JP2018090692A - Rubber-containing graft polymer, thermoplastic resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an impact strength modifier for improving impact resistance of a resin with a small amount of addition, and to provide a thermoplastic resin composition and a thermoplastic resin molding excellent in impact resistance.SOLUTION: A rubber-containing graft polymer is obtained by graft polymerization of a graft part (B) containing one or two or more vinyl-based monomer units as a main component with a polyorganosiloxane/polyalkyl (meth)acrylate-based composite rubber (A), where the total amount of a crosslinking agent and a graft crosslinking agent used during polyalkyl (meth)arylate polymerization in the composite rubber (A) is within a range of 0.1-1.2 pts.mass with respect to 100 pts.mass of the used alkyl(meth)acrylate monomer, and a polyorganosiloxane content in the rubber-containing graft polymer is within a range of 0.25-9.7 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a rubber-containing graft polymer that exhibits high impact resistance when added to a thermoplastic resin. The present invention also relates to a thermoplastic resin composition comprising the rubber-containing graft polymer and another thermoplastic resin, and a molded product thereof.

  Some thermoplastic resins have insufficient impact resistance, and various impact strength modifiers are added. For example, as an impact strength modifier used by adding to a vinyl chloride resin, MBS resin obtained by graft polymerization of methyl methacrylate, styrene, acrylonitrile or the like to a butadiene-based rubber-like polymer can be mentioned. However, when MBS modifier is mixed with a thermoplastic resin, the impact resistance is improved, but the weather resistance may decrease. When the molded product is used outdoors, the impact resistance decreases. There is. It is considered that the main cause of the decrease in impact resistance due to this weather resistance is based on the ultraviolet degradation of the butadiene units constituting the MBS resin.

Therefore, methyl methacrylate, styrene or acrylonitrile is grafted onto a crosslinked alkyl (meth) acrylate rubber polymer comprising an alkyl (meth) acrylate and a crosslinking agent, thereby improving the weather resistance of the MBS resin and impact resistance. There is a method of providing (Patent Document 1).
There are also many known techniques for improving the impact resistance of general-purpose thermoplastic resins such as methacrylic resins, polystyrene resins, acrylonitrile / styrene resins, and polycarbonate.
An impact strength modifier obtained by grafting a vinyl monomer to a polyorganosiloxane / acrylic composite rubber has also been proposed (Patent Documents 2 to 4).
In addition, not only impact resistance such as vinyl chloride resin, but also the requirement to improve workability such as gelation speed, it is possible to achieve both impact resistance and workability with a polymer that satisfies specific conditions. It has been proposed (patent documents 5 and 6).

Japanese Patent Publication No. 51-28117 Japanese Patent No. 2608439 Japanese Patent No. 2608469 Japanese Patent No. 3142686 JP-A-7-286016 JP-A-7-286017

  However, even with the above-described method, it has not been possible to obtain impact resistance that gives a resin composition having a sufficiently excellent balance of physical properties. An object of this invention is to provide the impact strength modifier which improves the impact resistance of resin by small amount addition. Another object of the present invention is to provide a thermoplastic resin composition and a thermoplastic resin molded article excellent in impact resistance.

The present invention
[1] A graft part (B) mainly composed of one or more vinyl monomer units is graft-polymerized on the polyorganosiloxane / polyalkyl (meth) acrylate composite rubber (A). 100 parts by mass of the alkyl (meth) acrylate monomer to be used is a rubber-containing graft polymer in which the total amount of the crosslinking agent and grafting agent used in the polymerization of the polyalkyl (meth) acrylate in the composite rubber (A) Rubber-containing graft having a polyorganosiloxane content in the rubber-containing graft polymer in the range of 0.25 to 9.7% by weight based on 0.1 to 1.2 parts by weight of the rubber. Polymer.
[2] A thermoplastic resin composition comprising the rubber-containing graft polymer according to [1] and another thermoplastic resin.
[3] A molded product obtained by molding the thermoplastic resin composition according to [2].
About.

  According to the present invention, an impact strength modifier that improves the impact resistance of a resin by adding a small amount can be obtained. Moreover, according to this invention, the thermoplastic resin composition and thermoplastic resin molding which are excellent in impact resistance are obtained.

  In the graft copolymer of the present invention, a polyorganosiloxane / polyalkyl (meth) acrylate composite rubber (A) is used.

  For example, forced emulsion polymerization is preferred as a method for producing polyorganosiloxane. For example, a latex obtained by emulsifying a siloxane-based mixture containing an organosiloxane and a graft-crossing agent and, if necessary, a siloxane-based crosslinking agent with an emulsifier and water is sheared by high-speed rotation. Use a homomixer that produces fine particles by force or a homogenizer that produces fine particles using a jet generated by a high-pressure generator, then polymerize at high temperature using an acid catalyst, and then neutralize the acid with an alkaline substance. . As a method for adding an acid catalyst used for polymerization, a method of mixing with a siloxane mixture, an emulsifier and water is preferable, but as a more preferable manufacturing method, a forced emulsification step is used and a reaction is performed when a polyorganosiloxane latex is manufactured. After the catalyst is introduced into the raw material system, the forced emulsification step is performed at the same time as the temperature is raised, and the pre-emulsifier and the forced emulsifier capable of generating a pressure of 5 MPa or more are used to achieve the desired particle size distribution. Can be obtained.

As the organosiloxane used for the polymerization of the polyorganosiloxane, dimethylsiloxane (DMC) is used as a main raw material, and examples thereof include a dimethylsiloxane-based cyclic body having 3 or more members, and a 3 to 7 members are preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These may be used alone or in combination of two or more. Organosiloxane is cyclic organosiloxane oligomer, trimer 1-10% by weight, tetramer 30-95% by weight, 5mer 5-40% by weight, hexamer or more from 0-10% by weight. It is preferable to use what makes the oligomer mixture which becomes a raw material.

  As the graft crossing agent, a vinyl polymerizable functional group-containing siloxane can be used. Vinyl-polymerizable functional group-containing siloxane contains vinyl-polymerizable functional groups and can be bonded to dimethylsiloxane via a siloxane bond, and various kinds of vinyl-polymerizable functional groups containing vinyl polymerizable functional groups are considered in consideration of reactivity with dimethylsiloxane. Alkoxysilane compounds are preferred. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, methacryloyloxysilane such as γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; vinylphenylsilane such as p-vinylphenyldimethoxymethylsilane Mercapto such as γ-mercaptopropyldimethoxymethylsilane and γ-mercaptopropyltrimethoxysilane; Or the like can be used Rokisan. In addition, these vinyl polymerizable functional group containing siloxane can be used individually or in mixture of 2 or more types.

  A siloxane crosslinking agent can be used as the crosslinking agent. Specifically, trifunctional or tetrafunctional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and the like can be used.

  As the emulsifier used in the production of the polyorganosiloxane, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzenesulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. Particularly preferred are sodium alkylbenzene sulfonate and sodium lauryl sulfate. The method of mixing the siloxane mixture, the emulsifier, water and / or the acid catalyst includes mixing by high-speed stirring, mixing by a high-pressure emulsifier such as a homogenizer, etc., but using a preliminary emulsifier such as an in-line mixer and 5 MPa or more. A method using a device such as a homogenizer capable of generating the pressure is preferable because the particle size distribution of the polyorganosiloxane latex can be controlled to a desired distribution.

  Examples of the acid catalyst used for the polymerization of polyorganosiloxane include aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid and sulfonic acids containing aromatics, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. It is done. These acid catalysts may be used alone or in combination of two or more. Of these, aliphatic-substituted benzenesulfonic acid is preferable, and n-dodecylbenzenesulfonic acid is particularly preferable because it is excellent in stabilizing action of the polyorganosiloxane latex. Moreover, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the appearance defect of the resin composition due to the emulsifier component of the polyorganosiloxane latex can be reduced.

  The polymerization temperature when polymerizing the polyorganosiloxane is preferably 50 ° C. or higher, more preferably 80 ° C. or higher. When raising the temperature to such a desired temperature, as described above, forced emulsification is preferably performed simultaneously. The polymerization time of the polyorganosiloxane is 2 hours or more after reaching the desired temperature, more preferably 5 hours or more when the acid catalyst is mixed with the siloxane mixture, emulsifier and water and polymerized by atomization. In the case of dropping the latex in which the siloxane mixture is finely divided into the aqueous solution of the acid catalyst, it is preferable to hold for about 1 hour after the end of dropping of the latex. The polymerization can be stopped by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as caustic soda, caustic potash or sodium carbonate.

  Examples of the alkyl (meth) acrylate used in the composite rubber (A) of the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, ethoxyethoxyethyl acrylate, and methoxytripropylene glycol acrylate. 4-hydroxybutyl acrylate, lauryl methacrylate, stearyl methacrylate and the like. These alkyl (meth) acrylates are used alone or in combination of two or more. Further, in this monomer, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl monomers other than alkyl (meth) acrylates such as methacrylic acid-modified silicone and fluorine-containing vinyl compounds are 30% by mass or less. You may contain as a copolymerization component in the range.

  In the polymerization of the alkyl (meth) acrylate, either or both of a crosslinking agent and a graft crossing agent are used. As the crosslinking agent and graft crossing agent, for example, monomers having two or more unsaturated bonds in the molecule can be used alone or in combination. Examples of the crosslinking agent include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, divinylbenzene, and polyfunctional methacrylic group-modified silicone. 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. The usage-amount of a crosslinking agent and a graft crossing agent needs to be 0.1-1.2 mass parts with respect to 100 mass parts of polyalkyl (meth) acrylates. If the amount used is less than 0.1 parts by mass, it is not preferable because it is difficult to recover the powder, and if it exceeds 1.2 parts by mass, impact resistance is reduced, which is not preferable.

  The polymerization method is not particularly limited, but usually emulsion polymerization, if necessary, forced emulsion polymerization may be used, and when 2-ethyl acrylate, lauryl methacrylate, stearyl methacrylate is selected as the monomer constituting the acrylic rubber component Since it is poor in water solubility, it is preferable to produce the acrylic rubber (A1) component by a forced emulsion polymerization method.

  The ratio of polyorganosiloxane / alkyl (meth) acrylate constituting the composite rubber (A) is preferably in the range of 0.28 / 99.72 to 10.90 / 89.10. If it is less than 0.28% by mass, the impact resistance at low temperature becomes a problem. Conversely, if it is too much, the mechanical properties after the heat aging test are deteriorated.

  It is preferable that 90% by mass or more of the composite rubber (A) used in the graft copolymer of the present invention has a particle diameter of 80 to 180 nm. The particle diameter described above is a particle diameter measured by capillary hydrodynamic flow fractionation. It is preferable that the composite rubber does not contain particles having a particle diameter exceeding 250 μm.

  Examples of the vinyl monomer constituting the graft part (B) in the graft copolymer include aromatic alkenyl compounds such as styrene, α-methylstyrene, and vinyl toluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; Acrylic esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; various vinyl monomers such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile can be exemplified, and these can be used alone or in combination of two or more. May be used. In addition, if necessary, the vinyl monomer may be ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene having two or more unsaturated bonds in the molecule. Uses cross-linking agents such as glycol dimethacrylate, divinylbenzene, polyfunctional methacrylic group-modified silicones, and graft crossing agents such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, etc., as long as the intended purpose is not impaired. To do.

  Preferred examples of the alkyl (meth) acrylate used for the composite rubber (A) and the graft part (B) described above are as follows. For the composite rubber (A), an alkyl (meta) having an alkyl group having 1 to 18 carbon atoms. ) A monomer mainly composed of acrylate, and the graft part (B) is a monomer mainly composed of alkyl methacrylate having an alkyl group having 1 to 18 carbon atoms.

  In the graft copolymer of the present invention, it is preferable that 80% by mass or more of the composite rubber (A) is contained in 100% by mass of the graft copolymer. This content is preferably less than 99.9 mass because if the content is too high, the powder recoverability decreases. Since workability etc. become enough, it is still more preferable to set it as 90 mass% or less.

  In particular, in order to balance impact resistance and other mechanical properties at a high level, the amount of polyorganosiloxane in the rubber-containing graft polymer is preferably in the range of 0.25 to 9.7% by mass.

  The rubber-containing graft polymer of the present invention is obtained by coagulating and recovering from the rubber-containing graft polymer latex obtained as described above. The coagulation method of the rubber-containing graft polymer latex is, for example, contacting the latex with hot water in which the coagulant is dissolved, coagulating the polymer with stirring to form a slurry, and dehydrating the generated precipitate. The method of drying is mentioned.

  Examples of the coagulant include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as formic acid and acetic acid; and inorganic salts such as aluminum sulfate, magnesium sulfate, calcium acetate, calcium chloride, and calcium sulfate. Of these, calcium chloride and calcium acetate are preferred because they do not impair the heat-and-moisture resistance properties of the polycarbonate resin and flame retardancy.

  The graft copolymer obtained as described above can be used by blending with a thermoplastic resin as an impact strength modifier.

  Specific examples of the resin to which the impact strength modifier is added include hard, semi-rigid, soft vinyl chloride resin (PVC), chlorinated vinyl chloride resin (CPVC resin), polypropylene (PP), polyethylene (PE) Olefin resins such as polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylic acid ester / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer Styrenic resin (St resin) such as coalescence (SMA), ABS, ASA, AES, acrylic resin (Ac resin) such as polymethyl methacrylate (PMMA), polycarbonate resin (PC resin), polyamide Resin (PA resin), polyethylene terephthalate (PET) and polybutylene terephthalate Polyester resins (PEs resins) such as silicate (PBT), (modified) polyphenylene ether resins (PPE resins), polyoxymethylene resins (POM resins), polysulfone resins (PSO resins), Engineering plastics such as polyarylate resin (PAr resin), polyphenylene resin (PPS resin), thermoplastic polyurethane resin (PU resin), styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane Elastomers, polyester elastomers, polyamide elastomers, fluorine elastomers, 1,2-polybutadiene, thermoplastic elastomers (TPE) such as trans 1,4-polyisoprene, PC resins / St resin alloys such as PC / ABS, PV / PVC resin such as ABS / St resin alloy, PA resin such as PA / ABS / St resin alloy, PA resin / TPE alloy, PA resin such as PA / PP / Polyolefin resin alloy, PBT Resin / TPE, PC resin such as PC / PBT / PEs resin alloy, polyolefin resin / TPE, alloy between olefin resins such as PP / PE, PPE such as PPE / HIPS, PPE / PBT, PPE / PA Polymer alloys such as PVC resin alloys, PVC resins such as PVC / PMMA / Ac resin alloys, and the like.

  The blending amount of the graft copolymer is preferably 0.1 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the thermoplastic resin from the viewpoint of the performance of the obtained thermoplastic resin composition. On the other hand, it is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. In the thermoplastic resin composition of the present invention, conventional stabilizers, fillers, and the like can be added depending on the purpose at the time of compounding, kneading, molding, etc., as long as the physical properties are not impaired. .

  Examples of stabilizers include lead stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite and lead silicate, metals such as potassium, magnesium, barium, zinc, cadmium and lead. Metal soap stabilizers derived from fatty acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, ricinoleic acid, linoleic acid, behenic acid, alkyl Group, ester group and fatty acid salt, maleate, organotin stabilizer derived from sulfide, Ba—Zn, Ca—Zn, Ba—Ca—Sn, Ca—Mg—Sn, Ca -Zn-Sn-based, Pb-Sn-based, Pb-Ba-Ca-based composite metal soap-based stabilizers, metal groups such as barium and zinc, 2-ethylhexanoic acid, isodeca Acids, branched fatty acids such as trialkylacetic acid, unsaturated fatty acids such as oleic acid, ricinoleic acid and linoleic acid, alicyclic acids such as naphthenic acid, aromatic acids such as carboxylic acid, benzoic acid, salicylic acid and substituted derivatives thereof Usually, metal salt stabilizers derived from two or more organic acids, these stabilizers are dissolved in organic solvents such as petroleum hydrocarbons, alcohols, glycerin derivatives, phosphites, epoxy compounds, coloring inhibitors In addition to metal-based stabilizers such as transparency improvers, light stabilizers, antioxidants, plate-out inhibitors, and metal salt liquid stabilizers formulated with stabilizers such as lubricants, epoxy resins, epoxidized Epoxy compounds such as soybean oil, epoxidized vegetable oil, epoxidized fatty acid alkyl ester, phosphorus is alkyl group, aryl group, cycloalkyl group, Organic phosphorous acid ester substituted with a ruxoxyl group and having an aromatic compound such as dihydric alcohol such as propylene glycol, hydroquinone, bisphenol A, bisphenol dimerized with BHT, sulfur, methylene group, etc. UV absorbers such as hindered phenol, salicylic acid ester, benzophenone, benzotriazole, light stabilizers of hindered amine or nickel complex salt, UV screening agents such as carbon black, rutile titanium oxide, trimerolpropane, pentaerythritol, sorbitol, mannitol, etc. Sulfur-containing compounds such as polyhydric alcohols, β-aminocrotonates, 2-phenylindole, diphenylthiourea, dicyandiamide and other nitrogen-containing compounds, dialkylthiodipropionic acid esters , Acetoacetate, dehydroacetic acid, keto compounds such as β- diketones, organic silicon compounds, non-metallic stabilizers such as boric acid esters and the like, which are used alone or in combination.

  Examples of the filler include carbonates such as heavy calcium carbonate, precipitated calcium carbonate, and colloidal calcium carbonate, titanium oxide, clay, talc, mica, silica, carbon black, graphite, glass beads, glass fibers, carbon fibers, Examples thereof include inorganic materials such as metal fibers, organic fibers such as polyamide, organic materials such as silicone, and natural organic materials such as wood flour.

  Other impact strength modifiers such as MBS, ABS, AES, NBR, EVA, chlorinated polyethylene, acrylic rubber, polyalkyl (meth) acrylate rubber-based graft copolymer, thermoplastic elastomer, (meth) acrylic acid ester Alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, pyromet , Alkyl esters of fatty acid polybasic acids such as dibutyl adipate, dioctyl adipate, dithiononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphoric acid such as tricresyl phosphate Polycarboxylic acids such as stealth, adipic acid, azelaic acid, sebacic acid, phthalic acid and ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol Polyester plasticizers such as polycondensates with polyhydric alcohols such as polycondensates having a molecular weight of about 600 to 8,000 sealed with monohydric alcohol or monovalent carboxylic acid, epoxidized soybean oil, epoxidized linseed oil, etc. , Epoxy plasticizers such as epoxidized tall oil fatty acid-2-ethylhexyl, plasticizers such as chlorinated paraffin, pure hydrocarbons such as liquid paraffin and low molecular weight polyethylene, fatty acids such as halogenated hydrocarbons, higher fatty acids and oxy fatty acids , Fatty acid amides such as fatty acid amides, Cole ester, fatty alcohol ester of fatty acid (ester wax), metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester of polyglycerol, etc. Flame retardants such as esters, (meth) acrylic acid ester copolymers, these lubricants, chlorinated paraffin, aluminum hydroxide, antimony trioxide, halogen compounds, (meth) acrylic acid ester copolymers, imide copolymers Heat resistance improvers such as polymers, styrene / acrylonitrile copolymers, mold release agents, crystal nucleating agents, fluidity improvers, colorants, antistatic agents, conductivity-imparting agents, surfactants, antifogging agents, foaming An agent, an antibacterial agent and the like can be added.

  There is no restriction | limiting in particular in the method of manufacturing a thermoplastic resin composition, Although a normal method can be used, Usually, manufacturing with a melt mixing method is preferable. Moreover, you may use a small amount of solvent as needed. As an apparatus to be used, an extruder, a Banbury mixer, a roller, a kneader, etc. can be mentioned as an example, and these are operated batchwise or continuously. The mixing order of the components is not particularly limited. In addition, the obtained thermoplastic resin composition is not limited in its use, for example, miscellaneous goods such as building materials, automobiles, toys, and stationery, and molding that requires impact resistance such as OA equipment and home appliances. Widely used in goods.

  By molding the thermoplastic resin composition of the present invention, the molded article of the present invention can be obtained. The molded body of the present invention is preferably molded by an injection molding method. According to the injection molding method, a molded body having a complicated shape can be produced.

  The molded article of the present invention may be formed into a film or sheet by the extrusion molding method of the thermoplastic resin composition of the present invention. Further, the molded body of the present invention may be a plate molded by an injection molding method or an extrusion molding method.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “parts” represents “parts by mass”, “%” represents “% by mass”, and commercially available reagents were used.

(Production Example 1) Production of polyorganosiloxane rubber (S1) 2 parts of tetraethoxysilane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and dimethylcyclosiloxane (about 5% hexamethylcyclotrisiloxane, octamethylcyclotetra 97.5 parts of a mixture of about 75% siloxane and about 20% decamethylcyclohexasiloxane was mixed to obtain 100 parts of a siloxane mixture. A mixture obtained by adding 100 parts of the above mixed siloxane to 200 parts of distilled water in which 10 parts of sodium dodecylbenzenesulfonate was dissolved was pre-emulsified with an in-line mixer manufactured by Tokushu Kika Co., Ltd. and then forcibly emulsified with a homogenizer. The pressure of the homogenizer was 29 MPa. Next, the separable flask charged with 200 parts of distilled water in advance was heated to 80 ° C., and the above-mentioned forced emulsified solution forcibly emulsified while maintaining the temperature was dropped in 5 hours, and further maintained at 80 ° C. for 2 hours. After cooling to 20 ° C., the pH of the latex was neutralized to 7.4 with an aqueous sodium hydroxide solution to complete the polymerization and obtain a polyorganosiloxane rubber (S1).

(Production Example 2) Production of Graft Copolymer (G-1) The polyorganosiloxane rubber (S1) latex obtained above was sampled to be 5.0 parts as its solid content, and equipped with a stirrer. Put in a separable flask, add so that the amount of distilled water in the system is 195 parts, then, 84 parts of n-butyl acrylate containing 1.0% allyl methacrylate as a monomer of the (meth) acrylate rubber component, Then, a mixed solution of 0.32 part of tert-butyl hydroperoxide was charged and stirred for 10 minutes, and this mixed solution was infiltrated into the polyorganosiloxane rubber (A-S1). Further, 0.4 parts of polyoxyethylene ether sulfate was added, and the mixture was further stirred for 10 minutes, followed by nitrogen substitution, and the system was heated to 50 ° C., 0.002 parts of ferrous sulfate, ethylenediaminetetraacetic acid diacetate. A mixed solution of 0.006 part of sodium salt, 0.26 part of Rongalite and 5 parts of distilled water was charged to start radical polymerization, and then held at an internal temperature of 70 ° C. for 2 hours to complete the polymerization, and the latex of the composite rubber (A) Got.

  To this composite rubber (A), 0.06 part of tert-butyl hydroperoxide and 15 parts of methyl methacrylate were added dropwise at 70 ° C. over 15 minutes, and then kept at 70 ° C. for 4 hours to graft onto the composite rubber (A). The polymerization was complete. The polymerization rate of methyl methacrylate was 99.4%. The obtained graft copolymer latex was dropped into 200 parts of hot water of 5.0% calcium acetate, coagulated, separated, washed, dried at 75 ° C. for 16 hours, and powdered graft copolymer (G- 1) was obtained.

[Example 1]
The rubber-containing graft polymer (G-1) obtained in each production example was blended with various thermoplastic resins (matrix resins) to produce pellets. Specifically, it is mixed for 4 minutes with a Henschel mixer at six ratios shown in Table 1 below (formulations 1 to 6), melt-kneaded at a cylinder temperature of 240 to 300 ° C. using a 30 mmφ twin screw extruder, and pellets It was shaped into a shape. In addition, each thermoplastic resin used as the matrix was dried under the drying conditions recommended for each product, and used after eliminating the influence of hydrolysis caused by residual moisture and the like.

The symbols in Table 1 indicate the following.
“PC”: polycarbonate resin (bisphenol A type polycarbonate having a viscosity average molecular weight of about 22,000)
“PBT”: polyester resin (polytetrabutylene terephthalate having an intrinsic viscosity [η] of 1.05)
“ABS”: ABS resin (manufactured by UMG ABS, trade name RB)
“SAN”: Styrene-acrylonitrile copolymer (trade name AP-H, manufactured by UMG ABS Co., Ltd.)
"PLA": Polylactic acid resin (manufactured by Nature Works, trade name 4032D)
“POM”: Polyacetal resin (product name: AP789)

  Using the pellets made of the thermoplastic resin composition thus obtained, the impact resistance and the wet heat resistance were evaluated according to the following methods. The results are shown in Table 2 below.

<Impact resistance test>
Using the obtained pellets, Charpy test pieces (4 mm × 10 mm × 80 mm: notch depth = 2 mm) were produced by injection molding. The Charpy impact strength (kJ / m ² ) at 23 ° C. and −30 ° C. was measured on the test piece immediately after molding in accordance with ISO179.

<Moisture and heat resistance test>
The Charpy test piece produced as described above was placed in ESPEC Corporation constant temperature and humidity chamber Platinum J series (model: PR-1J) adjusted to a temperature of 85 ° C. and a humidity of 85% for 400 hours, and then 23 ° C. according to ISO179. The impact resistance after the moist heat resistance test was evaluated by measuring the Charpy impact strength (kJ / m ² ).

[Example 2]
<Flame retardance evaluation>
Compliant with vertical combustion test (UL94V) specified in UL94 of the US Underwriters Laboratories (UL) standard, combustion time during combustion test using 1.6 mm thick injection molded test piece and drip during combustion It was evaluated by sex. The formulations used and the results are shown in Table 3. The molding conditions were in accordance with the method described above.

The symbols in Table 3 indicate the following: “PC”: polycarbonate resin (bisphenol A type polycarbonate having a viscosity average molecular weight of about 22,000)
“PTFE”: manufactured by Mitsubishi Rayon Co., Ltd .: polytetrafluoroethylene (trade name: Metabrene A-3750)
“PX200”: manufactured by Daihachi Chemical Co., Ltd., composite phosphate ester (trade name PX200)

[Examples 3 to 7]
Next, an example of an inorganic reinforcing resin containing the following inorganic reinforcing agents (glass fiber (GF), talc) will be shown. The impact modifiers used are shown in Table 4. As a performance test, a Charpy impact resistance test was performed. The results in this test are shown in Table 4.

The symbols in Table 4 indicate the following.
“PC”: polycarbonate resin (bisphenol A type polycarbonate having a viscosity average molecular weight of about 22,000)
“GF”: Mitsubishi Engineering Plastics Co., Ltd., trade name Iupilon GS2030M9001
“Talc”: Hayashi Kasei Co., Ltd., trade name: Nanotalc FG-15 (1.5 μm)

[Examples 8 to 17]
Examples blended with vinyl chloride resin are shown in Tables 5 and 6, and Tables 7 and 8. Tables 9 and 10 show examples of blending with chlorinated vinyl chloride resin. The physical properties were evaluated by using the following composition, obtaining a flat roll sheet having a 100 cm square and a thickness of 3 mm, and then press-molding and cutting out. The evaluation item is Charpy impact strength. For Charpy impact strength, a sample conforming to ISO 179 was cut out from the flat plate, and Charpy impact strength (kJ / m ² ) at 23 ° C. and −30 ° C. was measured.

  As shown in each table, each of the thermoplastic resin compositions of the examples in which the impact resistance modifier based on the present invention was blended with the resin was excellent in impact resistance. Also, the impact strength after the wet heat resistance test was hardly lowered. Similarly, in the flame retardant formulation, excellent mechanical properties were exhibited while exhibiting excellent flame retardancy. Similarly, good mechanical properties were exhibited with respect to the fiber strong resin.

  As described above, the impact resistance modifier of the present invention is added in a small amount to improve the impact resistance of each thermoplastic resin, and to maintain the moisture and heat resistance characteristics of the obtained molded article well. Furthermore, even if various flame retardants are used in flame retardant applications, flame retardant defects due to the impact resistance modifier are not caused. The thermoplastic resin composition of the present invention is a composition excellent in various properties described above, and is a very useful resin material in various fields.

By using the rubber-containing graft polymer of the present invention as an impact strength modifier, it is possible to improve impact resistance, particularly impact resistance after a moist heat resistance test.
The thermoplastic resin composition and molded article of the present invention are excellent in impact resistance, and are suitably used in the field of building materials, the field of office automation equipment such as printers, the field of electrical and electronics such as mobile phones, the field of automobiles, and the field of optical parts. be able to.

Claims (3)

A rubber-containing graft obtained by graft-polymerizing a polyorganosiloxane / polyalkyl (meth) acrylate composite rubber (A) with a graft part (B) containing one or more vinyl monomer units as a main component. The total amount of the crosslinking agent and graft crossing agent used in the polymerization of the polyalkyl (meth) acrylate in the composite rubber (A) is 100 parts by mass of the alkyl (meth) acrylate monomer used. A rubber-containing graft polymer having a content of 0.1 to 1.2 parts by mass and a polyorganosiloxane content in the rubber-containing graft polymer of 0.25 to 9.7% by mass. A thermoplastic resin composition comprising the rubber-containing graft polymer according to claim 1 and another thermoplastic resin. The molded object formed by shape | molding the thermoplastic resin composition of Claim 2.