JP2006312659A - Polymer powder, method for producing the same, thermoplastic resin composition, and molding of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer powder which can give a molding improved in impact resistance without detriment to color developability and having good handleability, to provide a method for producing the powder, to provide a thermoplastic resin composition capable of giving a molding excellent in impact resistance and color developability, and to provide a molding excellent in impact resistance and color developability. <P>SOLUTION: Use is made of a polymer powder prepared by mixing a latex containing a graft copolymer (A) having a glass transition temperature of 80°C or higher as measured on the outermost layer and having a volume-mean particle diameter of 500 to 1,000 nm with a latex containing an acrylic copolymer (B) having a volume-mean particle diameter equal to or smaller than 1/10 of that of the graft copolymer (A) in such a ratio that 0.5 to 5 pts.mass acrylic copolymer (B) is present per 100 pts.mass graft copolymer (A), coagulating the resultant latex, and recovering the coagulum. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer powder, a production method thereof, a thermoplastic resin composition containing the polymer powder, and a molded article.

  Molded products made of thermoplastic resins are widely used in various products such as automobiles, electrical / electronic devices, OA devices such as printers. These molded products are required to have impact resistance, color development, fluidity during molding, weather resistance, and the like. Therefore, an impact strength modifier is blended in the thermoplastic resin. However, when an impact strength modifier is blended, the balance between the impact resistance and color developability of the molded product often becomes a problem.

  Patent Publication 1 discloses that a number average particle diameter obtained by graft polymerization of a vinyl monomer on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate as an impact strength modifier is 300 to 2000 nm. The following silicone / acrylic composite rubber graft copolymers are disclosed. And by blending the graft copolymer, it is said that the impact resistance of the molded product is improved and the color developability is not lowered.

However, when such graft copolymer particles having a large particle diameter are collected as a powder from latex by a normal coagulation method, the fusion of the primary particles does not proceed sufficiently, so that a large amount of fine powder is contained. A powder is obtained. The powder containing a large amount of fine powder is remarkably poor in handleability, and the fine powder is scattered in the drying process, resulting in a decrease in the powder recovery rate.
JP 2004-359889 A

  The object of the present invention is to improve the impact resistance without deteriorating the color developability of the molded product, and to provide a polymer powder with good handleability, its production method; excellent impact resistance and color developability The object is to provide a thermoplastic resin composition capable of obtaining a molded article; and a molded article excellent in impact resistance and color development.

  The polymer powder of the present invention has a latex containing a graft copolymer (A) having an outermost layer glass transition temperature of 80 ° C. or higher and a volume average particle diameter of 500 to 1000 nm, and a volume average particle diameter. The latex containing the acrylic copolymer (B), which is 1/10 or less of the graft copolymer (A), and the acrylic copolymer (B) is 0 with respect to 100 parts by mass of the graft copolymer (A). It is mixed at a ratio of 5 to 5 parts by mass, solidified and recovered.

  The method for producing a polymer powder of the present invention comprises a latex containing a graft copolymer (A) having a glass transition temperature of an outermost layer of 80 ° C. or higher and a volume average particle diameter of 500 to 1000 nm, and a volume average A latex containing an acrylic copolymer (B) having a particle diameter of 1/10 or less of that of the graft copolymer (A), and an acrylic copolymer (B) with respect to 100 parts by mass of the graft copolymer (A). ) Is mixed at a ratio of 0.5 to 5 parts by mass, and then solidified and recovered.

The thermoplastic resin composition of the present invention contains 1 to 30 parts by mass of the polymer powder of the present invention and 99 to 70 parts by mass of the thermoplastic resin [however, the total of the polymer powder and the thermoplastic resin is 100. It is a mass part].
The molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention.

The polymer powder of the present invention can improve impact resistance without deteriorating the color developability of the molded product, and has good handleability.
According to the method for producing a polymer powder of the present invention, it is possible to obtain a polymer powder that can improve impact resistance without deteriorating the color developability of a molded product and has good handleability.
According to the thermoplastic resin composition of the present invention, a molded article excellent in impact resistance and color developability can be obtained.
The molded article of the present invention is excellent in impact resistance and color development.

<Graft copolymer (A)>
Examples of the graft copolymer (A) include a core / shell type graft copolymer.
Examples of the core portion include various rubber polymers. Examples of the rubbery polymer include composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate, acrylic rubber made of polyalkyl (methacrylate), and the like. Of these, a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate is preferable in that it has excellent low-temperature impact strength.

  As the shell portion, a one-layer structure formed by graft polymerization of a vinyl monomer on the core portion in one step, or a vinyl monomer in the presence of the graft polymer obtained in the previous step The thing of the multilayer structure formed by graft-polymerizing a body is mentioned. The shell part is formed by copolymerizing 90 to 100% by weight of methyl methacrylate and 0 to 10% by weight of other vinyl monomers, and has excellent thermal stability and compatibility with the thermoplastic resin. It is preferable at the point which is excellent in.

  The ratio of the core part to the shell part (core part / shell part) is preferably 50/50 to 80/20. If the core portion / shell portion is within this range, the balance between impact resistance and color developability when added to the thermoplastic resin will be good.

In the graft copolymer (A), the glass transition temperature of the outermost layer of the shell portion needs to be 80 ° C. or higher. When the glass transition temperature of the outermost layer is less than 80 ° C., the color developability of the molded product is lowered. The glass transition temperature of the outermost layer is obtained by the following Fox equation when the outermost layer is a copolymer composed of monomers a, b, c.
1 / Tg = ma / Tga + mb / Tgb + mc / Tgc +.
Tg: Tg [K] of copolymer, ma: mass fraction of monomer a, Tga: Tg [K] of homopolymer obtained from monomer a, mb: mass fraction of monomer b, Tgb: Tg [K] of the homopolymer obtained from the monomer b, mc: Mass fraction of the monomer c, Tgc: Tg [K] of the homopolymer obtained from the monomer c.

  The volume average particle diameter of the graft copolymer (A) is 500 to 1000 nm. By setting the volume average particle size of the graft copolymer (A) within this range, the balance between the impact resistance and the color developability of the molded product becomes good. In particular, when the volume of particles smaller than 300 nm is 20% or less of the total particle volume, the balance between impact resistance and color developability is further improved. The “volume average particle diameter” in the present invention is a value measured by a laser diffraction type particle size distribution measuring device (LA-910, manufactured by Horiba, Ltd.).

(Composite rubber-based graft copolymer)
Specific examples of the graft copolymer (A) include a composite rubber graft copolymer obtained by graft polymerization of a vinyl monomer to a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate. Can be mentioned.

  The content of the polyorganosiloxane is preferably 5 to 30% by mass and more preferably 5 to 15% by mass in the composite rubber-based graft copolymer (100% by mass). If the polyorganosiloxane content is less than 5% by mass, the impact resistance of the molded product may be insufficient. When the content of the polyorganosiloxane exceeds 30% by mass, the color developability of the molded product may be impaired.

  The content of the polyalkyl (meth) acrylate is adjusted so that the content of the composite rubber in the composite rubber-based graft copolymer is 50 to 80% by mass. From the viewpoint of balance.

  The content of the composite rubber is preferably 50 to 80% by mass and more preferably 60 to 75% by mass in the composite rubber-based graft copolymer (100% by mass). When the content of the composite rubber is less than 50% by mass, the impact resistance of the molded product may be insufficient. When the content of the composite rubber exceeds 80% by mass, the color developability (pigment colorability) of the molded product is lowered, and other excellent characteristics such as heat resistance tend to be lost.

(Composite rubber)
The composite rubber is a composite rubber having a structure in which 1 to 99% by mass of polyorganosiloxane and 99 to 1% by mass of polyalkyl (meth) acrylate are entangled with each other so that they cannot be separated.
The polyorganosiloxane is preferably a polyorganosiloxane containing a vinyl polymerizable functional group obtained by polymerizing dimethyl siloxane, a vinyl polymerizable functional group-containing siloxane, and, if necessary, a siloxane-based crosslinking agent.

  The vinyl polymerizable functional group-containing siloxane contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane through a siloxane bond. Considering the reactivity with dimethylsiloxane, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysilane such as γ-methacryloyloxypropylethoxydiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane; β-acryloyloxyethyldimethoxymethylsilane, γ-acryloyloxypropyldimethoxymethylsilane, γ-acryloyloxypropylmethoxy Dimethylsilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyl Butoxy diethyl silane, .gamma. acryloyloxypropyl ethoxymethyl diethoxymethylsilane, .delta. acryloyl acryloyloxy silanes such as oxy butyl diethoxy methyl silane. A vinyl polymerizable functional group containing siloxane may be used individually by 1 type, and may be used as a mixture of 2 or more types.

  Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

  As a method for producing polyorganosiloxane, a mixture of dimethylsiloxane and a vinyl polymerizable functional group-containing siloxane, or a mixture containing a siloxane-based crosslinking agent as necessary is emulsified with an emulsifier and water to form a latex. The latex is microparticulated using a homomixer that microparticulates with a shearing force generated by high-speed rotation or a homogenizer that microparticulates with a jet output from a high-pressure generator, and then polymerized at a high temperature with an acid catalyst. The method of summing is mentioned.

Examples of the method for adding the acid catalyst include a method in which an aqueous acid solution is mixed with a siloxane mixture, an emulsifier, and water; a method in which a latex in which a siloxane mixture has been finely divided is dropped into a hot acid aqueous solution at a constant rate. Considering the ease of control of the particle diameter of the polyorganosiloxane, a method of polymerizing by mixing an acid aqueous solution having no micelle forming ability with a siloxane mixture, an emulsifier and water is preferable.
Examples of the method of mixing the siloxane mixture, emulsifier, water and / or acid catalyst include a method of mixing by high-speed stirring, a method of mixing by a high-pressure emulsifier such as a homogenizer, and the like. A method using a homogenizer is a preferable method because the particle size distribution of the polyorganosiloxane latex becomes narrow.

As the emulsifier, an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate, sodium lauryl sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, and the like. In particular, sodium alkylbenzene sulfonate and sodium lauryl sulfate are preferable.
Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. An acid catalyst may be used individually by 1 type, and may be used in combination of 2 or more type. Of these, mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid are preferred. When a mineral acid having no micelle forming ability is used, the particle size distribution of the polyorganosiloxane latex can be narrowed, and the appearance defect of the molded product due to the emulsifier component of the polyorganosiloxane latex can be reduced.

  The volume average particle diameter of the polyorganosiloxane is preferably 200 to 1000 nm, and more preferably 250 to 500 nm. When the volume average particle diameter of the polyorganosiloxane is less than 200 nm, the amount of polyalkyl (meth) acrylate necessary for obtaining the composite rubber increases, and thus impact resistance may be impaired. When the volume average particle diameter of the polyorganosiloxane exceeds 1000 nm, the appearance and impact resistance of the molded product may be deteriorated.

The polyalkyl (meth) acrylate is a polymer of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate.
The polyalkyl (meth) acrylate is formed by impregnating a polyorganosiloxane latex with an alkyl (meth) acrylate component composed of an alkyl (meth) acrylate and a polyfunctional alkyl (meth) acrylate, and then polymerizing it. .

  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; alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Methacrylate is mentioned. An alkyl (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type. Considering the impact resistance and molding gloss of the molded product, alkyl acrylates having an alkyl group having 1 to 8 carbon atoms are preferred, and n-butyl acrylate is particularly preferred.

  Examples of the polyfunctional alkyl (meth) acrylate include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, Examples include allyl isocyanurate. A polyfunctional alkyl (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

The composite rubber is produced by adding an alkyl (meth) acrylate component to a polyorganosiloxane latex and polymerizing it with the action of a normal radical polymerization initiator.
Examples of the method for adding alkyl (meth) acrylate include a method in which polyorganosiloxane latex and alkyl (meth) acrylate are mixed together; a method in which alkyl (meth) acrylate is dropped into polyorganosiloxane latex at a constant rate. .
Examples of radical polymerization initiators include peroxides, azo initiators, and redox initiators in which an oxidizing agent / reducing agent is combined. Among these, a redox initiator is preferable, and a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide is particularly preferable.

(Vinyl monomer)
Examples of vinyl monomers include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate, and butyl. Examples include acrylic acid esters such as acrylates; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. A vinyl monomer may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable to use methyl methacrylate as a main component of the shell portion, and it is preferable to use 90 to 100% by mass of methyl methacrylate and alkyl acrylate in combination with the heat stability during the molding process of the thermoplastic resin composition. It is further preferable from the point. The vinyl-based monomer needs to be selected so that the glass transition temperature of the outermost layer of the shell portion is 80 ° C. or higher.

<Acrylic copolymer (B)>
Examples of the acrylic copolymer (B) include copolymers of alkyl (meth) acrylates.
Examples of the alkyl (meth) acrylate include methyl methacrylate, ethyl methacrylate, normal propyl methacrylate, isopropyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate and the like; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate Alkyl acrylates such as pentyl acrylate, hexyl acrylate, heptyl acrylate and octyl acrylate; aromatic alkenyl compounds such as styrene and α-methylstyrene.

  It is preferable that the glass transition temperature of an acrylic copolymer (B) is 20 degrees C or less. When the glass transition temperature of the acrylic copolymer (B) exceeds 20 ° C., in order to reduce the proportion of fine powder in the polymer powder, the graft copolymer (A) latex and the acrylic copolymer (B) latex The effect of adding the acrylic copolymer (B) becomes small, for example, it becomes necessary to increase the temperature at the time of mixing and solidifying, making it difficult to produce polymer powder with ordinary solidification equipment. The glass transition temperature of the acrylic copolymer (B) is determined by the above-mentioned Fox.

  The volume average particle size of the acrylic copolymer (B) needs to be 1/10 or less of the graft copolymer (A). When the volume average particle diameter of the acrylic copolymer (B) is larger than this range, the graft copolymer (A) latex and the acrylic copolymer (B) latex are mixed and coagulated to sufficiently In order to make it fuse | melt, it is necessary to increase the addition amount of an acrylic copolymer (B), and the impact resistance of a molded article will not fully express.

The acrylic copolymer (B) is produced by subjecting an alkyl (meth) acrylate to emulsion polymerization by allowing a radical polymerization initiator to act in the presence of an emulsifier.
As the emulsifier, an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. In particular, sodium alkylbenzene sulfonate is preferable because the volume average particle diameter can be reduced with a small addition amount.

  As for the addition amount of an emulsifier, 0.5-5 mass parts is preferable with respect to 100 mass parts of acrylic copolymers (B). When the addition amount of the emulsifier is less than 0.5 parts by mass, it is difficult to make the volume average particle diameter of the acrylic copolymer (B) within the target range. When the added amount of the emulsifier exceeds 5 parts by mass, it is possible to reduce the volume average particle diameter, but a large amount of the emulsifier remains in the obtained polymer powder, resulting from decomposition of the remaining emulsifier. There is a risk of causing poor appearance of the molded product.

  Examples of radical polymerization initiators include peroxides, azo initiators, redox initiators combined with oxidizing agents and reducing agents, and the like. Among these, a redox initiator is preferable, and a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide is particularly preferable.

<Polymer powder>
The polymer powder of the present invention comprises a latex containing a graft copolymer (A) and a latex containing an acrylic copolymer (B) in an acrylic copolymer with respect to 100 parts by mass of the graft copolymer (A). The polymer (B) is mixed at a ratio of 0.5 to 5 parts by mass, solidified and recovered.
The amount of the acrylic copolymer (B) is 0.5 to 5 parts by mass with respect to 100 parts by mass of the graft copolymer (A). By setting the content of the acrylic copolymer (B) within this range, it is possible to obtain a powder with good handling properties with less generation of fine powder without impairing the characteristics as the graft copolymer (B). .

<Method for producing polymer powder>
The polymer powder of the present invention comprises a latex containing a graft copolymer (A) and a latex containing an acrylic copolymer (B) in an acrylic copolymer with respect to 100 parts by mass of the graft copolymer (A). After the polymer (B) is mixed at a ratio of 0.5 to 5 parts by mass, it is solidified by adding a coagulant and recovered.

When a coagulant is added to the latex containing only the graft copolymer (A), the content of fine powder is increased, and a polymer powder with extremely poor handling properties can be obtained.
Further, when the acrylic copolymer (B) is added after the coagulant is added to the latex of the graft copolymer (A) and coagulated, there is a high possibility that only the acrylic copolymer (B) is aggregated. Become. Therefore, it is necessary to increase the addition amount of the acrylic copolymer (B) in order to sufficiently fuse the graft copolymer (A), and it is difficult for the molded product to exhibit sufficient impact resistance. Become.

  Examples of the coagulant include polyvalent metal salts. Examples of the polyvalent metal salt include halides, sulfates, acetates, etc., such as magnesium, calcium, aluminum, and zinc. Of these, calcium acetate has a low reactivity of the product after reacting with an alkylbenzene sulfonic acid emulsifier which is an emulsifier used in the production of the graft copolymer (A) and the acrylic copolymer (B), This is preferable because generation of decomposition gas hardly occurs when the thermoplastic resin composition is molded.

  When the graft copolymer (A) latex and the acrylic copolymer (B) latex are mixed and the polymer powder is solidified and collected, a plurality of tanks are usually used. In order to obtain a polymer powder (C) having a uniform and desired particle size, the slurry concentration, the amount of coagulant added, the temperature, the stirring rotation speed, and the residence time of the polymer in each tank are appropriately controlled.

  The latex is preferably supplied so that the slurry concentration (solid content) of each layer is in the range of 5 to 20% by mass. When the slurry concentration is less than 5% by mass, not only the productivity is deteriorated, but also the fine powder in the polymer powder may be increased. When the slurry concentration exceeds 20% by mass, the viscosity of the slurry in which latex is agglomerated becomes remarkably high, which may make stirring difficult.

  The addition amount of the coagulant is preferably 0.5 to 10 parts by mass in terms of solid content with respect to 100 parts by mass of the mixture (solid content) of the graft copolymer (A) and the acrylic copolymer (B). . If the addition amount of the coagulant is less than 0.5 parts by mass, the aggregation may not be completed and the yield may be reduced. When the addition amount of the coagulant exceeds 10 parts by mass, the amount of the metal salt remaining in the polymer powder increases, so that when the thermoplastic resin composition is molded, the decomposition easily proceeds, and the molded appearance There is a risk of causing problems such as deterioration.

The temperature and stirring conditions of each tank will be described for equipment divided into three tanks.
The first tank is a tank in which a coagulant is added to latex. The temperature of the first tank is preferably 40 to 70 ° C. When the temperature of the first tank is less than 40 ° C., when the polymer is agglomerated into a slurry, the particle size becomes too small, so that stirring becomes difficult, and furthermore, the proportion of fine powder in the polymer powder is There is a possibility that it becomes high and the handling property is deteriorated. When the temperature of the first tank exceeds 80 ° C., the particle diameter when it becomes a slurry becomes too large, so it takes a long time to dry the polymer powder, and further, a metal salt used as a coagulant. Is not sufficiently washed away, it may cause decomposition when the thermoplastic resin composition is molded.

  The second tank controls the particle diameter of the slurry obtained in the first tank uniformly and serves as a preheating tank before being sent to the third tank. As for the temperature of a 2nd tank, the temperature of a 1st tank + 10-30 degreeC is preferable. If the temperature of the second tank is less than the temperature of the first tank + 10 ° C., it becomes difficult to sufficiently raise the temperature of the slurry sent to the third tank, and the fusion does not proceed sufficiently, and the polymer powder There is a possibility that the ratio of fine powder in the inside becomes high. When the temperature of the second tank exceeds the temperature of the first tank + 30 ° C., the fusion proceeds sufficiently, but a polymer powder in which fine powder and coarse powder are mixed is obtained. It may be difficult to obtain.

<Thermoplastic resin>
Examples of the thermoplastic resin include almost all thermoplastic resins that are generally known. Specific examples of the thermoplastic resin include a vinyl chloride resin (PVC), a chlorinated polyethylene resin, a chlorinated vinyl chloride resin, a vinylidene chloride resin and the like, a hard, semi-rigid, and soft chlorine-containing resin; polypropylene (PP), Olefin resins such as polyethylene (PE); polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate-styrene copolymer (MS), styrene-acrylonitrile copolymer (SAN), styrene-maleic anhydride Copolymer (SMA), styrene resin (St resin) such as acrylonitrile-butadiene-styrene resin (ABS), acrylate-styrene-acrylonitrile resin (ASA), acrylonitrile-ethylenepropylene rubber-styrene resin (AES); poly Methyl methacrylate (PM A) acrylic resins (Ac resins); polycarbonate resins (PC resins); polyamide resins (PA resins); polyester resins (PEs) such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) Resin); polylactic acid resin, thermoplastic polyvinyl alcohol resin, polybutylene succinate, other biodegradable natural raw materials, petroleum-derived environmentally friendly resins (biodegradable resins); (modified) polyphenylene ether resins ( PPE resin), polyoxymethylene resin (POM resin), polysulfone resin (PSO resin), polyarylate resin (PAr resin), polyphenylene resin (PPS resin), thermoplastic polyurethane resin Engineering plastics such as (PU resin); Thermoplastic elastomers (TPE) such as olefin elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, fluorine elastomers, 1,2-polybutadiene, trans 1,4-polyisoprene; PC resin such as PC / ABS / St resin alloy, PVC resin such as PVC / ABS / St resin alloy, PA resin such as PA / ABS / St resin alloy, PA resin / TPE alloy, PA / Alloys between PA-based resins such as PP / polyolefin-based resin alloys, PBT-based resins / TPE, PC-based resins such as PC / PBT / PEs-based resin alloys, polyolefin-based resins / TPE, olefin-based resins such as PP / PE , PPE / HIPS, PPE / PBT, PPE Polymer alloys such as PPE resin alloys such as / PA, PVC resins such as PVC / PMMA / Ac resin alloys, and the like. A thermoplastic resin may be used individually by 1 type, and may use 2 or more types together. Further, a compatibilizing agent such as a graft copolymer may be used in combination.

<Thermoplastic resin composition>
The thermoplastic resin composition of the present invention contains 1 to 30 parts by mass of the polymer powder of the present invention and 99 to 70 parts by mass of the thermoplastic resin [however, the total of the polymer powder and the thermoplastic resin is 100. It is part by mass]. When the polymer powder is less than 1 part by mass, the impact resistance of the molded product is not sufficiently exhibited. When the polymer powder exceeds 30 parts by mass, the original properties of the thermoplastic resin may be impaired, and the impact resistance and appearance of the molded product tend to be reduced.

  In the thermoplastic resin composition of the present invention, colorants such as pigments and dyes; reinforcing agents or fillers such as glass fibers, metal fibers, metal flakes, and carbon fibers; -Phenolic antioxidants such as di-butyl-4-methylphenol, 4,4'-butylidene-bis (3-methyl-6-t-butylphenol); tris (mixed, mono or dinylphenyl) phosphite, diphenyl Phosphite antioxidants such as isodecyl phosphite; sulfur antioxidants such as dilauryl thiodipropionate and dimyristyl thiodipropionate diasterial thiodipropionate; 2-hydroxy-4-octoxybenzophenone Benzotriazole purple such as 2- (2-hydroxy-5-methylphenyl) benzotriazole Light absorbers; light stabilizers such as bis (2,2,6,6) -tetramethyl-4-piperidinyl); antistatic agents such as hydroxylalkylamines and sulfonates; ethylene bisstearylamide, metal soaps, etc. Lubricant: Add various additives such as tetrabromphenol A, decabromophenol oxide, TBA epoxy oligomer, TBA polycarbonate oligomer, antimony trioxide, TPP, phosphate ester and other flame retardants, and adjust to the desired physical properties. Also good.

  The thermoplastic resin composition of the present invention is preferably prepared by a melt mixing method. Moreover, you may use a small amount of solvent as needed. Examples of the apparatus to be used include an extruder, a Banbury mixer, a roller, and a kneader. These are operated batchwise or continuously. The mixing order of the components is not particularly limited. The thermoplastic resin composition thus prepared may be processed into a pellet form.

<Molded product>
The molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention. Examples of the molding method include known molding methods such as injection molding, extrusion molding, and roll molding.
The molded article of the present invention is widely used for applications that require impact resistance, such as building materials, automobiles, toys, stationery and other miscellaneous goods, OA equipment, and home appliances.

  Hereinafter, the present invention will be described by way of examples. In this embodiment, “part” and “%” mean “part by mass” and “% by mass” unless otherwise specified.

(Volume average particle diameter)
The volume average particle diameters of the graft copolymer (A) and the acrylic copolymer (B) in the latex in the reference example were measured using a laser diffraction type particle size distribution analyzer (LA910, manufactured by Horiba, Ltd.). .

(Glass-transition temperature)
The glass transition temperature of the outermost layer of the graft copolymer (A) and the acrylic copolymer (B) was calculated by the Fox equation using the glass transition temperature values in the fifth edition polymer handbook.

(Fusion strength)
The fusion strength of the polymer powder in the examples was measured as follows.
The polymer powder obtained by the coagulation operation was put into a laser diffraction particle size distribution measuring apparatus (LA910, manufactured by Horiba, Ltd.) together with distilled water containing 0.1% of a surfactant, and the particle size distribution was measured. Then, after irradiating with ultrasonic waves at an intensity of 40 W for 5 minutes, the particle size distribution was measured again. From the respective particle size distributions, the ratio of particles having a particle size of 10 μm or less was calculated on a volume basis and indicated as the fusion strength of the polymer powder.

(Izod impact strength)
The Izod impact strength of the molded product was measured by the method of ASTM D258.
(Pigment coloring)
The pigment colorability (color developability) of the molded product was evaluated by comparing L * values obtained by measuring according to JIS Z 8729 (L * a * b * object color display method). .

[Reference Example 1]
Production of polyorganosiloxane latex (L-1):
To 100 parts of octamethylcyclotetrasiloxane, 2 parts of tetraethoxysilane and 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane were mixed to obtain a siloxane-based mixture. To this was added 150 parts of distilled water in which 1.00 part of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm for 5 minutes with a homomixer, and then passed twice through a homogenizer at a pressure of 20 MPa to provide a stable premixed organosiloxane. An emulsion was obtained.

The above emulsion was placed in a separable flask equipped with a cooling condenser, and a mixture of 0.20 parts of sulfuric acid and 31.8 parts of distilled water was added over 3 minutes.
The emulsion was maintained at 80 ° C. for 7 hours and then cooled. Subsequently, this reaction product was kept at room temperature for 12 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex (L-1).
A part of the polyorganosiloxane latex was dried at 180 ° C. for 30 minutes and the solid content was determined to be 32.1%. The volume average particle diameter of the polyorganosiloxane in this latex was 384 nm.

[Reference Example 2]
Production of graft copolymer (A-1):
After collecting 31.15 parts of polyorganosiloxane latex (L-1) (10.0 parts in terms of solid content) in a separable flask and adding and mixing 200 parts of distilled water, n-butyl acrylate (BA) 59 A mixture of 0.1 part, 0.9 part allyl methacrylate (AMA) and 0.24 part tertiary butyl hydroperoxide was added.
The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the temperature was raised to 50 ° C. When the liquid temperature reached 50 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of distilled water was added, and radicals were added. Polymerization was started. In order to complete the polymerization of butyl acrylate, this state was maintained for 1 hour to obtain a latex of a composite rubber of polyorganosiloxane and polybutyl acrylate.

  After the liquid temperature of this latex dropped to 65 ° C., a mixture of 28.5 parts of methyl methacrylate (MMA), 1.5 parts of BA, and 0.21 part of tertiary butyl hydroperoxide was added dropwise over 1 hour for polymerization. It was. After completion of the dropping, the temperature was kept at 60 ° C. or higher for 1 hour, followed by cooling to obtain a latex of graft copolymer (A-1) in which methyl methacrylate and n-butyl acrylate were graft-polymerized on the composite rubber. Table 1 shows the glass transition temperature and volume average particle diameter of the outermost layer.

[Reference Example 3]
Production of graft copolymer (A′-2):
A latex of graft copolymer (A′-2) was obtained in the same manner as in Reference Example 2, except that the amounts of MMA and BA to be graft-polymerized on the composite rubber were changed to the amounts shown in Table 1. Table 1 shows the glass transition temperature and volume average particle diameter of the outermost layer.

[Reference Example 4]
Production of acrylic copolymer (B-1):
A separable flask equipped with a cooling condenser was charged with 50 parts of MMA, 50 parts of BA, 0.5 part of tertiary butyl hydroperoxide, 2 parts of sodium dodecylbenzenesulfonate, and 192 parts of distilled water and stirred for 1 hour under a nitrogen stream. Thereafter, the temperature was raised to 50 ° C.
When the liquid temperature reaches 50 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite are dissolved in 30 parts of distilled water is added, and radicals are added. Polymerization was started. After completion of the polymerization, the reaction was held for 1 hour to complete the radical polymerization to obtain an acrylic copolymer (B-1) latex. Table 2 shows the glass transition temperature and the volume average particle diameter.

[Reference Example 5]
Production of acrylic copolymer (B′-2):
An acrylic copolymer (B′-2) latex was obtained in the same manner as in Reference Example 4 except that the amount of sodium dodecylbenzenesulfonate was changed to the amount shown in Table 2. Table 2 shows the glass transition temperature and the volume average particle diameter.

[Reference Example 6]
Production of acrylic copolymer (B′-3):
A latex of an acrylic copolymer (B′-3) was obtained in the same manner as in Reference Example 5 except that the amounts of MMA and BA were changed to the amounts shown in Table 2. Table 2 shows the glass transition temperature and the volume average particle diameter.

[Example 1]
Production of polymer powder (C-1):
After mixing the graft copolymer (A-1) latex (100 parts, solid content conversion) and the acrylic copolymer (B-1) latex (2 parts, solid content conversion), a 1.5% calcium acetate aqueous solution The mixture was added to a 60 ° C. stirring tank containing 100 parts over 10 minutes to cause coagulation. Subsequently, the temperature was raised to 95 ° C., and stirring was further continued for 10 minutes to complete solidification. The solidified product was separated using a filter cloth, washed thoroughly with water, and dried with a dryer at 70 ° C. for 12 hours to obtain a polymer powder (C-1) by blending operation. Table 3 shows the particle morphology and fusion strength.

[Comparative Example 1]
Production of polymer powder (C′-2):
After the graft copolymer (A-1) latex (100 parts, solid content conversion) was added to a 90-95 ° C. stirring tank containing 1.5% calcium acetate solution over 10 minutes and coagulated Acrylic copolymer (B-1) latex (2 parts, solid content conversion) was added. Subsequently, the temperature was raised to 95 ° C., and stirring was further continued for 10 minutes to complete solidification. The solidified product was separated using a filter cloth, washed thoroughly with water, and dried for 12 hours in a dryer at 70 ° C. to obtain a polymer powder (C′-2) by post-addition operation. Table 3 shows the particle morphology and fusion strength.

[Comparative Example 2]
Production of polymer powder (C′-3):
Polymer by blending operation in the same manner as in Example 1 except that the acrylic copolymer (B-1) latex was changed to acrylic copolymer (B′-2) latex and the coagulation temperature was changed to 70 ° C. A powder (C′-3) was obtained. Table 3 shows the particle morphology and fusion strength.

[Comparative Example 3]
Production of polymer powder (C′-4):
A polymer powder (C′-4) is obtained by a post-addition operation in the same manner as in Comparative Example 1, except that the acrylic copolymer (B-1) latex is changed to an acrylic copolymer (B′-2) latex. It was. Table 3 shows the particle morphology and fusion strength.

[Comparative Example 4]
Production of polymer powder (C′-5):
A polymer powder (C) was prepared in the same manner as in Example 1 except that the acrylic copolymer (B-1) latex was changed to an acrylic copolymer (B′-3) latex and the coagulation temperature was changed to 80 ° C. It was tried to obtain '-5), but it did not solidify even when the solidification temperature was 100 ° C or higher. Table 3 shows the particle morphology and fusion strength.

[Comparative Example 5]
Production of polymer powder (C′-6):
The graft copolymer (A-1) latex was changed to the graft copolymer (A'-2) latex, and the acrylic copolymer (B-1) latex was changed to the acrylic copolymer (B'-3) latex. The polymer powder (C′-6) was obtained by the post-addition operation in the same manner as in Comparative Example 1 except that the coagulation temperature was changed to 50 to 60 ° C. and the solidification temperature was changed to 70 to 75 ° C. . Table 3 shows the particle morphology and fusion strength.

[Example 2]
5 parts of polymer powder (C-1), 95 parts of polycarbonate (Teflon FN1700A, manufactured by Idemitsu Petroleum Co., Ltd.) and 0.1 part of carbon black were mixed and mixed for 4 minutes with a Henschel mixer, and then 30 mmΦ It was melt-kneaded with a shaft extruder and shaped into a pellet to obtain a thermoplastic resin composition. Further, a 1/4 inch Izod test piece and a 10 cm square flat plate were obtained by injection molding, and used for evaluation of Izod impact strength and pigment colorability.

[Comparative Example 6]
A 1/4 inch Izod test piece and a 10 cm square flat plate were obtained in the same manner as in Example 2 except that the polymer powder (C-1) was changed to the polymer powder (C′-4), and the Izod impact strength was obtained. And used for evaluation of pigment colorability.

[Comparative Example 7]
A 1/4 inch Izod test piece and a 10 cm square plate were obtained in the same manner as in Example 2 except that the polymer powder (C-1) was changed to the polymer powder (C′-6), and the Izod impact strength was obtained. And used for evaluation of pigment colorability.

  As is clear from the results of Tables 3 and 4, the polymer powder of the present invention is a polymer powder that has a high fusion strength, and that is less likely to generate fine powder and has good handleability. The molded product used had a low L * value obtained by hue measurement and exhibited excellent pigment colorability. Also, the mechanical properties were excellent.

Molded articles made of the thermoplastic resin composition containing the polymerizable powder of the present invention have a good balance between impact resistance and color developability, such as building materials, automobiles, toys, stationery and other miscellaneous goods, OA equipment, and home appliances. It is widely used for applications that require impact resistance such as.

Claims (4)

  A latex containing a graft copolymer (A) having an outermost layer glass transition temperature of 80 ° C. or higher and a volume average particle diameter of 500 to 1000 nm, and a volume average particle diameter of the graft copolymer (A); The latex containing the acrylic copolymer (B) that is 1/10 or less is 0.5 to 5 parts by mass of the acrylic copolymer (B) with respect to 100 parts by mass of the graft copolymer (A). Polymer powder mixed, coagulated and recovered at a ratio.   A latex containing a graft copolymer (A) having an outermost layer glass transition temperature of 80 ° C. or higher and a volume average particle diameter of 500 to 1000 nm, and a volume average particle diameter of the graft copolymer (A); The latex containing the acrylic copolymer (B) that is 1/10 or less is 0.5 to 5 parts by mass of the acrylic copolymer (B) with respect to 100 parts by mass of the graft copolymer (A). A method for producing a polymer powder, characterized by solidifying and collecting after mixing at a ratio. 1 to 30 parts by mass of the polymer powder according to claim 1;
99 to 70 parts by mass of a thermoplastic resin [however, the total of the polymer powder and the thermoplastic resin is 100 parts by mass]. A molded article formed by molding the thermoplastic resin composition according to claim 3.