 160 nm or less.
Standard deviation (SD) = (YZ)/2

The method for measuring the particle size of the rubbery polymer (A) of the present invention is as described in the Synthesis Examples section below.

<Acetone swelling degree>
The rubbery polymer (A) of the present invention has a degree of swelling with acetone of 500 to 1500%, preferably 500 to 1200%, more preferably 600 to 1000%, still more preferably 700 to 900%.

That is, the same operation as in the measurement of the gel content is performed, and the degree of swelling is calculated by the following equation.
Swelling degree (%) = (W _S - W _d )/W _d × 100
where _WS is the swollen polymer weight and _Wd is the dry polymer weight.

When the degree of swelling of the rubbery polymer (A) is less than 500%, the thermoplastic resin blended with the graft copolymer (B) using the rubbery polymer (A) and the graft copolymer (D) The fluidity, impact resistance, and molding appearance of the composition become inferior, and when it exceeds 1500%, the molding appearance of the thermoplastic resin composition and the speed dependence of the molding appearance become inferior.

[1-1-2] Graft copolymer (B)
The graft copolymer (B) of the present invention comprises the rubbery polymer (A) of the present invention and at least one monomer selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide (hereinafter referred to as , may be referred to as a “graft monomer component”) to form a graft layer.
The graft monomer component may contain vinyl compounds other than aromatic vinyl, (meth)acrylic acid ester, and vinyl cyanide.

The graft ratio of the graft layer of the graft copolymer (B) was calculated by the following method, and the graft ratio was determined by this method also in the synthesis examples given later.

<Calculation of graft ratio>
80 mL of acetone is added to 2.5 g of the graft copolymer (B) and the mixture is refluxed in a hot water bath at 65° C. for 3 hours to extract acetone-soluble matter. The remaining acetone-insoluble matter is separated by centrifugation, dried and weighed. From the mass of the acetone-insoluble matter in the resulting graft copolymer (B) and the mass of the rubbery polymer (A) used in the production of the graft copolymer (B), using the following formula: Calculate the graft ratio.

The graft ratio of the graft copolymer (B) of the present invention is preferably 10 to 90%, more preferably 30 to 85%. If the graft ratio of the graft copolymer (B) is within the above range, it is possible to obtain a molded product with good impact resistance and molding appearance.

The (meth)acrylic acid ester to be graft-polymerized to the rubbery polymer (A) of the present invention is one of those exemplified as the (meth)acrylic acid esters used in the production of the rubbery polymer (A) of the present invention, or Two or more kinds can be used. The aromatic vinyl and vinyl cyanide are one of the aromatic vinyl and vinyl cyanide exemplified as other vinyl compounds that are used as necessary in the production of the rubbery polymer (A) of the present invention. Or 2 or more types can be used.

The graft layer constituting the graft copolymer (B) may contain vinyl compounds other than the (meth)acrylic acid ester, aromatic vinyl, and vinyl cyanide described above. Other vinyl compounds include (meth)acrylic acid esters, cross-linking agents, and other vinyl compounds used as necessary in the production of the rubbery polymer (A) of the present invention. ) One or more of vinyl compounds other than acrylic acid esters, aromatic vinyls, and vinyl cyanides.

As the graft monomer component forming the graft layer of the graft copolymer (B), when a mixture of aromatic vinyl, preferably styrene, and vinyl cyanide, preferably acrylonitrile is used, the obtained graft copolymer ( B) is preferable because it has excellent thermal stability. In this case, the ratio of aromatic vinyl such as styrene and vinyl cyanide such as acrylonitrile is preferably 50 to 90% by mass of aromatic vinyl and 10 to 50% by mass of vinyl cyanide (however, aromatic vinyl The total amount of vinyl and vinyl cyanide is 100% by mass).

The graft layer of the graft copolymer (B) is obtained by emulsion graft polymerization of 90 to 10% by mass of the graft monomer component with respect to 10 to 90% by mass of the rubbery polymer (A). is preferable because the appearance of the thermoplastic resin molded article obtained using this graft copolymer (B) is excellent (however, the total amount of the rubbery polymer (A) and the graft monomer component is 100% by mass) .). More preferably, the ratio is 30 to 70 mass % of the rubbery polymer (A) and 70 to 30 mass % of the graft monomer component.

As a method of graft polymerization of the graft monomer component to the rubbery polymer (A), the grafting monomer component is added to the latex of the rubbery polymer (A) obtained by miniemulsion polymerization. A method of polymerizing in multiple stages is mentioned. When the polymerization is carried out in multiple stages, it is preferable to add the vinyl monomer in portions or continuously in the presence of the rubber latex of the rubbery polymer (A). Good polymerization stability can be obtained by such a polymerization method, and a latex having a desired particle size and particle size distribution can be stably obtained. Examples of the polymerization initiator used for this graft polymerization include the same radical polymerization initiators as those used for the mini-emulsion polymerization in the method for producing the rubbery polymer (A) of the present invention.

When the graft monomer component is polymerized on the rubbery polymer (A), the latex of the rubbery polymer (A) is stabilized and the average particle size of the obtained graft copolymer (B) is controlled. For this purpose, emulsifiers can be added. The emulsifier used here is not particularly limited, but includes the same emulsifiers as the emulsifiers used in the mini-emulsion polymerization in the method for producing the rubbery polymer (A) of the present invention. preferable. The amount of the emulsifier to be used when the graft monomer component is graft-polymerized to the rubbery polymer (A) is not particularly limited, but is from 0.1 to 0.1 per 100 parts by mass of the obtained graft copolymer (B). 10 parts by mass is preferable, and 0.2 to 5 parts by mass is more preferable.

Although the method for recovering the graft copolymer (B) from the latex of the graft copolymer (B) obtained by emulsion polymerization is not particularly limited, the following methods may be mentioned.
The latex of the graft copolymer (B) is poured into hot water in which a coagulant is dissolved to solidify the graft copolymer (B). Next, the solidified graft copolymer (B) is redispersed in water or hot water to form a slurry, and the emulsifier residue remaining in the graft copolymer (B) is eluted into water and washed. Next, the slurry is dehydrated with a dehydrator or the like, and the resulting solid is dried with a flash dryer or the like to recover the graft copolymer (B) as powder or particles.

The coagulant includes inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.), and the like. A coagulant is appropriately selected according to the type of emulsifier. For example, when only a carboxylate (fatty acid salt, rosin acid soap, etc.) is used as an emulsifier, any coagulant may be used. When using an emulsifier such as sodium alkylbenzenesulfonate which exhibits stable emulsifying power even in an acidic range, an inorganic acid is insufficient and a metal salt must be used.

The volume average particle size of the graft copolymer (B) of the present invention produced as described above using the rubbery polymer (A) having the preferred volume average particle size and particle size distribution is preferably 210. ~900 nm, more preferably 350-600 nm. If the volume average particle size of the graft copolymer (B) is within the above range, molding obtained from a thermoplastic resin composition in which the graft copolymer (B) and the graft copolymer (D) described below are blended The product has better impact resistance.

Furthermore, the particle size of the graft copolymer (B) of the present invention is expressed by X representing the volume average particle size (X), and the cumulative value of the frequency from the upper limit of the particle size distribution curve is 10%. The particle diameter is represented by Y as the upper frequency limit 10% volume particle diameter (Y), and the particle diameter at which the cumulative value of the frequency from the lower limit in the particle diameter distribution curve reaches 10% is the lower frequency 10% volume particle diameter (Z ), the fluidity of the thermoplastic resin composition containing the graft copolymer (B) and the impact resistance of the resulting molded article are obtained by satisfying the following (3) or (4): , is preferable because molding appearance and surface gloss are improved.
(3) The volume average particle diameter (X) is X ≤ 350 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.3X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0.55X. is. More preferably, Y≦1.25X and Z≧0.70X.
(4) The volume average particle diameter (X) is X = 350 to 1100 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.60X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0. .50X. More preferably, Y≦1.50X and Z≧0.55X.

Furthermore, when the particle size of the graft copolymer (B) of the present invention is represented by the above X, Y, and Z, the standard deviation (SD) shown below can be used as a measure of the particle size distribution, The smaller the SD, the narrower the particle size distribution. Good properties, molded appearance, and surface gloss. From this point of view, the SD of the graft copolymer (B) of the present invention is preferably 210 nm or less, more preferably 180 nm or less, still more preferably 160 nm or less.
Standard deviation (SD) = (YZ)/2

The method for measuring the particle size of the graft copolymer (B) of the present invention is as described in the Synthesis Examples section below.

[1-2] Component (D)
[1-2-1] Rubber polymer (C)
The rubbery polymer (C) constituting the graft copolymer (D) of the present invention, which is the component (D), will be described below.

The rubbery polymer (C) of the present invention comprises a silicone rubbery polymer (S) and/or a silicone-acrylic rubbery polymer (SA) and has a volume average particle diameter of 50 to 190 nm. be. That is, as the rubbery polymer, in addition to the silicone rubbery polymer (S) and the silicone-acrylic rubbery polymer (SA), an acrylic rubbery polymer, a diene rubbery polymer, an olefin There are also diene-based and acrylic-based composite rubbery polymers, but in the present invention, among these rubbery polymers, from the viewpoint of the impact resistance, molded appearance, and weather resistance of the resulting molded article , a silicone rubbery polymer (S) and/or a silicone-acrylic rubbery polymer (SA). Among these, it is particularly preferable to use a silicone-acrylic rubbery polymer (SA), which has excellent weather resistance and is economically efficient.
As the rubbery polymer (C), in addition to the silicone rubbery polymer (S) and/or the silicone-acrylic rubbery polymer (SA), one of the other rubbery polymers mentioned above. Or you may use 2 or more types together.

<Silicone rubbery polymer (S)>
The silicone-based rubbery polymer (S) is not particularly limited, but polyorganosiloxane having a vinyl polymerizable functional group is preferred. In particular, it consists of 0.3 to 3 mol% of siloxane units containing a vinyl polymerizable functional group and 97 to 99.7 mol% of dimethylsiloxane units, and silicon atoms having 3 or more siloxane bonds are present in polydimethylsiloxane. More preferred is a polyorganosiloxane containing 1 mol % or less of the total silicon atoms in the total silicon atoms.

Examples of the dimethylsiloxane constituting the polyorganosiloxane include dimethylsiloxane-based cyclic bodies having three or more membered rings. Among them, 3- to 7-membered rings are preferred. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These can be used alone or in combination of two or more.

The vinyl-polymerizable functional group-containing siloxane is not limited as long as it contains a vinyl-polymerizable functional group and can bond with dimethylsiloxane via a siloxane bond. However, considering the reactivity with dimethylsiloxane, Various alkoxysilane compounds containing vinyl polymerizable functional groups are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, Methacryloyloxysiloxanes such as γ-methacryloyloxypropyldiethoxymethylsilane and ∂-methacryloyloxybutyldiethoxymethylsilane, vinyl siloxanes such as tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxymethylsilane and γ-mercaptopropyl Mercaptosiloxanes such as dimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane are included. These vinyl-polymerizable functional group-containing siloxanes can be used singly or in combination of two or more.

The silicone-based rubbery polymer (S) may contain a siloxane-based cross-linking agent as a constituent component, if necessary.
Examples of siloxane-based cross-linking agents include tri- or tetra-functional silane-based cross-linking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The method for producing the silicone-based rubbery polymer (S) is not limited. For example, it can be produced by the following method.
First, a siloxane-based cross-linking agent is added to a siloxane mixture composed of dimethylsiloxane and a siloxane having a vinyl polymerizable functional group, if necessary, followed by emulsification with an emulsifier and water to obtain a siloxane mixture aqueous dispersion. Next, the siloxane mixture aqueous dispersion is microparticulated by using a homomixer that microparticulates by shearing force generated by high-speed rotation, a homogenizer that micronizes by the ejection force of a high-pressure generator, or the like. Here, it is preferable to use a high-pressure emulsifying device such as a homogenizer, because the distribution of the particle size of the silicone-based rubbery polymer (S) is narrowed. Next, the micronized siloxane mixture aqueous dispersion is added to an acid aqueous solution containing an acid catalyst and polymerized at a high temperature. Then, the reaction solution is cooled and further neutralized with an alkaline substance such as caustic soda, caustic potash, sodium carbonate or the like to terminate the polymerization, thereby obtaining a silicone rubbery polymer (S) dispersed in an aqueous dispersion.

An anionic emulsifier is preferable as the emulsifier in the production of the silicone rubbery polymer (S). Examples of anionic emulsifiers include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzenesulfonate and sodium laurylsulfonate are preferred. These emulsifiers are used in the range of about 0.05 to 5 parts by mass with respect to 100 parts by mass (as solid content) of the siloxane mixture.

Acid catalysts used for polymerization include sulfonic acids such as aliphatic sulfonic acids, aliphatic-substituted benzenesulfonic acids and aliphatic-substituted naphthalenesulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. These acid catalysts can be used singly or in combination of two or more. Among these, aliphatic-substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred, because of its excellent stabilizing effect on the aqueous dispersion of the silicone-based rubbery polymer (S). In addition, when n-dodecylbenzenesulfonic acid and mineral acid such as sulfuric acid are used together, the emulsifier used in the aqueous dispersion of the silicone rubbery polymer (S) affects the color developability of the thermoplastic resin composition. can be minimized.

The volume-average particle size of the silicone-based rubbery polymer (S) in the aqueous dispersion is within the range of the volume-average particle size of the rubbery polymer (C), which will be described later. In addition, it is preferably 10 to 120 nm, more preferably 30 to 90 μm, because it can prevent an increase in the viscosity of the aqueous dispersion and the formation of coagulum during production of the silicone rubbery polymer (S).
As a method for controlling the volume average particle size of the silicone rubbery polymer (S), for example, the method described in JP-A-5-279434 can be employed.

<Silicone-based acrylic rubbery polymer (SA)>
The silicone-acrylic composite rubbery polymer (SA) is composed of the silicone rubbery polymer (S) and the acrylic rubbery polymer (Ca).

The acrylic rubbery polymer (Ca) is a copolymer having units derived from (meth)acrylic acid ester and either or both of units derived from a crosslinking agent and units derived from a graft crossing agent. is preferred.
Examples of the (meth)acrylic acid ester include the same (meth)acrylic acid esters as those exemplified as the (meth)acrylic acid ester used in the production of the rubber polymer (A) described above. Therefore, n-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferred. (Meth)acrylic acid esters may be used alone or in combination of two or more.

Examples of the cross-linking agent include those exemplified as the cross-linking agent used in the production of the rubbery polymer (A) described above. The cross-linking agents may be used singly or in combination of two or more.

Graft crossing agents include allyl (meth)acrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, diallyldimethylammonium chloride and the like. The graft crossing agent may be used singly or in combination of two or more.

In the acrylic rubbery polymer (Ca), the total amount of the units derived from the cross-linking agent and the units derived from the graft crossing agent is determined from the viewpoint of the impact resistance and molded appearance of the resulting molded product. It is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, even more preferably 0.5 to 2% by mass, based on the total 100% by mass of all units constituting (Ca).

The method for producing the acrylic rubbery polymer (Ca) is not particularly limited. For example, a method of obtaining an aqueous dispersion of an acrylic rubbery polymer (Ca) by miniemulsion polymerization as described above; A method of obtaining an aqueous dispersion of an acrylic rubbery polymer (Ca) by emulsion polymerization of a mixture of rubber components; Agglomeration or co-enlarging method: in the presence of either an acrylic rubbery polymer (Ca) aqueous dispersion or another rubber component aqueous dispersion, a monomer mixture constituting the other is polymerized to form a composite. and the like.

The content of the silicone rubbery polymer (S) in the silicone-acrylic composite rubbery polymer (SA) (100% by mass) is preferably 1 to 20% by mass, more preferably 3 to 18% by mass. . When the content of the silicone-based rubbery polymer (S) is at least the lower limit of the above range, the impact resistance of the obtained molded article is more excellent, and when it is at most the upper limit of the above range, the impact resistance is more excellent. Excellent.

The method for producing the silicone-acrylic composite rubbery polymer (SA) is not particularly limited. For example, a method of hetero-aggregating or co-enlarging an aqueous dispersion of the silicone rubbery polymer (S) and an aqueous dispersion of the acrylic rubbery polymer (Ca), which are separately produced, and a silicone rubbery polymer. In either one of the aqueous dispersion of (S) and the aqueous dispersion of the acrylic rubbery polymer (Ca), a method of forming a polymer in the other to form a composite, and the like can be mentioned. Among them, since the impact resistance and color development properties of the molded article are more excellent, in the aqueous dispersion of the silicone rubber polymer (S), a (meth)acrylic acid ester monomer, a cross-linking agent and a graft cross-linking agent are used. A preferred method is emulsion polymerization of a monomer component containing either one or both of the agents.

Preferred specific examples of emulsifiers used in emulsion polymerization include sodium or potassium salts of fatty acids such as oleic acid, stearic acid, myristic acid, stearic acid and palmitic acid, sodium lauryl sulfate, sodium N-lauroyl sarcosinate and alkenyl succinate. dipotassium acid, sodium alkyldiphenyl ether disulfonate, sodium polyoxyethylene alkylphenyl ether sulfate, and the like.
As the emulsifier, an acid-type emulsifier having two or more functional groups in one molecule or a salt thereof is preferable because the generation of gas during molding of the thermoplastic resin composition can be further suppressed. Sodium diphenyl ether disulfonate is preferred.

<Gel content>
The rubbery polymer (C) of the present invention preferably has a gel content of 10% or more, more preferably 20% or more, still more preferably 30 to 100%.
If the rubbery polymer (C) has a gel content of 10% or more, the graft copolymer (D) using this rubbery polymer (C) and the above graft copolymer (B) are blended. A molded article obtained from the thermoplastic resin composition has excellent impact resistance.
The gel content of the rubbery polymer (C) is determined by the same method as for the rubbery polymer (A).

<Acetone swelling degree>
The rubbery polymer (C) of the present invention preferably has a degree of swelling with acetone of 800 to 2000%, more preferably 1000 to 1800%, still more preferably 1300 to 1700%.
If the degree of swelling of the rubbery polymer (C) is within the above range, the aforementioned graft copolymer (B) and the graft copolymer (D) using this rubbery polymer (C) are blended. The thermoplastic resin composition has an excellent balance between impact resistance, molded appearance, and velocity dependence of molded appearance.
The acetone swelling degree of the rubbery polymer (C) is determined by the same method as for the rubbery polymer (A).

<Particle size>
The particle size of the rubbery polymer (C) of the present invention is 50 to 190 nm, preferably 90 to 130 nm, in terms of volume average particle size. When the volume average particle size is less than 50 nm, the fluidity and impact resistance of the thermoplastic resin obtained by blending the graft copolymer (B) and the graft copolymer (D) using this rubbery polymer (C) are deteriorated. If it exceeds 190 nm, the molding appearance and speed dependence of the molding appearance become inferior.

[1-2-2] Graft copolymer (D)
The graft copolymer (D) of the present invention comprises the rubbery polymer (C) of the present invention and at least one monomer selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide (hereinafter referred to as , may be referred to as a “graft monomer component”) to form a graft layer.
The graft monomer component may contain vinyl compounds other than aromatic vinyl, (meth)acrylic acid ester, and vinyl cyanide.

The graft ratio of the graft layer of the graft copolymer (D) is calculated by the same method as for the graft copolymer (B) of the present invention.
The graft ratio of the graft copolymer (D) of the present invention is preferably 10-90%, more preferably 20-50%. If the graft ratio of the graft copolymer (D) is within the above range, it is possible to obtain a molded product with good impact resistance and molding appearance.

The (meth)acrylic acid ester, aromatic vinyl, vinyl cyanide, and other vinyl compounds used as necessary to be graft-polymerized to the rubbery polymer (C) of the present invention are the graft copolymer of the present invention ( The same explanations as in the explanation of B) can be applied.

When a mixture of aromatic vinyl, preferably styrene, and vinyl cyanide, preferably acrylonitrile, is used as the graft monomer component forming the graft layer of the graft copolymer (D), the resulting graft copolymer ( D) is preferable because it has excellent thermal stability. In this case, the ratio of aromatic vinyl such as styrene and vinyl cyanide such as acrylonitrile is preferably 50 to 90% by mass of aromatic vinyl and 10 to 50% by mass of vinyl cyanide (however, aromatic vinyl The total amount of vinyl and vinyl cyanide is 100% by mass).

The graft layer of the graft copolymer (D) is obtained by emulsion graft polymerization of 90 to 10% by mass of the graft monomer component with respect to 10 to 90% by mass of the rubbery polymer (C). If there is, the appearance of the thermoplastic resin molded article obtained using this graft copolymer (D) is excellent, which is preferable (however, the total of the rubbery polymer (C) and the graft monomer component is 100% by mass ). More preferably, the ratio is 30 to 70 mass % of the rubbery polymer (C) and 70 to 30 mass % of the graft monomer component.

The graft copolymer (D) of the present invention can be obtained by using the rubbery polymer (C) in place of the rubbery polymer (A) in the same manner as the graft copolymer (B) of the present invention. can be manufactured.
Moreover, the method of recovering the graft copolymer (D) from the latex of the graft copolymer (D) obtained by emulsion polymerization can also be carried out in the same manner as the graft copolymer (B) described above.

The volume average particle size of the graft copolymer (D) of the present invention produced using the rubbery polymer (C) having the preferred volume average particle size described above is usually 50 to 190 nm, preferably 90 to 130 nm. . When the volume average particle size of the graft copolymer (D) is less than 50 nm, the fluidity of the thermoplastic resin composition obtained by blending the graft copolymer (B) and this graft copolymer (D) is obtained. If the particle size exceeds 190 nm, the molding appearance of the resulting molded article and the speed dependence of the molding appearance will be inferior.

[1-3] Component (E)
The thermoplastic resin (E) of the present invention, which is the component (E), is a thermoplastic resin other than the graft copolymer (B) of the present invention and the graft copolymer (D) of the present invention. , polystyrene, acrylonitrile-styrene copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate- One or more of styrene-acrylonitrile copolymers, polycarbonates, polyamides, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyphenylene ether-polystyrene composites can be used. Among these, acrylonitrile-styrene copolymers are preferred from the viewpoint of impact resistance and fluidity.

[1-4] Content of each component In the thermoplastic resin composition of the present invention, the graft copolymer (B) of component (B) and the graft copolymer (D) of component (D) are thermoplastic The ratio of the rubbery polymer (A) to the total 100% by mass of the rubbery polymer (A) and the rubbery polymer (C) in the resin composition is 10 to 95% by mass, and the rubbery polymer (C) is preferably contained so that the ratio of is 5 to 90% by mass.
In particular, it is preferable that the content of the rubbery polymer (A) is 30 to 80% by mass and the content of the rubbery polymer (C) is 20 to 70% by mass.
If the ratio of the rubbery polymer (A) and the ratio of the rubbery polymer (C) are within the above ranges, the impact resistance can be expressed with a small rubber content, and the molding appearance and molding appearance are improved. The molding speed dependency is also excellent.

The total content (rubber content) of the rubbery polymer (A) and the rubbery polymer (C) in the thermoplastic resin composition of the present invention is the graft copolymer (B), the graft copolymer ( It is preferably 0.1 to 90% by mass, more preferably 10 to 40% by mass, and even more preferably 15 to 30% by mass, based on the total 100% by mass of D) and thermoplastic resin (E). If the rubber content is within the above range, the fluidity of the thermoplastic resin composition, the impact resistance of the molded article, the low-temperature impact resistance, the molded appearance, the speed dependence of the molded appearance, and the weather resistance will be further improved. Become.

Further, in the thermoplastic resin composition of the present invention, the total content of the graft copolymer (B) and the graft copolymer (D) is the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E) is preferably 0.2 to 99% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 40% by mass. That is, the content of the thermoplastic resin (E) in the thermoplastic resin composition of the present invention is 100% by mass in total of the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E). 1 to 99.8% by mass is preferable, 40 to 90% by mass is more preferable, and 60 to 80% by mass is even more preferable. If the total content of the graft copolymer (B) and the graft copolymer (D) and the content of the thermoplastic resin (E) are within the above ranges, the flowability and molding of the thermoplastic resin composition Good balance of physical properties such as impact resistance, low-temperature impact resistance, molded appearance, speed dependence of molded appearance, and weather resistance.

[1-5] Additives The thermoplastic resin composition of the present invention may contain, in addition to the above-described resin components, various additives that are commonly used in thermoplastic resin compositions.
Examples of additives include coloring agents such as pigments and dyes, fillers (carbon black, silica, titanium oxide, etc.), flame retardants, stabilizers, reinforcing agents, processing aids, heat-resistant agents, antioxidants, weather-resistant agents, Release agents, plasticizers, antistatic agents, and the like are included.
These additives may be added in the step of preparing the pre-emulsion in the production of the rubbery polymer (A) of the present invention, as described above.

[1-6] Method for producing thermoplastic resin composition The thermoplastic resin composition of the present invention comprises a graft copolymer (B), a graft copolymer (D), a thermoplastic resin (E), and Additives are mixed and dispersed with a V-type blender, Henschel mixer, etc. according to the above, and the resulting mixture is melt-kneaded using a kneader such as an extruder, Banbury mixer, pressure kneader, rolls, etc. manufactured.

The mixing order of each component is not particularly limited as long as all the components are uniformly mixed. For example, a method of mixing a powdery graft copolymer (B) and a graft copolymer (D) with a thermoplastic resin (E); and then graft copolymerizing to obtain a powder of the graft copolymer (B) and the graft copolymer (D), and mixing the obtained powder with the thermoplastic resin (E); the graft copolymer (B) A method of mixing the latex and the graft copolymer (D) latex and mixing the resulting powder with the thermoplastic resin (E); ) by simultaneously synthesizing the rubbery polymer (A) and the rubbery polymer (C), followed by graft copolymerization to obtain a graft copolymer (B) and a graft copolymer (C) A method of obtaining a powder of and mixing it with the thermoplastic resin (E).

[2] Molded article The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention, and has impact resistance, low-temperature impact resistance, molded appearance, speed dependence of molded appearance, and weather resistance. And excellent in color development, gloss, etc.

Examples of methods for molding the thermoplastic resin composition of the present invention include injection molding, injection compression molding, extrusion, blow molding, vacuum molding, air pressure molding, calender molding and inflation molding. mentioned. Among these, the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and can obtain molded articles with high dimensional accuracy.

The molded article of the present invention obtained by molding the thermoplastic resin composition of the present invention is excellent in impact resistance, low-temperature impact resistance, molded appearance, weather resistance, gloss, color development, etc. It is suitable for OA equipment, building materials, and the like.

Examples of industrial applications of the molded article of the present invention formed by molding the thermoplastic resin composition of the present invention include vehicle parts, particularly various exterior and interior parts used without coating, wall materials, building materials such as window frames. parts, tableware, toys, household appliance parts such as vacuum cleaner housings, television housings, air conditioner housings, interior parts, ship parts, communication equipment housings, and the like.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention.
In the following, "parts" means "parts by mass" and "%" means "% by mass".

[Measurement of volume average particle size]
Rubber polymers (A-1) to (A-24), graft copolymers (B-1) to (B-23), rubber polymer (C-1) produced in Synthesis Examples and Comparative Synthesis Examples ~ (C-9), and the volume average particle diameter (X) of the graft copolymers (D-1) ~ (D-9) is determined by the dynamic light scattering method using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd. asked.
In addition, the particle size distribution is obtained in the same manner as above, the particle size at the upper frequency limit of 10% is defined as the upper frequency limit of 10% volume particle diameter (Y), and the particle diameter at the frequency lower limit of 10% is defined as the frequency lower limit of 10% volume particle diameter (Y). Z), and the ratio to the volume average particle size (X) was calculated.
Also, as a measure of the particle size distribution, the standard deviation (nm) was calculated using the following formula.
Standard deviation (SD) = (YZ)/2

[Measurement of the amount of agglomerates]
Rubber polymers (A-1) to (A-23), graft copolymers (B-1) to (B-23), rubber polymer (C-1) produced in Synthesis Examples and Comparative Synthesis Examples (C-9) and graft copolymers (D-1) to (D-9) were filtered through a 100-mesh wire mesh, and the coagulum remaining on the 100-mesh wire mesh was dried and weighed. , respectively, rubbery polymers (A-1) to (A-23), graft copolymers (B-1) to (B-23), rubbery polymers (C-1) to (C-9) , the ratio (% by mass) to the graft copolymers (D-1) to (D-9) was determined. The smaller the amount of coagulum, the more rubbery polymers (A-1) to (A-23), the graft copolymers (B-1) to (B-23), the rubbery polymers (C-1) to ( C-9) and the latexes of the graft copolymers (D-1) to (D-9) have good production stability.

[Production and Evaluation of Rubber Polymer (A)]
<Synthesis Example I-1: Production of rubbery polymer (A-1)>
A rubbery polymer (A-1) was produced with the following formulation.

[Formulation]
n-butyl acrylate (BA) 94.5 parts allyl methacrylate (AMA) 0.5 parts 1,3-butanediol dimethacrylate (1,3-BDMA) 5.0 parts liquid paraffin (LP) 2.0 parts Dipotassium alkenyl succinate (ASK) 0.2 parts Dilauroyl peroxide (LPO) 0.6 parts Distilled water 400 parts

n-Butyl acrylate (Log P = 1.9), liquid paraffin (Log P > 6.0), allyl methacrylate (Log P = 1.5), 1,3-butanediol dimethacrylate (Log P = 2.7 ), dilauroyl peroxide, distilled water, and dipotassium alkenyl succinate were charged, and stirred at room temperature for 5 minutes at 9000 rpm using a “High Flex Disperser HG92” manufactured by SMT Co., Ltd. to obtain a mixture. A pre-emulsion was obtained by treating the resulting mixture twice at a pressure of 20 MPa and a flow rate of 135 L/Hr using a "high-pressure homogenizer H3-1D" manufactured by Sanmaru Kikai Kogyo Co., Ltd. The volume average particle size of the obtained pre-emulsion was 300 nm.

A reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer was charged with the obtained pre-emulsion. and radical polymerization was initiated. The liquid temperature rose to 78°C due to the polymerization of the acrylate component. The temperature was maintained at 75°C for 30 minutes to complete the polymerization of the acrylate component. The time required for production was 70 minutes, and a latex of rubbery polymer (A-1) having a solid content of 18.5%, an amount of coagulum of 0.01% and a volume average particle diameter (X) of 300 nm was obtained. The resulting latex of rubbery polymer (A-1) had a gel content of 99% and an acetone swelling degree of 510%.

<Synthesis Examples I-2 to I-17, Comparative Synthesis Examples I-1 to I-4: Production of rubbery polymers (A-2) to (A-21)>
Rubber polymers (A-2) to (A-21) were prepared in the same manner as in Synthesis Example I-1, except that the (meth)acrylic acid ester, cross-linking agent, and emulsifier were changed as shown in Tables 1 and 2. ) of latex was obtained.
Tables 1 and 2 collectively show the evaluation results of the rubbery polymers (A-1) to (A-21).

<Comparative Synthesis Example I-5: Production of rubbery polymer (A-22)>
A rubbery polymer (A-22) was produced with the following formulation.

[Formulation]
n-butyl acrylate (BA) 98.5 parts allyl methacrylate (AMA) 0.5 parts 1,3-butanediol dimethacrylate (1,3-BDMA) 1.0 parts t-butyl hydroperoxide 0.25 parts Ferrous sulfate 0.0002 parts Sodium formaldehyde sulfoxylate 0.33 parts Disodium ethylenediaminetetraacetate 0.0004 parts Dipotassium alkenylsuccinate (ASK) 1.0 parts Distilled water 400 parts

100 parts of distilled water, 0.05 parts of dipotassium alkenicosuccinate, 4.925 parts of n-butyl acrylate, and 0 parts of allyl methacrylate were placed in a nitrogen-purged reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device. 0.025 parts, 0.05 parts of 1,3-butanediol dimethacrylate, and 0.05 parts of t-butyl hydroperoxide are charged, heated to 60° C., then ferrous sulfate, sodium formaldehyde sulfoxylate, ethylenediaminetetraacetic acid di Sodium was added and allowed to react for 60 minutes. Then, 300 parts of distilled water, 0.95 parts of dipotassium alkenyl succinate, 93.575 parts of n-butyl acrylate, 0.475 parts of allyl methacrylate, 0.95 parts of 1,3-butanediol dimethacrylate, t-butyl A mixture of 0.2 parts of hydroperoxide was pumped in dropwise over a period of 300 minutes. After completion of dropping, the temperature was maintained at 75° C. for 30 minutes to complete the polymerization of the acrylate component to obtain a latex of rubbery polymer (A-22). The time required for production was 420 minutes, and the solid content of the rubbery polymer (A-22) in the obtained latex was 19.1%, the amount of coagulum was 0.54%, and the volume average particle diameter (X) was was 270 nm, the upper frequency limit 10% volume particle diameter (Y) was 440 nm, and the lower frequency 10% volume particle diameter (Z) was 110 nm.
The resulting latex of composite rubbery polymer (A-22) had a gel content of 85% and an acetone swelling degree of 660%.

<Comparative Synthesis Example I-6: Production of rubbery polymer (A-23)>
A rubbery polymer (A-23) was produced by the following procedure.

<Production of acid group-containing copolymer latex (K)>
First, an acid group-containing copolymer latex (K) was produced with the following formulation.

[Formulation]
Distilled water 200 parts Potassium oleate 2.0 parts Sodium dioctylsulfosuccinate 4.0 parts Ferrous sulfate heptahydrate 0.003 parts Disodium ethylenediaminetetraacetate 0.009 parts Sodium formaldehyde sulfoxylate 0.3 parts Acrylic acid n-butyl 82 parts methacrylic acid 18 parts cumene hydroperoxide 0.5 parts

Distilled water, potassium oleate, sodium dioctylsulfosuccinate, ferrous sulfate heptahydrate, disodium ethylenediaminetetraacetate, sodium formaldehyde sulfonate were added to a reactor equipped with a reagent injection vessel, cooling tubes, jacket heater and stirring device. The xylate was charged under nitrogen flow and heated to 60°C. When the temperature reached 60° C., a mixture of n-butyl acrylate, methacrylic acid and cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, aging was continued for 2 hours at 60° C. to obtain an acid group-containing copolymer latex (K) having a solid content of 33%, a polymerization conversion rate of 96%, and a volume average particle size of 150 nm. .

<Production of rubbery polymer (A-23)>
Using the resulting acid group-containing copolymer latex (K), a rubbery polymer (A-23) was produced according to the following formulation.

[Formulation]
n-butyl acrylate (BA) 98.5 parts allyl methacrylate (AMA) 0.5 parts 1,3-butanediol dimethacrylate (1,3-BDMA) 1.0 parts t-butyl hydroperoxide 0.2 parts Dipotassium alkenyl succinate (ASK) 1.3 parts Distilled water 390 parts Sodium formaldehyde sulfoxylate 0.3 parts Ferrous sulfate heptahydrate 0.0002 parts Disodium ethylenediaminetetraacetate 0.0004 parts Distilled water 10 parts

n-Butyl acrylate, allyl methacrylate, 1,3-butanediol dimethacrylate, t-butyl hydroperoxide, distilled water, alkenyl are placed in a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring device. After dipotassium succinate was charged and the inside of the reactor was replaced with nitrogen, the contents were heated. At an internal temperature of 55° C., an aqueous solution consisting of sodium formaldehyde sulfoxylate, ferrous sulfate heptahydrate, disodium ethylenediaminetetraacetate and distilled water was added to initiate polymerization. After the heat of polymerization was confirmed, the jacket temperature was raised to 75° C., and the polymerization was continued until the heat of polymerization was no longer confirmed, and was held for 30 minutes. The volume average particle size of the resulting rubbery polymer was 100 nm. 1 part of a 5% sodium pyrophosphate aqueous solution was added thereto as a solid content (pH of the mixed solution was 9.1), and the jacket temperature was controlled so that the inner temperature was 70°C.

At an internal temperature of 70° C., 4 parts of the acid group-containing copolymer latex (K) as a solid content was added, and the mixture was stirred for 30 minutes while maintaining the internal temperature of 70° C. to enlarge the mixture. The time required for production was 100 minutes. The diameter (X) was 300 nm, the upper limit frequency 10% volume particle diameter (Y) was 570 nm, and the lower frequency 10% volume particle diameter (Z) was 200 nm.
The resulting latex of the composite rubbery polymer (A-23) had a gel content of 86% and an acetone swelling degree of 1070%.

<Comparative Synthesis Example I-24: Production of rubbery polymer (A-24)>
A rubbery polymer (A-24) was produced in the same manner as in Synthesis Example I-1, except that the hydrophobic substance was changed to 0 parts.
The pre-emulsion had a volume-average particle size of 1600 nm and was consolidated during the radical polymerization.

[Production and Evaluation of Graft Copolymer (B)]
<Synthesis Example II-1: Production of graft copolymer (B-1)>
A reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirrer is charged with raw materials according to the following composition. did.

[Formulation]
Water (including water in rubbery polymer (A-1) latex) 230 parts Rubbery polymer (A-1) latex 50 parts (as solid content)
Dipotassium alkenyl succinate (ASK) 0.5 parts Sodium formaldehyde sulfoxylate 0.3 parts Ferrous sulfate heptahydrate 0.001 parts Disodium ethylenediaminetetraacetate 0.003 parts

Then, the temperature was raised to 80° C. while dropping a mixture containing acrylonitrile (AN), styrene (ST) and t-butyl hydroperoxide in the following composition over 100 minutes.

[Formulation]
Acrylonitrile (AN) 12.5 parts Styrene (ST) 37.5 parts t-butyl hydroperoxide 0.2 parts

After completion of dropping, the temperature was maintained at 80° C. for 30 minutes and then cooled to obtain a latex of graft copolymer (B-1). The solid content of the graft copolymer (B-1) in the resulting latex was 29.7%, the amount of coagulum was 0.02%, the volume average particle diameter was 340 nm, and the graft ratio was 55%.
Next, 100 parts of a 1.5% sulfuric acid aqueous solution is heated to 80° C., and while stirring the aqueous solution, 100 parts of the graft copolymer (B-1) latex is gradually added dropwise to the aqueous solution to obtain a graft copolymer ( B-1) was solidified, and the temperature was raised to 95° C. and held for 10 minutes.
The solidified product was then dehydrated, washed and dried to obtain a powdery graft copolymer (B-1).

<Synthesis Examples II-2 to II-17, Comparative Synthesis Examples II-1 to II-6: Production of graft copolymers (B-2) to (B-23)>
In the same manner as in Synthesis Example II-1, except that latexes of the rubbery polymers (A-2) to (A-23) were used instead of the latex of the rubbery polymer (A-1). Graft copolymers (B-2) to (B-23) were obtained, respectively.

Tables 3 and 4 collectively show the particle size, aggregate amount, and graft ratio of each of the graft copolymers (B-1) to (B-23).

[Production and Evaluation of Rubber Polymer (C)]
<Synthesis Example III-1: Production of Silicone Rubber Polymer (S-1)>
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. To this, 300 parts of distilled water containing 0.9 parts of sodium dodecylbenzenesulfonate dissolved is added, and after stirring at 10,000 rpm for 2 minutes with a homomixer, it is passed through a homogenizer once at a pressure of 30 MPa, and a stable premixed organo A siloxane latex was obtained.

Separately, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device to prepare a 2% dodecylbenzenesulfonic acid aqueous solution. While this aqueous solution was heated to 85° C., the premixed organosiloxane latex was added dropwise over 4 hours, and after the completion of dropwise addition, the temperature was maintained for 1 hour and cooled. After the reaction solution was allowed to stand at room temperature for 48 hours, it was neutralized with an aqueous sodium hydroxide solution to obtain a latex of silicone rubbery polymer (S-1). A portion of the silicone-based rubbery polymer (S-1) latex was dried at 170° C. for 30 minutes to determine the solid content concentration, which was 17.3%. The volume average particle size of the silicone rubbery polymer (S-1) dispersed in the latex was 30 nm.

<Synthesis Examples III-2 to III-3: Production of Silicone Rubber Polymers (S-2) and (S-3)>
Latexes of silicone rubber polymers (S-2) and (S-3) were prepared in the same manner as in Synthesis Example III-1, except that the amount of sodium dodecylbenzenesulfonate was changed as shown in Table 5. Obtained.
Table 5 shows the measurement results of the volume average particle size of the silicone rubber polymers (S-1) to (S-3).

<Synthesis Example III-4: Production of silicone-acrylic rubbery polymer (SA)>
A silicone-acrylic rubbery polymer (SA-1) was produced with the following formulation.
[Formulation]
Water (including water in silicone rubbery polymer (S-1) latex) 230 parts Silicone rubbery polymer (S-1) latex (as solid content) 7.0 parts dipotassium alkel succinate (ASK) 0.5 parts ferrous sulfate heptahydrate 0.0001 parts disodium ethylenediaminetetraacetate 0.0003 parts sodium formaldehyde sulfoxylate 0.24 parts n-butyl acrylate (BA) 92.0 parts allyl methacrylate 0.5 parts Part 1,3-butylene glycol dimethacrylate (1,3-BDMA)
0.5 parts t-butyl hydroperoxide 0.088 parts

A reactor equipped with a reagent injection container, a cooling pipe, a jacket heater, and a stirring device was charged with the latex of the silicone rubbery polymer (S-1) and dipotassium alkel succinate, and then distilled water was added and mixed. . The atmosphere was replaced with nitrogen by passing a nitrogen stream through the reactor, and when the temperature inside the reactor reached 60°C, ferrous sulfate, disodium ethylenediaminetetraacetic acid and sodium formaldehyde sulfoxylate were added. was dissolved in distilled water. Thereafter, a mixture of nitrogen-substituted n-butyl acrylate, allyl methacrylate, 1,3-butylene glycol dimethacrylate and t-butyl hydroperoxide was added over 60 minutes for radical polymerization. After the dropwise addition, this state was maintained for 1 hour, and the polymerization was continued until the heat of polymerization was no longer confirmed to obtain a latex of a rubbery polymer (SA-1). The volume average particle size of the rubbery polymer (SA-1) dispersed in the latex was 60 nm.

<Synthesis Examples III-5 to III-10, Comparative Synthesis Examples III-1 to 2: Production of Silicone-Acrylic Rubber Polymers (SA-2) to (SA-9)>
In the same manner as in Synthesis Example III-4, except that the type of silicone rubber polymer (S), the amount of emulsifier used, and the dropping time were changed as shown in Table 6, silicone-acrylic rubber weights were obtained. Coalesced (SA-2) to (SA-9) latexes were obtained.
Table 6 summarizes the volume average particle size and the amount of coagulum of the silicone-acrylic rubbery polymers (SA-1) to (SA-9).

<Synthesis Examples IV-1 to IV-7, Comparative Synthesis Examples IV-1 to IV-2: Production of graft copolymers (D-1) to (D-9)>
Synthesis Example II-1 except that latexes of silicone-acrylic rubbery polymers (SA-1) to (SA-9) were used instead of the latex of the rubbery polymer (A-1). Graft copolymers (D-1) to (D-9) were obtained in the same manner as above.

Table 7 summarizes the particle size, amount of coagulum, and graft ratio of the obtained graft copolymers (D-1) to (D-9).

[Production and Evaluation of Thermoplastic Resin Composition]
<Examples 1 to 33, Comparative Examples 1 to 9: Production of thermoplastic resin composition>
Graft copolymers (B-1) to (B-23), graft copolymers (D-1) to (D-9), and acrylonitrile (AN)-styrene (ST) produced by a suspension polymerization method A copolymer ("UMG AXS Resin S102N" manufactured by UMG AS Co., Ltd.) was mixed using a Henschel mixer at the blending ratios shown in Tables 8 to 11, and the mixture was supplied to an extruder heated to 240 ° C., Pellets 1 were obtained by kneading.
Also, 100 parts of Pellets 1 and 0.8 parts of carbon black were mixed using a Henschel mixer, and this mixture was supplied to an extruder heated to 240° C. and kneaded to obtain Black Pellets 2 .

[Preparation of test piece]
Using the pellet 1 of the thermoplastic resin composition, using a 4-ounce injection molding machine (manufactured by Japan Steel Works, Ltd.), under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and an injection rate of 20 g / sec. By molding, a rod-shaped molding 1 having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was obtained.
Similarly, black pellets 2 of the thermoplastic resin composition were injection molded under the conditions of a cylinder temperature of 240° C., a mold temperature of 60° C., and an injection rate of 20 g/sec. A plate-shaped compact 2 was obtained.
In addition, the black pellet 2 of the thermoplastic resin composition is injection molded under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and an injection rate of 150 g / sec to form a plate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm. Got 3 bodies.

[evaluation]
<Measurement of Charpy impact value>
In accordance with ISO 179-1: 2013 edition, under the conditions of test temperatures of 23 ° C and -20 ° C, Charpy impact strength (impact direction: edge wise) was measured. Higher Charpy impact strength means better impact resistance.

<Measurement of Melt Volume Rate (MVR)>
The MVR of pellet 1 was measured under conditions of 220° C.-98 N according to the ISO 1133 standard. The MVR is a measure of the moldability of the thermoplastic resin composition.

<Evaluation of color development>
The lightness L ^* of molded product 2 was measured by the SCE method using a spectrophotometer (“CM-3500d” manufactured by Konica Minolta Optips, Inc.). Let the measured L ^* be “L ^* (ma)”. The lower the L ^* , the blacker the color, and the better the color developability was determined.
"Luminance L ^* " means the value of lightness (L ^* ) among the color values in the L ^* a ^* b ^* color system adopted in JIS Z8729.
The “SCE method” means a method of measuring color by using a spectrophotometer conforming to JIS Z 8722 and removing specularly reflected light with a light trap.

<Measurement of surface gloss>
Using a "digital variable angle gloss meter UGV-5D" manufactured by Suga Test Instruments Co., Ltd., reflectance (%) of the surface of the molded body 2 at an incident angle of 60 ° and a reflection angle of 60 ° is measured in accordance with JIS K 7105. It was measured. A higher reflectance means a better surface appearance.

<Speed dependence of molding appearance>
A spectrophotometer ("CM-3500d" manufactured by Konica Minolta Optips Co., Ltd.) was used to measure the difference in lightness L ^* between molded body 2 and molded body 3 by the SCE method.
Speed dependency of molded appearance=absolute value of L* of molded article 2−L* of molded article 3 It was judged that the smaller the lightness difference, the better the speed dependence of the molded appearance.

<Weather resistance>
Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), molded article 2 was treated for 1000 hours under the conditions of a black panel temperature of 63° C. and a cycle condition of 60 minutes (12 minutes of rainfall). Then, the degree of discoloration (ΔE) before and after the treatment was measured with a color difference meter and evaluated according to the following criteria.
The smaller ΔE is, the better the weather resistance is, and ◯ or more is judged to have weather resistance.
A: 0 or more and less than 3. It does not discolor and does not impair the design of molded products.
○: 3 or more and less than 5; Almost no discoloration, does not impair the design of the molded product.
Δ: 5 or more and less than 10. It is slightly discolored, impairing the design of the molded product.
×: 10 or more. Large discoloration, impairing the design of the molded product.

<Gas generation/adhesion amount test>
Using the pellet 1, as shown in FIG. 1, the injected molten resin flows from the sprue 11 through the runners 12 and 13 in two directions, is injected from the side gates 14 and 15, and joins in the mold to form a weld. Injection molding was performed on the mold 10 forming the surface. At that time, a short shot is taken so that the molten resin 20 is in an unfused state without forming a weld surface at the center part in the mold 10, and a gas pool is formed in the mold 10. 100 shots were injection molded. After injection molding, the fat-like deposit adhering to the portion of the mold 10a where the unfused portion was exposed was measured as the amount of gas adhering.
If the gas generated during molding accumulates in the mold in a greasy state, this deposit migrates to the molded product side and deteriorates the appearance of the molded product. It must be removed by cleaning, resulting in poor continuous moldability. The smaller the amount of gas adhering, the better the continuous moldability.
The gas adhering substance was dissolved in chloroform, added to 0.1 g of potassium bromide, quickly mixed well while taking care not to absorb moisture, and then placed in a tableting machine and tableted under pressure. When the obtained tablets were measured with a Fourier transform infrared spectrophotometer "FT-720" manufactured by Horiba, Ltd., peaks of decomposition products of the emulsifier and hydrophobic substances were observed.

The above evaluation results are shown in Tables 8-11.

The results of each example and comparative example have revealed the following.
Graft copolymers (B-1) to (B-17) using the rubbery polymers (A-1) to (A-17) of the present invention, the silicone-acrylic rubbery polymer of the present invention ( The graft copolymers (D-1 to (D-7) using SA-1) to (SA-7) have less coagulum, and the graft copolymers (B-1) to (B-17 ) and the thermoplastic resin compositions of Examples 1 to 33 using the graft copolymers (D-1) to (D-7) have impact resistance, low-temperature impact resistance, fluidity (moldability), color development , gloss, molded appearance, speed dependence of molded appearance, and weather resistance.

On the other hand, in the graft copolymers (B-18) and (B-19), the acetone swelling degree of the rubbery polymers (A-18) and (A-19) used is outside the scope of the present invention. The thermoplastic resin compositions of Comparative Examples 1 and 2 using the graft copolymers (B-18) and (B-19) have good impact resistance, low temperature impact resistance, fluidity (moldability), color developability, Inferior in any of gloss, molding appearance, speed dependence of molding appearance.
In the graft copolymers (B-20) and (B-21), the particle size of the rubbery polymers (A-20) and (A-21) used is outside the scope of the present invention. The thermoplastic resin compositions of Comparative Examples 3 and 4 using the polymers (B-20) and (B-21) have good impact resistance, low-temperature impact resistance, fluidity (moldability), color developability, gloss, Inferior in either molding appearance or speed dependence of molding appearance.
The graft copolymer (B-22) using the rubbery polymer (A-22) produced by seed polymerization takes a long time to produce, is inferior in production stability, and produces new particles, resulting in a particle size distribution. The thermoplastic resin composition of Comparative Example 5 using this graft copolymer (B-22) is inferior in impact resistance and fluidity.
The graft copolymer (B-23) using the rubbery polymer (A-23) due to the enlargement was produced by agglomeration of the rubber, and therefore there were some small particles that were not agglomerated, resulting in a wide particle size distribution. The thermoplastic resin composition of Comparative Example 6 using this graft copolymer (B-23) was inferior in impact resistance and fluidity.
For the graft copolymers (D-8) and (D-9), the particle size of the silicone-acrylic rubber polymer (SA-8) and (SA-9) used is outside the scope of the present invention. Therefore, the thermoplastic resin compositions of Comparative Examples 7 and 8 using the graft copolymers (D-8) and (D-9) have good impact resistance, low temperature impact resistance, fluidity (moldability), and color development. It was inferior in any of properties, molding appearance, speed dependence of molding appearance.
As in Comparative Example 9, when only the graft copolymer (B-4) was used and the graft copolymer (D) was not used, the deformation of the rubber was large, and the molded appearance and the speed dependence of the molded appearance were affected. inferior.

[Production and Evaluation of Thermoplastic Resin Composition by Simultaneous Production of Graft Copolymer (B) and Graft Copolymer (D)]
A rubber-like polymer (A) and a rubber-like polymer (C) were simultaneously produced according to the following formulation.

49.25 parts of n-butyl acrylate, 1.0 part of liquid paraffin, 0.25 part of allyl methacrylate, 0.5 part of 1,3-butanediol dimethacrylate, 0.3 part of dilauroyl peroxide, and distilled water in a container 200 parts of dipotassium alkenyl succinate and 0.1 part of dipotassium alkenyl succinate were charged, and the mixture was stirred at room temperature for 5 minutes at 9000 rpm using "High Flex Disperser HG92" manufactured by SMT Co., Ltd. to obtain a mixture. A pre-emulsion was obtained by treating the resulting mixture twice at a pressure of 20 MPa and a flow rate of 135 L/Hr using a "high-pressure homogenizer H3-1D" manufactured by Sanmaru Kikai Kogyo Co., Ltd. The volume average particle size of the obtained pre-emulsion was 300 nm.

A reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device was charged with the obtained pre-emulsion, and 3.5 parts (as a solid content) of a latex of a silicone-based rubbery polymer (S-3). , n-butyl acrylate 45.75 parts, allyl methacrylate 0.25 parts, 1,3-butanediol dimethacrylate 0.5 parts, t-butyl hydroperoxide 0.1 parts, distilled water 183 parts, alkenyl succinic acid After charging 0.75 parts of dipotassium and sufficiently replacing the inside of the reactor with nitrogen, the internal temperature was raised to 60° C. with stirring, and 0.12 parts of sodium formaldehyde sulfoxylate and 0 ferrous sulfate heptahydrate were added. 0.00005 parts, 0.00015 parts of disodium ethylenediaminetetraacetate and 5 parts of distilled water were added to initiate radical polymerization. The liquid temperature rose to 78°C due to the polymerization of the acrylate component. The temperature was maintained at 75°C for 30 minutes to complete the polymerization of the acrylate component. The time required for the production was 70 minutes, and the composite rubber had a solid content of 18.5%, an amount of coagulum of 0.07%, a gel content of 93%, an acetone swelling degree of 1150%, and peaks at particle sizes of 100 nm and 350 nm. A polymer latex was obtained.

Subsequently, raw materials were charged according to the following composition, and after the interior of the reactor was sufficiently replaced with nitrogen, the internal temperature was raised to 75° C. while stirring.

[Formulation]
Water (including water in composite rubbery polymer latex) 230 parts composite rubbery polymer latex 50 parts (as solid content)
Dipotassium alkenyl succinate 0.5 parts Sodium formaldehyde sulfoxylate 0.3 parts Ferrous sulfate heptahydrate 0.001 parts Disodium ethylenediaminetetraacetate 0.003 parts

Then, the temperature was raised to 80° C. while dropping a mixture containing acrylonitrile (AN), styrene (ST) and t-butyl hydroperoxide in the following composition over 100 minutes.
[Formulation]
Acrylonitrile (AN) 12.5 parts Styrene (ST) 37.5 parts t-butyl hydroperoxide 0.2 parts

After completion of dropping, the mixture was maintained at a temperature of 80° C. for 30 minutes and then cooled to obtain a latex of a graft copolymer. The resulting latex had a graft copolymer solid content of 29.7%, a coagulum content of 0.10%, and a graft ratio of 53%.
Next, 100 parts of a 1.5% sulfuric acid aqueous solution is heated to 80° C., and while stirring the aqueous solution, 100 parts of the graft copolymer latex is gradually added dropwise to the aqueous solution to solidify the graft copolymer. C. and held for 10 minutes.
The solidified product was then dehydrated, washed and dried to obtain a powdery graft copolymer.

35 parts of the resulting graft copolymer and 65 parts of an acrylonitrile-styrene copolymer ("UMG AXS Resin S102N" manufactured by UMG AB) were mixed using a Henschel mixer, and the mixture was heated to 240°C. It was supplied to an extruder and kneaded to obtain pellets 1.

Also, 100 parts of Pellets 1 and 0.8 parts of carbon black were mixed using a Henschel mixer, and this mixture was supplied to an extruder heated to 240° C. and kneaded to obtain Black Pellets 2 .

Using the above ^pellets , a test piece was prepared in the same manner as in Example ¹ and evaluated in the same manner. , MVR 24 cm ³ /10 min, color development (L ^* ) 6.0, surface gloss 96%, speed dependence of molding appearance (ΔL ^* ) 0.5, weather resistance ◎, gas adhesion amount 0.1 mg, and implemented It had properties equivalent to those of the thermoplastic resin composition of Example 4.

The thermoplastic resin composition of the present invention is excellent in moldability, and its molded article has good impact resistance, low-temperature impact resistance, molding appearance, speed dependence of molding appearance, weather resistance, color development, and gloss. It is. The balance of moldability, impact resistance, low-temperature impact resistance, molding appearance, speed dependence of molding appearance, weather resistance, color development, and gloss is much better than that of moldings made from conventional thermoplastic resin compositions. Because of its excellent properties, the thermoplastic resin composition of the present invention and its molded article have extremely high utility value as various industrial materials.

10 mold 11 sprue 12, 13 runners 14, 15 side gate 20 molten resin

Claims (8)

A thermoplastic composition comprising the following component (B), component (D), and component (E).
Component (B): Polymerization reaction of a raw material mixture containing a (meth)acrylic acid ester, a cross-linking agent, and a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group. A rubbery polymer (A) having an acetone swelling degree of 500 to 1500% and a volume average particle size of 200 to 800 nm, an aromatic vinyl, a (meth)acrylic acid ester and a vinyl cyanide. Graft copolymer (B) in which at least one selected is graft-polymerized
Component (D): A silicone -acrylic rubbery polymer (SA) having a volume average particle size of 50 to 190 nm, comprising a silicone rubbery polymer (S) and an acrylic rubbery polymer (Ca) . A silicone-acrylic rubbery polymer, wherein the content of the silicone-based rubbery polymer (S) in 100% by mass of the silicone-acrylic rubbery polymer (SA) is 1 to 20% by mass. A graft copolymer (D) in which at least one selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide is graft-polymerized to a rubbery polymer (C) consisting of (SA) .
Component (E): thermoplastic resin (E) other than graft copolymer (B) and graft copolymer (D) 2. The method according to claim 1, wherein the hydrophobic substance has a logarithm [logP] value of 6, which is the ratio [c1/c2] of the concentration [c1] for 1-octanol and the concentration [c2] for water. A thermoplastic resin composition which is the above hydrophobic substance. 3. In claim 1 or 2, the component (B) and the component (D) are combined with the rubbery polymer (A) in the component (B) and the rubbery polymer (C) in the component (D). A thermoplastic resin composition containing the rubbery polymer (A) at a ratio of 10 to 95% by mass out of a total of 100% by mass. 4. In any one of claims 1 to 3, the volume average particle size (X) of the rubbery polymer (A) is represented by X, and the cumulative value of the frequency from the upper limit of the particle size distribution curve is 10%. The particle diameter at the point where the upper limit frequency is 10% volume particle diameter (Y) is represented by Y, and the particle diameter at which the cumulative value of the frequency from the lower limit in the particle size distribution curve reaches 10% is the 10% lower frequency volume particle diameter. When the diameter (Z) is represented by Z, the volume average particle diameter (X), the upper limit frequency 10% volume particle diameter (Y) and the lower frequency 10% volume particle diameter (Z) of the rubbery polymer (A) are , a thermoplastic resin composition that satisfies the following (1) or (2).
(1) The volume average particle diameter (X) is 200 ≤ X < 300 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.6X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0 .5X.
(2) The volume average particle diameter (X) is X = 300 to 800 nm, the upper frequency limit 10% volume particle diameter (Y) is Y ≤ 1.8X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≥ 0. .4X. 4. In any one of claims 1 to 4, the total of the rubbery polymer (A) in the graft copolymer (B) and the rubbery polymer (C) in the graft copolymer (D) The content is 0.1 to 90% by mass in the total 100% by mass of the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E), and the graft copolymer (B ) and the total content of the graft copolymer (D) is 0.2 to 0.2 in the total 100% by mass of the graft copolymer (B), the graft copolymer (D), and the thermoplastic resin (E) A thermoplastic resin composition of 99% by mass. A method for producing a thermoplastic resin composition according to any one of claims 1 to 5,
A mixing step of mixing a (meth)acrylic acid ester, a cross-linking agent, a hydrophobic substance having a hydrocarbon group selected from an alkyl group having 12 or more carbon atoms, an alkenyl group and a cycloalkyl group, an emulsifier, and water, and the mixing step The rubbery polymer (A) is produced through a mini-emulsification step of mini-emulsifying the mixture (a) obtained in 1. and a polymerization step of polymerizing the mini-emulsion obtained in the mini-emulsion-forming step,
a step of graft-polymerizing at least one selected from aromatic vinyl, (meth)acrylic acid ester and vinyl cyanide to the obtained rubbery polymer (A) to produce the graft copolymer (B); A method for producing a thermoplastic resin composition comprising: A molded article obtained by molding the thermoplastic resin composition according to any one of claims 1 to 5. A method for producing a molded product, comprising molding the thermoplastic resin composition obtained by the production method according to claim 6.

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