JP5473496B2 - Graft copolymer and production method thereof, thermoplastic resin composition, and molded article - Google Patents

Description

  The present invention relates to a graft copolymer, a method for producing the same, a thermoplastic resin composition in which the graft copolymer is blended with a thermoplastic resin, and a molded article obtained by molding the thermoplastic resin composition.

  Molded products using thermoplastic resins are widely used in various fields including the home appliance field, electrical / electronic equipment field, and office automation equipment such as printers. The molded article is required to have excellent impact resistance, flame retardancy, weather resistance and the like, and the resin composition used for molding is required to have excellent fluidity. In particular, in recent years, thinner and lighter molded products have been promoted for the purpose of cost reduction. Therefore, it is necessary to obtain sufficient impact resistance, fluidity, and flame retardancy even if the weight and thickness are reduced.

Then, the method shown below is shown as a method of improving functions, such as impact resistance of a molded article using a thermoplastic resin, and a flame retardance.
For example, a method of blending a composite rubber graft copolymer obtained by graft polymerization of a vinyl monomer into a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber is disclosed (Patent Document 1). Yes.
In addition, a method (Patent Document 2) is disclosed in which a polyfunctional vinyl monomer and a graft copolymer obtained by graft polymerization of another vinyl monomer are blended with a low-crosslinking polyorganosiloxane rubber. Yes.

However, in the method described in Patent Document 1, the composite rubber contains a polyalkyl (meth) acrylate rubber as a combustible component, and the vinyl monomer constituting the graft portion is a polyfunctional vinyl monomer. Since it does not contain, there exists a tendency for a flame retardance to fall with the increase in the compounding quantity of a graft copolymer.
Further, in the method described in Patent Document 2, since a low-crosslinked polyorganosiloxane rubber is used and the content of the polyorganosiloxane rubber is low, a good flame retardancy is obtained with a thin molded product. Although obtained, the impact resistance, particularly the impact resistance at low temperatures, is not sufficient.

JP 2000-17029 A Japanese Patent Laid-Open No. 2003-238639

  The present invention relates to a graft copolymer that provides a resin composition having excellent impact resistance and fluidity at a low temperature and sufficient flame retardancy, especially by blending it with a thermoplastic resin, a method for producing the same, and the graft copolymer. It is an object of the present invention to provide a thermoplastic resin composition in which a coalescence is blended with a thermoplastic resin, and a molded product obtained by molding the thermoplastic resin composition.

The present invention employs the following configuration in order to solve the above problems.
[1] Polyorganosiloxane rubber (A) having a toluene insoluble content obtained by polymerizing organosiloxane of 50% by mass or more ( excluding composite rubber containing an acrylic rubber component) Existence of 75 to 93% by mass under, 7 to 25% by weight vinyl monomer (B) containing a polyfunctional vinyl monomer and (b1) a process for the preparation of the graft copolymer to graft polymerization, the polyfunctional vinyl monomer The manufacturing method of the graft copolymer whose mass ratio of (b1) is 0.3-10 mass% with respect to 100 mass% of graft copolymers.
[2] A graft copolymer obtained by the production method according to [1].
[3] The graft copolymer according to the above [2], wherein the number average particle size measured with a capillary particle size distribution analyzer is 200 to 1,000 nm.
[4] A thermoplastic resin composition in which the graft copolymer according to [2] or [3] is blended in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
[5] The thermoplastic resin composition according to [4], further including a modified fluororesin comprising a mixed powder of a hard polymer obtained by polymerizing a vinyl monomer and a fluororesin. object.
[6] A molded product obtained by molding the thermoplastic resin composition according to [4] or [5].

The graft copolymer of the present invention is blended with a thermoplastic resin to give a thermoplastic resin composition having excellent impact resistance and fluidity particularly at a low temperature and sufficient flame retardancy.
Further, since the thermoplastic resin composition of the present invention contains the graft copolymer, it has excellent impact resistance and fluidity especially at low temperatures and has sufficient flame retardancy.
Moreover, since the molded article of the present invention is obtained by molding the thermoplastic resin composition, it has excellent impact resistance particularly at low temperatures and has sufficient flame retardancy.

  The graft copolymer of the present invention (hereinafter referred to as “the present graft copolymer”) is a graft obtained by polymerizing the vinyl monomer (B) in the presence of the polyorganosiloxane rubber (A) described later. It is a copolymer.

The polyorganosiloxane rubber (A) is a polyorganosiloxane rubber obtained by polymerizing organosiloxane and having a toluene insoluble content of 50% by mass or more. The polyorganosiloxane rubber (A) does not include a composite rubber containing an acrylic rubber component.
The polyorganosiloxane rubber (A) is preferably a polyorganosiloxane rubber having a vinyl polymerizable functional group (hereinafter referred to as “siloxane rubber (A1)”).
The siloxane rubber (A1) is obtained by polymerizing the following components (a1) to (a3).
Component (a1): Dimethylsiloxane.
Component (a2): Siloxane having a vinyl polymerizable functional group.
Component (a3): Siloxane-based crosslinking agent.

As a component (a1), the dimethylsiloxane type | system | group cyclic body of 3 or more member ring is mentioned, for example, The thing of 3-7 membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Especially, it is preferable to use octamethylcyclotetrasiloxane as a main component from the point that control of particle diameter distribution is easy.
A component (a1) may be used individually by 1 type, and may use 2 or more types together.

Component (a2) is a siloxane compound having a vinyl polymerizable functional group and capable of binding to component (a1) via a siloxane bond. The component (a2) is a component for introducing a vinyl polymerizable functional group into the side chain or terminal of the polyorganosiloxane, and this vinyl polymerizable functional group is formed from the vinyl monomer (B) described later. It acts as a graft active site when chemically bonding to the vinyl (co) polymer.
Examples of the component (a2) include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyl. Methacryloyloxysilane such as ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane Vinylphenylsilane; γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. Mercaptopurine siloxanes.
A component (a2) may be used individually by 1 type, and may use 2 or more types together.

Examples of the component (a3) include trifunctional or tetrafunctional silane crosslinking agents. Examples thereof include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.
The component (a3) is preferably contained in the siloxane rubber (A1) in an amount of 1 to 5% by mass from the viewpoint of the strength and flame retardancy of the thermoplastic resin composition containing the graft copolymer.

As a method for producing the siloxane rubber (A1), for example, a siloxane mixture of the component (a1) and the component (a2) or a siloxane mixture further containing the component (a3) is emulsified with an emulsifier and water to obtain an organosiloxane latex. The organosiloxane latex is made into fine particles by using a homomixer that makes fine particles by shearing force generated by high-speed rotation or a homogenizer that makes fine particles by jet output from a high-pressure generator, and then polymerized at a high temperature using an acid catalyst. Then, a method of neutralizing the acid with an alkaline substance to obtain a polyorganosiloxane latex can be mentioned.
Examples of a method for adding an acid catalyst used for polymerization include a method of mixing with a siloxane mixture, an emulsifier and water, and a method of dropping an organosiloxane latex in which a siloxane mixture is finely divided into a high-temperature acid aqueous solution at a constant rate. Can be mentioned.
As a method for producing the siloxane rubber (A1), from the viewpoint of easy control of the particle size of the siloxane rubber (A1), polymerization is performed by mixing a siloxane mixture, an emulsifier and water with an acid aqueous solution having no micelle-forming ability. The method of performing is preferred.

As the emulsifier used for the production of the siloxane rubber (A1), an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium lauryl sulfate, sodium alkylbenzene sulfonate, and sodium polyoxyethylene nonylphenyl ether sulfate. Of these, sodium alkylbenzenesulfonate is particularly preferable.
These emulsifiers may be used individually by 1 type, and may use 2 or more types together.

Examples of the acid catalyst used for the polymerization of the siloxane rubber (A1) 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. Can be mentioned. Among these, it is preferable to use mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid that do not have the ability to form micelles. By using mineral acids, it becomes easy to narrow the particle size distribution of the polyorganosiloxane latex, and it is easy to reduce appearance defects of the resin composition due to the emulsifier component of the polyorganosiloxane latex. Moreover, it is preferable also at the point of the impact strength improvement in low temperature.
These acid catalysts may be used alone or in combination of two or more.

  Examples of the method of mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst include mixing by high-speed stirring and mixing by a high-pressure emulsifier such as a homogenizer, but the particle size distribution of the polyorganosiloxane latex is narrowed. Therefore, a method using a homogenizer is preferable.

50-95 degreeC is preferable and, as for the polymerization temperature at the time of manufacturing a polyorganosiloxane type rubber (A), 70-90 degreeC is more preferable.
The polymerization time of the polyorganosiloxane rubber (A) is preferably 2 to 15 hours, preferably 5 to 10 hours when the acid catalyst is mixed with a siloxane mixture, an emulsifier and water and polymerized after finely divided. More preferred.
The polymerization can be stopped by cooling the reaction solution and neutralizing the polyorganosiloxane latex with an alkaline substance such as sodium hydroxide, potassium hydroxide, or sodium carbonate.

  The number average particle diameter of the polyorganosiloxane rubber (A) is preferably 50 to 600 nm, and more preferably 100 to 500 nm. Here, the number average particle diameter means a value measured by a capillary type particle size distribution measuring instrument. When the number average particle diameter is 50 nm or more, impact resistance at low temperatures is easily developed. Moreover, if the said number average particle diameter is 600 nm or less, it will be easy to suppress the flame retardance fall of the thermoplastic resin composition which mix | blended this graft copolymer.

The toluene insoluble content of the polyorganosiloxane rubber (A) is 50% by mass or more, and preferably 80% by mass or more. If the toluene insoluble content is 50% by mass or more, excellent impact resistance is obtained, and if it is 80% by mass or more, impact resistance is further improved.
The toluene insoluble matter can be measured by the following method.
The polyorganosiloxane rubber (A) component is extracted from the polyorganosiloxane latex using 2-propanol, dried at room temperature, and then the 2-propanol component is completely removed with a vacuum dryer. After 0.5 g of the obtained polyorganosiloxane rubber (A) was precisely weighed, it was immersed in 80 mL of toluene at room temperature for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and then polyorganosiloxane rubber (A ) Is weighed again to measure the mass fraction (% by mass) of the toluene insoluble matter.
The toluene insoluble content of the polyorganosiloxane rubber (A) can be controlled by adjusting the content of the component (a3) in the polyorganosiloxane rubber (A). The higher the content of component (a3), the higher the toluene insoluble content of the polyorganosiloxane rubber (A).

A vinyl monomer (B) is a vinyl monomer containing a polyfunctional vinyl monomer (b1).
The polyfunctional vinyl monomer (b1) is a monomer having two or more polymerizable unsaturated bonds in the molecule. For example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, ethylene Examples include glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. Of these, allyl methacrylate is preferred because of its high effect of developing impact resistance, fluidity and flame retardancy.
These polyfunctional vinyl monomers (b1) may be used alone or in combination of two or more.

Examples of the vinyl monomer (b2) other than the polyfunctional vinyl monomer (b1) in the vinyl monomer (B) include aromatic vinyl monomers such as styrene, α-methylstyrene and vinyltoluene. Body; methacrylates such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate; and vinyl cyanide monomers such as acrylonitrile and methacrylonitrile.
These other vinyl monomers (b2) may be used alone or in combination of two or more.

Moreover, this graft copolymer polymerizes other monomers (C) other than the vinyl monomer (B), as long as the impact resistance, fluidity and flame retardancy are not impaired. You may let them. Examples of the other monomer (C) include an unsaturated carboxylic acid monomer and a maleimide monomer.
Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, (anhydrous) maleic acid, fumaric acid, and itaconic acid.
Examples of the maleimide monomer include maleimide, N-methylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, and N-cyclohexylmaleimide.

  Graft polymerization in which the vinyl monomer (B) is polymerized in the presence of the polyorganosiloxane rubber (A) is a radical polymerization method in which the vinyl monomer (B) is added to the latex of the polyorganosiloxane rubber (A). Can be carried out in one or more stages.

The amount of the polyorganosiloxane rubber (A) used in the polymerization of the graft copolymer (100% by mass) is 75 to 93% by mass, and preferably 80 to 90% by mass.
When the amount of the polyorganosiloxane rubber (A) used is 75% by mass or more, sufficient flame retardancy is exhibited. Moreover, if the said usage-amount of a polyorganosiloxane type rubber (A) is 93 mass% or less, sufficient impact resistance will express.

  The usage-amount of the vinyl monomer (B) in superposition | polymerization of this graft copolymer (100 mass%) is 7-25 mass%, and 10-20 mass% is preferable. When the amount of the vinyl monomer (B) used is 7% by mass or more, excellent impact resistance is exhibited. Moreover, if the said usage-amount of a vinyl monomer (B) is 25 mass% or less, sufficient flame retardance will express.

The amount of the polyfunctional vinyl monomer (b1) used in the polymerization of the graft copolymer (100% by mass) is 0.3 to 10% by mass, preferably 0.5 to 7% by mass, 5 mass% is more preferable. When the amount of the polyfunctional vinyl monomer (b1) used is 0.3% by mass or more, impact resistance and flame retardancy are improved, and the ratio of low molecular weight components is likely to increase due to the chain transfer effect. Fluidity is improved. Moreover, if the said usage-amount of a polyfunctional vinyl monomer (b1) is 10 mass% or less, impact resistance will improve.
The content of the polyfunctional vinyl monomer (b1) in the vinyl monomer (B) is the amount of the polyfunctional vinyl monomer (b1) used in the polymerization of the graft copolymer described above. It can be set as appropriate within the range to satisfy.

  Moreover, it is preferable that this graft copolymer makes a total amount of polyorganosiloxane rubber (A) and a vinyl monomer (B) 100 mass%, without using another monomer (C). .

Examples of the radical polymerization initiator include organic peroxides, inorganic peroxides, azo initiators, and redox initiators in which an oxidizing agent and a reducing agent are combined.
Examples of the organic peroxide include cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxide, t-butyl peroxylaurate, lauroyl. Examples include peroxide, succinic acid peroxide, cyclohexane non-peroxide, and acetylacetone peroxide.
Examples of inorganic peroxides include potassium persulfate and ammonium persulfate.
Examples of the azo initiator include 2,2′-azobisisobutyronitrile and 2,2′-azobis-2,4-dimethylvaleronitrile.
Examples of the redox initiator include an initiator in which ferrous sulfate / ethylenediaminetetraacetic acid disodium salt / longalite / hydroperoxide is combined.
The radical polymerization initiator is preferably an organic peroxide or an inorganic peroxide because of its high reactivity. Redox initiators are also preferred, and initiators that combine ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, longalite, and hydroperoxide are more preferred.

In the graft polymerization, in addition to the polyorganosiloxane rubber (A) and the vinyl monomer (B), various chain transfer agents may be added to adjust the molecular weight or graft ratio of the graft copolymer. .
Examples of the chain transfer agent include t-dodecyl mercaptan, n-octyl mercaptan, n-tetradecyl mercaptan, and n-hexyl mercaptan.

In the graft polymerization, an emulsifier may be added to stabilize the polymerization latex and to control the average particle size of the graft copolymer.
As the emulsifier used for graft polymerization, a cationic emulsifier, an anionic emulsifier, and a nonionic emulsifier are preferable, and a sulfonate emulsifier, a sulfate emulsifier, and a carboxylate emulsifier are more preferable. In particular, when an object to be blended with the obtained graft copolymer is a thermoplastic resin having an ester bond, a sulfonate emulsifier is more preferable from the viewpoint of suppressing hydrolysis.

For this graft copolymer, the graft copolymer latex produced by the above method is poured into hot water in which metal salts such as calcium chloride, calcium acetate, magnesium sulfate, and aluminum sulfate are dissolved, and salted out and solidified. By separating the graft copolymer by the method, it can be recovered in a powder form. The graft copolymer may be recovered by a spray drying method.
In particular, when the target to be blended with the obtained graft copolymer is a thermoplastic resin having an ester bond, it is preferably recovered by salting out with a calcium salt in order to suppress hydrolysis.

The number average particle size of the graft copolymer measured by a capillary type particle size distribution analyzer is preferably 200 to 1,000 nm, and more preferably 250 to 600 nm.
If the number average particle diameter is 200 nm or more, impact resistance at low temperatures can be sufficiently exhibited. Moreover, if the said number average particle diameter is 1,000 nm or less, it will be easy to suppress the flame retardance fall of the thermoplastic resin composition which mix | blended this graft copolymer.

The mass average molecular weight (hereinafter referred to as “Mw”) of the acetone-soluble component of the graft copolymer is preferably 50,000 or less, and more preferably 1,000 to 50,000.
If the Mw is 50,000 or less, it is possible to prevent a decrease in dispersibility of the graft copolymer in a thermoplastic resin, and it is easy to develop excellent fluidity without impairing flame retardancy. If the Mw is 1,000 or more, it becomes easy to develop sufficient flame retardancy and impact resistance without reducing the dispersibility of the graft copolymer in the thermoplastic resin.

The thermoplastic resin composition of the present invention is a composition obtained by blending the above-mentioned graft copolymer with a thermoplastic resin.
As the thermoplastic resin compounded with the graft copolymer, generally known thermoplastic resins can be used, for example, olefin resins such as polypropylene (PP) and polyethylene (PE); polystyrene (PS), High impact polystyrene (HIPS), (meth) acrylic acid ester / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA), acrylonitrile / butadiene / styrene copolymer Polymer (ABS), acrylonitrile / styrene / acrylate copolymer (ASA), styrene resin (St resin) such as acrylonitrile / ethylene-propylene-diene / styrene (AES); polymethyl methacrylate (PMMA), etc. Acrylic resin (Ac resin); Polycarbonate resin (PC resin); Polyamide resin (PA resin); Polyester resin (PEs resin) such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); (Modified) Polyphenylene ether resin ( 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); styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene Thermoplastic elastomer (TPE) such as trans 1,4-polyisoprene; PC resin such as PC / ABS / St resin alloy, PVC resin such as polyvinyl chloride (PVC) / ABS / St resin alloy, PA resin such as PA / ABS / St resin resin alloy, PA resin / TPE alloy, PA resin such as PA / PP / polyolefin resin alloy, PBT resin / TPE, PC resin such as PC / PBT / Alloys of olefin resins such as PEs resin alloys, polyolefin resins / TPE, PP / PE, PPE resin alloys such as PPE / HIPS, PPE / PBT, PPE / PA, PVC resins such as PVC / PMMA / Examples include polymer alloys such as Ac resin alloys; hard, semi-hard, and soft vinyl chloride resins.
These thermoplastic resins 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.

The compounding quantity of this graft copolymer in a thermoplastic resin composition is 1-20 mass parts with respect to 100 mass parts of thermoplastic resins, and it is preferable that it is 2-10 mass parts.
When the blending amount of the present graft copolymer is 1 part by mass or more, excellent impact resistance and flame retardancy are exhibited. Moreover, if the said compounding quantity of this graft copolymer is 20 mass parts or less, it can prevent that the original property of a thermoplastic resin is impaired.

Further, the thermoplastic resin composition of the present invention has various additives in addition to the thermoplastic resin and the present graft copolymer for the purpose of adjusting to desirable physical properties and characteristics as long as the original purpose is not impaired. May be added.
Examples of additives include pigments, dyes, glass fibers, metal fibers, metal flakes, carbon fibers and other reinforcing agents, fillers, 2,6-di-butyl-4-methylphenol, 4,4′-butylidene- Phenolic antioxidants such as bis (3-methyl-6-t-butylphenol), phosphite antioxidants such as tris (mixed, mono and dinylphenyl) phosphite, diphenyl isodecyl phosphite, dilaurylthio Sulfur-based antioxidants such as dipropionate and dimyristylthiodipropionate diasterial thiodipropionate, 2-hydroxy-4-octoxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole and the like Benzotriazole UV absorber, bis (2,2,6,6-tetramethyl-4-piperi Light stabilizers such as diynyl), antistatic agents such as hydroxylalkylamines and sulfonates, lubricants such as ethylene bisstearylamide, metal soaps, tetrabromophenol A, decabromophenol oxide, tetrabromobisphenol A (TBA) epoxy Oligomers, TBA polycarbonate oligomers, antimony trioxide, triphenyl phosphite (TPP), flame retardants such as phosphate esters, PTFE (polytetrafluoroethylene), hard polymers obtained by polymerizing vinyl monomers and fluorine And a modified fluorine resin (anti-dripping agent made of PTFE modified with a vinyl polymer) made of a mixed powder with a resin.

The modified fluororesin is a mixture of a hard polymer obtained by polymerizing one or more vinyl monomers and a fluororesin, and in a liquid (latex) in which the fluororesin is dispersed. Can be obtained by a method of polymerizing a vinyl monomer or a method of mixing a hard polymer obtained by polymerizing a vinyl monomer and a fluororesin in latexes or solids.
Examples of the vinyl monomer include aromatic vinyl monomers such as styrene; vinyl cyanide monomers such as acrylonitrile; acrylates such as methyl acrylate; methacrylates such as methyl methacrylate.
As the modified fluororesin, modified PTFE is preferable. Examples of commercially available modified PTFE include, for example, trade names “Metabrene A3800”, “Metabrene A3750” (above, manufactured by Mitsubishi Rayon Co., Ltd.), trade names “TSAD001”, “CX-500” (above, Pacific Interchem ( Product name) “Blendex 449” (manufactured by Chemtura Inc.).

  When blending the modified fluororesin, the blending amount of the modified fluororesin in the thermoplastic resin composition is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin, 5 parts by mass is more preferable. If the compounding quantity of a fluorine resin containing material is 0.05 mass part or more, a flame retardance will improve. Moreover, if the compounding quantity of a fluorine-type resin containing material is 10 mass parts or less, a shaping | molding external appearance will not be impaired.

The method of blending the graft copolymer with a thermoplastic resin to produce a thermoplastic resin composition is not particularly limited, but a melt mixing method is preferably used. Moreover, you may use a small amount of solvent as needed.
The thermoplastic resin composition of the present invention comprises a thermoplastic resin and the present graft copolymer, which are essential components, and a predetermined amount of optional components, if necessary, roll, Banbury mixer, single screw extruder, twin screw extruder, etc. It can be prepared by kneading with an ordinary kneader. These can be operated batchwise or continuously, and the mixing order of each component is not particularly limited.
The thermoplastic resin composition of the present invention is preferably in the form of pellets.

The molded article of the present invention is obtained by molding the above-described thermoplastic resin composition. The molded article of the present invention has excellent impact resistance and sufficient flame retardancy.
The use of the molded article of the present invention is not particularly limited. For example, it is necessary to have impact resistance and flame retardancy at low temperatures such as building materials, automobiles, toys, stationery, and other miscellaneous goods, as well as OA equipment, home appliances and the like. Can be widely used for molded products.
The manufacturing method of the molded article of this invention can use a well-known manufacturing method except using the thermoplastic resin composition of this invention.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description. In the present embodiment, “part” means “part by mass”.
Each measurement in this example was performed as follows.
[Measurement of Number Average Particle Diameter (dn))
A latex containing particles is diluted with distilled water to prepare a 0.1 mL sample of diluted latex having a concentration of about 3%, and the number average is obtained using a capillary type particle size distribution analyzer (CHDF2000, manufactured by MATEC (USA)). The particle size was measured. The measurement conditions were a flow rate of 1.4 mL / min, a pressure of about 2.76 MPa (about 4,000 psi), and a temperature of 35 ° C. For the measurement, a capillary cartridge for particle separation and a carrier liquid were used, and the liquidity was made almost neutral.
Before the measurement, a standard curve was prepared by measuring monodisperse polystyrene having a known particle size (manufactured by DUKE (USA)) as a standard particle size material and measuring the particle size at a total of 12 points of 20 to 800 nm. Regarding the number average particle size, the analysis value in the number distribution of the particle size measurement results was defined as the number average particle size.

[Measurement of insoluble toluene]
From the polyorganosiloxane rubber latex obtained in this example, the polyorganosiloxane rubber component was extracted with 2-propanol and dried at room temperature, and then the 2-propanol component was completely removed with a vacuum dryer. did.
After 0.5 g of the obtained polyorganosiloxane rubber was precisely weighed, it was immersed in 80 mL of toluene at room temperature for 24 hours, centrifuged at 12,000 rpm for 60 minutes, and the separated polyorganosiloxane rubber was weighed again. And the mass fraction (mass%) of toluene insoluble content was measured.

[Measurement of graft ratio]
1 g of the graft copolymer powder obtained in this example was dissolved in 50 g of acetone, refluxed and extracted at 70 ° C. for 6 hours, and then centrifuged (CRG SERIES, manufactured by Hitachi, Ltd.). And centrifuged at 14,000 rpm for 30 minutes at 4 ° C.
Next, the solution was removed by decantation, the precipitate was separated, dried at 50 ° C. for 24 hours in a vacuum dryer, and the mass of the precipitate was measured. The graft ratio (unit: mass%) was calculated by the following formula.
Graft rate = mass of precipitate after drying / 1 × 100

[Measurement of Mw of acetone-soluble matter]
The acetone-soluble component (part removed by decantation) obtained by the above method was subjected to molecular weight measurement using gel permeation chromatography (GPC). The measurement conditions of GPC are as follows, and Mw was determined from a calibration curve using standard polystyrene.
Apparatus: “HLC8220” (manufactured by Tosoh Corporation)
Column: “TSKgel SuperHZM-M” (manufactured by Tosoh Corporation)
(Inner diameter 4.6 mm × length 15 cm × 4, exclusion limit 4 × 10 ⁶ )
Eluent: THF (tetrahydrofuran)
Eluent flow rate: 0.35 mL / min Measurement temperature: 40 ° C.
Sample injection volume: 10 μL (sample concentration 0.1%)

[Shock resistance]
According to ASTM D-256, impact resistance was evaluated by performing an Izod impact test at 23 ° C. and −30 ° C. using notched 1/8 inch bars and 1/4 inch bars.

[Flame retardance]
Flame retardance was evaluated by a UL94V test using a 1/16 inch combustion rod.

[Liquidity]
The flowability was evaluated by measuring the melt flow rate (MFR) in accordance with JIS K7210 using pellets of the resin composition as a sample. The measurement conditions of MFR are as follows (1) and (2). Condition (1) was applied to the thermoplastic resin composition not containing a phosphate ester flame retardant, and condition (2) was applied to a thermoplastic resin composition containing a phosphate ester flame retardant.
Condition (1): Measurement temperature 280 ° C., load 5.0 kgf.
Condition (2): Measurement temperature 260 ° C., load 2.16 kgf.

[Production Example 1] Production of polyorganosiloxane rubber (A-1) latex The following raw material mixture was stirred with a homomixer at 10,000 rpm for 5 minutes and then passed twice through a homogenizer at a pressure of 20 MPa for stable premixing. Latex (a-1) was obtained.
Raw material mixture:
Ingredient (a1) “TSF404” (trade name, octamethylcyclotetrasiloxane, manufactured by Momentive Performance Materials Japan Co., Ltd.) 96 parts Ingredient (a2) “KBM502” (trade name, γ-methacryloyloxypropyldimethoxymethyl) Silane, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Component (a3) “AY43-101” (trade name, tetraethoxysilane, manufactured by Toray Dow Corning Silicone Co., Ltd.) 2 parts Anionic emulsifier sodium dodecylbenzenesulfonate 00 parts Deionized water 150 parts

Next, 250 parts of the premixed latex (a-1) was put into a separable flask equipped with a cooling tube, and a mixture of 0.20 parts of sulfuric acid and 49.8 parts of deionized water was added dropwise over 3 minutes. Thereafter, the aqueous solution was heated to 80 ° C. for 7 hours for polymerization, and then cooled. Next, the reaction product was kept at room temperature for 6 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber (A-1) latex.
The polyorganosiloxane rubber (A-1) latex was dried at 180 ° C. for 30 minutes to obtain a solid content (hereinafter, the same method was used as a method for measuring the solid content). The solid content was 29.8%. The number average particle size of the latex was 420 nm.

[Production Example 2] Production of polyorganosiloxane rubber (A-2) latex The following raw material mixture was stirred with a homomixer at 10,000 rpm for 5 minutes and then passed twice through a homogenizer at a pressure of 20 MPa for stable premixing. Latex (a-2) was obtained.
Raw material mixture:
Ingredient (a1) “TSF404” (trade name, manufactured by Momentive Performance Materials Japan) 96 parts Ingredient (a2) “KBM502” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Ingredient (a3) "AY43-101" (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) 2 parts Anionic emulsifier Sodium dodecylbenzenesulfonate 0.67 parts Acid catalyst Dodecylbenzenesulfonic acid 0.67 parts Deionized water 200 parts

In a separable flask equipped with a cooling tube, 300 parts of the premixed latex (a-2) was charged, polymerized by holding for 7 hours while heating to 80 ° C., and then cooled. Next, the reaction product was kept at room temperature for 6 hours, and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber (A-2) latex.
The solid content of the polyorganosiloxane rubber (A-2) latex was 29.3%, and the number average particle size was 140 nm.

[Production Example 3] Production of polyorganosiloxane rubber (A-3) latex The following raw material mixture was stirred with a homomixer at 10,000 rpm for 5 minutes and then passed twice through a homogenizer at a pressure of 20 MPa for stable premixing. Latex (a-3) was obtained.
Raw material mixture:
Ingredient (a1) “TSF404” (trade name, manufactured by Momentive Performance Materials Japan) 96 parts Ingredient (a2) “KBM502” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts Ingredient (a3) "AY43-101" (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) 2 parts Anionic emulsifier Sodium dodecylbenzenesulfonate 1.00 parts Deionized water 200 parts

Further, 10 parts of dodecylbenzenesulfonic acid and 90 parts of deionized water were added to a separable flask equipped with a cooling tube to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid.
In a state where the aqueous solution of dodecylbenzenesulfonic acid is heated to 85 ° C., 300 parts of the premixed latex (a-3) is dropped over 2 hours, and after completion of dropping, the temperature is kept at 85 ° C. for 3 hours and then cooled. did. Next, the reaction product was kept at room temperature for 6 hours, and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane rubber (A-3) latex.
The solid content of the polyorganosiloxane rubber (A-3) latex was 17.7%, and the number average particle size was 65 nm.

[Production Example 4] polyorganosiloxane-based rubber (A-4) latex production component raw materials (a1), "YF393 7" (trade name from "TSF404", Momendibu Performance Materials Japan Co., Ltd. ) A polyorganosiloxane rubber (A-4) latex was obtained in the same manner as in Production Example 1 except that
The solid content of the polyorganosiloxane rubber (A-4) latex was 29.1%, and the number average particle size was 260 nm.

[Production Example 5] Production of polyorganosiloxane-based rubber (X-1) latex Polyorganosiloxane-based in the same manner as in Production Example 1 except that 98 parts of octamethylcyclotetrasiloxane and 0 parts of tetraethoxysilane were changed. A rubber (X-1) latex was obtained.
The number average particle diameter of the polyorganosiloxane rubber (X-1) latex was 410 nm.
Table 1 shows the composition of each polyorganosiloxane rubber of Production Examples 1 to 5, and the measurement results of the number average particle diameter dn and the toluene insoluble matter.

However, the abbreviations in Table 1 have the following meanings.
TSF404: “TSF404” (trade name, octamethylcyclotetrasiloxane, manufactured by Momentive Performance Materials Japan Co., Ltd.)
KBM502: “KBM502” (trade name, γ-methacryloyloxypropyldimethoxymethylsilane, manufactured by Shin-Etsu Chemical Co., Ltd.)
AY43-101: “AY43-101” (trade name, tetraethoxysilane, manufactured by Toray Dow Corning Silicone Co., Ltd.)
YF393 7 : “YF393 7 ” (trade name, manufactured by Momentive Performance Materials Japan Co., Ltd.)

[Example 1]
(Production of graft copolymer (1) powder)
The following first raw material mixture is put into a separable flask, nitrogen substitution is performed through a nitrogen stream in the flask, the temperature is raised while stirring, and when the liquid temperature reaches 50 ° C., the following reducing agent aqueous solution is put into one stage. The eye polymerization was started and the liquid temperature was maintained at 70 ° C. for 1 hour in order to complete the polymerization of the allyl methacrylate component.
First raw material mixture:
Polyorganosiloxane rubber (A-1) latex 268.5 parts
(80 parts in terms of polymer)
Polyfunctional vinyl monomer (b1) Allyl methacrylate 1 part Polymerization initiator Cumene hydroperoxide 0.3 part Deionized water 200 parts Reducing agent aqueous solution:
Ferrous sulfate 0.001 parts Ethylenediaminetetraacetic acid disodium salt 0.003 parts Rongalite 0.24 parts Deionized water 10 parts

Next, the following second raw material mixture is dropped over 10 minutes, the liquid temperature is kept at 60 ° C. or higher for 1 hour to perform the second stage polymerization, and then cooled to obtain the graft copolymer (1) latex. Obtained.
Second raw material mixture:
Other vinyl monomer (b2) Methyl methacrylate 17 parts Other vinyl monomer (b2) Butyl acrylate 2 parts Polymerization initiator Cumene hydroperoxide 0.20 parts

  500 parts of an aqueous solution in which calcium acetate is dissolved at a ratio of 5% by mass is heated to 60 ° C. with stirring, and 340 parts of the graft copolymer (1) latex is gradually dropped into the aqueous solution to coagulate, and separated and washed with water. And then dried to obtain a graft copolymer (1) powder.

(Manufacture of thermoplastic resin composition)
A resin composition was obtained by molding into the pellet form by melt-kneading the following blending components at 280 ° C. with a 30 mmφ twin-screw extruder (PCM-30, manufactured by Ikegai Seisakusho). Next, the obtained resin composition was molded at 280 ° C. with a 100-t injection molding machine (SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.) to obtain Izod test pieces and combustion test pieces.
Ingredients:
Graft copolymer (1) Powder 5 parts Thermoplastic resin “Iupilon S2000F” (trade name, bisphenol A type polycarbonate, viscosity average molecular weight of about 22,000, manufactured by Mitsubishi Engineering Plastics)
100 parts Phenol-based antioxidant "Irganox 245" (trade name, manufactured by Ciba Japan) 0.3 parts Phosphorus-based antioxidant "ADK STAB PEP36" (trade name, manufactured by ADEKA Corporation)
0.3 part Anti-drip agent Metablen A-3800 (trade name, acrylic modified polytetrafluoroethylene, manufactured by Mitsubishi Rayon Co., Ltd.) 1 part

[Examples 2 to 6, 8 to 13]
Graft copolymer (2) powder to graft copolymer (6) powder, graft copolymer (8) in the same manner as in Example 1 except that the composition was changed as shown in Tables 2 and 3. Powder to graft copolymer (13) powder was obtained. In addition, using the obtained graft copolymer (2) powder to graft copolymer (6) powder, graft copolymer (8) powder to graft copolymer (13) powder, Except having changed as shown in Tables 2 and 3, a thermoplastic resin composition was produced in the same manner as in Example 1 to obtain Izod test pieces and combustion test pieces.

[Examples 14 to 20]
A thermoplastic resin composition was produced in the same manner as in Example 1 except that the same graft copolymer (3) powder as in Example 3 was used and the blending composition was changed as shown in Table 3, and an Izod test piece was produced. And a combustion specimen was obtained.

[Comparative Example 1]
Except not using the graft copolymer, the thermoplastic resin composition was manufactured similarly to Example 1, and the Izod test piece and the combustion test piece were obtained.

[Comparative Examples 2 to 4]
A graft copolymer (14) powder to a graft copolymer (16) powder were obtained in the same manner as in Example 1 except that the blending composition was changed as shown in Table 4. Further, using the obtained graft copolymer (14) powder to graft copolymer (16) powder, a thermoplastic resin composition was produced in the same manner as in Example 1, and an Izod test piece and a combustion test were produced. I got a piece.

[Comparative Example 5]
(Production of graft copolymer (17) powder)
234.9 parts (70 parts in terms of polymer) of the polyorganosiloxane rubber (A-1) latex obtained in Production Example 1 was put into a separable flask, 200 parts of deionized water was added and mixed, and then butyl acrylate. A mixture of 9 parts, 1 part allyl methacrylate and 0.3 part cumene hydroperoxide was added. Subsequently, nitrogen substitution was performed in the flask through a nitrogen stream, and the temperature was increased while stirring. When the liquid temperature reached 50 ° C., the same reducing agent aqueous solution as in Example 1 was added to start radical polymerization. In order to complete the polymerization of the allyl methacrylate component, the liquid temperature was maintained at 70 ° C. for 1 hour to obtain a latex of a composite rubber of polyorganosiloxane rubber and polybutyl acrylate.

Next, after adding the following first raw material mixture to the latex of the composite rubber, the liquid temperature was kept at 70 ° C. for 1 hour to perform the first stage polymerization. Then, the following 2nd raw material mixture is dripped over 20 minutes, and after completion | finish of dripping, the state of temperature 70 degreeC or more is hold | maintained for 1 hour, superposition | polymerization of the 2nd step is performed, and it cools after that and a graft copolymer ( 17) A latex was obtained.
First raw material mixture:
Polyfunctional vinyl monomer (b1) Allyl methacrylate 5 parts Polymerization initiator Cumene hydroperoxide 0.3 part Second raw material mixture:
Other vinyl monomer (b2) Methyl methacrylate 13 parts Other vinyl monomer (b2) Butyl acrylate 2 parts Polymerization initiator Cumene hydroperoxide 0.20 parts

  Next, 500 parts of an aqueous solution in which calcium acetate is dissolved at a ratio of 5% by mass is heated to 60 ° C. while stirring, and 340 parts of the graft copolymer (17) latex is gradually added dropwise thereto to coagulate the latex. After separation, washing with water and drying, a graft copolymer (17) powder was obtained.

(Manufacture of thermoplastic resin composition)
A thermoplastic resin composition was produced in the same manner as in Example 1 by using the obtained graft copolymer (17) powder.
Moreover, the Izod test piece and the combustion test piece were obtained like Example 1 using this thermoplastic resin composition.

[Comparative Example 6]
(Production of graft copolymer (18) latex)
After putting 268.5 parts (80 parts in terms of polymer) of the polyorganosiloxane rubber (A-1) latex obtained in Production Example 1 into a separable flask and adding and mixing 200 parts of deionized water, The mixture was purged with nitrogen through a nitrogen stream, and when the temperature was raised while stirring and the liquid temperature reached 50 ° C., the same reducing agent aqueous solution as in Example 1 was added to bring the liquid temperature to 70 ° C.
Subsequently, after dropping the following raw material mixture over 20 minutes, polymerization was carried out while maintaining a temperature of 70 ° C. or higher for 1.5 hours, followed by cooling to obtain a graft copolymer (18) latex.
Raw material mixture:
Other vinyl monomer (b2) Methyl methacrylate 18 parts Other vinyl monomer (b2) Butyl acrylate 2 parts Polymerization initiator Cumene hydroperoxide 0.20 parts

  Next, 500 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% by mass was heated to 60 ° C. and stirred, and 340 parts of the graft copolymer (18) latex was gradually added dropwise to solidify, separated, and washed with water. After drying, a graft copolymer (18) powder was obtained.

(Manufacture of thermoplastic resin composition)
A thermoplastic resin composition was produced in the same manner as in Example 1 by using the obtained graft copolymer (18) powder.
Moreover, the Izod test piece and the combustion test piece were obtained using this thermoplastic resin composition.
Tables 2 to 4 show the compositions of Examples 1 to 6, 8 to 20 and Comparative Examples 1 to 6, and evaluation results of impact resistance and flame retardancy.

However, the abbreviations in Tables 2 to 4 have the following meanings.
BA: butyl acrylate AMA: allyl methacrylate MMA: methyl methacrylate PhMA: phenyl methacrylate AN: acrylonitrile St: styrene PC: “Iupilon S2000F” (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
Irg245: “Irganox 245” (trade name, manufactured by Ciba Japan Co., Ltd.)
PEP36: “ADK STAB PEP36” (trade name, manufactured by ADEKA Corporation)
CD1: “Full-on CD-1” (trade name, manufactured by Asahi Glass Co., Ltd.)
A3800: “Metabrene A-3800” (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
TPP: “TPP” (trade name, manufactured by Daihachi Chemical Co., Ltd.)
CR733S: “CR733S” (trade name, manufactured by Daihachi Chemical Co., Ltd.)
CR741: "CR741" (trade name, manufactured by Daihachi Chemical Co., Ltd.)
PX200: “PX200” (trade name, manufactured by Daihachi Chemical Co., Ltd.)

As shown in Tables 2 and 3, the thermoplastic resin compositions of Examples 1 to 6, 8 to 20 containing the graft copolymer of the present invention have excellent impact resistance, fluidity and flame retardancy. It was. Further, the Izod impact strength at −30 ° C. was high, and the impact resistance was excellent even at a low temperature.

On the other hand, the resin composition of Comparative Example 1 not using the graft copolymer had a long total combustion time in the UL94V test and was inferior in flame retardancy and inferior in impact resistance at low temperatures. .
The resin composition of Comparative Example 2 using the polyorganosiloxane rubber (X-1) having a low toluene insoluble content was inferior in impact resistance at low temperatures as compared with the resin composition of Example 3.
The resin composition of Comparative Example 3 having a low polyorganosiloxane rubber (A) content is inferior to the resin composition of Example 3 in fluidity and impact resistance at low temperatures, and has a UL94V test. The total burning time was long and the flame retardancy was poor.
The resin composition of Comparative Example 4 in which the content of the polyorganosiloxane rubber (A) was too high was inferior in impact resistance at low temperatures as compared with the resin compositions of Examples 2 and 5.
Instead of the polyorganosiloxane rubber (A), the resin composition of Comparative Example 5 using a composite rubber in which butyl acrylate was compounded with the polyorganosiloxane rubber (A-1) was used in Examples 3, 9 and 10 Compared with the resin composition, the total combustion time of the UL94V test was long and the flame retardancy was significantly inferior.
The resin composition of Comparative Example 6 using the graft copolymer produced without using the polyfunctional vinyl monomer (b1) has lower impact resistance at a lower temperature than the resin compositions of Examples 1 to 3. The total combustion time of the UL94V test was long and the flame retardancy was remarkably inferior.

Claims (6)

Polyorganosiloxane rubber (A) having a toluene insoluble content obtained by polymerizing organosiloxane of 50 mass% or more ( excluding composite rubber containing an acrylic rubber component) In the presence of 75 to 93 mass%, 7 to 25 wt% vinyl monomer (B) containing a polyfunctional vinyl monomer and (b1) a process for the preparation of the graft copolymer to graft polymerization,
The manufacturing method of the graft copolymer whose mass ratio of the said polyfunctional vinyl monomer (b1) is 0.3-10 mass% with respect to 100 mass% of graft copolymers.   A graft copolymer obtained by the production method according to claim 1.   The graft copolymer according to claim 2, wherein the number average particle diameter measured by a capillary type particle size distribution analyzer is 200 to 1,000 nm.   The thermoplastic resin composition by which the graft copolymer of Claim 2 or 3 was mix | blended 1-20 mass parts with respect to 100 mass parts of thermoplastic resins.   Furthermore, the thermoplastic resin composition of Claim 4 with which the modified | denatured fluororesin which consists of a mixed powder of the hard polymer obtained by superposing | polymerizing a vinyl monomer and fluororesin was mix | blended.   A molded product obtained by molding the thermoplastic resin composition according to claim 4 or 5.