WO2014208716A1 - ポリオルガノシロキサン含有グラフト共重合体、熱可塑性樹脂組成物及び成形体 - Google Patents
ポリオルガノシロキサン含有グラフト共重合体、熱可塑性樹脂組成物及び成形体 Download PDFInfo
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- WO2014208716A1 WO2014208716A1 PCT/JP2014/067132 JP2014067132W WO2014208716A1 WO 2014208716 A1 WO2014208716 A1 WO 2014208716A1 JP 2014067132 W JP2014067132 W JP 2014067132W WO 2014208716 A1 WO2014208716 A1 WO 2014208716A1
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- polyorganosiloxane
- mass
- graft copolymer
- rubber
- containing graft
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention improves the low-temperature impact resistance of a thermoplastic resin composition obtained by adding to a thermoplastic resin, and exhibits high pigment coloration and flame retardancy in a molded product obtained from this thermoplastic resin composition.
- the present invention relates to a polyorganosiloxane-containing graft copolymer that can be produced.
- the present invention also relates to a thermoplastic resin composition having high low-temperature impact resistance, pigment colorability, and flame retardancy, and a molded product thereof.
- Aromatic polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and because of its excellent characteristics, it can be used as a material in the automotive field, OA equipment field, electrical / electronic field, etc. Widely used.
- molded products obtained from aromatic polycarbonate resins may be used without coating, mainly for applications such as electrical and electronic equipment casings and home appliances, to reduce product costs. Therefore, there is a demand for higher pigment colorability than in the past.
- Patent Document 1 discloses a graft copolymer obtained by graft-polymerizing a vinyl monomer to a composite rubber composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber, and the number average particle diameter thereof is 300 to 300.
- a graft copolymer having a particle size of 2000 nm and the proportion of particles less than 300 nm in all particles being 20% by volume or less.
- the graft copolymer described in Patent Document 1 is insufficient in pigment colorability and flame retardancy for use in applications such as electrical / electronic equipment casings and home appliances.
- Patent Document 2 discloses a polyorganosiloxane containing an aryl group and at least one monomer selected from a vinyl cyanide monomer unit, an aromatic alkenyl monomer unit, and an alkyl (meth) acrylate unit.
- a composite rubber-like polymer in which a polymer having a body unit as a constituent is combined at least one selected from a vinyl cyanide monomer unit, an aromatic alkenyl unit, and an alkyl (meth) acrylate unit
- a graft copolymer obtained by graft polymerization of monomer units has been proposed.
- the mass average particle diameter of the graft copolymer described in Patent Document 2 is smaller than 300 nm, the low-temperature impact strength and pigment colorability are not sufficient for use in applications such as electronic / electric equipment casings and home appliances.
- JP 2004-331726 A Japanese Patent Laid-Open No. 2002-020443
- Charpy impact strength [kJ / m 2 ] measured under the following “measurement conditions” for “test piece 1”, “test piece 2” or “test piece 3” produced under the following “production conditions” ]
- test pieces 1 and 2 [Conditions for preparing test pieces 1 and 2]: (A) 3 parts by mass of a polyorganosiloxane-containing graft copolymer, (B) 97 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics) (C) Irganox 1076 (manufactured by BASF) 0.1 parts by mass, (D) 0.1 part by weight of ADK STAB 2112 (made by ADEKA), (E) Carbon black # 960 (made by Mitsubishi Chemical Corporation) 0.1 mass part.
- A 3 parts by mass of a polyorganosiloxane-containing graft copolymer
- B 97 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics)
- C Irganox 1076 (manufactured by BASF)
- test piece 1 length 80 mm, width 10 mm, Thickness 4 mm, with V notch
- test piece 2 length 100 mm, width 50 mm, thickness 2 mm
- test piece 3 [Conditions for preparing test piece 3]: (A) 5 parts by mass of a polyorganosiloxane-containing graft copolymer, (B) 89.5 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics) (E) Carbon black # 960 (manufactured by Mitsubishi Chemical Corporation) 0.1 parts by mass, (F) 5 parts by mass of an aromatic phosphate ester flame retardant (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) (G) 0.5 parts by mass of polytetrafluoroethylene-containing powder (Methbrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
- a devolatilizing extruder (PCM-30 manufactured by Ikegai Co., Ltd.) in which the above five types of materials (a), (b), (e), (f), (g) were blended and heated to a barrel temperature of 280 ° C. ) And kneading and extruding under the conditions of a screw speed of 150 rpm to obtain pellets.
- This pellet was molded with a 100-ton injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 90 ° C. to form “test piece 3” (length 127 mm, width 12. 7 mm, thickness 1.6 mm).
- the Charpy impact strength is measured for “Test piece 1” which was left in an atmosphere of ⁇ 30 ° C. for 12 hours or more by a method according to ISO 179.
- the content of the polyorganosiloxane (A1) in the rubber (A) is 40 to 80% by mass, and the content of the vinyl polymer (A2) is 60 to 20% by mass.
- the vinyl polymer (A2) is obtained by polymerizing the vinyl monomer for rubber (a2) using a radical polymerization initiator having a solubility in water at 20 ° C. of 5% by mass or less.
- the polyorganosiloxane-containing graft copolymer according to any one of [6] to [6].
- the radical polymerization initiator is cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, t-butylperoxyneodecanoate, t-butylperoxyneoheptanoate, t- Butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyro Selected from the group consisting of nitrile, dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-butyronitrile)
- the rubber vinyl monomer (a2) contains 0.1 to 10% by mass of a crosslinkable monomer based on a total of 100% by mass of the rubber vinyl monomer (a2).
- the polyorganosiloxane-containing graft copolymer according to any one of [10].
- An aryl (meth) in which the vinyl monomer for grafting (b) is an aromatic vinyl monomer, an alkyl (meth) acrylate, a vinyl cyanide monomer, or an ester group is a phenyl group or a substituted phenyl group
- thermoplastic resin composition comprising the polyorganosiloxane-containing graft copolymer according to any one of [1] to [13] and a thermoplastic resin.
- thermoplastic resin composition according to [14] or [15], wherein the thermoplastic resin is a polycarbonate resin.
- thermoplastic resin composition and a molded body having higher pigment colorability, low temperature impact resistance and flame retardancy.
- polyorganosiloxane containing graft copolymer which can provide the thermoplastic resin composition and molded object which have such performance can be provided.
- (meth) acrylate means at least one of “acrylate” and “methacrylate”.
- the polyorganosiloxane-containing graft copolymer may be simply referred to as “graft copolymer”.
- the polyorganosiloxane-containing graft copolymer of the present invention polymerizes the graft vinyl monomer (b) in the presence of the rubber (A) containing the polyorganosiloxane (A1) and the vinyl polymer (A2).
- the rubber (A) has a refractive index in the range of 1.47 to 1.56, and the rubber (A) has a volume average particle diameter in the range of 300 to 2000 nm.
- a polymer hereinafter sometimes referred to as “the graft copolymer 1 of the present invention” is preferable.
- the polyorganosiloxane (A1) is a polymer containing an organosiloxane unit as a constituent unit.
- the polyorganosiloxane can be obtained by polymerizing an organosiloxane or an “organosiloxane mixture” containing at least one kind of an organosiloxane and components used as necessary. Examples of components used as necessary include a siloxane-based crosslinking agent, a siloxane-based graft crossing agent, and a siloxane oligomer having a terminal blocking group.
- any of chain organosiloxane, alkoxysilane compound, and cyclic organosiloxane can be used.
- an alkoxysilane compound and a cyclic organosiloxane are preferable, and a cyclic organosiloxane is more preferable because of high polymerization stability and a high polymerization rate.
- the alkoxysilane compound is preferably a bifunctional alkoxysilane compound, such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dipropoxydimethylsilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, Examples thereof include methylphenyldiethoxysilane.
- the cyclic organosiloxane is preferably a 3- to 7-membered ring.
- hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetra Mention may be made of methyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These can be used individually by 1 type or in combination of 2 or more types.
- the main component is preferably octamethylcyclotetrasiloxane because the particle size distribution can be easily controlled.
- organosiloxane it is preferable to use an organosiloxane that is a cyclic dimethylsiloxane and / or a bifunctional dialkylsilane compound because a graft copolymer having higher low-temperature impact resistance can be obtained.
- the cyclic dimethylsiloxane is a cyclic siloxane having two methyl groups on a silicon atom, and examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These can be used individually by 1 type or in combination of 2 or more types.
- the bifunctional dialkylsilane compound is a silane compound having two alkoxy groups and two alkyl groups on the silicon atom, and examples thereof include dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, and dipropoxydimethylsilane. These can be used individually by 1 type or in combination of 2 or more types.
- siloxane crosslinking agent those having a siloxy group are preferable.
- siloxane-based crosslinking agent By using a siloxane-based crosslinking agent, a polyorganosiloxane having a crosslinked structure can be obtained.
- the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane.
- An agent can be mentioned. Among these, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is more preferable.
- the content of the siloxane-based crosslinking agent is preferably 0 to 30% by mass and more preferably 0.1 to 30% by mass in 100% by mass of the organosiloxane mixture.
- the siloxane-based graft crossing agent has a siloxy group and a functional group polymerizable with a vinyl monomer.
- a siloxane-based graft crossing agent By using a siloxane-based graft crossing agent, a polyorganosiloxane having a functional group polymerizable with a vinyl monomer can be obtained. Since the polyorganosiloxane has a functional group capable of polymerizing with a vinyl monomer, the polyorganosiloxane, a vinyl monomer for rubber (a2) and a vinyl monomer for graft (b) described later are grafted by radical polymerization. Can be made.
- siloxane-based graft crossing agent examples include siloxanes represented by the formula (I).
- R 1 represents a methyl group, an ethyl group, a propyl group, or a phenyl group.
- R 2 represents an organic group in the alkoxyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a phenyl group.
- n represents 0, 1 or 2.
- R represents any group represented by formulas (I-1) to (I-4).
- R 3 and R 4 each represent hydrogen or a methyl group
- p represents an integer of 1 to 6.
- Examples of the functional group represented by the formula (I-1) include a methacryloyloxyalkyl group.
- Examples of the siloxane having this group include the following. ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylethoxydiethylsilane, ⁇ -methacryloyloxypropyl Diethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane, etc.
- Examples of the functional group represented by the formula (I-2) include a vinylphenyl group.
- Examples of the siloxane having this group include vinylphenylethyldimethoxysilane.
- Examples of the siloxane having a functional group represented by the formula (I-3) include vinyltrimethoxysilane and vinyltriethoxysilane.
- Examples of the functional group represented by the formula (I-4) include a mercaptoalkyl group.
- Examples of the siloxane having this group include the following. ⁇ -mercaptopropyldimethoxymethylsilane, ⁇ -mercaptopropylmethoxydimethylsilane, ⁇ -mercaptopropyldiethoxymethylsilane, ⁇ -mercaptopropylethoxydimethylsilane, ⁇ -mercaptopropyltrimethoxysilane and the like.
- siloxane-based graft crossing agents can be used singly or in combination of two or more.
- the content of the siloxane-based graft crossing agent is preferably 0 to 20% by mass and more preferably 0.05 to 20% by mass with respect to 100% by mass of the organosiloxane mixture.
- siloxane oligomer having a terminal blocking group refers to a siloxane oligomer having an alkyl group or the like at the end of an organosiloxane oligomer and stopping the polymerization of polyorganosiloxane.
- siloxane oligomer having a terminal blocking group examples include hexamethyldisiloxane, 1,3-bis (3-glycidoxypropyl) tetramethyldisiloxane, and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. And methoxytrimethylsilane.
- the mixture is polymerized at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance to obtain a polyorganosiloxane latex.
- an “organosiloxane mixture” is used as a raw material for polymerization will be described, but the same production process can be applied to the case where “organosiloxane” is used.
- emulsion preparation methods include a method using a homomixer that makes fine particles by shearing force by high-speed rotation, a method that mixes by high-speed agitation using a homogenizer that makes fine particles by jet output from a high-pressure generator, etc. Is mentioned.
- a method using a homogenizer is a preferable method because the particle size distribution of the polyorganosiloxane latex becomes narrow.
- a method for mixing the acid catalyst during the polymerization (1) a method in which an acid catalyst is added together with an organosiloxane mixture, an emulsifier and water and mixed, and (2) an acid catalyst aqueous solution is added to an emulsion of the organosiloxane mixture.
- examples thereof include a method of adding all at once, and (3) a method in which an emulsion of an organosiloxane mixture is dropped into a high-temperature acid catalyst aqueous solution at a constant rate and mixed. Since it is easy to control the particle diameter of the polyorganosiloxane, a method of maintaining an emulsion of the organosiloxane mixture at a high temperature and then adding the acid catalyst aqueous solution all at once is preferable.
- the polymerization temperature is preferably 50 ° C. or higher, and more preferably 70 ° C. or higher.
- the polymerization time is usually 2 hours or longer, preferably 5 hours or longer when the acid catalyst aqueous solution is added all at once to the emulsion of the organosiloxane mixture for polymerization.
- the resulting latex is polymerized at a high temperature of 50 ° C. It can also be held at the following temperature for about 5 to 100 hours.
- the polymerization reaction of the organosiloxane mixture can be terminated by neutralizing the latex to pH 6 to 8 with an alkaline substance such as sodium hydroxide, potassium hydroxide, or an aqueous ammonia solution.
- an alkaline substance such as sodium hydroxide, potassium hydroxide, or an aqueous ammonia solution.
- the emulsifier used in the above production method is not particularly limited as long as the organosiloxane mixture can be emulsified, but an anionic emulsifier or a nonionic emulsifier is preferable.
- the anionic emulsifier include sodium alkylbenzene sulfonate, sodium alkyldiphenyl ether disulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, and sodium polyoxyethylene nonyl phenyl ether sulfate.
- nonionic emulsifiers include the following. Polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol and the like. These emulsifiers can be used individually by 1 type or in combination of 2 or more types.
- the amount of the emulsifier used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane mixture.
- the particle diameter of the polyorganosiloxane latex can be adjusted to a desired value. If the usage-amount of an emulsifier is 0.05 mass part or more, the emulsification stability of the emulsion of an organosiloxane mixture will be enough.
- the amount of the emulsifier is 10 parts by mass or less, the amount of the emulsifier remaining in the powder of the graft copolymer can be sufficiently reduced, so that the heat decomposability and surface of the resin composition containing the graft copolymer and the resin can be reduced. Deterioration of appearance can be suppressed.
- Examples of the acid catalyst used for polymerization of the organosiloxane mixture 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. These acid catalysts can be used alone or in combination of two or more.
- the use of mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid can narrow the particle size distribution of the polyorganosiloxane latex, and further, the thermal decomposition of the molded product due to the emulsifier component in the polyorganosiloxane latex. It is possible to achieve a reduction in property and a reduction in appearance defects.
- the amount of the acid catalyst used is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the organosiloxane.
- the amount of the acid catalyst used is 0.005 parts by mass or more, the polyorganosiloxane can be polymerized in a short time.
- the usage-amount of an acid catalyst is 5 mass parts or less, a molded article with favorable thermal decomposition resistance and an external appearance can be obtained.
- the amount of the acid catalyst used is a factor that determines the particle size of the polyorganosiloxane
- the amount of the acid catalyst used is 0.005 to 1.5 mass to obtain a polyorganosiloxane having a particle size described later. More preferably, it is a part.
- the mass average particle diameter of the polyorganosiloxane latex is preferably in the range of 250 to 1000 nm.
- the volume average particle diameter of the rubber (A) can be adjusted within the range of 300 to 2000 nm.
- the “mass average particle diameter / number average particle diameter (Dw / Dn)” of the polyorganosiloxane latex is preferably in the range of 1.0 to 1.7.
- Dw / Dn number average particle diameter
- Dw and Dn values measured by the following method can be adopted.
- the particle size is measured using a CHDF2000 particle size distribution meter manufactured by MATEC, USA. The median diameter is used as the average particle diameter.
- the measurement can be performed under the following standard conditions recommended by MATEC.
- Cartridge dedicated capillary cartridge for particle separation (trade name; C-202), Carrier liquid: dedicated carrier liquid (trade name: 2XGR500), Carrier liquid: almost neutral, Carrier liquid flow rate: 1.4 ml / min, Carrier liquid pressure: about 4,000 psi (2,600 kPa), Measurement temperature: 35 ° C Sample usage: 0.1 ml.
- the standard particle size substance 12 types of particles having a particle size of 40 to 800 nm, which are monodisperse polystyrene with a known particle size manufactured by DUKE, USA, are used.
- an emulsifier may be added as necessary for the purpose of improving mechanical stability.
- the emulsifier the same anionic emulsifier and nonionic emulsifier as those exemplified above are preferable.
- vinyl polymer (A2) examples include a polymer obtained by polymerizing a vinyl monomer for rubber (a2).
- vinyl monomer for rubber (a2) examples include the following monomers.
- Aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyltoluene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate; ethyl acrylate, n-propyl acrylate, n-butyl acrylate Alkyl acrylates such as i-butyl acrylate and 2-ethylhexyl acrylate; phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2,4, Estes such as 6-tribromophenyl (meth) acrylate, monochlorophenyl
- the vinyl monomer for rubber (a2) is an aromatic vinyl monomer and / or ester. It is preferable to use an aryl (meth) acrylate whose group is a phenyl group or a substituted phenyl group. That is, the vinyl polymer (A2) is preferably a polymer containing an aromatic vinyl monomer unit and / or an aryl (meth) acrylate unit in which the ester group is a phenyl group or a substituted phenyl group.
- the content of the vinyl polymer (A2) in 100% by mass of the rubber (A) is preferably 15 to 90% by mass, more preferably 20 to 60% by mass, and 45 to 60%. More preferably, it is mass%.
- the rubber vinyl monomer (a2) preferably contains a crosslinkable monomer.
- the crosslinkable monomer include the following polyfunctional monomers. Allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, dimethacrylic acid ethylene glycol diester, dimethacrylic acid propylene glycol diester, dimethacrylic acid 1,3-butylene glycol diester, dimethacrylic acid 1,4-butylene glycol diester 1,6-hexanediol diacrylate, triallyl trimellate, and the like. These can be used alone or in combination of two or more.
- the content of the crosslinkable monomer in 100% by mass of the vinyl monomer for rubber (a2) is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass.
- the content is more preferably 0.3 to 5% by mass, and particularly preferably 0.3 to 3% by mass. It is more preferable that the content of the crosslinkable monomer is 0.1% by mass or more and 10% by mass or less because the low temperature impact resistance of the graft copolymer is improved.
- a manufacturing method of a vinyl polymer (A2) there is no restriction
- a manufacturing method of a vinyl polymer (A2) for example, although it can manufacture by an emulsion polymerization method, a suspension polymerization method, and a fine suspension polymerization method, it is preferable to use an emulsion polymerization method.
- radical polymerization initiator used for polymerization of the vinyl monomer for rubber (a2) an azo initiator, a peroxide, and a redox initiator that is a combination of a peroxide and a reducing agent are used. These can be used alone or in combination of two or more. Of these, azo initiators and redox initiators are preferred.
- azo initiator examples include the following. 2,2'-azobisisobutyronitrile, dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis Oil-soluble azo initiators such as (2-butyronitrile), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis [N- (2-carboxymethyl) -2-methylpropiona Midine] hydrate, 2,2′-azobis- (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride Water-soluble azo initiators such as These can be used individually by 1 type or in combination of 2 or more types.
- peroxides include the following. Inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, succinic acid peroxide, t- Butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-butyl Organic peroxides such as peroxy-2-ethylhexanoate. These can be used individually by 1 type or in combination of 2 or more types.
- Inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, diisopropylbenzene hydroperoxide, p-
- a peroxide When a peroxide is combined with a reducing agent to form a redox initiator, the above peroxide, a reducing agent such as sodium formaldehyde sulfoxylate, L-ascorbic acid, fructose, dextrose, sorbose, inositol, and sulfuric acid It is preferable to use a combination of monoiron and ethylenediaminetetraacetic acid disodium salt. These reducing agents can be used individually by 1 type or in combination of 2 or more types.
- the radical polymerization initiator used for the polymerization of the vinyl monomer for rubber (a2) preferably has a solubility in water at 20 ° C. of 5% by mass or less, more preferably 2% by mass or less. preferable. By polymerizing using this radical polymerization initiator, a graft copolymer having excellent low-temperature impact resistance can be obtained.
- the solubility of the radical polymerization initiator in water at 20 ° C. can be known from catalogs of various radical polymerization initiators.
- the amount of radical polymerization initiator used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass in total of the monomers when an azo initiator is used.
- the amount of peroxide used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.
- the amount of the reducing agent used is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of monomers.
- the rubber (A) of the present invention contains a polyorganosiloxane (A1) and a vinyl polymer (A2).
- Examples of the rubber (A) include rubbers having the following structures (1) to (3). (1) A rubber having a multilayer structure in which a core of polyorganosiloxane (A1) is covered with a shell of a vinyl polymer (A2), (2) A rubber having a multilayer structure in which the core of the vinyl polymer (A2) is covered with a shell of the polyorganosiloxane (A1), (3) Composite rubber containing polyorganosiloxane (A1) and vinyl polymer (A2).
- the rubber (A) is preferably a “composite rubber” containing a polyorganosiloxane (A1) and a vinyl polymer (A2).
- the graft copolymer obtained from such a composite rubber has good low-temperature impact resistance.
- the rubber (A) is more preferably a “composite rubber” composed of a polyorganosiloxane (A1) and a vinyl polymer (A2).
- the refractive index of the rubber (A) is in the range of 1.47 to 1.56, preferably in the range of 1.47 to 1.54, preferably 1.47 to 1.53. More preferably, it is within the range, and further preferably within the range of 1.49 to 1.52.
- a resin composition excellent in pigment colorability and low-temperature impact resistance can be obtained. If the refractive index of rubber
- the refractive index of the rubber (A) can be adjusted by adjusting the content of the polyorganosiloxane in the rubber (A), the type of vinyl monomer for rubber (a2) and the amount used.
- n1, n2, n3,...” Represents the refractive index of each monomer homopolymer at 20 ° C., and values described in POLYMER HANDBOOK 4th Edition can be used.
- v1, v2, v3,...” Represents the volume fraction of each monomer.
- the rubber (A) of the present invention preferably has a polyorganosiloxane (A1) content of 40 to 80% by mass and a vinyl polymer (A2) content of 60 to 20% by mass. More preferably, the content of A1) is 40 to 55% by mass, and the content of the vinyl polymer (A2) is 60 to 45% by mass. Low-temperature impact resistance of the resin composition containing the graft copolymer by setting the content of the polyorganosiloxane (A1) to 40 to 80% by mass and the content of the vinyl polymer (A2) to 60 to 20% by mass. , The pigment colorability and the flame retardancy balance become good.
- the content of the alkyl (meth) acrylate unit in the rubber (A) is preferably 0 to 35% by mass and 0 to 30% by mass based on the total 100% by mass of the rubber (A). Is more preferably 0 to 20% by mass, and particularly preferably 0 to 15% by mass.
- the resin composition containing the graft copolymer has a good balance of low-temperature impact resistance, pigment colorability, and flame retardancy.
- Rubber having the structure of (1) A method of polymerizing the rubber vinyl monomer (a2) in the presence of a polyorganosiloxane latex to obtain a rubber (A) latex, (2) Rubber having a structure: vinyl polymer (A2) A method of polymerizing an organosiloxane mixture in the presence of latex to obtain a latex of rubber (A), Rubber having the structure of (3): [3-1] A rubber vinyl monomer (a2) is added to the polyorganosiloxane latex, and the rubber vinyl monomer (a2) is impregnated into the polyorganosiloxane particles, and then the rubber vinyl monomer (a2) is added.
- the vinyl monomer for rubber (a2) is added to a polyorganosiloxane latex, impregnated in the polyorganosiloxane, and then a known radical polymerization initiator is used. Is used for polymerization.
- examples of the method for adding the vinyl monomer for rubber (a2) include a method in which the entire amount thereof is added to the polyorganosiloxane latex at once, or a method in which the vinyl monomer is added dropwise at a constant rate.
- an emulsifier can be added to stabilize the latex and control the particle diameter of rubber (A).
- the emulsifier include the same emulsifiers as those used in the production of the polyorganosiloxane latex, and anionic emulsifiers and nonionic emulsifiers are preferable.
- the volume average particle diameter (Dv) of rubber (A) is in the range of 300 to 2000 nm. If the volume average particle diameter of the rubber (A) is 300 nm or more, it is preferable because the low-temperature impact resistance and pigment colorability of the resin composition containing the graft copolymer are improved. A volume average particle diameter of 2000 nm or less is preferable because the surface appearance and low-temperature impact resistance of the molded product are improved.
- the volume average particle diameter of the rubber (A) is preferably in the range of 300 to 1000 nm, preferably in the range of 400 to 1000 nm, from the viewpoint of achieving a good balance between the low temperature impact resistance and the pigment colorability of the resin composition. It is more preferable that
- the volume average particle diameter / number average particle diameter (Dv / Dn) of the rubber (A) is preferably in the range of 1.0 to 2.0, and preferably in the range of 1.0 to 1.5. More preferred. Dv / Dn represents the particle size distribution, and the closer to 1.0, the higher the monodispersity. If Dv / Dn is 2.0 or less, the pigment colorability of the resin composition is good, which is preferable. The method for measuring Dv / Dn will be described later in the Examples section.
- the grafting vinyl monomer (b) is polymerized in the presence of the rubber (A) to form a graft portion made of a vinyl polymer on the rubber (A), thereby obtaining a polyorganosiloxane-containing graft copolymer. be able to.
- Examples of the vinyl monomer for grafting (b) include the following. Aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyltoluene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate; ethyl acrylate, n-butyl acrylate, methyl acrylate, etc.
- Aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyltoluene
- alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate
- ethyl acrylate, n-butyl acrylate, methyl acrylate etc.
- Alkyl acrylates Alkyl acrylates; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromophenyl (meth) acrylate, 2, Estes such as 4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, and trichlorophenyl (meth) acrylate
- Aryl (meth) acrylate group is a phenyl group or substituted phenyl group. These can be used individually by 1 type or in combination of 2 or more types.
- the grafting vinyl monomer (b) may contain a crosslinkable monomer.
- the amount of the crosslinkable monomer used in 100% by mass of the grafting vinyl monomer (b) is: It is preferable that it is 0.005 mass% or less.
- the refractive index of the “polymer” obtained when the grafting vinyl monomer (b) is polymerized alone is in the range of 1.50 to 1.60. It is preferable that By setting the refractive index of the polymer within the range of 1.50 to 1.60, the low-temperature impact resistance and pigment colorability of the resin composition can be further improved.
- the refractive index of the polymer is more preferably in the range of 1.52 to 1.59.
- the refractive index of the polymer is calculated using the same formula as the refractive index of the rubber (A).
- the type and amount of the grafting vinyl monomer (b) are adjusted so that the refractive index of the polymer is in the range of 1.50 to 1.60.
- the grafting vinyl monomer (b) is an aromatic vinyl monomer, an alkyl (meth) acrylate, or vinyl cyanide. It is preferable to contain at least one selected from the group consisting of an aryl (meth) acrylate in which the monomer and the ester group are a phenyl group or a substituted phenyl group. Moreover, it is more preferable to contain the aryl (meth) acrylate whose ester group is a phenyl group or a substituted phenyl group from a compatible viewpoint of a graft copolymer and a thermoplastic resin.
- the content of the one or more monomers is preferably 5 to 100% by mass, more preferably 20 to 100% by mass, and more preferably 50 to 100% by mass with respect to 100% by mass of the vinyl monomer for grafting. More preferably, it is 100 mass%.
- the content of the rubber (A) in the graft copolymer is preferably 10 to 99% by mass with respect to 100% by mass of the graft copolymer. If the rubber (A) content is 10% by mass or more, the low temperature impact strength of the resin composition will be sufficient, and if it is 99% by mass or less, the surface appearance of the molded product will be good. From the viewpoint of making the low-temperature impact strength of the resin composition better, the content of the rubber (A) is more preferably 50 to 95% by mass with respect to 100% by mass of the graft copolymer, and 65 to 90% by mass. % Is more preferable.
- Examples of the graft copolymerization method include a method in which the vinyl monomer (b) for grafting is added to the latex of the rubber (A) and the polymerization is performed in one or more stages. When polymerizing in multiple stages, it is preferable to divide the total amount of the vinyl monomer for grafting (b) in the presence of the latex of the rubber (A), and add or sequentially add to polymerize. .
- Such a polymerization method has good polymerization stability and can stably obtain a latex having a desired particle size and particle size distribution.
- an emulsifier can be added as necessary.
- the emulsifier used for the polymerization of the graft portion include the same emulsifiers as those described above when the rubber (A) is produced, and anionic emulsifiers and nonionic emulsifiers are preferable.
- Examples of the polymerization initiator used for the polymerization of the graft portion include the same polymerization initiators used for producing the rubber (A), and azo initiators and redox initiators are preferable.
- a spray drying method or a coagulation method can be used.
- the spray drying method is a method in which the latex of the graft copolymer is sprayed in the form of fine droplets in a dryer and dried by applying a heating gas for drying.
- Examples of the method for generating fine droplets include a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type.
- the capacity of the dryer may be a small capacity as used in a laboratory or a large capacity as used industrially.
- the temperature of the heating gas for drying is preferably 200 ° C. or less, and more preferably 120 to 180 ° C. Two or more types of graft copolymer latices produced separately may be spray dried together.
- an optional component such as silica can be added to the latex of the graft copolymer and spray dried.
- the coagulation method is a method of coagulating the latex of the graft copolymer, separating the graft copolymer, collecting it, and drying it.
- a graft copolymer latex is introduced into hot water in which a coagulant is dissolved, salted out, and solidified to separate the graft copolymer.
- the graft copolymer in which the moisture content is reduced by dehydration or the like is recovered from the separated wet graft copolymer.
- the recovered graft copolymer is dried using a press dehydrator or a hot air dryer.
- the coagulant examples include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, and acids such as sulfuric acid, and calcium acetate is particularly preferable.
- inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate
- acids such as sulfuric acid, and calcium acetate is particularly preferable.
- These coagulants can be used singly or in combination of two or more, but when two or more are used, it is necessary to select a combination that does not form a water-insoluble salt.
- the combined use of calcium acetate and sulfuric acid or a sodium salt thereof is not preferable because a calcium salt insoluble in water is formed.
- the above-mentioned coagulant is usually used as an aqueous solution.
- the concentration of the aqueous solution of the coagulant is preferably 0.1% by mass or more, particularly 1% by mass or more from the viewpoint of stably coagulating and recovering the graft copolymer. Further, from the viewpoint of reducing the amount of the coagulant remaining in the recovered graft copolymer and preventing the deterioration of the molding appearance of the molded product, the concentration of the coagulant aqueous solution is 20% by mass or less, particularly 15% by mass. The following is preferable.
- the amount of the coagulant aqueous solution is not particularly limited, but is preferably 10 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the latex.
- the method of bringing the latex into contact with the coagulant aqueous solution is not particularly limited, but the following methods are usually mentioned.
- (1) A method in which a latex is continuously added to the coagulant aqueous solution while stirring the coagulant aqueous solution and maintained for a certain period of time.
- (2) The coagulant aqueous solution and the latex are continuously mixed in a container equipped with a stirrer at a constant ratio.
- the temperature at which the latex is brought into contact with the coagulant aqueous solution is not particularly limited, but is preferably 30 ° C. or higher and 100 ° C. or lower.
- the contact time is not particularly limited.
- the agglomerated graft copolymer is washed with about 1 to 100 times by weight of water, and the wet graft copolymer separated by filtration is dried using a fluidized dryer or a pressure dehydrator.
- the drying temperature and drying time may be appropriately determined depending on the obtained graft copolymer.
- the graft copolymer may be directly sent to an extruder or a molding machine for producing the resin composition, and mixed with a thermoplastic resin to obtain a molded body. Is possible.
- the graft copolymer is preferably recovered using a coagulation method from the viewpoint of the thermal decomposition resistance of a resin composition obtained by mixing with a thermoplastic resin.
- the graft copolymer of the present invention has a Charpy impact measured under the following “measurement conditions” for “test piece 1”, “test piece 2” or “test piece 3” produced under the following “production conditions”.
- a polymer having strength [kJ / m 2 ], L *, and flame retardancy shown in the following (1) to (3) (hereinafter referred to as “graft copolymer 2 of the present invention”) Preferably).
- Charpy impact strength at ⁇ 30 ° C. is 20 kJ / m 2 or more, (2) L * is 8 or less, (3) Flame retardancy is V1 or V0.
- test pieces 1 and 2 [Conditions for preparing test pieces 1 and 2]: (A) 3 parts by mass of a polyorganosiloxane-containing graft copolymer, (B) 97 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics) (C) Irganox 1076 (manufactured by BASF) 0.1 parts by mass, (D) 0.1 part by weight of ADK STAB 2112 (made by ADEKA), (E) Carbon black # 960 (made by Mitsubishi Chemical Corporation) 0.1 mass part.
- A 3 parts by mass of a polyorganosiloxane-containing graft copolymer
- B 97 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics)
- C Irganox 1076 (manufactured by BASF)
- test piece 1 length 80 mm, width 10 mm, Thickness 4 mm, with V notch
- test piece 2 length 100 mm, width 50 mm, thickness 2 mm
- test piece 3 [Conditions for preparing test piece 3]: (A) 5 parts by mass of a polyorganosiloxane-containing graft copolymer, (B) 89.5 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 24,000 (Iupilon S-2000F manufactured by Mitsubishi Engineering Plastics) (E) Carbon black # 960 (manufactured by Mitsubishi Chemical Corporation) 0.1 parts by mass, (F) 5 parts by mass of an aromatic phosphate ester flame retardant (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.) (G) 0.5 parts by mass of polytetrafluoroethylene-containing powder (Methbrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
- a devolatilizing extruder (PCM-30 manufactured by Ikegai Co., Ltd.) in which the above five types of materials (a), (b), (e), (f), (g) were blended and heated to a barrel temperature of 280 ° C. ) And kneading and extruding under the conditions of a screw speed of 150 rpm to obtain pellets.
- This pellet was molded with a 100-ton injection molding machine (SE-100DU manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 90 ° C. to form “test piece 3” (length 127 mm, width 12. 7 mm, thickness 1.6 mm).
- the Charpy impact strength is measured for “Test piece 1” which was left in an atmosphere of ⁇ 30 ° C. for 12 hours or more by a method according to ISO 179.
- thermoplastic resin composition using the “graft copolymer 2 of the present invention” satisfying the performance shown in the above (1) to (3) has good low-temperature impact resistance, pigment colorability, and flame retardancy. is there.
- the Charpy impact strength at ⁇ 30 ° C. is preferably 23 kJ / m 2 or more, and L * is preferably 6 or less.
- the graft copolymer 2 of the present invention is obtained by polymerizing the vinyl monomer for grafting (b) in the presence of the rubber (A) containing the polyorganosiloxane (A1) and the vinyl polymer (A2).
- a graft copolymer to be obtained wherein the refractive index of the rubber (A) is in the range of 1.47 to 1.56, and the volume average particle diameter of the rubber (A) is in the range of 300 to 2000 nm.
- a certain graft copolymer is preferable.
- the increase in Charpy impact strength at ⁇ 30 ° C. increases the volume average particle diameter of rubber (A) within the range of 300 to 2000 nm and increases the content of polyorganosiloxane (A1) in rubber (A). This can be achieved.
- the reduction of L * should be achieved by setting the volume average particle diameter of rubber (A) within the range of 300 to 2000 nm and setting the refractive index of rubber (A) to 1.47 to 1.56. Can do.
- the volume average particle diameter of the rubber (A) is in the range of 300 to 2000 nm, and the content of the polyorganosiloxane (A1) in the rubber (A) is increased. This can be achieved.
- the graft copolymer 1 of the present invention or “the graft copolymer 2 of the present invention” can be mixed with a thermoplastic resin and used as a thermoplastic resin composition.
- thermoplastic resin that can be used in the present invention is not particularly limited, and examples thereof include one or more resins selected from thermoplastic resins and thermoplastic elastomers.
- thermoplastic resin examples include the following. Olefin resins such as polypropylene (PP) and polyethylene (PE); polystyrene (PS), high impact polystyrene (HIPS), (meth) acrylate / styrene copolymer (MS), styrene / acrylonitrile copolymer (SAN), Styrene / maleic anhydride copolymer (SMA), acrylonitrile / butadiene / styrene copolymer (ABS), acrylic ester / styrene / acrylonitrile copolymer (ASA), acrylonitrile / ethylene / propylene rubber / styrene copolymer (ASA) Styrene (St) resin such as AES); Acrylic (Ac) resin such as polymethyl methacrylate (PMMA); Polycarbonate (PC) resin; Polyamide (PA) resin; Polyethylene tertyrene (PS), polyethylene
- thermoplastic elastomer examples include the following. Styrene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, polyester elastomer, polyamide elastomer, fluorine elastomer, 1,2-polybutadiene, trans 1,4-polyisoprene, etc. Among these, urethane elastomers, polyester elastomers, and polyamide elastomers are preferable.
- thermoplastic resins the following are preferable.
- St resin PC resin, PA resin, PET resin, PBT resin, (m-) PPE resin, POM resin, PU resin, alloy of PC resin such as PC / ABS and St resin, PA such as PA / ABS Alloy of resin and St resin, alloy of PA resin and TPE, alloy of PA resin such as PA / PP and polyolefin resin, alloy of PC resin such as PC / PBT and PEs resin, PPE / PBT, Alloys of PPE resin such as PPE / PA and other resins.
- polycarbonate resins are more preferable, and aromatic polycarbonate resins are particularly preferable from the viewpoint of maximizing the effect of improving pigment colorability.
- the aromatic polycarbonate resin is an optionally branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic hydroxy compound or a small amount thereof with a diester of phosgene or carbonic acid.
- the production method of the aromatic polycarbonate resin is not particularly limited, and a known method, that is, a phosgene method (interfacial polymerization method), a melting method (transesterification method) or the like is employed.
- a phosgene method interfacial polymerization method
- a melting method transesterification method
- an aromatic polycarbonate resin produced by a melting method and having an adjusted terminal OH group amount can also be used.
- aromatic polycarbonate resin examples include the following. Iupilon S-1000, Iupilon S-2000, Iupilon S-3000, Iupilon H-3000 or Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics), Panlite L1250, Panlite L1225 or Panlite K1300 (Teijin Chemicals ( Etc.).
- the content of the graft copolymer in a total of 100% by mass of the thermoplastic resin and the graft copolymer is preferably 0.5 to 90% by mass, and more preferably 0.5 to 20% by mass. If the content of the graft copolymer is 0.5% by mass or more, a resin composition excellent in impact resistance can be obtained, and if it is 20% by mass or less, a resin composition excellent in surface appearance is obtained. If the content is 0.5 to 20% by mass, a resin composition excellent in impact resistance and surface appearance can be obtained.
- thermoplastic resin composition can contain various additives as long as it does not depart from the object of the present invention.
- Additives include, for example, stabilizers such as phenol-based stabilizers, phosphorus-based stabilizers, ultraviolet absorbers, and amine-based light stabilizers; flame-retardant agents such as phosphorus-based, bromine-based, silicone-based, and organometallic salt-based materials; Examples include modifiers for imparting various physical properties such as hydrolyzability; fillers such as titanium oxide and talc; dyes and pigments; and plasticizers.
- thermoplastic resin is an aromatic polycarbonate resin
- the following can be used as additives, for example.
- Flameproofing agent for example, fluorinated polyolefin, silicone and aramid fiber
- lubricant for example, fluorinated polyolefin, silicone and aramid fiber
- mold release agent for example, pentaerythritol tetrastearate
- nucleating agent for example, antistatic agent, stabilizer, filler
- Reinforcing agents eg, glass fibers, carbon fibers, mica, kaolin, talc, CaCO 3 and glass flakes
- dyes and pigments e.g, glass fibers, carbon fibers, mica, kaolin, talc, CaCO 3 and glass flakes
- dyes and pigments e.g, glass fibers, carbon fibers, mica, kaolin, talc, CaCO 3 and glass flakes
- dyes and pigments for example.
- the method for preparing the thermoplastic resin composition of the present invention is not particularly limited, but the graft copolymer, the thermoplastic resin, and various additives used as necessary are mixed by a V-type blender or a Henschel mixer.
- the mixture can be dispersed and melt-kneaded using an extruder or a Banbury mixer, a pressure kneader, a kneader such as a roll, or the like. These components can be mixed batchwise or continuously, and the mixing order of the components is not particularly limited.
- the melt-kneaded product can be made into pellets and used for various moldings.
- thermoplastic resin composition examples include a method of molding a thermoplastic resin composition or a mixture of the graft copolymer powder and the thermoplastic resin with an injection molding machine.
- the use of the molded body is not particularly limited, and can be widely used industrially as a material in the automotive field, OA equipment field, electric / electronic field, and the like.
- Examples 1 to 8 and Comparative Examples 1 to 4 are examples relating to the production and evaluation of graft copolymers
- Examples 9 to 24 and Comparative Examples 5 to 14 are examples relating to the production and evaluation of thermoplastic resin compositions. It is.
- “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
- Solid content A polyorganosiloxane latex having a mass w of 1 was dried with a hot air drier at 180 ° C. for 30 minutes, a mass w 2 of the residue after drying was measured, and a solid content [%] was calculated by the following formula. .
- Solid content [%] w 2 / w 1 ⁇ 100
- Volume average particle diameter, number average particle diameter, Dv / Dn “Rubber latex” or “graft copolymer latex” is diluted with deionized water, and rubber particles and graft copolymer are used with a laser diffraction / scattering particle size distribution analyzer (SALD-7100, manufactured by Shimadzu Corporation). The volume average particle diameter Dv and the number average particle diameter Dn of the combined particles were measured, and Dv / Dn was calculated.
- the refractive index calculated from the monomer composition of the rubber (A) or graft copolymer was used.
- the median diameter was used as the particle diameter.
- the sample concentration of the rubber latex was appropriately adjusted so as to be within an appropriate range in the scattering intensity monitor attached to the apparatus.
- the emulsion is then placed in a separable flask having a capacity of 5 liters equipped with a cooling condenser, the emulsion is heated to a temperature of 80 ° C., and then a mixture of 0.20 parts of sulfuric acid and 49.8 parts of distilled water. Was continuously charged over 3 minutes.
- the polymerization reaction was carried out while maintaining the state heated to 80 ° C. for 7 hours, and then cooled to room temperature (25 ° C.), and the resulting reaction product was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex (A S -1).
- the solid content of the polyorganosiloxane latex (A S -1) was 29.8%.
- the latex had a number average particle size (Dn) of 384 nm, a mass average particle size (Dw) of 403 nm, and Dw / Dn of 1.05 as measured by a capillary particle size distribution meter.
- the emulsion was put in a separable flask having a capacity of 5 liters equipped with a cooling condenser, and then the emulsion was heated to a temperature of 80 ° C., and this temperature was maintained for 7 hours to cause a polymerization reaction. 25 ° C.) and the resulting reaction was kept at room temperature for 6 hours. Thereafter, a 5% aqueous sodium hydroxide solution was added to neutralize the reaction solution to pH 7.0 to obtain a polyorganosiloxane latex (A S -2).
- the solid content of the polyorganosiloxane latex (A S -2) was 28.5%.
- the latex had a number average particle size (Dn) of 190 nm, a mass average particle size (Dw) of 90 nm, and Dw / Dn of 2.11.
- Example 1 Taken polyorganosiloxane latex (A S -1) 100.67 parts obtained in Production Example 1 (30.0 parts of a polymer basis) to the separable flask 5-liter, was added to 160 parts of deionized water Mixed. Next, a mixture of 39 parts of styrene (St), 1.0 part of allyl methacrylate (AMA) and 0.16 part of cumene hydroperoxide (CHP) was added to the separable flask, and the mixture was stirred at room temperature for 1 hour. Impregnated with organosiloxane. In addition, this mixture is a mixture of the vinyl monomer (a2) for rubber
- St styrene
- AMA allyl methacrylate
- CHP cumene hydroperoxide
- the nitrogen atmosphere in the flask was replaced by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C.
- the liquid temperature reached 50 ° C.
- 0.003 part of disodium ethylenediaminetetraacetate (EDTA) and 0.24 part of sodium formaldehyde sulfoxylate (SFS) were removed.
- An aqueous solution dissolved in 10 parts of ionic water was added to initiate radical polymerization.
- a liquid mixture of 28.5 parts of methyl methacrylate (MMA), 1.5 parts of methyl acrylate (MA) and 0.16 parts of t-butyl hydroperoxide (t-BH) at a liquid temperature of 65 ° C. was dropped into the latex over 1 hour to initiate and continue the graft polymerization reaction. After completion of the dropping, the temperature was kept at 60 ° C. or higher for 1 hour and then cooled to room temperature to obtain a latex of the polyorganosiloxane-containing graft copolymer (G-1).
- the refractive index of the graft part was 1.489.
- the volume average particle diameter (Dv) of the graft copolymer particles was 525 nm.
- Example 8 100.67 parts (30.0 parts in terms of polymer) of the polyorganosiloxane latex (A S -1) obtained in Production Example 1 was collected in a separable flask, 160 parts of deionized water was added and mixed, and then St39 A mixture of 1.0 part of AMA and 1.0 part of AMA was added and stirred at room temperature for 1 hour to impregnate polyorganosiloxane.
- the nitrogen atmosphere in the flask was replaced by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 50 ° C.
- an aqueous solution in which 0.2 part of potassium persulfate (KPS) was dissolved in 10 parts of deionized water was added to initiate radical polymerization.
- KPS potassium persulfate
- the temperature of 65 ° C. is maintained for 1 hour from the time when the liquid temperature is lowered to 65 ° C., and rubber containing polyorganosiloxane and styrene (A-8) Latex was obtained.
- Example 8 rubber (A-12) latex and polyorganosiloxane-containing graft copolymer were used in the same manner as in Example 8 except that the type and amount of each raw material used were changed to the conditions shown in Table 1. A coalescence (G-12) was produced, and further a graft copolymer powder was obtained. Table 1 shows the evaluation results of the rubber and graft copolymer obtained in the same manner as in Example 1. The numerical values in parentheses in the column of polyorganosiloxane and vinyl monomer (a2) in Table 1 indicate the composition ratio (% by mass) in 100% by mass of rubber (A).
- the obtained pellets were dried at 80 ° C. for 12 hours and then supplied to a 100-ton injection molding machine (trade name: SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was performed at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. The “test piece 1” and the “test piece 2” were obtained. Subsequently, Charpy impact strength and pigment colorability were measured using each test piece. The evaluation results are shown in Table 2.
- the obtained pellets were dried at 80 ° C. for 12 hours and then supplied to a 100-ton injection molding machine (trade name: SE-100DU, manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was performed at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C.
- Each “test piece 1 ′” (length 80 mm, width 10 mm, thickness 4 mm, with V notch), each “test piece 2 ′” (length 100 mm, width 50 mm, thickness 2 mm) and each “test piece 3” (Length 127 mm, width 12.7 mm, thickness 1.6 mm).
- Each specimen was then subjected to Charpy impact strength, pigment colorability measurement, and UL-94V test. The evaluation results are shown in Table 3.
- PX-200 An aromatic phosphate ester flame retardant (PX-200 manufactured by Daihachi Chemical Industry Co., Ltd.)
- A-3800 Polytetrafluoroethylene-containing powder (Metbrene A-3800 manufactured by Mitsubishi Rayon Co., Ltd.).
- the graft copolymers (G-1) to (G-8) of Examples 1 to 8 use rubbers (A-1) to (A-8) because styrene is used as the vinyl monomer (a2) for rubber. ) In the range of 1.47 to 1.56, and the volume average particle diameter of each of these rubbers was in the range of 300 to 2000 nm.
- the refractive indexes of the rubbers (A-9) and (A-11) were lower than 1.47.
- graft copolymers (G-10) and (G-12) of Comparative Examples 2 and 4 have a small particle diameter of the polyorganosiloxane latex (A S -2) and (A S -3), rubber
- the volume average particle diameters of (A-10) and (A-12) were smaller than 300 nm.
- thermoplastic resin compositions (H-1) to (H-8) of Examples 9 to 16 were prepared from the respective rubbers (A) constituting the respective graft copolymers (G-1) to (G-8).
- -1) to (A-8) have a refractive index in the range of 1.47 to 1.56, and the rubber has a volume average particle diameter in the range of 300 to 2000 nm. Both pigment colorability was good.
- thermoplastic resin composition (H-9) of Comparative Example 5 was poor in pigment colorability because the refractive index of each rubber (A-9) constituting each graft copolymer was low.
- thermoplastic resin compositions (H-10) and (H-12) of Comparative Examples 6 and 8 are the volume averages of the rubbers (A-10) and (A-12) constituting the respective graft copolymers. Due to the small particle size, the low-temperature impact resistance and pigment colorability were poor.
- thermoplastic resin composition (H-13) of Comparative Example 9 did not contain a graft copolymer, the low-temperature impact resistance was poor.
- the refractive indexes of the rubbers (A-1) to (A-8) constituting the graft copolymer are 1.47. Since the rubber had a volume average particle diameter in the range of 300 to 200 nm and the rubber had a volume average particle diameter in the range of 300 to 200 nm, all of the low temperature impact resistance, pigment colorability and flame retardancy were good.
- thermoplastic resin composition (I-9) of Comparative Example 10 had poor pigment colorability due to the low refractive index of the rubber (A-9) constituting the graft copolymer.
- thermoplastic resin composition (I-10) of Comparative Example 11 had poor low-temperature impact resistance and pigment colorability due to the small volume average particle diameter of the rubber (A-10) constituting the graft copolymer. .
- thermoplastic resin composition (I-11) of Comparative Example 12 was poor in flame retardancy because the polyorganosiloxane content in the rubber (A-11) constituting the graft copolymer was low.
- thermoplastic resin composition (I-12) of Comparative Example 13 the volume average particle diameter of the rubber (A-12) constituting the graft copolymer is small, and the polyorganosiloxane content in the rubber is low. Furthermore, the low temperature impact resistance and flame retardancy were poor.
- thermoplastic resin composition (I-13) of Comparative Example 14 did not contain a graft copolymer, the low-temperature impact resistance and flame retardancy were poor.
- the molded body obtained from the graft copolymer or thermoplastic resin composition of the present invention can be widely used industrially as a material in the automotive field, OA equipment field, electrical / electronic field and the like.
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Abstract
Description
(1)-30℃におけるシャルピー衝撃強度が20kJ/m2以上、
(2)L*が8以下、
(3)難燃性がV1又はV0。
(a)ポリオルガノシロキサン含有グラフト共重合体3質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)97質量部、
(c)Irganox1076(BASF製)0.1質量部、
(d)アデカスタブ2112(ADEKA製)0.1質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部。
(a)ポリオルガノシロキサン含有グラフト共重合体5質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)89.5質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部、
(f)芳香族リン酸エステル系難燃剤(大八化学工業(株)製PX-200)5質量部、
(g)ポリテトラフルオロエチレン含有粉体(三菱レイヨン(株)製メタブレンA-3800)0.5質量部。
ISO 179に準拠する方法により、-30℃の雰囲気下で12時間以上放置した「試験片1」について、シャルピー衝撃強度を測定する。
JISZ8722に準じた下記の測定条件にて、「試験片2」について三刺激値(XYZ)を測定する。次いでCIE色差式を用いてL*値を算出する。
装置:分光式色差計SE-2000(日本電色工業株式会社製、0-45°後分光方式)、
測定範囲:380~780nm、
測定光源:C光(2°視野)。
UL-94V(垂直燃焼試験)に準じて「試験片3」について難燃性を測定する。
本発明のポリオルガノシロキサン含有グラフト共重合体は、ポリオルガノシロキサン(A1)及びビニル重合体(A2)を含有するゴム(A)の存在下で、グラフト用ビニル単量体(b)を重合して得られる重合体であって、前記ゴム(A)の屈折率が1.47~1.56の範囲内であり、前記ゴム(A)の体積平均粒子径が300~2000nmの範囲内である重合体(以下、「本発明のグラフト共重合体1」という場合がある。)であることが好ましい。
ポリオルガノシロキサン(A1)は、オルガノシロキサン単位を構成単位として含有する重合体である。ポリオルガノシロキサンは、オルガノシロキサンまたは、オルガノシロキサンと必要に応じて使用される成分を1種以上含む「オルガノシロキサン混合物」を重合することにより得ることができる。必要に応じて使用される成分としては、シロキサン系架橋剤、シロキサン系グラフト交叉剤、及び末端封鎖基を有するシロキサンオリゴマー等が挙げられる。
ポリオルガノシロキサン(A1)の製造方法としては特に制限はなく、例えば、以下の製造方法を採用できる。まず、オルガノシロキサン、必要に応じてシロキサン系架橋剤、必要に応じてシロキサン系グラフト交叉剤、及び必要に応じて末端封鎖基を有するシロキサンオリゴマーを含むオルガノシロキサン混合物を、乳化剤と水によって乳化させてエマルションを調製する。その後、該混合物を酸触媒を用いて高温下で重合させ、次いでアルカリ性物質により酸を中和してポリオルガノシロキサンのラテックスを得る。尚、以下の製造方法の説明においては、重合用の原料として「オルガノシロキサン混合物」を用いた場合について説明するが、「オルガノシロキサン」を用いた場合についても同様の製造プロセスを適用できる。
カートリッジ:専用の粒子分離用キャピラリー式カートリッジ(商品名;C-202)、
キャリア液:専用キャリア液(商品名;2XGR500)、
キャリア液の液性:ほぼ中性、
キャリア液の流速:1.4ml/分、
キャリア液の圧力:約4,000psi(2,600kPa)、
測定温度:35℃、
試料使用量:0.1ml。
また、標準粒子径物質としては、米国DUKE社製の粒子径既知の単分散ポリスチレンで、40~800nmの粒子径の範囲内の12種類の粒子が用いられる。
本発明のビニル重合体(A2)としては、ゴム用ビニル単量体(a2)を重合して得られる重合体が挙げられる。
ゴム用ビニル単量体(a2)としては、例えば以下の単量体が挙げられる。スチレン、α-メチルスチレン、ビニルトルエン等の芳香族ビニル単量体;メチルメタクリレート、エチルメタクリレート、n-ブチルメタクリレート、i-ブチルメタクリレート等のアルキルメタクリレート;エチルアクリレート、n-プロピルアクリレート、n-ブチルアクリレート、i-ブチルアクリレート、2-エチルヘキシルアクリレート等のアルキルアクリレート;フェニル(メタ)アクリレート、4-t-ブチルフェニル(メタ)アクリレート、ブロモフェニル(メタ)アクリレート、ジブロモフェニル(メタ)アクリレート、2,4,6-トリブロモフェニル(メタ)アクリレート、モノクロルフェニル(メタ)アクリレート、ジクロルフェニル(メタ)アクリレート、トリクロルフェニル(メタ)アクリレート等のエステル基がフェニル基または置換フェニル基であるアリール(メタ)アクリレート;アクリロニトリル、メタクリロニトリル等のシアン化ビニル単量体等。これらは1種を単独でまたは2種以上を組み合わせて用いることができる。
本発明のゴム(A)は、ポリオルガノシロキサン(A1)及びビニル重合体(A2)を含有する。ゴム(A)としては、以下の(1)~(3)の構造を有するゴムを例示することができる。
(1)多層構造を有し、ポリオルガノシロキサン(A1)のコアがビニル重合体(A2)のシェルで被覆された構造を有するゴム、
(2)多層構造を有し、ビニル重合体(A2)のコアがポリオルガノシロキサン(A1)のシェルで被覆された構造を有するゴム、
(3)ポリオルガノシロキサン(A1)及びビニル重合体(A2)を含有する複合ゴム。
<数式1>
n=v1n1+v2n2+v3n3+・・・
なお、式中の「n1、n2、n3、・・・」は各単量体の単独重合体の20℃における屈折率を表し、POLYMER HANDBOOK 4th Editionに記載の値が使用できる。式中、「v1、v2、v3、・・・」は各単量体の体積分率を表す。
(1)の構造を有するゴム:ポリオルガノシロキサンラテックスの存在下に、ゴム用ビニル単量体(a2)を重合して、ゴム(A)のラテックスを得る方法、
(2)の構造を有するゴム:ビニル重合体(A2)ラテックスの存在下に、オルガノシロキサン混合物を重合して、ゴム(A)のラテックスを得る方法、
(3)の構造を有するゴム:
[3-1]ポリオルガノシロキサンラテックスにゴム用ビニル単量体(a2)を添加し、ポリオルガノシロキサン粒子にゴム用ビニル単量体(a2)を含浸させた後にゴム用ビニル単量体(a2)を重合してゴム(A)のラテックスを得る方法、及び、
[3-2]ビニル重合体(A2)ラテックスにオルガノシロキサン混合物を添加し、ビニル重合体(A2)粒子にオルガノシロキサン混合物を含浸させた後にオルガノシロキサンを重合してゴム(A)のラテックスを得る方法。
(3)の構造を有するゴムを得る方法としては、粒子径の調整のしやすさの観点から前記[3-1]の方法が好ましい。
上記ゴム(A)の存在下でグラフト用ビニル単量体(b)を重合し、ゴム(A)にビニル重合体からなるグラフト部を形成することで、ポリオルガノシロキサン含有グラフト共重合体を得ることができる。
本発明のグラフト共重合体は、下記の「作製条件」で作製された「試験片1」、「試験片2」または「試験片3」について、下記の「測定条件」で測定されるシャルピー衝撃強度[kJ/m2]、L*、及び難燃性が、以下の(1)~(3)で示される性能を有する重合体(以下、「本発明のグラフト共重合体2」という場合がある。)であることが好ましい。
(1)-30℃におけるシャルピー衝撃強度が20kJ/m2以上、
(2)L*が8以下、
(3)難燃性がV1又はV0。
(a)ポリオルガノシロキサン含有グラフト共重合体3質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)97質量部、
(c)Irganox1076(BASF製)0.1質量部、
(d)アデカスタブ2112(ADEKA製)0.1質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部。
(a)ポリオルガノシロキサン含有グラフト共重合体5質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)89.5質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部、
(f)芳香族リン酸エステル系難燃剤(大八化学工業(株)製PX-200)5質量部、
(g)ポリテトラフルオロエチレン含有粉体(三菱レイヨン(株)製メタブレンA-3800)0.5質量部。
ISO 179に準拠する方法により、-30℃の雰囲気下で12時間以上放置した「試験片1」について、シャルピー衝撃強度を測定する。
JISZ8722に準じた下記の測定条件にて、「試験片2」について三刺激値(XYZ)を測定する。次いでCIE色差式を用いてL*値を算出する。
装置:分光式色差計SE-2000(日本電色工業株式会社製、0-45°後分光方式)、
測定範囲:380~780nm、
測定光源:C光(2°視野)。
UL-94V(垂直試験法)に準じて「試験片3」について難燃性を測定する。
「本発明のグラフト共重合体1」または「本発明のグラフト共重合体2」は、熱可塑性樹脂と混合して熱可塑性樹脂組成物として使用することができる。
熱可塑性樹脂としては、例えば以下のものが挙げられる。ポリプロピレン(PP)、ポリエチレン(PE)等のオレフィン系樹脂;ポリスチレン(PS)、ハイインパクトポリスチレン(HIPS)、(メタ)アクリレート・スチレン共重合体(MS)、スチレン・アクリロニトリル共重合体(SAN)、スチレン・無水マレイン酸共重合体(SMA)、アクリロニトリル・ブタジエン・スチレン共重合体(ABS)、アクリル酸エステル・スチレン・アクリロニトリル共重合体(ASA)、アクリロニトリル・エチレン・プロピレンゴム・スチレン共重合体(AES)等のスチレン(St)系樹脂;ポリメチルメタクリレート(PMMA)等のアクリル(Ac)系樹脂;ポリカーボネート(PC)樹脂;ポリアミド(PA)樹脂;ポリエチレンテレフタレート(PET)、ポリブチレンテレフタレート(PBT)等のポリエステル(PEs)樹脂;(変性)ポリフェニレンエーテル((m-)PPE)樹脂、ポリオキシメチレン(POM)樹脂、ポリスルフォン(PSO)樹脂、ポリアリレート(PAr)樹脂、ポリフェニレン(PPS)樹脂等のエンジニアリングプラスチックス;熱可塑性ポリウレタン(PU)樹脂;硬質塩化ビニル樹脂、半硬質塩化ビニル樹脂、軟質塩化ビニル樹脂等の塩化ビニル(PVC)系樹脂;PC/ABS等のPC樹脂とSt系樹脂とのアロイ;PVC/ABS等のPVC系樹脂とSt系樹脂とのアロイ;PA/ABS等のPA樹脂とSt系樹脂とのアロイ;PA樹脂と熱可塑性エラストマー(TPE)とのアロイ;PA/PP等のPA樹脂とポリオレフィン系樹脂とのアロイ;PC/PBT等のPC樹脂とPEs樹脂とのアロイ;PP/TPE、PP/PE等のオレフィン系樹脂同士のアロイ;PPE/HIPS、PPE/PBT、PPE/PA等のPPE系樹脂とその他の樹脂のアロイ;PVC/PMMA等のPVC系樹脂とアクリル系樹脂とのアロイ等。
熱可塑性樹脂組成物は、本発明の目的を逸脱しない範囲であれば、各種添加剤を含有することができる。添加剤としては、例えば、フェノール系安定剤、燐系安定剤、紫外線吸収剤、アミン系光安定剤等の安定剤;燐系、ブロム系、シリコーン系、有機金属塩系等の難燃剤;耐加水分解性等の各種物性を付与するための改質剤;酸化チタン、タルク等の充填剤;染顔料;可塑剤が挙げられる。
本発明の熱可塑性樹脂組成物の調製方法は特に限定されないが、グラフト共重合体と、熱可塑性樹脂と、必要に応じて使用される各種添加剤とを、V型ブレンダーやヘンシェルミキサー等により混合分散させ、この混合物を押出機またはバンバリーミキサー、加圧ニーダー、ロール等の混練機等を用いて溶融混練することにより調製できる。これらの各成分の混合はバッチ的又は連続的に実施することができ、各成分の混合順序は特に限定されない。溶融混練物はペレットにして、各種の成形に用いることができる。
熱可塑性樹脂組成物の成形方法としては、例えば、熱可塑性樹脂組成物、又はグラフト共重合体粉体と熱可塑性樹脂の混合物を、射出成形機で成形する方法が挙げられる。
(1)固形分
質量w1のポリオルガノシロキサンのラテックスを180℃の熱風乾燥機で30分間乾燥し、乾燥後の残渣の質量w2を測定し、下記式により固形分[%]を算出した。
固形分[%]=w2/w1×100
(2)体積平均粒子径、数平均粒子径、Dv/Dn
「ゴムラテックス」又は「グラフト共重合体ラテックス」を脱イオン水で希釈し、レーザー回折/散乱式粒子径分布測定装置((株)島津製作所製SALD-7100)を用いてゴム粒子及びグラフト共重合体粒子の体積平均粒子径Dv、数平均粒子径Dnを測定し、Dv/Dnを算出した。
JIS K 7111に準じて、温度23℃及び-30℃にて、試験片(長さ80.0mm×幅10.0mm×厚み4mm、Vノッチ付き)のシャルピー衝撃強度を測定した。
JISZ8722に準じた下記の測定条件にてカーボンブラックで着色した厚さ2mmの試験片の三刺激値(XYZ)を測定した。次いでCIE色差式を用いてL*値を算出した。
装置:分光式色差計SE-2000(日本電色工業株式会社製、0-45°後分光方式)、
測定範囲:380~780nm、
測定光源:C光(2°視野)。
1/16インチの試験片(長さ127mm、幅12.7mm、厚さ1.6mm)について、UL-94V試験(垂直試験法)を行った。
テトラエトキシシラン(TEOS)2部、γ-メタクリロイロキシプロピルジメトキシメチルシラン(DSMA)2部及び、オクタメチルシクロテトラシロキサン(モメンティブ・パフォーマンス・マテリアルズ・ジャパン(株)製、製品名:TSF404)96部を混合してオルガノシロキサン混合物100部を得た。脱イオン水150部中にドデシルベンゼンスルホン酸ナトリウム(DBSNa)1部を溶解した水溶液を、前記混合物中に添加し、ホモミキサーにて10,000rpmで5分間攪拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
DSMA2部、オクタメチルシクロテトラシロキサン(製品名:TSF404)73部、ジフェニルジエトキシシラン(信越シリコーン(株)製、製品名:LS-5300)25部を混合してオルガノシロキサン混合物100部を得た。次に、脱イオン水200部中に、DBSNa及びドデシルベンゼンスルホン酸(DBSH)をそれぞれ1部溶解した水溶液を、前記混合物中に添加し、ホモミキサーにて10,000rpmで5分間攪拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
TEOS2部、DSMA2部、及びオクタメチルシクロテトラシロキサン(製品名:TSF404)96部を混合してオルガノシロキサン混合物100部を得た。脱イオン水300部中にDBSNa0.68部を溶解した水溶液を前記混合物中に添加し、ホモミキサーにて10,000rpmで2分間攪拌した後、ホモジナイザーに20MPaの圧力で2回通し、安定な予備混合エマルションを得た。
製造例1において得たポリオルガノシロキサンラテックス(AS-1)100.67部(ポリマー換算で30.0部)を容量5リットルのセパラブルフラスコ内に採取し、脱イオン水160部を添加し混合した。次いでこのセパラブルフラスコ内に、スチレン(St)39部、アリルメタクリレート(AMA)1.0部、クメンハイドロパーオキサイド(CHP)0.16部の混合物を添加し、室温で1時間撹拌を続けポリオルガノシロキサンに含浸させた。尚、この混合物はビニル重合体(A2)の原料となるゴム用ビニル単量体(a2)の混合物である。
実施例1において用いた各原料の種類及び量を表1に示す条件に変更したこと以外は実施例1と同様にして、それぞれ、ゴム(A-2)~(A-7)、(A-9)~(A-11)のラテックス、並びに、ポリオルガノシロキサン含有グラフト共重合体(G-2)~(G-7)、(G-9)~(G-11)を製造し、更にグラフト共重合体の粉体を得た。実施例1と同様にして行った各ゴム及び各グラフト共重合体の評価結果を表1に示す。
製造例1において得たポリオルガノシロキサンラテックス(AS-1)100.67部(ポリマー換算で30.0部)をセパラブルフラスコ内に採取し、脱イオン水160部を添加混合したのち、St39部、AMA1.0部の混合物を添加し、室温で1時間撹拌してポリオルガノシロキサンに含浸させた。
実施例8において、用いた各原料の種類、及び量を表1に示す条件に変更したこと以外は実施例8と同様にして、ゴム(A-12)のラテックス及びポリオルガノシロキサン含有グラフト共重合体(G-12)を製造し、更にグラフト共重合体の粉体を得た。実施例1と同様にして行ったゴム及びグラフト共重合体の評価結果を表1に示す。表1中の、ポリオルガノシロキサン及びビニル単量体(a2)の欄の括弧内の数値はゴム(A)100質量%に占める組成比(質量%)を示す。
St:スチレン
nBA:n-ブチルアクリレート
AMA:アリルメタクリレート
MMA:メチルメタクリレート
PhMA:フェニルメタクリレート
MA:メチルアクリレート
tBH:t-ブチルハイドロパーオキサイド
CHP:クメンハイドロパーオキサイド
KPS:過硫酸カリウム。
各ポリオルガノシロキサン含有グラフト共重合体(G-1)~(G-12)の粉体、及び、ポリカーボネート樹脂(三菱エンジニアリングプラスチックス(株)製、商品名;ユーピロンS-2000F、粘度平均分子量24,000)を、表2に記載の比率で配合し、さらに添加剤としてIrganox1076(BASF製)0.1部、アデカスタブ2112(ADEKA製)0.1部、及び着色剤としてカーボンブラック#960(三菱化学(株)製)0.1部を加え、混合した。該配合物を、30mmΦ二軸押出機(L/D=30)に供給してシリンダー温度280℃及びスクリュー回転数150rpmで溶融混合して押出して、熱可塑性樹脂組成物(H-1)~(H-13)のペレットを得た。
ポリオルガノシロキサン含有グラフト共重合体(G-1)~(G-12)の粉体、及びポリカーボネート樹脂(三菱エンジニアリングプラスチックス(株)製、商品名;ユーピロンS-2000F、粘度平均分子量24,000)を、表3に記載の比率で配合し、さらに着色剤としてカーボンブラック#960(三菱化学(株)製)0.1部を加え、混合した。該配合物を、30mmΦ二軸押出機(L/D=30)に供給してシリンダー温度280℃及びスクリュー回転数150rpmで溶融混合して押出して、熱可塑性樹脂組成物(I-1~13)のペレットを得た。
PX-200:芳香族リン酸エステル系難燃剤(大八化学工業(株)製PX-200)、
A-3800:ポリテトラフルオロエチレン含有粉体(三菱レイヨン(株)製メタブレンA-3800)。
実施例1~8のグラフト共重合体(G-1)~(G-8)は、ゴム用ビニル単量体(a2)としてスチレンを用いているためゴム(A-1)~(A-8)の屈折率が1.47~1.56の範囲内であり、またこれらの各ゴムの体積平均粒子径は300~2000nmの範囲内であった。
Claims (17)
- 下記の「作製条件」で作製された「試験片1」、「試験片2」または「試験片3」について、下記の「測定条件」で測定されるシャルピー衝撃強度[kJ/m2]、L*及び難燃性が、以下の(1)~(3)で示される性能を有する、ポリオルガノシロキサン含有グラフト共重合体:
[(1)-30℃におけるシャルピー衝撃強度が20kJ/m2以上、
(2)L*が8以下、
(3)難燃性がV1又はV0。
〔試験片1及び2の作製条件〕:
(a)ポリオルガノシロキサン含有グラフト共重合体3質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)97質量部、
(c)Irganox1076(BASF製)0.1質量部、
(d)アデカスタブ2112(ADEKA製)0.1質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部。
上記の5種類の材料(a)~(e)を配合し、バレル温度280℃に加熱した脱揮式押出機((株)池貝製PCM-30)にてスクリュー回転数150rpmの条件で混練し押出してペレットを得る。このペレットを100t射出成形機(住友重機(株)製SE-100DU)にて、シリンダー温度280℃、金型温度90℃の条件で成形して「試験片1」(長さ80mm、幅10mm、厚み4mm、Vノッチ付き)および「試験片2」(長さ100mm、幅50mm、厚み2mm)を得る。
〔試験片3の作製条件〕:
(a)ポリオルガノシロキサン含有グラフト共重合体5質量部、
(b)粘度平均分子量24,000の芳香族ポリカーボネート樹脂(三菱エンジニアリングプラスチック(株)製ユーピロンS-2000F)89.5質量部、
(e)カーボンブラック#960(三菱化学(株)製)0.1質量部、
(f)芳香族リン酸エステル系難燃剤(大八化学工業(株)製PX-200)5質量部、
(g)ポリテトラフルオロエチレン含有粉体(三菱レイヨン(株)製メタブレンA-3800)0.5質量部。
上記の5種類の材料(a)、(b)、(e)、(f)、(g)を配合し、バレル温度280℃に加熱した脱揮式押出機((株)池貝製PCM-30)にてスクリュー回転数150rpmの条件で混練し押出してペレットを得る。このペレットを100t射出成形機(住友重機(株)製SE-100DU)にて、シリンダー温度280℃、金型温度90℃の条件で成形して「試験片3」(長さ127mm、幅12.7mm、厚み1.6mm)を得る。
〔シャルピー衝撃強度の測定条件〕:
ISO 179に準拠する方法により、-30℃の雰囲気下で12時間以上放置した「試験片1」について、シャルピー衝撃強度を測定する。
〔L*の測定条件〕:
JISZ8722に準じた下記の測定条件にて、「試験片2」について三刺激値(XYZ)を測定する。次いでCIE色差式を用いてL*値を算出する。
装置:分光式色差計SE-2000(日本電色工業株式会社製、0-45°後分光方式)、
測定範囲:380~780nm、
測定光源:C光(2°視野)。
〔難燃性の測定条件〕:
UL-94V(垂直燃焼試験)に準じて「試験片3」について難燃性を測定する。] - ポリオルガノシロキサン(A1)及びビニル重合体(A2)を含有するゴム(A)の存在下で、グラフト用ビニル単量体(b)を重合して得られるポリオルガノシロキサン含有グラフト共重合体であって、該ゴム(A)の屈折率が1.47~1.56の範囲内であり、該ゴム(A)の体積平均粒子径が300~2000nmの範囲内であるポリオルガノシロキサン含有グラフト共重合体。
- 前記ゴム(A)がポリオルガノシロキサン(A1)及びビニル重合体(A2)を含有する複合ゴムである請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ポリオルガノシロキサン(A1)がオルガノシロキサンを含むオルガノシロキサン混合物を重合したものであり、該オルガノシロキサンが環状ジメチルシロキサン及び/又は2官能性ジアルキルシラン化合物である請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ゴム(A)の体積平均粒子径が400~1000nmの範囲内である請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ゴム(A)中のポリオルガノシロキサン(A1)の含有量が40~80質量%であり、ビニル重合体(A2)の含有量が60~20質量%である請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ビニル重合体(A2)が、20℃における水への溶解度が5質量%以下のラジカル重合開始剤を用いてゴム用ビニル単量体(a2)を重合したものである請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ラジカル重合開始剤が、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、p-メンタンハイドロパーオキサイド、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシネオヘプタノエート、t-ブチルパーオキシピバレート、1,1,3,3-テトラメチルブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、2,2’-アゾビスイソブチロニトリル、ジメチル2,2’-アゾビス(2-メチルプロピオネート)、2,2’-アゾビス(2,4-ジメチルバレロニトリル)、2,2’-アゾビス(2-ブチロニトリル)からなる群より選ばれる少なくとも1種である請求項7に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ビニル重合体(A2)が芳香族ビニル単量体単位及び/又はエステル基がフェニル基若しくは置換フェニル基であるアリール(メタ)アクリレート単位を含有する請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ゴム(A)が、該ゴム(A)の合計100質量%を基準として、アルキル(メタ)アクリレート単位を0~35質量%含有する請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記ゴム用ビニル単量体(a2)が、該ゴム用ビニル単量体(a2)の合計100質量%を基準として、架橋性単量体を0.1~10質量%含有する請求項7に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記グラフト用ビニル単量体(b)が、芳香族ビニル単量体、アルキル(メタ)アクリレート、シアン化ビニル単量体、エステル基がフェニル基若しくは置換フェニル基であるアリール(メタ)アクリレートからなる群より選ばれる少なくとも一種を含有する請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 前記グラフト用ビニル単量体(b)を重合して得られる重合体の屈折率が1.50~1.60の範囲内である請求項2に記載のポリオルガノシロキサン含有グラフト共重合体。
- 請求項1~13のいずれか1項に記載のポリオルガノシロキサン含有グラフト共重合体と熱可塑性樹脂とを含む熱可塑性樹脂組成物。
- 前記熱可塑性樹脂組成物100質量%中の前記ポリオルガノシロキサン含有グラフト共重合体の含有量が0.5~90質量%である、請求項14に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂がポリカーボネート樹脂である請求項14に記載の熱可塑性樹脂組成物。
- 請求項14に記載の熱可塑性樹脂組成物を成形してなる成形体。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TR201821192T4 (tr) * | 2013-06-28 | 2019-01-21 | Mitsubishi Chem Corp | Poliorganosiloksan içeren graft kopolimer, termoplastik reçine bileşimi ve kalıplanmış ürün. |
CN105542176B (zh) * | 2016-02-04 | 2017-08-29 | 广东优科艾迪高分子材料有限公司 | 一种高流动性和低温韧性的改性聚碳酸酯及其制备方法 |
EP3561006B1 (en) | 2016-12-26 | 2021-02-24 | Nippon Sheet Glass Company, Limited | Glitter pigment, pigment-containing composition, and pigment-containing coated object |
US10480189B2 (en) * | 2017-11-06 | 2019-11-19 | Johns Manville | Aerogel containing construction board |
WO2021014735A1 (ja) * | 2019-07-19 | 2021-01-28 | 東レ株式会社 | 透明熱可塑性樹脂組成物およびその成形品 |
CN113174111B (zh) * | 2021-05-26 | 2022-09-02 | 广州华邦电器工业有限公司 | 一种耐热性和阻燃性良好的改性abs树脂及制备方法 |
TWI832255B (zh) * | 2022-05-23 | 2024-02-11 | 簡單綠能股份有限公司 | 防焦性之橡膠產品的製法及防焦性之橡膠產品 |
CN116554697B (zh) * | 2023-06-08 | 2024-04-23 | 安徽中纤新材料有限公司 | 玻纤复合pa单6制备高韧性复合材料的加工工艺 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02238012A (ja) * | 1988-11-14 | 1990-09-20 | General Electric Co <Ge> | ポリオルガノシロキサン/ポリビニルをベースとしたメタクリレート又はアクリレートグラフト重合体 |
JPH11189607A (ja) * | 1997-12-26 | 1999-07-13 | Kanegafuchi Chem Ind Co Ltd | 架橋樹脂粒子の製法 |
JP2002020443A (ja) | 2000-07-06 | 2002-01-23 | Mitsubishi Rayon Co Ltd | グラフト共重合体およびこれを含む熱可塑性樹脂組成物ならびにその成形品 |
JP2002531649A (ja) * | 1998-12-04 | 2002-09-24 | ゼネラル・エレクトリック・カンパニイ | 乳化重合シリコーン−アクリレートゴム耐衝撃性改良剤、熱可塑性ブレンド及び製造方法 |
JP2003238793A (ja) * | 2002-02-19 | 2003-08-27 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
JP2004331726A (ja) | 2003-05-01 | 2004-11-25 | Mitsubishi Rayon Co Ltd | グラフト共重合体およびこれを用いた熱可塑性樹脂組成物 |
JP2004359889A (ja) * | 2003-06-06 | 2004-12-24 | Mitsubishi Rayon Co Ltd | シリコーン/アクリル複合ゴム系グラフト共重合体および熱可塑性樹脂組成物 |
US7956105B2 (en) * | 2004-12-31 | 2011-06-07 | Cheil Industries Inc. | Silicone impact modifier with high refractive index and method for preparing the same |
JP2011179016A (ja) * | 2011-06-17 | 2011-09-15 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3617267A1 (de) * | 1986-05-23 | 1987-11-26 | Bayer Ag | Kerbschlagzaehe pfropfpolymerisate |
US5045595A (en) * | 1988-11-14 | 1991-09-03 | General Electric Company | Polyorganosiloxane/polyvinyl-based graft polymers, process and thermoplastic compositions containing the same |
JP2926378B2 (ja) * | 1994-01-10 | 1999-07-28 | 三菱レイヨン株式会社 | グラフト共重合体および樹脂組成物 |
JP3450450B2 (ja) * | 1994-05-26 | 2003-09-22 | 三菱レイヨン株式会社 | グラフト共重合体およびその熱可塑性樹脂組成物 |
JPH0892318A (ja) * | 1994-09-22 | 1996-04-09 | Sumitomo Chem Co Ltd | ポリスチレン系樹脂組成物及びその製造方法 |
JP4702998B2 (ja) * | 2000-12-05 | 2011-06-15 | 株式会社カネカ | ゴム変性樹脂およびそれを含有する熱可塑性樹脂組成物 |
US20030181573A1 (en) | 2001-07-05 | 2003-09-25 | Nobuo Miyatake | Flame-retardant thermoplastic resin composition |
TW200504153A (en) | 2003-04-11 | 2005-02-01 | Kaneka Corp | Graft copolymer containing polyorganosiloxane, resin composition containing the same and process for preparing emulsion of polyorganosiloxane |
US7589151B2 (en) * | 2004-03-05 | 2009-09-15 | Mitsubishi Rayon Co., Ltd. | Thermoplastic resin composition and molded article comprising the same |
US7541401B2 (en) * | 2004-12-31 | 2009-06-02 | Cheil Industries Inc. | Impact modifier for a polymer composition and method for preparing the same |
CN102203170B (zh) | 2008-08-29 | 2014-02-19 | 三菱丽阳株式会社 | 含有聚硅氧烷系聚合物的乙烯基聚合物粉体及其制造方法、树脂组合物以及成形体 |
KR101282707B1 (ko) * | 2009-12-30 | 2013-07-05 | 제일모직주식회사 | 코어-쉘 구조를 포함하는 그라프트 공중합체로 이루어지는 실리콘계 충격보강제 및 이를 포함하는 열가소성 조성물 |
US9315634B2 (en) | 2010-12-28 | 2016-04-19 | Mitsubishi Rayon Co., Ltd. | Graft copolymer, production method therefor, resin composition, and molded article |
KR101556455B1 (ko) * | 2011-02-09 | 2015-10-01 | 미쯔비시 레이온 가부시끼가이샤 | 폴리오르가노실록산 라텍스, 그것을 사용한 그래프트 공중합체, 열가소성 수지 조성물 및 성형체 |
JP2012136713A (ja) * | 2012-04-16 | 2012-07-19 | Hitachi Chemical Co Ltd | コアシェルポリマ |
TR201821192T4 (tr) * | 2013-06-28 | 2019-01-21 | Mitsubishi Chem Corp | Poliorganosiloksan içeren graft kopolimer, termoplastik reçine bileşimi ve kalıplanmış ürün. |
-
2014
- 2014-06-27 TR TR2018/21192T patent/TR201821192T4/tr unknown
- 2014-06-27 CN CN201480047453.8A patent/CN105492476B/zh active Active
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- 2014-06-27 TW TW103122348A patent/TWI601762B/zh active
- 2014-06-27 KR KR1020157036364A patent/KR101747592B1/ko active IP Right Grant
-
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- 2017-11-02 US US15/801,615 patent/US10246585B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02238012A (ja) * | 1988-11-14 | 1990-09-20 | General Electric Co <Ge> | ポリオルガノシロキサン/ポリビニルをベースとしたメタクリレート又はアクリレートグラフト重合体 |
JPH11189607A (ja) * | 1997-12-26 | 1999-07-13 | Kanegafuchi Chem Ind Co Ltd | 架橋樹脂粒子の製法 |
JP2002531649A (ja) * | 1998-12-04 | 2002-09-24 | ゼネラル・エレクトリック・カンパニイ | 乳化重合シリコーン−アクリレートゴム耐衝撃性改良剤、熱可塑性ブレンド及び製造方法 |
JP2002020443A (ja) | 2000-07-06 | 2002-01-23 | Mitsubishi Rayon Co Ltd | グラフト共重合体およびこれを含む熱可塑性樹脂組成物ならびにその成形品 |
JP2003238793A (ja) * | 2002-02-19 | 2003-08-27 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
JP2004331726A (ja) | 2003-05-01 | 2004-11-25 | Mitsubishi Rayon Co Ltd | グラフト共重合体およびこれを用いた熱可塑性樹脂組成物 |
JP2004359889A (ja) * | 2003-06-06 | 2004-12-24 | Mitsubishi Rayon Co Ltd | シリコーン/アクリル複合ゴム系グラフト共重合体および熱可塑性樹脂組成物 |
US7956105B2 (en) * | 2004-12-31 | 2011-06-07 | Cheil Industries Inc. | Silicone impact modifier with high refractive index and method for preparing the same |
JP2011179016A (ja) * | 2011-06-17 | 2011-09-15 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3015484A4 |
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WO2018225582A1 (ja) | 2017-06-06 | 2018-12-13 | 三菱ケミカル株式会社 | ポリオルガノシロキサン含有グラフト共重合体、熱可塑性樹脂組成物及び成形体 |
CN110709437A (zh) * | 2017-06-06 | 2020-01-17 | 三菱化学株式会社 | 含聚有机硅氧烷的接枝共聚物、热塑性树脂组合物及成形体 |
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CN110709437B (zh) * | 2017-06-06 | 2022-07-05 | 三菱化学株式会社 | 含聚有机硅氧烷的接枝共聚物、热塑性树脂组合物及成形体 |
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Also Published As
Publication number | Publication date |
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EP3015484A1 (en) | 2016-05-04 |
CN105492476A (zh) | 2016-04-13 |
KR20160014668A (ko) | 2016-02-11 |
US20180127579A1 (en) | 2018-05-10 |
TW201512250A (zh) | 2015-04-01 |
JPWO2014208716A1 (ja) | 2017-02-23 |
TWI601762B (zh) | 2017-10-11 |
US10246585B2 (en) | 2019-04-02 |
US20160137836A1 (en) | 2016-05-19 |
CN105492476B (zh) | 2020-08-14 |
JP6332026B2 (ja) | 2018-05-30 |
TR201821192T4 (tr) | 2019-01-21 |
CN111440275B (zh) | 2023-04-14 |
EP3015484B1 (en) | 2018-10-24 |
KR101747592B1 (ko) | 2017-06-14 |
US9834673B2 (en) | 2017-12-05 |
CN111440275A (zh) | 2020-07-24 |
EP3015484A4 (en) | 2016-05-04 |
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