JP2005344080A - Rubbery polymer-containing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubbery polymer-containing material useful in compounding applications for improving its powder properties and improving the properties of thermoplastic resins, to provide a method for producing the material, and to provide a thermoplastic resin composition obtained by compounding this material in a thermoplastic resin. <P>SOLUTION: The rubbery polymer-containing material comprises powdery particles 50-150μm in size and powdery particles 200-500μm in size, wherein the former powdery particles account for ≥25 mass% of the total particles, while the latter powdery particles ≥15 mass% of the total particles. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an improvement in powder characteristics of a rubbery polymer-containing material, a rubbery polymer-containing material that is useful in a compounding for improving the properties of a thermoplastic resin, a method for producing the same, and a thermoplastic resin The present invention relates to a thermoplastic resin composition formed by blending with the above.

As a method for imparting impact resistance to a thermoplastic resin, a method of blending a rubber-like elastic body is known. For example, polyvinyl chloride resin is a resin with excellent mechanical and chemical properties, so it is widely used in various fields, but many studies have been conducted to improve the shortcomings of low impact resistance. Has been done.
Up to now, rubber polymers such as those obtained by graft polymerization of monomers such as methyl methacrylate, styrene and acrylonitrile on ABS resin, MBS resin and polyacrylic acid alkyl ester rubber polymer have been improved in impact resistance. A method for imparting impact resistance by blending with a polyvinyl chloride resin as a resin has been proposed.
Such a rubbery polymer may be produced as a powder, but the handleability of the powder may be a problem. Specifically, there are cases where a blocking phenomenon in which the powder solidifies during storage and clogging of a hopper or a transportation line due to insufficient fluidity of the powder.
In order to improve the powder characteristics, various methods have been studied. For example, a powder composition comprising a rubbery polymer, a specific vinyl polymer and a lubricant has been proposed (for example, Patent Document 1). .
Also, spray drying a mixture obtained by mixing 1 to 300 parts by weight of a metal or a metal compound having an average particle diameter of 50 μm or less with respect to 100 parts by weight of a polymer emulsion (solid content) having a glass transition temperature of −40 ° C. or higher. A method for producing powder particles suitable for uses such as an antistatic agent, a paint, and an electromagnetic shielding agent is disclosed (for example, Patent Document 2).
Further, 100 parts by mass of the rubber-containing graft copolymer powder and a surface treatment with a fatty acid, an average particle size of 5.0 μm or less, an apparent density of 0.35 g / ml or less, Mg, Ca, Ba, Zn A graft copolymer mixed powder effective for improving the impact resistance of a resin, characterized by containing 0.01 to 5.0 parts by mass of an inorganic fine powder containing an element selected from the group consisting of Thus, there has been disclosed a graft copolymer mixed powder capable of avoiding clogging, blocking and the like during powder transportation (for example, Patent Document 3).
Further, a method has been proposed in which a processing aid is added to a rubber-containing graft copolymer having a rubber content of 80 to 96% to improve both powder characteristics and impact resistance (Patent Document 4). .
Further, in order to develop impact resistance, the rubber-containing graft copolymer having an average particle size of 0.15 μm at the time of latex is 5% or more and less than 50%, and the rubber-containing graft of 0.03 to 0.13 μm. A method of mixing 50% or more of a copolymer has been proposed (for example, Patent Document 5).
Japanese Patent No. 3132040 JP-A-5-295123 JP 2002-265743 A JP 2001-181453 A JP 2001-323129 A

However, in the methods described in Patent Documents 1 to 3 described above, a powder effect is improved by adding an additive having a lubricity effect to the rubber polymer, and a certain effect is recognized. However, due to the dispersibility of the additive having a slipping effect, the appearance of the molded product may be defective in appearance, or the impact resistance may be reduced due to a decrease in the rubber component.
Further, in the method described in the cited document 4, a rubber-containing graft copolymer that is generally used has a high rubber content, so that the powder characteristics are likely to deteriorate and a dispersion defect is likely to occur during molding. The surface appearance of may become poor.
Furthermore, in the method described in the cited document 5, although a certain effect is recognized in improving the impact resistance, the rubber-containing graft copolymer having a small average particle diameter at the time of latex is a majority component. In such a case, the powder characteristics tend to be lowered.
In view of the above situation, the object of the present invention is to improve the powder characteristics of a rubbery polymer-containing material, a rubbery polymer-containing material useful in applications to be compounded to improve the properties of a thermoplastic resin, and this It is an object of the present invention to provide a production method and a thermoplastic resin composition obtained by blending this with a thermoplastic resin.

The gist of the present invention is that 50 to 150 μm powder particles and 200 to 500 μm powder particles are contained, and the content of all particles occupied by 50 to 150 μm powder particles is 25% by mass or more. The rubbery polymer-containing material has a content of 15% by mass or more in all particles occupied by 200 to 500 μm powder particles.
The gist of the present invention resides in a thermoplastic resin composition obtained by blending the rubber-like polymer-containing material into a thermoplastic resin.

  The rubbery polymer-containing material of the present invention has excellent powder properties and is useful in applications that are compounded to improve the properties of thermoplastic resins. In addition, the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with a thermoplastic resin has excellent lubricity at the time of molding, has excellent surface appearance and impact resistance, It can be used for the production of molded products.

Hereinafter, the present invention will be described in detail.
The rubbery polymer used in the present invention is obtained by graft polymerization of a monomer to a rubbery polymer.
[Rubber polymer]
The rubbery polymer of the present invention includes a diene rubbery polymer, a polyalkyl (meth) acrylate rubbery polymer, a polyorganosiloxane rubbery polymer, a polyorganosiloxane and an alkyl (meth) acrylate rubber. A composite polyorganosiloxane / acrylic composite rubbery polymer or the like can be used.
(Diene rubber)
Examples of the diene rubber include polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and polychloroprene.
Preferably, the monomer used for rubber polymerization is a diene monomer such as 1,3-butadiene (sometimes referred to as Bd), isoprene, chloroprene, etc., when the total amount of the monomers is 100% by mass. It consists of one or two or more vinyl monomers that can be copolymerized with the diene monomer.
Examples of vinyl monomers copolymerizable with diene monomers include styrene (sometimes referred to as St), aromatic vinyl such as α-methylstyrene, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, Acrylic acid alkyl esters such as ethyl acrylate and n-butyl acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, vinyl halides such as vinyl chloride and vinyl bromide, vinylidene chloride, odor Vinylidene halides such as vinylidene halide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, ethylene glycol glycidyl ether and other vinyl monomers having a glycidyl group, divinylbenzene, ethyl Glycol dimethacrylate, polyfunctional monomers such as 1,3-butylene glycol dimethacrylate may be used. These vinyl monomers can be used alone or in combination of two or more.
As a polymerization method for the diene rubber, an emulsion polymerization method is usually used.
In the emulsion polymerization of the diene rubber in the present invention, a known emulsifier can be used as an emulsifier, for example, alkali metal salts of higher fatty acids such as disproportionated rosin acid, oleic acid and stearic acid, sulfonic acid type , And sulfuric acid alkali metal salts can be used alone or in combination of two or more. In the case where powder recovery of the rubber-containing graft copolymer is carried out by spray drying, among these, sulfonic acid-based and sulfuric acid-based alkali metal salts are preferable.
Specific examples of the sulfonic acid-based or sulfuric acid-based alkali metal salt include, for example, alkylbenzene sulfonate alkali metal salts such as sodium dodecylbenzene sulfonate, primary alkyl alkali metal sulfates such as sodium lauryl sulfate, and secondary alkyl alkali metal salts. Etc. These emulsifiers can be used alone or in combination of two or more. By using the emulsifier, when molding a thermoplastic resin composition obtained by blending the rubber polymer-containing material of the present invention with a thermoplastic resin, the lubricity becomes good and long-term without causing plate-out and the like. Production stability can be ensured.
In addition, an emulsifying dispersant can be used for the purpose of improving the polymerization stability. Specific examples of the emulsifying dispersant include, for example, a sodium salt of β-naphthalenesulfonic acid formalin condensate.
As a polymerization method of the diene rubber, a multistage polymerization method of one stage or two stages or more can be adopted. In the case of multi-stage polymerization, a part of the monomer used for the polymerization is previously charged into the reaction system, and after the start of polymerization, the remaining monomer is added all at once or dividedly or continuously. It is preferable. By adopting such a polymerization method, the polymerization stability is improved, and a diene rubber latex having a desired particle size and particle size distribution can be stably prepared.
The average particle diameter of the diene rubber latex is generally 50 to 400 nm, preferably 70 to 300 nm in terms of weight average particle diameter (dw). When the weight average particle diameter (dw) is 50 nm or more, the impact resistance of the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with the thermoplastic resin is sufficiently improved, and the weight average particle diameter is increased. When the thickness is 400 nm or less, a molded article having a good surface appearance can be obtained, and a balance between impact resistance and transparency when added to a polyvinyl chloride resin can be achieved.

(Polyalkyl (meth) acrylate rubbery polymer)
The polyalkyl (meth) acrylate rubbery polymer is a rubbery polymer obtained by polymerizing a (meth) acrylic monomer or a mixture thereof as a main component. The (meth) acrylic monomer is not particularly limited, but (meth) acrylate is generally used. Specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tridecyl acrylate, ethoxyethoxyethyl acrylate, methoxytripropylene glycol acrylate, and 4-hydroxybutyl acrylate. , Lauryl acrylate, lauryl methacrylate, stearyl methacrylate and the like. These can be used alone or in combination of two or more.
The rubbery polymer is preferably a polymer having a glass transition temperature of 0 ° C. or less from the viewpoint of impact resistance, and particularly n-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, tridecyl acrylate. It is preferable to use alkyl (meth) acrylates such as lauryl methacrylate and tridecyl methacrylate. Moreover, when using (meth) acrylate [stearyl methacrylate etc.] which has crystallinity near room temperature, it is good to mix and use the monomer which melt | dissolves this.

The polyalkyl (meth) acrylic rubbery polymer may be a (co) polymer obtained by simply polymerizing one or more of the monomers, but is particularly higher in low-temperature impact strength. A composite rubber that exhibits physical properties is preferable.
Preferable examples of the composite rubber include a (meth) acrylic acid ester of an alcohol having a branched side chain or an alcohol having an alkyl group having 13 or more carbon atoms, or a hydroxyl group, a methoxy group or an ethoxy group (meta ) A composite rubber mainly composed of an acrylic rubber (AR1) component containing at least one acrylic ester as a constituent component and an acrylic rubber (AR2) component containing n-butyl acrylate as a constituent component. The glass transition temperature (Tg1) derived from the AR1 component is lower than the glass transition temperature (Tg2) derived from the acrylic rubber (AR2) component. Such a composite rubber can impart higher low temperature impact resistance as compared with a simple copolymer type rubber.
As the constituent component of the acrylic rubber (AR1) component, 2-ethylhexyl acrylate, ethoxyethyl acrylate, methoxytripropylene glycol acrylate, 4-hydroxybutyl acrylate, tridecyl methacrylate, tridecyl acrylate, stearyl methacrylate, and stearyl acrylate are particularly preferable. .
The composite rubber usually contains 5 to 95% by mass of the acrylic rubber (AR1) component and 95 to 5% by mass of the acrylic rubber (AR2) component, preferably 10 to 90% by mass of the acrylic rubber (AR1) component and the acrylic rubber. It contains 90 to 10% by mass of (AR2) component, more preferably 10 to 80% by mass of acrylic rubber (AR1) component and 90 to 20% by mass of acrylic rubber (AR2) component. These ranges are significant in terms of superiority over copolymer type rubber.
The monomer used for obtaining the rubber-like polymer usually contains a monomer having two or more unsaturated bonds in the molecule, and its content is preferably 2% by mass or less, and 1.5% by mass. % Or less is more preferable. A monomer having two or more unsaturated bonds in the molecule functions as a crosslinking agent or a graft crossing agent. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicone, and the like. Examples of the graft crossing agent include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents can be used alone or in combination of two or more.
When the composite rubber is used as a rubbery polymer, the use amount of the crosslinking agent or graft crossing agent for the acrylic rubber (AR1) component and the acrylic rubber (AR2) component is based on the use amount (% by mass) for each component. As a result, it is preferable that the amount used for the (AR2) component is larger than that for the (AR1) component.
The rubbery polymer may have two or more glass transition temperatures at 10 ° C. or lower. In that case, the glass transition temperature (Tg1) derived from the acrylic rubber (AR1) component is preferably lower than the glass transition temperature (Tg2) derived from the acrylic rubber (AR2) component. When the glass transition temperature satisfies such conditions, the resulting impact resistance modifier exhibits higher impact resistance. This is also a feature that it is a composite rubber, and is also different from a simple copolymer.
Here, the glass transition temperature of the polymer is measured as a Tan δ transition point by a dynamic mechanical property analyzer (hereinafter referred to as “DMA”). In general, a polymer obtained from a monomer has an inherent glass transition temperature, and a single transition point is observed alone (single component or multiple component random copolymer), but a mixture of multiple components, Alternatively, a unique transition point is observed in each of the composite polymers. For example, in the case of two components, two transition points are observed by measurement. Two peaks are observed in the Tan δ curve measured by DMA. When the composition ratio is uneven or when the transition temperature is close, each peak may approach and may be observed as a peak having a shoulder portion, but it is a simple 1 seen in the case of a single component. It can be distinguished because it is different from the peak curve.
When copolymerizing using a mixture of a (meth) acrylic monomer and another monomer, examples of the other monomer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyltoluene. In addition, various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methacrylic acid-modified silicone, and fluorine-containing vinyl compounds may be contained as a copolymerization component. The amount of other monomers used is preferably 30% by mass or less.
In producing a rubbery polymer, various conventionally known surfactants such as anionic, nonionic, and cationic can be used as an emulsifier or a dispersion stabilizer. Moreover, 2 or more types of surfactant can also be mixed and used as needed.

(Polyorganosiloxane / acrylic composite rubbery polymer containing polyorganosiloxane and alkyl (meth) acrylate rubber)
The polyorganosiloxane / acrylic composite rubber-like polymer containing polyorganosiloxane and alkyl (meth) acrylate rubber has a polyorganosiloxane component of 1 to 99% by weight and an alkyl (meth) acrylate rubber component of 99 to 1% by weight. % (The total amount of both components is preferably 100% by weight).
The polyorganosiloxane / acrylic composite rubber-like polymer may be produced by any method. First, a latex of polyorganosiloxane is prepared by emulsion polymerization, and then a monomer constituting an alkyl (meth) acrylate rubber. It is preferred to polymerize the body after impregnating it with particles of polyorganosiloxane latex.
The polyorganosiloxane rubber component constituting the composite rubber can be prepared by emulsion polymerization using the following organosiloxane and cross-linking agent (CI). In that case, a graft crossing agent (GI) can also be used together.
Examples of the organosiloxane include various cyclic members having a 3-membered ring or more, and a 3- to 6-membered ring is preferably used. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. These may be used alone or in combination of two or more. The amount of these used is 50% by weight or more, preferably 70% by weight or more in the polyorganosiloxane component.
As the crosslinking agent (CI), a trifunctional or tetrafunctional silane crosslinking agent such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane. Etc. are used. In particular, tetrafunctional crosslinking agents are preferred, and tetraethoxysilane is particularly preferred among these. The amount of the crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane component.
As the graft crossing agent (GI), a compound capable of forming a unit represented by the following formula is used.
^{_{CH 2 = C (R 2)}} -COO- (CH 2) p-SiR 1 n O (3-n) / 2 (GI-1)
_{^{CH 2 = C (R 2)}} -C 6 H 4 -SiR 1 n O (3-n) / 2 (GI-2)
_{^{CH 2 = CH-SiR 1 n}} O (3-n) / 2 (GI-3)
_{^{HS- (CH 2) p-SiR}} 1 n O (3-n) / 2 (GI-4)
(In the formula, R 1 is a methyl group, an ethyl group, a propyl group, or a phenyl group, R 2 is a hydrogen atom or a methyl group, n is 0, 1 or 2, and p is a number from 1 to 6.)
The (meth) acryloyloxysiloxane capable of forming the unit of the above formula (GI-1) can form an effective graft chain because of its high grafting efficiency, and is advantageous in terms of impact resistance.
In addition, methacryloyloxysiloxane is particularly preferable as the unit capable of forming the unit of the above formula (GI-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyl. Examples include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, and γ-methacryloyloxybutyldiethoxymethylsilane.
A vinyl siloxane is mentioned as what can form the unit of the said formula (GI-2), As a specific example, a tetramethyltetravinylcyclotetrasiloxane is mentioned.
As what can form the unit of the said formula (GI-3), p-vinylphenyl dimethoxymethylsilane is mentioned. Moreover, (gamma) -mercaptopropyl dimethoxymethylsilane, (gamma) -mercaptopropyl methoxydimethylsilane, (gamma) -mercaptopropyl diethoxymethylsilane etc. are mentioned as what can form the unit of a formula (GI-4).
The amount of the grafting agent used is 0 to 10% by weight, preferably 0.5 to 5% by weight in the polyorganosiloxane component.
The polyorganosiloxane component latex can be produced by a method described in, for example, US Pat. Nos. 2,891,920 and 3,294,725. In the practice of the present invention, for example, a mixed solution of an organosiloxane, a cross-linking agent (CI), and, optionally, a graft crossing agent (GI) is mixed with, for example, a homogenizer in the presence of a sulfonic acid-based emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. It is preferable to manufacture by the method of carrying out shear mixing with water using etc. Alkylbenzenesulfonic acid is suitable because it acts as an emulsifier for organosiloxane and at the same time serves as a polymerization initiator. In this case, it is preferable to use an alkylbenzene sulfonic acid metal salt, an alkyl sulfonic acid metal salt, or the like in combination because it has an effect of maintaining a stable polymer during graft polymerization.
Next, the alkyl (meth) acrylate rubber component constituting the composite rubber can be synthesized using the following alkyl (meth) acrylate, crosslinking agent (CII), and graft crossing agent (GII).
Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. In particular, the use of n-butyl acrylate is preferable.
Examples of the crosslinking agent (CII) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like.
Examples of the graft crossing agent (GII) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and grafting agents is 0.1 to 20% by weight in the polyalkyl (meth) acrylate component.
The polymerization of the alkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate and crosslinking agent into the latex of the polyorganosiloxane component neutralized by the addition of an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or sodium carbonate. In addition, after adding a graft crossing agent and impregnating the polyorganosiloxane particles, a normal radical polymerization initiator is allowed to act. As the polymerization proceeds, a latex of a composite rubber of a polyorganosiloxane component and a polyalkyl (meth) acrylate component is obtained. In carrying out the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of a polyalkyl (meth) acrylate component has a repeating unit of n-butyl acrylate. Composite rubber is preferably used.
The composite rubber thus prepared by emulsion polymerization can be graft copolymerized with a vinyl monomer, and the gel content measured by extraction with toluene at 90 ° C. for 4 hours should be 80% by weight or more. preferable.

(Preparation of rubbery polymer)
The rubbery polymer in the present invention is prepared by graft-copolymerizing a vinyl monomer to the above-mentioned rubbery polymer.
For example, in the presence of a latex containing a rubber-like polymer, a monomer having an alkyl methacrylate as a main component, for example, one or more alkyl methacrylates, and, if desired, a copolymer thereof. A rubbery polymer can be prepared by graft polymerization of a monomer mixture composed of a polymerizable vinyl monomer in one or more stages.
Specific examples of vinyl monomers copolymerizable with methacrylic acid alkyl esters include, for example, aromatic vinyl such as styrene, α-methylstyrene, halogen-substituted products thereof, and alkyl-substituted styrene, ethyl acrylate, and n-butyl. Acrylic acid alkyl esters such as acrylate, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether. . These monomers can be used alone or in combination of two or more.
When a diene rubbery polymer is used as the rubbery polymer, the content of the diene rubbery polymer in the rubbery polymer is usually preferably 50 to 90% by mass, more preferably 55 to 85% by mass. is there. When the content of the diene rubbery polymer is 50% by mass or more, the impact resistance of the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with the thermoplastic resin is improved, and the diene type When the content of the rubber component is 90% by mass or less, the dispersibility of the rubbery polymer-containing material of the present invention in the thermoplastic resin is improved, and impact resistance and the like are maintained while maintaining the excellent properties of the thermoplastic resin. The physical properties of can be improved.
When an alkyl (meth) acrylate rubber polymer or a polyorganosiloxane / acrylic composite rubber polymer is used as the rubber polymer, the content of these rubber polymers is usually preferably 80 to 99% by mass, More preferably, it is 80-95 mass%. When the content of these rubber components is 80% by mass or more, the impact resistance of the thermoplastic resin composition obtained by blending the rubbery polymer-containing material of the present invention with the thermoplastic resin is improved. When the content of is 99% by mass or less, the dispersibility of the rubber polymer-containing material of the present invention in the thermoplastic resin is improved, and physical properties such as impact resistance are maintained while maintaining the excellent properties of the thermoplastic resin. Can be improved.

As the method of graft polymerization, an emulsion polymerization method is usually used in the same manner as the polymerization of the rubbery polymer. In the present invention, as in the case of rubber polymerization, known emulsifiers can be used. For example, alkali metal salts of higher fatty acids such as disproportionated rosin acid, oleic acid, stearic acid, sulfonic acid, sulfuric acid These can be used alone or in combination of two or more thereof, such as alkali metal salts. In the case where powder recovery of the rubber-containing graft copolymer is carried out by spray drying, among these, sulfonic acid-based and sulfuric acid-based alkali metal salts are preferable. Specific examples of the sulfonic acid-based or sulfuric acid-based alkali metal salts include alkylbenzene sulfonic acid alkali metal salts such as sodium dodecylbenzene sulfonate (sometimes referred to as DBSNa), sodium lauryl sulfate (sometimes referred to as SLS), and the like. Examples thereof include primary alkyl alkali metal salts of sulfuric acid and secondary alkyl alkali metal salts of sulfuric acid.
In addition, an emulsifying dispersant can be used for the purpose of improving the polymerization stability. Specific examples of the emulsifying dispersant include a sodium salt of β-naphthalenesulfonic acid formalin condensate. These emulsifiers or emulsifying dispersants can be used alone or in combination of two or more.
An emulsifier is used at the time of superposition | polymerization of a rubber-like polymer so that it may preferably become 1-10 mass parts with respect to 100 mass parts of rubber-like polymers, More preferably, it is 1-8 mass parts. When the amount of the emulsifier used is 1 part by mass or more, aggregates are not generated during the polymerization. On the other hand, when the amount of the emulsifier used is 10 parts by mass or less, there is no foaming during the polymerization, thereby improving productivity. It is preferable because a molded article having a good surface appearance can be obtained. In addition, when a sulfonic acid-based or sulfuric acid-based alkali metal salt is used, the powder characteristics of the rubber polymer-containing material of the present invention are improved, and the rubber polymer-containing material of the present invention is further blended with a thermoplastic resin. When the thermoplastic resin composition is molded, the slipperiness becomes good and sufficient long-term molding stability can be obtained, and the releasability from the mold is also improved.

The rubbery polymer-containing material of the present invention contains powder particles having a particle diameter of 50 to 150 μm and powder particles having a particle diameter of 200 to 500 μm, and is contained in all particles occupied by the powder particles having a particle diameter of 50 to 150 μm. Is 25 mass% or more, and the content ratio in all particles occupied by powder particles having a particle diameter of 200 to 500 μm is 15 mass% or more.
The 50-150 μm powder particles are effective in improving the powder characteristics of the 20-500 μm powder particles. When the content of the powder particles of 50 to 150 μm in the total particles is 25% by mass or more and the content of the powder particles of 200 to 500 μm in the total particles is 15% by mass or more, the powder characteristic effect is exhibited. The If one of the above requirements is out of the range, the particle size distribution of the powder becomes wide and the handleability of the powder deteriorates.
The rubber polymer of the present invention comprises a rubber polymer (A) containing 65 to 150% by mass of powder particles of 50 to 150 μm and 60 mass of powder particles of 200 to 500 μm in all particles. It is preferable to obtain a rubbery polymer having the constitution of the present invention by blending with a rubbery polymer (B) containing at least%.
By containing the powder particles of 50 to 150 μm in an amount of 65% by mass or more based on the total particles, the effect of improving the powder characteristics is improved. Moreover, the molded article with a favorable shaping | molding external appearance can be obtained by containing 200 mass% or more of powder particles of 200-500 micrometers in all the particles.
For powder particles of 50 to 150 μm, the following effects are exhibited. That is, when the particle diameter of the powder is 50 μm or more, the amount of extremely fine powder is small and the handleability of the powder is good. On the other hand, if the particle diameter of the powder is 150 μm or less, the powder property improving effect of the rubbery polymer-containing material is good.
Moreover, the following effects are expected for powder particles of 200 to 500 μm. That is, when the average particle size of the powder is 200 μm or more, the handleability of the powder is good. On the other hand, if the average particle diameter of the powder is 500 μm or less, a molded product having a good molded appearance can be obtained without causing poor dispersion during molding.
The feature of the present invention is to use powder particles of 50 to 150 μm to improve the powder characteristics of the powder particles of 200 to 500 μm, both of which are mainly composed of rubber. It is possible to achieve both the modification of the powder characteristics and the provision of impact resistance to the molded product.

In the present invention, in order to further improve the powder characteristics, the inorganic fine powder is selected from the group consisting of Si-based compounds and Ti-based compounds and Mg, Al, Ca, Ba and Zn chlorides, carbonates and sulfates. Inorganic fine powders composed of the above compounds can be used.
Examples of the Si compound include silicon dioxide and diatomaceous earth, and examples of the Ti compound include titanium oxide. Examples of Mg, Al, Ca, Ba and Zn chlorides, carbonates and sulfates include, for example, magnesium carbonate, calcium carbonate, barium sulfate, clay, talc, calcium metasilicate, and the like. These compounds may be natural products or synthetic products. An inorganic fine powder can be used 1 type or in combination of 2 or more types. Of these, silicon dioxide and calcium salts are preferred. Although it does not restrict | limit especially as silicon dioxide, All kinds of silicon dioxides, such as hydrophobic silica and hydrophilic silica, can be used. Although it does not restrict | limit especially as a calcium salt, Among these, calcium carbonate is preferable. Calcium carbonate is inexpensive and can effectively improve the powder characteristics of the rubbery polymer-containing material without significantly increasing the cost.
When these inorganic fine powders are used in the present invention, these inorganic fine powders are preferably mixed in an amount of 0.05 to 8.0 parts by mass with respect to 100 parts by mass of the rubbery polymer. If it is 0.05 parts by mass or more, the effect of improving the powder characteristics is sufficient, and if it is 8.0 parts by mass or less, a thermoplastic resin composition obtained by blending the rubber polymer-containing material of the present invention with a thermoplastic resin. The physical properties such as the surface appearance when the product is made into a molded product are improved.

Furthermore, a hard polymer can be used to improve the powder characteristics of the rubbery polymer-containing material of the present invention and to improve the molded appearance of the molded product. The hard copolymer is a hard copolymer having a glass transition temperature of 40 to 85 ° C. By adopting a constitution including a hard copolymer having a glass transition temperature of 85 ° C. or lower, the powder characteristics of the rubbery polymer-containing material can be improved. If the hard copolymer has a glass transition temperature of 85 ° C. or lower, the powder characteristics of the rubbery polymer-containing material will be excellent, and fine powder will not be generated. Moreover, the hard copolymer used by this invention uses the glass transition temperature of 40 degreeC or more. When the hard copolymer has a glass transition temperature of 40 ° C. or higher, the powder characteristics of the rubbery polymer-containing material are improved. Further, the weight average molecular weight (sometimes referred to as Mw) of the hard copolymer is usually preferably 200,000 to 5,000,000. When Mw is 200,000 or more, sufficient powder properties are obtained. Since an improvement effect is obtained, it is preferable, and when it is 5,000,000 or less, it is preferable because fish eyes do not occur in the molded product.
The glass transition temperature of the hard copolymer is expressed by the Fox equation from the glass transition temperature of the homopolymer of each monomer used for the synthesis of the hard copolymer and the weight fraction of each monomer unit in the hard copolymer. It may be calculated using a calculation formula such as, or may be measured using various measuring devices.
When these hard copolymers are used in the present invention, the amount of these hard copolymers is preferably in the range of 0.5 to 10 parts by mass when the rubbery polymer is 100 parts by mass. When the amount of the hard copolymer is 10 parts by mass or less, the impact resistance of the thermoplastic resin composition obtained by blending the rubber polymer-containing material of the present invention with the thermoplastic resin is improved, and When the amount is 0.5 parts by mass or more, the powder characteristics of the rubbery polymer-containing material are improved, which is preferable. The amount of the hard copolymer is more preferably in the range of 0.5 to 5 parts by mass.
In the present invention, the production method of the hard copolymer in the case of using these hard copolymers is not particularly limited, but is usually produced by emulsion polymerization, a monomer at the time of polymerization, a polymerization initiator, The emulsifier can be added by batch addition, continuous addition, divided addition, multistage addition, or the like. Moreover, you may add by these combinations.

The method for producing the rubbery polymer-containing material of the present invention is not particularly limited, and can be produced by a known method such as a wet coagulation method by aciding out or salting out or spray drying.
The rubbery polymer-containing material of the present invention comprises a rubbery polymer (A) containing 65 to 150% by mass of powder particles of 50 to 150 μm and powder particles of 200 to 500 μm in all particles. It is preferably obtained by mixing the rubber polymer (B) containing 60% by mass or more.
At this time, the rubbery polymer (A) and the rubbery polymer (B) are each produced by changing the production conditions of the wet coagulation method and spray drying, and in a known ratio such as a mixer. Can be mixed.

In the present invention, the rubbery polymer (A) is preferably obtained by spray-drying a rubbery polymer latex mainly composed of a diene rubber containing a sulfonic acid or sulfuric acid alkali metal salt.
The spray drying in the present invention is a method in which the polymerized latex is sprayed (miniaturized) in a dry gas (hot air) and recovered as a dry powder. The dryer shape, spraying device, etc. are known spray dryers, sprays The device can be used. Also, the capacity of the spray dryer is not particularly limited, and any capacity dryer from a small scale of a small scale to a large scale for industrial use can be used.
One or more apparatuses for spraying the rubbery polymer latex are installed in the upper part of the dryer, and the spraying system may be any system such as a rotating disk system, a pressure nozzle system, a 2 fluid nozzle system, and a pressurized 2 fluid nozzle system.
In the present invention, it is preferable to have an apparatus for separating and recovering the spray-dried dry powder from the dry gas. The method for recovering the dry powder from the dry gas is not particularly limited. In general, a cyclone using a centrifugal method or a bag filter using a filtration method is preferable.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention is formed by blending the above-mentioned rubbery polymer-containing material with a thermoplastic resin. The rubbery polymer-containing material may be in the form of powder, granules or pellets. The rubber polymer-containing material is preferably blended in an amount of 0.1 to 80 parts by weight, and more preferably 0.2 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the amount of the rubber polymer-containing material is 0.1 parts by mass or more, the impact resistance of the thermoplastic resin composition of the present invention is increased, and when it is 80 parts by mass or less, the molding of the thermoplastic resin composition of the present invention is performed. The appearance of the object is preferable, and the cost can be reduced.
Examples of the thermoplastic resin used in the resin composition of the present invention include polyvinyl chloride resins such as polyvinyl chloride (PVC) and polychlorinated vinyl chloride, olefin resins such as polypropylene and polyethylene, polystyrene, and high impact polystyrene. , (Meth) acrylic acid ester-styrene copolymer, styrene-acrylonitrile copolymer (PAS), styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylonitrile copolymer Polymers, styrene resins such as acrylonitrile-ethylene-styrene copolymers, acrylic resins such as polymethyl methacrylate, polycarbonate resins such as polycarbonate (PC), polyamide resins, polyethylene terephthalate (PE ), Polyester resins such as polybutylene terephthalate (PBT), (modified) polyphenylene ether resins, polyoxymethylene resins, polysulfone resins, polyarylate resins, polyphenylene sulfide resins, thermoplastic polyurethane resins, etc. Heat of engineering plastics, styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene, trans-1,4-polyisoprene, etc. A plastic elastomer (TPE) is mentioned. These can be used alone or in combination of two or more.
Since the effect of improving impact resistance due to the addition of the rubbery polymer-containing material of the present invention is remarkable, a polyvinyl chloride resin is preferably used as the thermoplastic resin. Specific examples of the polyvinyl chloride resin in the present invention include chlorine group-containing resins such as polyvinyl chloride and polychlorinated vinyl chloride, or 70% by mass or more of vinyl chloride and other copolymerizable with this. A copolymer with 30% by mass or less of monomer may be mentioned. Examples of the other copolymerizable monomer include vinyl bromide, vinylidene chloride, vinyl acetate, acrylic acid, methacrylic acid, and ethylene.

The mixing of the rubbery polymer-containing material of the present invention and the thermoplastic resin is not particularly limited, and a known mixing method can be employed. For example, it can be carried out by a kneader usually used for kneading thermoplastic resins. Specifically, it can be performed using, for example, a mixing roll, a calendar roll, a Banbury mixer, an extruder or the like.
Moreover, various additives, such as dye, a pigment, a stabilizer, a reinforcing material, a filler, a flame retardant, can be mix | blended with the thermoplastic resin composition of this invention as needed.
By molding the thermoplastic resin composition of the present invention, a molded product having improved physical properties such as impact resistance and surface appearance can be obtained. The molding method is not particularly limited, and for example, a method suitable for the thermoplastic resin composition of the present invention may be selected from known molding methods. Examples thereof include a method of molding using various molding machines such as a calendar molding machine, an extruder, an injection molding machine, a blow molding machine, and an inflation molding machine.

The present invention will be specifically described below with reference to examples. In this example, “part” represents “part by mass” unless otherwise specified. Moreover, in the present Example, in order to produce the sample test piece which consists of a thermoplastic polymer composition by mix | blending rubbery polymer containing material, the following thermoplastic resins were used.
PVC: Shin-Etsu Chemical Co., Ltd., TK-700 (trade name)
PC: Nippon Gee Plastic Co., Ltd., Lexan 141 (trade name)
PBT: Mitsubishi Rayon Co., Ltd., Toughpet N1000 (trade name)
ABS: manufactured by Ube Saikon Co., Ltd., UX050 (trade name)
PAS: Ube Saikon Co., Ltd., SR05B (trade name)

Moreover, various physical properties in each example and comparative example are measured by the following methods.
(1) Powder characteristics (1-1) Average particle diameter Using an evaluation device specified in JIS Z 8801, the particle size distribution of the powder was evaluated by the method specified in JIS R 6002, and JIS Z 8819 The average particle size of the powder was determined by a prescribed method.
(1-2) Powder flowability 50 g of rubber polymer-containing material powder was placed in a bulk specific gravity measuring device described in JIS K 6741, and the mass of the powder falling per 10 seconds was measured (unit: g / 10 seconds). The larger this value, the better the powder flowability.
(2) Izod impact strength When the thermoplastic resin is polyvinyl chloride, a composition obtained by blending the rubber polymer-containing material at 185 ° C. with a 6-inch roll is melt-kneaded for 3 minutes. A sample test piece was obtained by press molding at 9 MPa and 185 ° C.
When the thermoplastic resin is other than polyvinyl chloride, the composition obtained by blending the rubber polymer-containing material is pelletized at 260 ° C. with a 30 mm twin screw extruder, and then the pellet is dried at 90 ° C. for 12 hours. A sample test piece was obtained by injection molding at a molding temperature of 260 ° C. Izod impact strength was measured according to ASTM D256.
(3) Surface appearance of molded product When the thermoplastic resin is polyvinyl chloride, it is thickened at a resin temperature of 190 ° C. with a single screw extruder having a screw diameter of 30 mm from a composition obtained by blending a rubbery polymer-containing material. A 0.2 mm sheet was molded, and the surface appearance of the sheet, such as gloss and fish eyes, was visually evaluated in six stages of A, B, C, D, E, and F. The criteria are shown below. When the thermoplastic resin was other than polyvinyl chloride, the surface appearance of the test piece for the Izod impact test was evaluated in the same manner as described above. In addition, C or more was set as the pass.
A: The surface of the molded product is glossy, and surface appearance abnormalities such as fish eyes and flow marks are hardly recognized.
B: The surface of the molded article is glossy, and a very small number of fish eyes are recognized, but other surface appearance abnormalities are hardly recognized.
C: The surface of the molded article is glossy, and a small number of fish eyes are observed, but other surface appearance abnormalities are hardly recognized.
D: The gloss of the surface of the molded article is lowered and a small number of fish eyes are observed.
E: The gloss of the surface of the molded product is lowered, and a slightly larger fish eye is observed.
F: The gloss of the surface of the molded product is extremely lowered, and a large number of fish eyes are observed.
(4) Sticking time When the thermoplastic resin is polyvinyl chloride, this test was carried out as an index of slipperiness maintenance during processing. A composition obtained by blending a rubber polymer-containing material at 195 ° C. with a 6-inch roll is melt-kneaded, and the ease of peeling from the roll is confirmed at intervals of 1 minute, until it does not peel off from the roll. Time was evaluated. The longer this time, the better the lubricity.
(5) Torque at the time of extrusion This test was carried out as an index of lubricity at the time of processing when the thermoplastic resin is other than polyvinyl chloride. Torque was measured when the composition obtained by blending the rubbery polymer-containing material was pelletized at 260 ° C. with a 30 mm twin screw extruder. The smaller the torque value, the better the lubricity.

(Example 1) Production of rubbery polymer-containing material (C-1) (Preparation of diene rubbery polymer (AR))
The following substances were charged in a 70 L autoclave as the first monomer, and when the temperature was raised to 43 ° C., a redox initiator was added to the reactor to start the reaction, and the temperature was further raised to 65 ° C.
First monomer 1,3-butadiene 23.4 parts by mass Styrene 6.6 parts by mass p-menthane hydroperoxide 0.1 parts by mass Sodium pyrophosphate 0.5 parts by mass Sodium lauryl sulfate 0.1 parts by mass (Kao ( Co., Ltd., Emar 2F; trade name)
Deionized water 70 parts by mass Redox initiator Ferrous sulfate 0.0003 parts by mass Disodium ethylenediaminetetraacetate 0.0009 parts by mass Rongalite 0.3 parts by mass Deionized water 5 parts by mass The following start after 2 hours from the start of polymerization The agent was added into the reactor, and immediately after that, the following second monomer, emulsifier and deionized water were continuously added dropwise over 2 hours.
Initiator p-menthane hydroperoxide 0.2 parts by mass Second monomer 1,3-butadiene 54.6 parts by mass Styrene 15.4 parts by mass Emulsifier, deionized water sodium lauryl sulfate 1.9 parts by mass (Kao Corporation ) Made, Emar 2F; trade name)
75 parts by mass of deionized water The reaction was carried out for 15 hours from the start of polymerization to obtain a latex of a butadiene-based rubber polymer. The resulting butadiene-based rubbery polymer latex had a weight average particle size of 180 nm.
(Preparation of rubbery polymer latex (AG))
70 parts by mass of the butadiene rubber-like polymer latex obtained by the above polymerization as a solid content, 0.6 parts by mass of sodium lauryl sulfate (manufactured by Kao Corporation, Emar 2F; trade name), 0.6 parts by mass of Rongalite When charged in a flask purged with nitrogen and maintained at an internal temperature of 70 ° C., 7.5 parts by weight of methyl methacrylate, 1.5 parts by weight of ethyl acrylate, and 100 parts by weight of the above monomer mixture of cumene hydroperoxide The mixture containing 0.3 part by mass was added dropwise over 1 hour and held for 1 hour. Thereafter, in the presence of the polymer obtained in the previous step, a mixture containing 15 parts by mass of styrene and 0.3 part by mass of cumene hydroperoxide as 100 parts by mass of styrene as the second stage was taken for 1 hour. And then held for 3 hours.
Thereafter, in the presence of the polymer obtained in the first stage and the second stage, in the case where 6 parts by mass of methyl methacrylate and 100 parts by mass of methyl methacrylate were used as cumene hydroperoxide in the third stage, 0. A mixture containing 3 parts by mass was added dropwise over 0.5 hour and held for 1 hour, and then the polymerization was terminated to obtain a latex of a rubbery polymer mainly composed of a diene rubber-like polymer. 0.5 parts by mass of butylated hydroxytoluene was added to the obtained rubber polymer latex. The resulting butadiene-based rubbery polymer latex had a weight average particle size of 200 nm.
(Preparation of diene rubber polymer (A))
The rubber polymer latex was sprayed into a spray dryer to obtain a rubber polymer (A). The particle size distribution of the rubber polymer (A) powder was 70% by mass in the range of 50 to 150 μm and 10% by mass in the range of 200 to 500 μm.

(Preparation of diene rubber-like polymer (BR))
The following materials were charged into a 70 L autoclave and reacted for 15 hours at 50 ° C. with stirring to obtain a butadiene rubber polymer latex. The resulting butadiene-based rubbery polymer latex had a weight average particle size of 120 nm.
1,3-butadiene 78.0 parts by mass Styrene 22.0 parts by mass p-menthane hydroperoxide 0.4 parts by mass Sodium pyrophosphate 1.5 parts by mass Ferrous sulfate 0.02 parts by mass Dextrose 1.0 parts by mass Potassium oleate 3.0 parts by weight Deionized water 150 parts by weight (preparation of rubbery polymer latex (BG))
The butadiene rubber-like polymer latex was charged in a 70 parts by mass flask as a solid content and purged with nitrogen. Then, 0.8 parts by mass of anhydrous sodium sulfate was added as a 10% aqueous solution, and the mixture was stirred for 30 minutes. After adding 1 part of potassium oleate as a 7% aqueous solution and stabilizing, 0.6 part of Rongalite is added, 7.5 parts by weight of methyl methacrylate, 1.5 parts by weight of ethyl acrylate and cumene hydroperoxide are added to the above monomer. When the mixture was 100 parts by mass, a mixture containing 0.3 part by mass was added dropwise over 1 hour and then held for 1 hour. Thereafter, in the presence of the polymer obtained in the previous step, a mixture containing 15 parts by mass of styrene and 0.3 part by mass of cumene hydroperoxide as 100 parts by mass of styrene as the second stage was taken for 1 hour. And then held for 3 hours.
Thereafter, in the presence of the polymer obtained in the first stage and the second stage, in the case where 6 parts by mass of methyl methacrylate and 100 parts by mass of methyl methacrylate were used as cumene hydroperoxide in the third stage, 0. A mixture containing 3 parts by mass was added dropwise over 0.5 hour and then held for 1 hour, after which the polymerization was terminated to obtain a latex of a rubbery polymer mainly composed of a diene rubber. 0.5 parts by mass of butylated hydroxytoluene was added to the resulting rubbery polymer latex mainly composed of diene rubber. The resulting butadiene-based rubbery polymer latex had a weight average particle size of 180 nm.

(Preparation of diene rubbery polymer (B))
0.2% by weight sulfuric acid aqueous solution was added to the rubbery polymer latex for coagulation and solidified by heat treatment at 90 ° C. Thereafter, the coagulated product was washed with warm water and further dried to obtain a rubber polymer (B). The particle size distribution of the rubber polymer (B) powder was 22% by mass in the range of 50 to 150 μm and 65% by mass in the range of 200 to 500 μm.

Preparation of Rubber Polymer-Containing Material (C-1) The rubber polymer (A) and the rubber polymer (B) obtained above are provided with a cooling jacket so that the ratio is 50/50. The mixture was put into a Henschel mixer and mixed for 10 minutes while flowing cooling water through the jacket to obtain a rubbery polymer-containing material (C-1). The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

(Example 2) Production of rubbery polymer-containing material (C-2) The same as Example 1 except that the mixing ratio of the rubbery polymer (A) and the rubbery polymer (B) was 10/90. Thus, a rubbery polymer-containing material (C-2) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
(Example 3) Production of rubbery polymer-containing material (C-3) Same as Example 1 except that the mixing ratio of the rubbery polymer (A) and the rubbery polymer (B) was 30/70. Thus, a rubbery polymer-containing material (C-3) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
(Example 4) Production of rubbery polymer-containing material (C-4) The same as Example 1 except that the mixing ratio of the rubbery polymer (A) and the rubbery polymer (B) was 70/30. Thus, a rubbery polymer-containing material (C-4) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
(Example 5) Production of rubbery polymer-containing material (C-5) Same as Example 1 except that the mixing ratio of the rubbery polymer (A) and the rubbery polymer (B) was 90/10. Thus, a rubbery polymer-containing material (C-5) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

(Example 6) Production of rubbery polymer-containing material (C-6) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 97.5 parts of octamethylcyclotetrasiloxane were mixed, 100 parts of a siloxane mixture were obtained. 100 parts of a siloxane mixture is added to 200 parts of distilled water in which 0.67 parts of sodium dodecylbenzenesulfonate and 0.67 parts of dodecylbenzenesulfonic acid are dissolved, and the mixture is pre-stirred at 10,000 rpm with a homomixer, and then 200 kg / cm with a homogenizer. ^The mixture was emulsified and dispersed at a pressure of ² to obtain an organosiloxane emulsion. This was transferred to a separable flask equipped with a condenser and a stirring blade, heated at 80 ° C. for 5 hours with mixing and stirring, then allowed to stand at 20 ° C., and after 48 hours, the pH of the emulsion was adjusted to 7.0 with an aqueous sodium hydroxide solution. Thus, the polymerization was completed to obtain a latex containing polyorganosiloxane. The polymerization rate of the obtained polyorganosiloxane was 89.1%, and the average particle size of the polyorganosiloxane was 0.19 μm.
15 parts of this latex containing polyorganosiloxane was sampled as a solid, put into a separable flask equipped with a stirrer, added with 175 parts of distilled water, purged with nitrogen, heated to 50 ° C., and heated to n-butyl. A mixture of 73.4 parts acrylate, 1.6 parts allyl methacrylate and 0.3 parts tert-butyl hydroperoxide was charged and stirred for 30 minutes to allow the mixture to penetrate the polyorganosiloxane. Then, a mixture of 0.002 part of ferrous sulfate, 0.006 part of ethylenediaminetetraacetic acid disodium salt, 0.3 part of Rongalite and 10 parts of distilled water was charged to start radical polymerization, and then 2 at an internal temperature of 70 ° C. The polymerization was completed by maintaining for a while to obtain a latex of a polyorganosiloxane composite rubber-like polymer. A part of this latex was sampled and the average particle size of the polyorganosiloxane composite rubbery polymer was measured and found to be 0.22 μm.
A mixture of 10 parts of methyl methacrylate and 0.024 part of tert-butyl hydroperoxide was dropped into the latex containing the polyorganosiloxane composite rubber-like polymer at 60 ° C. for 15 minutes, and then 2 parts at 60 ° C. Holding for a time, the graft polymerization to the polyorganosiloxane composite rubber was completed. The polymerization rate of methyl methacrylate was 97.3%. The average particle size of the graft copolymer was 0.23 μm.

(Preparation of rubbery polymer (A))
The latex containing the graft copolymer is added at 40 ° C. so that the ratio of the calcium chloride aqueous solution having a concentration of 5% by mass is 1: 5, and then the temperature is raised to 90 ° C. to coagulate and washing with water. After repeating, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a rubbery polymer (A). The particle size distribution of the rubber polymer (A) powder was 71% by mass in the range of 50 to 150 μm and 10% by mass in the range of 200 to 500 μm.

(Preparation of rubbery polymer (B))
The latex containing the graft copolymer is added at 40 ° C. so that the ratio of the calcium chloride aqueous solution having a concentration of 5% by mass becomes 1: 2, and then the temperature is raised to 90 ° C. to coagulate and washed with water. After repeating, the solid content was separated and dried at 80 ° C. for 24 hours to obtain a rubbery polymer (B). The particle size distribution of the rubbery polymer (B) powder was 16% by mass in the range of 50 to 150 μm and 79% by mass in the range of 200 to 500 μm.

(Preparation of rubbery polymer-containing material (C-6))
The rubber polymer (A) and the rubber polymer (B) are put into a Henschel mixer equipped with a cooling jacket so that the ratio is 50/50, and mixed for 10 minutes while flowing cooling water through the jacket. A rubbery polymer-containing material (C-6) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

(Example 7) Production of rubbery polymer-containing material (C-7) 99.5 parts of 2-ethylhexyl acrylate and 0.5 parts of allyl methacrylate were mixed to obtain 100 parts of a (meth) acrylate monomer mixture. . As alkyl diphenyl ether sodium disulfonate, 100 parts of the above (meth) acrylate monomer mixture is added to 195 parts of distilled water in which 1 part of the registered trademark Perex SS-L commercially available from Kao Corporation is dissolved. After pre-stirring at 10,000 rpm with a mixer, it was emulsified and dispersed with a homogenizer at a pressure of 30 MPa to obtain a (meth) acrylate emulsion. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, heated with nitrogen substitution and mixed stirring, and when the temperature reached 50 ° C, 0.5 part of tert-butyl hydroperoxide was added, and the temperature was raised to 50 ° C. Then, a mixed solution of 0.002 part of ferrous sulfate, 0.006 part of disodium ethylenediaminetetraacetate, 0.26 part of Rongalite and 5 parts of distilled water was added and left for 5 hours to complete the polymerization and acrylic rubber. (AR1) component latex was obtained.
The polymerization rate of the obtained acrylic rubber (AR1) component latex was 99.5%. Further, 0.7 part of PELEX SS-L as a solid content was added to the obtained latex.
The acrylic rubber (AR1) component latex was collected to a solid content of 25 parts of poly 2 ethylhexyl acrylate containing allyl methacrylate, placed in a separable flask equipped with a stirrer, and the amount of distilled water in the system was 195 parts. Added to be. Next, a mixed liquid of 65 parts of n-butyl acrylate containing 2.0% of allyl methacrylate constituting the acrylic rubber (AR2) component and 0.32 part of tert-butyl hydroperoxide was charged and stirred for 10 minutes. The acrylic rubber (AR1) component particles were infiltrated. After further stirring for 10 minutes, the atmosphere was replaced with nitrogen, the temperature in the system was raised to 50 ° C., 0.002 part of ferrous sulfate, 0.006 part of ethylenediaminetetraacetic acid disodium salt, 0.26 part of Rongalite and distilled water. A polyalkyl (meth) acrylate system comprising an acrylic rubber (AR1) component and an acrylic rubber (AR2) component is prepared by charging 5 parts of the mixture and starting radical polymerization, and then maintaining the internal temperature at 70 ° C. for 2 hours to complete the polymerization. A latex (ARL1) of a composite rubbery polymer was obtained.
A mixed liquid of 0.06 part of tert-butyl hydroperoxide and 10 parts of methyl methacrylate was added dropwise to the polyalkyl (meth) acrylate composite rubber-like polymer latex (ARL1) at 70 ° C. over 15 minutes, and then 70 Holding at 4 ° C. for 4 hours, graft polymerization onto the polyalkyl (meth) acrylate composite rubber was completed. The polymerization rate of methyl methacrylate was 99.2%.
(Preparation of rubbery polymer (A))
The acrylic rubber-based graft copolymer latex was dropped into 200 parts of hot water containing 5% by weight of calcium acetate, coagulated, separated, washed and dried at 75 ° C. for 16 hours to obtain a rubbery polymer (A). . The particle size distribution of the rubber polymer (A) powder was 72% by mass in the range of 50 to 150 μm and 10% by mass in the range of 200 to 500 μm.
(Preparation of rubbery polymer (B))
The acrylic rubber-based graft copolymer latex is dropped into 200 parts of hot water of 1.5% by weight of calcium acetate, coagulated, separated, washed and dried at 75 ° C. for 16 hours to obtain a rubbery polymer (B). Obtained. The particle size distribution of the rubber polymer (B) powder was 16% by mass in the range of 50 to 150 μm and 82% by mass in the range of 200 to 500 μm.
(Preparation of rubbery polymer-containing material (C-7))
The rubber polymer (A) and the rubber polymer (B) are put into a Henschel mixer equipped with a cooling jacket so that the ratio is 50/50, and mixed for 10 minutes while flowing cooling water through the jacket. A rubbery polymer-containing material (C-7) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

(Comparative Example 1) Production of rubber polymer-containing material (D-1) Example 1 except that rubber polymer (B) in Example 1 was not used and only rubber polymer (A) was used. Similarly, a rubbery polymer-containing material (D-1) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
Comparative Example 2 Production of Rubber Polymer-Containing Material (D-2) Example 1 except that the rubber polymer (A) in Example 1 was not used and only the rubber polymer (B) was used. Similarly, a rubbery polymer-containing material (D-2) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
(Comparative Example 3) Production of Rubber Polymer-Containing Material (D-3) Example 6 except that only the rubber polymer (A) was used without using the rubber polymer (B) in Example 6. Similarly, a rubbery polymer-containing material (D-3) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

Comparative Example 4 Production of Rubber Polymer-Containing Material (D-4) Example 6 is the same as Example 6 except that the rubber polymer (A) in Example 6 is not used and only the rubber polymer (B) is used. Similarly, a rubbery polymer-containing material (D-4) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
(Comparative Example 5) Production of rubber polymer-containing material (D-5) Example 7 is the same as Example 7 except that the rubber polymer (B) in Example 7 is not used and only the rubber polymer (A) is used. Similarly, a rubbery polymer-containing material (D-5) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.
Comparative Example 6 Production of Rubber Polymer-Containing Material (D-6) Example 7 is the same as Example 7 except that the rubber polymer (A) in Example 7 is not used and only the rubber polymer (B) is used. Similarly, a rubbery polymer-containing material (D-6) was obtained. The powder characteristics of the obtained rubber polymer-containing material were evaluated. The results are shown in Table 1.

(Examples 8-18, Comparative Examples 7-16)
Using the thermoplastic resin and each rubber polymer-containing material obtained in the above Examples and Comparative Examples at the compounding ratios shown in Table 2, evaluation of Izod impact strength, sticking time, extrusion torque, and molded product surface appearance was performed. It was. The obtained results are shown in Table 2.
When the thermoplastic resin is polyvinyl chloride, 100 parts by mass of the polyvinyl chloride resin, 3 parts by mass of dioctyltin mercaptide as a stabilizer and a lubricant, 2 parts by mass of Metabrene P-551A (manufactured by Mitsubishi Rayon Co., Ltd.), 1 part by weight of METABLEN P-710 (manufactured by Mitsubishi Rayon Co., Ltd.) and a predetermined amount of each rubber polymer-containing material were mixed with a Henschel mixer for 10 minutes until 110 ° C. to obtain a vinyl chloride resin composition This was used for evaluation.

As shown in Table 1, it can be seen that the rubbery polymer-containing material of the present example is superior in powder flowability as compared with the comparative example.
In addition, as shown in Table 2, all the test pieces made of the thermoplastic resin composition of the examples have sufficient strength, and also the lubricity during molding and the surface of the obtained molded product. Excellent balance of appearance.

  The rubbery polymer-containing material of the present invention has excellent powder characteristics, and is blended to improve the characteristics of the thermoplastic resin, and the thermoplastic resin composition of the present invention thus obtained is It has excellent lubricity, has an excellent surface appearance and impact resistance, and is used for the production of various molded products.

Claims (2)

  50-150 μm powder particles and 200-500 μm powder particles are contained, the content of all particles occupied by 50-150 μm powder particles is 25% by mass or more, and 200-500 μm powder A rubbery polymer-containing material having a content of 15% by mass or more in all particles occupied by body particles.   A thermoplastic resin composition comprising the rubber polymer-containing material according to claim 1 blended with a thermoplastic resin.