JP6953867B2 - Composite rubber polymer, graft copolymer and thermoplastic resin composition - Google Patents

Description

The present invention provides a molded product having good moldability and well-balanced in impact resistance, low temperature impact resistance, mechanical strength, rigidity, appearance, and weather resistance. Composite rubber polymer and graft copolymer weight Regarding coalescence. The present invention also relates to a thermoplastic resin composition containing this graft copolymer and a molded product thereof.

Conventionally, thermoplastic resins such as styrene-acrylonitrile copolymer resin, α-methylstyrene-acrylonitrile copolymer resin, styrene-acrylonitrile-phenylmaleimide copolymer resin and the like are monomers that impart compatibility with these resins. Is widely used as a material imparted with impact resistance typified by ABS resin, ASA resin, etc. by blending a graft copolymer obtained by graft-polymerizing a rubbery polymer.
Among these, the ASA resin using a component such as (meth) acrylic acid ester rubber which is a saturated rubber in the rubbery polymer has a feature that good weather resistance can be imparted.

However, the ASA resin has a drawback that the impact resistance is inferior to that of the ABS resin. Therefore, for the purpose of improving this impact resistance, an ASA resin containing an acrylic acid ester-based rubber polymer in which rubber particles having different particle size distributions are combined as a constituent component has been proposed (Patent Documents 1 to 3). ).
However, in the conventional ASA resin, in order to exhibit sufficient impact resistance, it is necessary to increase the compounding ratio of the rubber component, and increasing the compounding ratio of the rubber component lowers the rigidity, which is severe in recent years. It was not enough to meet the needs.

JP-A-59-232138 Japanese Unexamined Patent Publication No. 04-225051 Japanese Unexamined Patent Publication No. 08-134312

The present invention provides a molded product having good moldability and well-balanced in impact resistance, low temperature impact resistance, mechanical strength, rigidity, appearance, and weather resistance. Composite rubber polymer and graft copolymer weight It is an object of the present invention to provide a coalesced product, a thermoplastic resin composition using the graft copolymer, and a molded product thereof.

As a result of diligent studies, the present inventors have obtained the above-mentioned object by using a graft copolymer using a composite rubber polymer obtained by polymerizing a (meth) acrylic acid ester and a cross-linking agent in the presence of a polyester resin. We have found that we can achieve the above, and have reached the present invention.

That is, the gist of the present invention is as follows.

[1] A composite rubbery polymer (B) in which a polyester resin (A) and a rubber component containing a (meth) acrylic acid ester (a) unit and a cross-linking agent (b) unit are composited.

[2] The composite rubbery polymer (B) according to [1], wherein the polyester resin (A) is an amorphous polyester resin.

[3] The composite rubber polymer (B) according to [1] or [2], which is obtained by polymerizing a (meth) acrylic acid ester (a) and a cross-linking agent (b) in the presence of a polyester resin (A). ).

[4] The volume average particle diameter (X) is represented by X, and the particle diameter at the point where the cumulative value of the frequency from the upper limit in the particle diameter distribution curve becomes 10% is Y as the frequency upper limit 10% volume particle diameter (Y). When the particle size where the cumulative value of the frequency from the lower limit in the particle size distribution curve is 10% is represented by Z as the lower limit of frequency 10% volume particle size (Z), the volume average particle size (X) , The composite according to any one of [1] and [3], wherein the frequency upper limit 10% volume particle diameter (Y) and the frequency lower limit 10% volume particle diameter (Z) satisfy the following (1) or (2). Rubberic polymer (B).
(1) The volume average particle diameter (X) is X <300 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.6X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0.7X. Is.
(2) The volume average particle diameter (X) is X = 300 to 800 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.7X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0. It is .6X.

[5] The composite rubber polymer (B) according to any one of [1] to [4] is mixed with (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d). A graft copolymer (C) obtained by graft-polymerizing at least one vinyl monomer selected from the above.

[6] A thermoplastic resin composition containing the graft copolymer (C) according to [5].

[7] A molded product obtained by molding the thermoplastic resin composition according to [6].

[8] Obtained by a miniemulsification step of miniemulsifying a mixture containing a polyester resin (A), a (meth) acrylic acid ester (a), a cross-linking agent (b), a hydrophobic substance, an emulsifier, and water. The method for producing a composite rubbery polymer (B) according to any one of [1] to [4], which comprises a polymerization step of polymerizing a miniemulsion.

[9] The composite rubbery polymer (B) obtained by the production method according to [8] is obtained from (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d). A method for producing a graft copolymer (C), which comprises graft-polymerizing at least one selected vinyl monomer to obtain a graft copolymer (C).

[10] A method for producing a thermoplastic resin composition using the graft copolymer (C) obtained by the production method according to [9].

[11] A method for producing a molded product for molding a thermoplastic resin composition obtained by the production method according to [10].

According to the rubbery polymer and the graft copolymer of the present invention, a molded product having an excellent balance of impact resistance, low temperature impact resistance, mechanical strength, rigidity, appearance and weather resistance can be obtained with good moldability. Can be provided to.

Embodiments of the present invention will be described in detail below.
In the present specification, the "unit" refers to a structural portion derived from a monomer compound (monomer) before polymerization, and for example, the "(meth) acrylic acid ester unit" refers to "(meth) acrylic acid". Refers to "structural part derived from ester". The content ratio of each monomer unit in the polymer corresponds to the content ratio of the monomer in the monomer mixture used for producing the polymer.
Further, "(meth) acrylic acid" means one or both of "acrylic acid" and "methacrylic acid". The same applies to "(meth) acrylate".
Further, the "molded article" means a product obtained by molding a thermoplastic resin composition.

[Composite rubber polymer (B)]
First, the composite rubbery polymer (B) of the present invention will be described.

The composite rubbery polymer (B) of the present invention is obtained by combining a polyester resin (A) with a rubber component containing a (meth) acrylic acid ester (a) unit and a cross-linking agent (b) unit. Yes, it is obtained by polymerizing the (meth) acrylic acid ester (a) and the cross-linking agent (b) in the presence of the polyester resin (A).
The composite rubber polymer (B) of the present invention preferably contains a polyester resin (A), a (meth) acrylic acid ester (a), a cross-linking agent (b), a hydrophobic substance, an initiator, an emulsifying agent, and water. It is produced by miniemulsion polymerization including a step of preparing a pre-emulsion (miniemulsion) from the raw material mixture containing the mixture and a step of polymerizing the obtained miniemulsion.

The preemulsion was obtained by preparing a raw material mixture containing a polyester resin (A), a (meth) acrylic acid ester (a), a cross-linking agent (b), a hydrophobic substance, an initiator, an emulsifier, and water. A method for producing the composite rubbery polymer (B) of the present invention by miniemulsion polymerization in which a preemulsion is polymerized will be described. In addition to the (meth) acrylic acid ester (a) and the cross-linking agent (b), the raw material mixture may contain other vinyl compounds that can be copolymerized with these, which are used as needed.

In miniemulsion polymerization, monomer oil droplets having a size of about 100 to 1000 nm are prepared by applying a strong shearing force using an ultrasonic oscillator or the like. At this time, the emulsifier molecule is preferentially adsorbed on the surface of the monomer oil droplet, and almost no free emulsifier or micelle is present in the aqueous medium. Therefore, in the ideal miniemulsion-based polymerization, the monomer radicals are not distributed into the aqueous phase and the oil phase, and the monomer oil droplets become the nuclei of the particles to proceed with the polymerization. As a result, the formed monomer oil droplets are directly converted into polymer particles, and the polyester resin (A) is not released to the outside of the system, and the polymer nanoparticles having a narrow particle size distribution containing the polyester resin (A) are produced. It becomes possible to obtain. Due to the polymer particles having a narrow particle size distribution, even particles having a large particle size, for example, a particle size of 200 nm or more, can exhibit good color development and a molded appearance.

On the other hand, it is difficult to control the composite of the polyester resin (A) and the particle size distribution in the polymer particles having a particle size of 200 nm or more produced by general emulsion polymerization, and the polymer particles have a wide particle size distribution. The production stability, the color development of the obtained molded product, and the molded appearance are inferior.

<Manufacturing method of composite rubber polymer (B)>
The miniemulsion polymerization for producing the composite rubbery polymer (B) of the present invention is not limited to this, but for example, polyester resin (A), (meth) acrylic acid ester (a), and a cross-linking agent ( b), a step of mixing a hydrophobic substance, preferably an initiator, a step of adding water and an emulsifier to the obtained mixture and applying a shearing force to prepare a preemulsion (miniemulsion), and polymerizing this mixture. A step of heating to the starting temperature for polymerization can be included. In the miniemulsion step, after mixing the monomer for polymerization and the emulsifier, for example, by carrying out a shearing step by ultrasonic irradiation, the monomer is torn off by the shearing force, and the monomer fine oil droplets covered with the emulsifier. Is formed. Then, by heating to the polymerization initiation temperature of the initiator, the monomer fine oil droplets are polymerized as they are in the presence of the polyester resin (A), and polymer fine particles containing the polyester resin (A) are obtained. Any known method can be used as the method of applying the shearing force for forming the miniemulsion, and the high shearing device capable of forming the miniemulsion is not limited to these, but for example, a high pressure pump and There is an emulsification device consisting of an interaction chamber, a device for forming a miniemulsion by ultrasonic energy or high frequency, and the like. Examples of the emulsifying device including a high-pressure pump and an interaction chamber include a "pressure homogenizer" manufactured by SPX Corporation APV and a "microfluidizer" manufactured by Paulec Co., Ltd., and a miniemulsion is produced by ultrasonic energy or high frequency. Examples of the device for forming include, but are not limited to, "Sonic Dismulsioner" manufactured by Fisher Scientific and "ULTRASONIC HOMOGENIZER" manufactured by Nissei Tokyo Office Co., Ltd.

From the viewpoint of workability, stability, manufacturability, etc., the amount of water solvent used in the miniemulsion is such that the solid content concentration of the reaction system after polymerization is about 5 to 50% by mass. It is preferably about 100 to 500 parts by mass with respect to 100 parts by mass of the mixture other than the above.

<Polyester resin (A)>
The polyester resin (A) is a polyester resin obtained by reacting a polybasic acid with a polyhydric alcohol, a polyester resin obtained by ring-opening polymerization of an aliphatic cyclic ester, and the like.

Examples of polybasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, trimellitic acid, trimesic acid, pyromellitic acid, benzoic acid, p-oxybenzoic acid, p-. (Hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, suberic acid, braslic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-Cyclohexanedicarboxylic acid, hexahydroorthophthalic acid, tricyclodecanedicarboxylic acid, tetrahydroterephthalic acid, tetrahydroorthophthalic acid, etc., or esters such as methyl esters of these acids, or derivatives such as anhydrides. Can be used. These polybasic acids can be used alone or in combination of two or more.

Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 1,4-butanediol. , 1,2-Butandiol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, tri Methylolpropane, trimethylolethane, glycerin, pentaerythritol, bisphenol-based ethylene oxide adduct, bisphenol-based propylene oxide adduct, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1 , 3-Cyclohexanediol, hydrogenated bisphenol A, spiroglycol, tricyclodecanediol, tricyclodecanedimethanol, resorcinol, 1,3-bis (2-hydroxyethoxy) benzene and the like are used. These polyhydric alcohols can be used alone or in combination of two.

The polyester resin (A) used in the present invention can be produced by a known method such as a melt polymerization method, a solution polymerization method, or a solid phase polymerization method.
The polyester resin (A) in the present invention is preferably an amorphous polyester resin having high solubility in the (meth) acrylic acid ester (a) described later.
Here, "non-crystalline" means that a clear melting point peak is not observed by differential scanning calorimetry (DSC) based on the "method for measuring the transition temperature of plastics" of JIS K 7121.

The molecular weight of the polyester resin (A) used in the present invention is not particularly limited, but the number average molecular weight (Mn) is 500 to 30,000, particularly from the viewpoint of solubility with the (meth) acrylic acid ester (a) described later. It is preferably about 1000 to 10000. Further, from the viewpoint of solubility in the (meth) acrylic acid ester (a) described later and impact resistance of the obtained molded product, the glass transition temperature (Tg) is −50 to 80 ° C., particularly −30 to 20 ° C. Is preferable.
Here, the number average molecular weight (Mn) is a polystyrene-equivalent value measured by gel permeation chromatography, and the glass transition temperature (Tg) is a value measured by a differential scanning calorimeter according to JIS K 7121. However, the catalog values can be adopted for commercial products.

Only one type of polyester resin (A) may be used, or two or more types of polybasic acids, polyhydric alcohols, and those having different physical characteristics may be used in combination.

As the polyester resin (A) used in the present invention, a commercially available product can also be used, for example, Byron (registered trademark) (manufactured by Toyobo Co., Ltd.), Elitel (registered trademark) (manufactured by Unitika Ltd.), Polyester. (Registered trademark) (manufactured by Nippon Synthetic Chemical Co., Ltd.), Arakid (registered trademark) (manufactured by Arakawa Chemical Industry Co., Ltd.), Esper (registered trademark) (manufactured by Hitachi Kasei Co., Ltd.), etc. can be used.

The amount of the polyester resin (A) used in the present invention is not particularly limited, but the polyester with respect to a total of 100 parts by mass of the polyester resin (A), the (meth) acrylic acid ester (a) described later, and the cross-linking agent (b). The proportion of the resin (A) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, and even more preferably 1 to 10 parts by mass.
When the amount of the polyester resin (A) used is less than the above lower limit, the rigidity and gloss of the molded product obtained by using the graft copolymer (C) of the present invention using the composite thermoplastic polymer (B) of the present invention. , The molded appearance tends to be inferior, and if it is more than the above upper limit, the solubility with the (meth) acrylic acid ester (a) becomes insufficient and the production stability is inferior, and the composite rubber polymer of the present invention ( The amount of gas generated during molding of the thermoplastic resin composition containing the graft copolymer (C) using B) is large, and the impact resistance of the obtained molded product tends to be inferior.

<(Meta) acrylic acid ester (a)>
Examples of the (meth) acrylic acid ester (a) constituting the composite rubber polymer (B) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. (Meta) acrylic acid ester having 1 to 18 carbon atoms in an alkyl group such as, etc .; 1 to 18 carbon atoms in an alkyl group such as n-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, etc. The methacrylic acid ester of. Among these (meth) acrylic acid esters (a), n-butyl (meth) acrylic acid, particularly n-butyl acrylic acid, is obtained because the impact resistance and gloss of the molded product obtained from the thermoplastic resin composition are improved. Butyl is preferred. One of these (meth) acrylic acid esters (a) may be used alone, or two or more thereof may be used in combination.
The (meth) acrylic acid ester (a) is based on 100 parts by mass of the total of the (meth) acrylic acid ester (a), the cross-linking agent (b) described later, and other vinyl compounds described below used as needed. It is preferable to use the (meth) acrylic acid ester (a) so that the ratio is 10 to 99.99 parts by mass, particularly 50 to 99.9 parts by mass, and particularly 80 to 99.5 parts by mass.
When the amount of the (meth) acrylic acid ester (a) used is within the above range, the thermoplastic resin composition is prepared by blending the graft copolymer (C) using the obtained composite rubber polymer (B). It has excellent impact resistance and weather resistance.

<Crosslinking agent (b)>
In the production of the composite rubber polymer (B) of the present invention, in order to introduce a crosslinked structure into the (meth) acrylic acid ester (a) component obtained from the above-mentioned (meth) acrylic acid ester (a), ( A cross-linking agent (b) is used together with the meta) acrylic acid ester (a). In the case of the crosslinked composite rubbery polymer (B) obtained by using the crosslinking agent (b), the crosslinked portion thereof is the (meth) acrylic acid described later used in the production of the graft copolymer (C) of the present invention. It also functions as a graft cross-linking point for graft bonding with at least one vinyl monomer selected from ester (a), aromatic vinyl (c), and vinyl cyanide (d).

Examples of the cross-linking agent (b) include allyl (meth) acrylate, butyrene (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and 1,3-butylene glycol 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, Polybutadienedi (meth) acrylate, Divinylbenzene, Trivinylbenzene, Triallyl cyanurate, Triallyl isocyanurate, Trimethylol propanedialyl ether, Pentaerythritol triallyl ether, Dialyldimethylammonium chloride, Polyglycerin poly (meth) acrylate , Polyester poly (meth) acrylate, polyurethane poly (meth) acrylate and the like. One of these may be used alone, or two or more thereof may be used in combination.

The amount of the cross-linking agent (b) used is not particularly limited, but the cross-linking agent is based on a total of 100 parts by mass of the (meth) acrylic acid ester (a), the cross-linking agent (b) and other vinyl compounds described later. The ratio of (b) is preferably 0.1 to 5.0 parts by mass, particularly preferably 0.3 to 3.0 parts by mass.
If the proportion of the cross-linking agent (b) is less than the above lower limit, a sufficient cross-linked structure cannot be obtained by using the cross-linking agent (b) in combination with the (meth) acrylic acid ester (a), and the impact resistance is improved. If it is more than the above upper limit, the effect as a rubber cannot be obtained due to excessive cross-linking, and the impact resistance becomes inferior.

<Other vinyl compounds>
The other vinyl compound used as needed is not particularly limited as long as it can be copolymerized with the (meth) acrylic acid ester (a) and the cross-linking agent (b). For example, aromatic vinyl (c) such as styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene; cyanide of acrylonitrile, methacrylonitrile and the like. Vinyl (d); Maleimides such as N-cyclohexylmaleimide and N-phenylmaleimide, maleic anhydride and the like can be mentioned. One of these may be used alone, or two or more thereof may be mixed and used.

When other vinyl compounds are used, the amount of the other vinyl compounds used is not particularly limited, but the other is based on 100 parts by mass of the (meth) acrylic acid ester (a), the cross-linking agent (b) and the other vinyl compounds. It is preferable to use the vinyl compound so that the proportion of the vinyl compound is 0 to 90 parts by mass, particularly 0.1 to 50 parts by mass, and particularly 0.3 to 30 parts by mass.

<Hydrophobic substance>
In the production of the composite rubbery polymer (B) of the present invention, it is preferable to use a hydrophobic substance in a predetermined ratio. When a hydrophobic substance is added when forming the pre-emulsion, the production stability of the mini-emulsion polymerization tends to be further improved, and the composite rubber polymer (B) suitable for the present invention can be produced.

Examples of the hydrophobic substance include hydrocarbons having 10 or more carbon atoms, alcohols having 10 or more carbon atoms, hydrophobic polymers having a mass average molecular weight (Mw) of less than 10000, and hydrophobic monomers, for example, alcohols having 10 to 30 carbon atoms. Vinyl ester, vinyl ether of alcohol having 12 to 30 carbon atoms, alkyl (meth) acrylate having 12 to 30 carbon atoms, carboxylic acid vinyl ester having 10 to 30 carbon atoms (preferably 10 to 22 carbon atoms), p-alkylstyrene. , Hydrophobic chain transfer agents, hydrophobic peroxides and the like. One of these may be used alone, or two or more thereof may be mixed and used.

More specifically, hydrophobic substances include hexadecane, octadecane, icosan, liquid paraffin, liquid isoparaffin, paraffin wax, polyethylene wax, olive oil, cetyl alcohol, stearyl acrylate, lauryl acrylate, stearyl acrylate, and lauryl methacrylate. , Stearyl methacrylate, polystyrene having a number average molecular weight (Mn) of 500 to 10000, poly (meth) acrylic acid ester and the like.

In the present invention, such a hydrophobic substance is applied to a total of 100 parts by mass of the above-mentioned (meth) acrylic acid ester (a), the cross-linking agent (b), and other vinyl compounds used as needed. It is preferably 0.1 to 10 parts by mass, more preferably 1 to 3 parts by mass. When the amount of the hydrophobic substance used is within the above range, the amount of gas generated during molding of the thermoplastic resin composition containing the graft copolymer (C) using the composite rubber polymer (B) obtained is small. , The obtained molded product has excellent impact resistance and weather resistance.

<Emulsifier>
Examples of the emulsifier used in producing the composite rubber polymer (B) of the present invention include carboxylic acids such as oleic acid, palmitic acid, stearic acid, alkali metal salts of logonic acid, and alkali metal salts of alkenyl succinic acid. Known emulsifiers such as acid emulsifiers, alkyl sulfate esters, sodium alkylbenzene sulfonates, sodium alkyl sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate, and other known emulsifiers can be used alone or in combination of two or more. Can be used.

The amount of the emulsifier added is 0.01 to 1. It is preferably 0 parts by mass, more preferably 0.05 to 0.5 parts by mass.

<Initiator>
The initiator is a radical polymerization initiator for radical polymerization of the above-mentioned (meth) acrylic acid ester (a), the cross-linking agent (b), and other vinyl compounds used as needed, for example, azo. Examples thereof include a polymerization initiator, a photopolymerization initiator, an inorganic peroxide, an organic peroxide, and a redox-based initiator in which an organic peroxide, a transition metal, and a reducing agent are combined. Of these, azo polymerization initiators, inorganic peroxides, organic peroxides, and redox-based initiators that can initiate polymerization by heating are preferable. Only one of these may be used, or two or more thereof may be used in combination.

Examples of the azo polymerization initiator include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 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-sixhexanecarboxylate) ), 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. Can be mentioned.

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

Examples of the organic peroxide include peroxyester compounds, and specific examples thereof include α, α'-bis (neodecanoyl peroxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,1,3. 3-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1- Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy2-hexylhexanoate, t-butylperoxy2-hexylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluole peroxide) ) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluole peroxide benzoate, 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 (4,5-di-t-) Butylperoxycyclohexyl) propane, α, α'-bis (t-butyl peroxide) diisopropylbenzene, dicumyl peroxide, 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-hexine, bis (t-butylperoxyisopropyl) benzene, bis (t-butylperoxy) trimethylcyclohexane, butyl Examples thereof include −bis (t-butylperoxy) valerate, t-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide, paramentan hydroperoxide and t-butylperoxybenzoate.

As the redox-based initiator, a combination of an organic peroxide, ferrous sulfate, a chelating agent and a reducing agent is preferable. For example, cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate, and dextrose, t-butyl hydroperoxide, sodium formaldehyde sulfoxylate (longalit), ferrous sulfate, and disodium ethylenediamine tetraacetate. Examples include combinations.

Of these, organic peroxides are particularly preferable as the initiator.

The amount of the initiator added is usually 5 parts by mass or less with respect to 100 parts by mass in total of the above-mentioned (meth) acrylic acid ester (a), the cross-linking agent (b), and other vinyl compounds used as needed. It is preferably 3 parts by mass or less, for example 0.001 to 3 parts by mass.

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

<Rubber component>
In the production of the composite rubber polymer (B) of the present invention, the composite rubber polymer (B) made of a composite rubber in which other rubber components are present in the step of producing the preemulsion is not impaired to the desired performance. It may be manufactured. In this case, examples of other rubber components include diene-based rubbers such as polybutadiene and polyorganosiloxane. Diene / (meth) acrylic acid ester-based rubber such as butyl rubber acrylate is composited by polymerizing the (meth) acrylic acid ester (a) and the cross-linking agent (b) in the presence of these rubber components. A composite rubbery polymer (B) containing a polyorganosyloxysan / (meth) acrylic acid ester-based composite rubber as a rubber component can be obtained. The composite rubber according to the present invention is not limited to these, and one type of rubber component to be combined may be used alone or two or more types may be used in combination.

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

<Particle size>
The particle size of the composite rubbery polymer (B) of the present invention is preferably 150 to 800 nm, more preferably 200 to 500 nm, and further preferably 250 to 400 nm in terms of volume average particle size. When the volume average particle size is within the above range, there are few agglomerates during polymerization, and the resistance of the thermoplastic resin composition containing the graft copolymer (C) using this composite rubber polymer (B). The impact resistance becomes better.

The particle size of the composite rubber polymer (B) of the present invention also represents the volume average particle size (X) by X, and the particles where the cumulative value of the frequency from the upper limit in the particle size distribution curve is 10%. The diameter is represented by Y as the frequency upper limit 10% volume particle diameter (Y), and the particle diameter at the point where the cumulative value of the frequency from the lower limit in the particle diameter distribution curve becomes 10% is the frequency lower limit 10% volume particle diameter (Z). When represented by Z, it is preferable to satisfy the following (1) or (2), and by satisfying the following (1) or (2), the graft using this composite rubber polymer (B) can be used. The impact resistance and molded appearance of the molded product obtained from the thermoplastic resin composition containing the polymer (C) are improved.
(1) The volume average particle diameter (X) is X ≦ 300 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.6X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0.7X. Is.
(2) The volume average particle diameter (X) is X = 300 to 1000 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.7X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0. It is .6X.

As for the particle size distribution of the composite rubbery polymer (B) of the present invention, more preferably, the frequency upper limit 10% volume particle size (Y) is Y ≦ 1.6X, and the frequency lower limit 10% volume particle size (Z) is Z. ≧ 0.7X.

The volume average particle size (X) and particle size distribution of the composite rubber polymer (B) of the present invention are measured by the methods described in the section of Examples described later.

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

That is, the latex of the composite rubber polymer (B) is coagulated and dried to obtain a polymer, and about 1 g of this polymer is precisely weighed (W ₀ ), and this is placed in about 50 g of acetone at a temperature of 23 ° C. for 48 hours. immersed in, after swelling the polymer, remove acetone by decantation, wherein, after the swollen polymer was accurately weighed (W _S), and dried under reduced pressure for 24 hours at 80 ° C., the polymer has absorbed acetone evaporation, removed again, and accurately weighed (W _d), to calculate the gel content by the following equation.
Gel content (%) = W _d / W ₀ x 100
Here, W _d is the weight of the dried polymer, and W ₀ is the weight of the polymer before immersion in acetone.

If the composite rubber polymer (B) has a gel content of 80% or more, the impact resistance of the thermoplastic resin composition containing the graft copolymer (C) using the composite rubber polymer (B) It will be excellent in sex.

<Acetone swelling degree>
The composite rubbery polymer (B) of the present invention has a degree of swelling with acetone in the range of preferably 500 to 1200%, more preferably 600 to 1000%, still more preferably 700 to 900%. Here, the degree of swelling due to acetone is a value obtained as follows.

That is, the same operation as in the above measurement of the gel content is performed, and the degree of swelling is calculated by the following formula.
The degree of swelling _{(%) = (W S -W} d) / W d × 100
Where W _S is the weight of the swollen polymer and W _d is the weight of the dried polymer.

In the composite rubber polymer (B) in which the degree of swelling of acetone is less than the above lower limit, the impact resistance of the thermoplastic resin composition containing the graft copolymer (C) using the composite rubber polymer (B). If the composite rubber polymer (B) is inferior to the above and exceeds the above upper limit, the molded appearance tends to be inferior.

[Graft copolymer (C)]
The graft copolymer (C) of the present invention is obtained by adding (meth) acrylic acid ester (a), aromatic vinyl (c), to the composite rubber polymer (B) of the present invention produced as described above. And at least one vinyl monomer selected from vinyl cyanide (d) is graft-polymerized. That is, a graft layer made of a polymerization reaction product of these vinyl monomers is formed on the composite rubber polymer (B) of the present invention.
With respect to the graft layer constituting the graft copolymer (C) of the present invention, a part or all of the above vinyl monomer is chemically and / or physically bonded to the composite rubber polymer (B). Refers to things.

The (meth) acrylic acid ester (a) graft-polymerized on the composite rubber polymer (B) of the present invention is a (meth) acrylic acid ester used for producing the composite rubber polymer (B) of the present invention. One or more of those exemplified as (a) can be used. The aromatic vinyl (c) and vinyl cyanide (d) are exemplified as other vinyl compounds used as necessary in the production of the composite rubbery polymer (B) of the present invention. (C), one or more of vinyl cyanide (d) can be used.
The graft ratio of the graft layer of the graft copolymer (C) can be calculated by the following method.

<Calculation of graft rate>
80 mL of acetone is added to 2.5 g of the graft copolymer (C), and the mixture is refluxed in a hot water bath at 65 ° C. for 3 hours to extract the acetone-soluble component. The residual acetone insoluble matter is separated by centrifugation, dried, and then the mass is measured to calculate the mass ratio of the acetone insoluble matter in the graft copolymer (C). The graft ratio is calculated from the mass ratio of the acetone insoluble matter in the obtained graft copolymer (C) using the following formula.

The graft ratio of the graft copolymer (C) of the present invention is preferably 10 to 90%, particularly preferably 30 to 85%. When the graft ratio of the graft copolymer (C) is within the above range, a molded product having good impact resistance and a molded appearance can be obtained by using the graft copolymer (C). When the graft ratio exceeds the above upper limit, the dispersibility of the graft copolymer (C) in the thermoplastic resin composition described later becomes good, the molded appearance becomes good, but the rigidity tends to decrease.

The graft layer constituting the graft copolymer (C) is a vinyl monomer other than the above-mentioned (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d). May be included. Other vinyl monomers include (meth) acrylic acid ester (a), cross-linking agent (b), and other vinyl compounds used as necessary in the production of the composite rubber polymer (B) of the present invention. Examples thereof include one or more vinyl compounds other than (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d).

When an aromatic vinyl (c), preferably a mixture of styrene and vinyl cyanide (d), preferably acrylonitrile is used as the vinyl monomer forming the graft layer, the heat of the graft copolymer (C) obtained is obtained. It is preferable because of its excellent stability. In this case, the ratio of aromatic vinyl (c) such as styrene to vinyl cyanide (d) such as acrylonitrile is 10 to 50% by mass of vinyl cyanide (d) with respect to 50 to 90% by mass of aromatic vinyl (c). It is preferably mass% (however, the total of aromatic vinyl (c) and vinyl cyanide (d) is 100% by mass).

The graft layer of the graft copolymer (C) is obtained by emulsifying and graft-polymerizing 90 to 10% by mass of a vinyl monomer with respect to 10 to 90% by mass of the composite rubber polymer (B). , It is preferable because the appearance of the molded product obtained by using this graft copolymer (C) is excellent (however, the total of the composite rubber polymer (B) and the vinyl monomer is 100% by mass). This ratio is more preferably 30 to 70% by mass of the composite rubber polymer (B) and 70 to 30% by mass of the vinyl monomer.

As a method for graft-polymerizing a vinyl monomer to the composite rubbery polymer (B), a vinyl monomer is added to the latex of the composite rubbery polymer (B) obtained by mini-emulsion polymerization, and one step or one step or A method of polymerizing in multiple stages can be mentioned. In the case of polymerization in multiple stages, it is preferable to carry out the polymerization by dividing or continuously adding the vinyl monomer in the presence of the rubber latex of the composite rubber polymer (B). By such a polymerization method, good polymerization stability can be obtained, and a latex having a desired particle size and particle size distribution can be stably obtained. Examples of the polymerization initiator used for this graft polymerization include the same initiators used for mini-emulsion polymerization for producing the composite rubber polymer (B) described above.

When the vinyl monomer is polymerized on the composite rubber polymer (B), the latex of the composite rubber polymer (B) is stabilized and the average particle size of the obtained graft copolymer (C) is controlled. To do so, an emulsifier can be added. The emulsifier used here is not particularly limited, and examples thereof include the same emulsifiers used in the mini-emulsion polymerization for producing the composite rubber polymer (B) described above, and anionic emulsifiers and nonionic emulsifiers are preferable. .. The amount of the emulsifier used when graft-polymerizing the vinyl monomer on the composite rubbery polymer (B) is not particularly limited, but is 0.1 to 100 parts by mass with respect to 100 parts by mass of the obtained graft copolymer (C). 10 parts by mass is preferable, and 0.2 to 5 parts by mass is more preferable.

The method for recovering the graft copolymer (C) from the latex of the graft copolymer (C) obtained by emulsion polymerization is not particularly limited, and examples thereof include the following methods.
The latex of the graft copolymer (C) is put into hot water in which a coagulant is dissolved to solidify the graft copolymer (C). Next, the solidified graft copolymer (C) is redispersed in water or warm water to form a slurry, and the emulsifier residue remaining in the graft copolymer (C) is eluted in water and washed. Next, the slurry is dehydrated with a dehydrator or the like, and the obtained solid is dried with an air flow dryer or the like to recover the graft copolymer (C) as powder or particles.
Examples of the coagulant include inorganic acids (sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, etc.), metal salts (calcium chloride, calcium acetate, aluminum sulfate, etc.) and the like. The 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 an emulsifier that exhibits stable emulsifying power even in an acidic region such as sodium alkylbenzene sulfonate is used as an emulsifier, an inorganic acid is insufficient and a metal salt needs to be used.

The particle size of the graft copolymer (C) of the present invention produced as described above using the composite rubbery polymer (B) of the present invention is usually less than 1000 nm in volume average particle size. The volume average particle size of the graft copolymer (C) of the present invention is measured by the method described in the section of Examples described later.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the above-mentioned graft copolymer (C) of the present invention, and is usually formed by mixing the graft copolymer (C) of the present invention with another thermoplastic resin. .. The content of the graft copolymer (C) in 100 parts by mass of the thermoplastic resin composition of the present invention is preferably 20 to 60 parts by mass. When the content of the graft copolymer (C) in the thermoplastic resin composition is less than 20 parts by mass, the amount of rubber is reduced and the impact resistance of the obtained molded product tends to be lowered. On the other hand, when the content of the graft copolymer (C) in the thermoplastic resin composition exceeds 60 parts by mass, the fluidity (moldability) and rigidity tend to be inferior.
Considering the balance between fluidity, impact resistance, rigidity, and other physical properties of the molded product, the content of the graft copolymer (C) in 100 parts by mass of the thermoplastic resin composition of the present invention is 25 to 40 parts by mass. Is more preferable.

The thermoplastic resin composition of the present invention may contain other thermoplastic resins and additives, if necessary.

Other thermoplastic resins include, for example, polyvinyl chloride, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-styrene-methyl methacrylate copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, α-methylstyrene-. Polystyrene, polyphenylene ether-polystyrene composites such as acrylonitrile copolymer, polymethyl methacrylate, methyl methacrylate-styrene copolymer, methyl methacrylate-N-phenylmaleimide copolymer, polycarbonate, polyamide, polyethylene terephthalate, polybutylene terephthalate, etc. One type or two or more types such as a body can be mentioned. Of these, an acrylonitrile-styrene copolymer is preferable from the viewpoint of impact resistance and fluidity.

Additives include, for example, colorants 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, etc. Examples include mold release agents, plasticizers, antistatic agents and the like.

The thermoplastic resin composition of the present invention was obtained by mixing and dispersing the graft copolymer (C) and, if necessary, other thermoplastic resins and additives with a V-type blender, a Henschel mixer or the like. It is produced by melt-kneading the mixture using an extruder, a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like.
The mixing order of each component is not particularly limited, and all the components may be mixed uniformly.

[Molding]
The molded product of the present invention is formed by molding the thermoplastic resin composition of the present invention, and is excellent in impact resistance, low temperature impact resistance, mechanical strength, rigidity, appearance, and weather resistance.

Examples of the molding method of the thermoplastic resin composition of the present invention include an injection molding method, an injection compression molding machine method, an extrusion method, a blow molding method, a vacuum molding method, a pneumatic molding method, a calendar molding method and an inflation molding method. Can be 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 a molded product with high dimensional accuracy.

Since the molded product of the present invention obtained by molding the thermoplastic resin composition of the present invention is excellent in impact resistance, low temperature impact resistance, mechanical strength, rigidity, appearance, and weather resistance, vehicle interior / exterior parts, OA Suitable for equipment, building materials, etc.

As an example of industrial use of the molded product of the present invention formed by molding the thermoplastic resin composition of the present invention, vehicle parts, particularly various exterior / interior parts used without painting, wall materials, building materials such as window frames, etc. Examples thereof include parts, tableware, toys, vacuum cleaner housings, television housings, home appliance parts such as air conditioner housings, interior parts, ship parts and communication equipment housings.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
In the following, "part" means "part by mass" and "%" means "% by mass".

[Measurement of volume average particle size]
The volume average particle diameters (X) of the composite rubbery polymers (B-1) to (B-10) produced in Examples and Comparative Examples and the graft copolymers (C-1) to (C-10) are , Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd. was used to obtain the results by a dynamic light scattering method.
Further, the particle size distribution is obtained by the same method as above, the particle size of the frequency upper limit of 10% is set as the frequency upper limit of 10% volume particle size (Y), and the particle size of the frequency lower limit of 10% is set as the frequency lower limit of 10% volume particle size (Y). Z), and the ratio to the volume average particle size (X) was calculated for each.

[Measurement of agglomerate amount]
The latex of the composite rubber polymers (B-1) to (B-10) produced in Examples and Comparative Examples and the latex of the graft copolymers (C-1) to (C-10) are filtered through a 100-mesh wire mesh. Then, the agglomerates remaining on the 100-mesh wire mesh were dried and weighed, and the composite rubber polymers (B-1) to (B-10) and the graft copolymers (C-1) to (C), respectively. The ratio (mass%) to -10) was determined. The smaller the amount of agglomerates, the better the production stability of the composite rubbery polymers (B-1) to (B-10) and the graft copolymers (C-1) to (C-10) latex.

[Manufacturing of composite rubber polymer]
In the following, for the production of the composite rubber polymer, as a commercially available polyester resin (A),
Polyester resin (A-1): "Byron (registered trademark) GK680" manufactured by Toyobo Co., Ltd. (Mn: 6000, Tg: 10 ° C)
It was used.

In the following Comparative Example I-1, the polyester resin (A-1) is not used, and a rubber polymer is produced instead of the composite rubber polymer. However, for convenience, this rubber polymer is produced. Is also described as "composite rubbery polymer".

<Example I-1: Production of rubbery polymer (B-1)>
A rubbery polymer (B-1) was produced with the following composition.

[Mixing]
Polyester resin (A-1) 0.5 part n-butyl acrylate (BA) 99.0 parts Allyl methacrylate (AMA) 1.0 part Liquid paraffin (LP) 0.6 part Dipotassium alkenyl succinate (ASK) 0 . 2 parts dilauroyl peroxide 0.6 parts distilled water 406 parts

In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, n-butyl acrylate and polyester resin (A-1) are stirred at room temperature for 2 hours, and the polyester resin (A-1) is agitated. It was dissolved in n-butyl acid. Subsequently, liquid paraffin, allyl methacrylate, dilauroyl peroxide, distilled water, and dipotassium alkenyl succinate were charged and sonicated at room temperature using ULTRASONIC HOMOGENIZER US-600 manufactured by Nissei Tokyo Office for 20 minutes with an amplitude of 35 μm. To obtain a pre-emulsion. The volume average particle size of the obtained latex was 350 nm.
The preemulsion was heated to 60 ° C. to initiate radical polymerization. Due to the polymerization of the acrylic acid ester component, the liquid temperature rose to 78 ° C. The temperature was maintained at 75 ° C. for 30 minutes to complete the polymerization of the acrylic acid ester component. The time required for production was 90 minutes, and a latex of a composite rubber polymer (B-1) having a solid content of 19.3%, an agglomerate amount of 0.1%, and a volume average particle size (X) of 350 nm was obtained. ..

<Examples I-2 to I-9, Comparative Example I-1: Production of composite rubbery polymers (B-2) to (B-10)>
The composites are the same as in Example I-1, except that the amounts of the polyester resin (A), the acrylic acid ester (a), the cross-linking agent (b), the hydrophobic substance, and the emulsifier are changed as shown in Table 1. Latexes of rubbery polymers (B-2) to (B-10) were obtained.

Table 1 summarizes the evaluation results of the composite rubbery polymers (B-3) to (B-10).

[Manufacturing and evaluation of graft copolymer]
<Example II-1: Production of graft copolymer (C-1)>
In a reactor equipped with a reagent injection container, a cooling tube, a jacket heater and a stirrer, the raw materials are charged with the following composition, the inside of the reactor is sufficiently replaced with nitrogen, and then the internal temperature is raised to 70 ° C. while stirring. bottom.

[Mixing]
Water (including water in rubber polymer latex) 230 parts Composite rubber polymer (B-1) latex 50 parts (as solid content)
Dipotassium alkenyl succinate 0.5 part Sodium formaldehyde sulfoxylate 0.3 part Ferrous sulfate 0.001 part Ethylenediaminetetraacetic acid disodium 0.003 part

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

[Mixing]
Acrylonitrile (AN) 12.5 parts Styrene (ST) 37.5 parts t-Butyl hydroperoxide 0.2 parts

After completion of the dropping, the temperature was maintained at 80 ° C. for 30 minutes and then cooled to obtain a latex of the graft copolymer (C-1). The solid content of the graft copolymer (C-1) in the obtained latex was 29.7%, the amount of agglomerates was 0.1%, the volume average particle size was 400 nm, and the graft ratio was 68%.
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 a graft copolymer (C-1) latex is gradually added dropwise to the graft copolymer (C-1). C-1) was solidified, further heated to 95 ° C., and held for 10 minutes.
Then, the solidified product was dehydrated, washed, and dried to obtain a powdery graft copolymer (C-1).

<Examples II-2 to II-9, Comparative Example II-1: Production of Graft Copolymers (C-2) to (C-10)>
The same as in Example II-1 except that the latexes of the composite rubbery polymers (B-2) to (B-10) were used instead of the latex of the composite rubbery polymer (B-1). The graft copolymers (C-2) to (C-10) were obtained, respectively. The volume average particle size, the amount of agglomerates, and the graft ratio of each of the graft copolymers (C-2) to (C-10) were as shown in Table 2.

[Manufacturing and evaluation of thermoplastic resin compositions]
<Examples III-1 to III-9, Comparative Examples III-1 to III-2: Production of Thermoplastic Resin Composition>
Table 3 shows the graft copolymers (C-1) to (C-10) and the acrylonitrile-styrene copolymer (“UMG AXS Resin S102N” manufactured by UMG ABS Co., Ltd.) produced by the suspension polymerization method. The mixture was mixed using a Henschel mixer at the blending ratio of the above, and the mixture was supplied to an extruder heated to 240 ° C. and kneaded to obtain pellet 1.
Further, 100 parts of pellet 1 and 0.8 part 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 pellet 2.

[Preparation of test piece]
Using pellet 1 of the above thermoplastic resin composition, each 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. Molding was performed to obtain a rod-shaped molded product 1 having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm.
Similarly, the black pellet 2 of the thermoplastic resin composition is molded into a plate shape having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm under the conditions of a cylinder temperature of 240 ° C., a mold temperature of 60 ° C., and an injection rate of 20 g / sec. I got body 2.

[evaluation]
<Measurement of Charpy impact strength>
According to ISO 179, the Charpy impact strength was measured in the molded product 1 under the atmosphere of 23 ° C. and −30 ° C.

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

<Bending strength and flexural modulus>
The bending strength and flexural modulus of the molded product 1 were measured according to the ISO 178 standard. Bending strength is a measure of the mechanical strength of a molded product, and flexural modulus is a measure of the rigidity of a molded product.

<Evaluation of color development>
^{The brightness L *} of the molded product 2 was measured by the SCE method using a spectrocolorimeter (“CM-3500d” manufactured by Konica Minolta Optips). Let the measured L ^* be "L ^* (ma)". The ^{lower the L *} , the blacker the color, and it was judged that the color development was good.
“Brightness L ^* ” means ^{the lightness value (L *} ) among the color values in the ^{L *} a ^* b ^* color system adopted in JIS Z 8729.
The "SCE method" means a method of measuring color by removing specularly reflected light by an optical trap using a spectrocolorimeter compliant with JIS Z 8722.

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

<Molding appearance>
Five molded bodies 2 were observed with an optical microscope (magnification: 200 times), the total number of agglomerates of 100 μm or more was measured, and evaluated according to the following criteria. “○” or “◎” indicates that the molded appearance is good.
◎ 0 to 5 agglomerates of 100 μm or more ○ 6 to 20 agglomerates of 100 μm or more × 21 or more agglomerates of 100 μm or more

<Weather resistance>
Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd.), the molded product 2 was treated for 1000 hours under the conditions of a black panel temperature of 63 ° C. and a cycle condition of 60 minutes (rainfall of 12 minutes). Then, the degree of discoloration (ΔE) before and after the treatment was measured and evaluated with a color difference meter.
The smaller ΔE, the better the weather resistance, and those with a value of ◯ or higher were judged to have weather resistance.
⊚: 0 or more and less than 3. It does not discolor and does not impair the design of the molded product.
◯: 3 or more and less than 5. There is almost no discoloration, and the design of the molded product is not impaired.
Δ: 5 or more and less than 10. The color is slightly discolored, which impairs the design of the molded product.
X: 10 or more. The color is greatly discolored, which impairs the design of the molded product.

The above evaluation results are shown in Table 3.

From the results of each example and comparative example, the following became clear.

The graft copolymers (C-1) to (C-9) of Examples II-1 to II-9 using the composite rubbery polymers (C-1) to (C-9) of the present invention are coagulated. The thermoplastic resin compositions of Examples III-1 to III-9 using the graft copolymers (C-1) to (C-9) have a small amount of lumps, and are impact-resistant, low-temperature impact-resistant, and mechanical. It is excellent in target strength (bending strength), rigidity (bending elastic modulus), fluidity (moldability), gloss, and molded appearance.
On the other hand, the graft copolymer (C-10) of Comparative Example II-1 using the composite rubbery polymer (C-10) which does not use the polyester resin (A-1) is made of the polyester resin (A). Since it is not contained, the thermoplastic resin composition of Comparative Example III-1 using this graft copolymer (C-10) is insufficient in bending elasticity, surface gloss, and molded appearance, and is insufficient in Comparative Example II-2. As described above, when the blending amount of the graft copolymer (C-10) is reduced, the mechanical strength (bending strength) and the rigidity (bending elasticity) are slightly improved, but the impact resistance and the molded appearance are poor. It became enough.

The thermoplastic resin composition of the present invention containing the graft copolymer (C) of the present invention using the composite rubber polymer (B) of the present invention has excellent moldability, and the molded product thereof has impact resistance. It has good low temperature impact resistance, mechanical strength, rigidity, molded appearance, and weather resistance. The balance between impact resistance, rigidity, molded appearance, and weather resistance is extremely excellent as compared with a molded product made of a conventional thermoplastic resin composition. Therefore, the thermoplastic resin composition of the present invention and the molded product thereof are used. , Very high utility value as various industrial materials.

Claims (8)

A composite rubber polymer (B) in which a polyester resin (A) and a rubber component containing a (meth) acrylic acid ester (a) unit and a cross-linking agent (b) unit are composited.
The polyester resin (A) is an amorphous polyester resin, and the polyester resin (A) is a non-crystalline polyester resin.
The (meth) acrylic acid ester (a) and the cross-linking agent (b) are polymerized in the presence of the polyester resin (A).
The ratio of the polyester resin (A) to 100 parts by mass in total of the polyester resin (A), the (meth) acrylic acid ester (a) and the cross-linking agent (b) is 0.1 to 30 parts by mass.
The ratio of the (meth) acrylic acid ester (a) to 100 parts by mass of the total of the (meth) acrylic acid ester (a), the cross-linking agent (b) and other vinyl compounds used as needed is 10 to 10. At 99.9 parts by mass, the proportion of the cross-linking agent (b) was 0.1 to 5.0 parts by mass.
The volume average particle diameter (X) measured by the dynamic light scattering method for the latex of the composite rubber polymer (B) is represented by X, and the dynamic light scattering method is used for the latex of the composite rubber polymer (B). The particle size at the point where the cumulative value of the frequency from the upper limit in the particle size distribution curve measured by is 10% is represented by Y as the frequency upper limit 10% volume particle size (Y), and from the lower limit in the particle size distribution curve. When the particle size at the point where the cumulative value of the frequency is 10% is represented by Z as the lower limit of frequency 10% volume particle diameter (Z), the volume average particle diameter (X) and the upper limit of frequency 10% volume particle diameter (Y). ) And the frequency lower limit of 10% volume particle diameter (Z) satisfies the following (1) or (2).
(1) The volume average particle diameter (X) is X <300 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.6X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0.7X. Is.
(2) The volume average particle diameter (X) is X = 300 to 800 nm, the frequency upper limit 10% volume particle diameter (Y) is Y ≦ 1.7X, and the frequency lower limit 10% volume particle diameter (Z) is Z ≧ 0. It is .6X. At least one vinyl single amount selected from (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d) in the composite rubber polymer (B) according to claim 1. A graft copolymer (C) obtained by graft-polymerizing a body. The thermoplastic resin composition containing the graft copolymer (C) according to claim 2. A molded product obtained by molding the thermoplastic resin composition according to claim 3. A miniemulsification step of miniemulsifying a mixture containing a polyester resin (A), a (meth) acrylic acid ester (a), a cross-linking agent (b), a hydrophobic substance, an emulsifier, and water, and the obtained miniemulsion. The method for producing a composite rubbery polymer (B) according to claim 1, which comprises a polymerization step of polymerizing. The composite rubbery polymer (B) obtained by the production method according to claim 5 is at least selected from (meth) acrylic acid ester (a), aromatic vinyl (c), and vinyl cyanide (d). A method for producing a graft copolymer (C), which comprises graft-polymerizing one kind of vinyl monomer to obtain a graft copolymer (C). A method for producing a thermoplastic resin composition using the graft copolymer (C) obtained by the production method according to claim 6. A method for producing a molded product for molding a thermoplastic resin composition obtained by the production method according to claim 7.