WO2004101658A1 - ゴム含有グラフト共重合体混合樹脂粉末およびその製造方法 - Google Patents
ゴム含有グラフト共重合体混合樹脂粉末およびその製造方法 Download PDFInfo
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- WO2004101658A1 WO2004101658A1 PCT/JP2004/006858 JP2004006858W WO2004101658A1 WO 2004101658 A1 WO2004101658 A1 WO 2004101658A1 JP 2004006858 W JP2004006858 W JP 2004006858W WO 2004101658 A1 WO2004101658 A1 WO 2004101658A1
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- Prior art keywords
- rubber
- graft copolymer
- copolymer
- containing graft
- powder
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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
- C08L51/04—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 rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
Definitions
- the present invention relates to a rubber-containing graft copolymer mixed resin powder and a method for producing the same.
- the present invention relates to a rubber-containing graft copolymer mixed resin powder and a method for producing the same. More specifically, the present invention relates to a rubber-containing graft copolymer-mixed resin powder obtained by improving the powder properties of a rubber-containing graft copolymer without reducing the impact strength improving performance, It relates to a manufacturing method.
- Rubber-containing graft copolymer powder is used as an impact strength modifier for hard plastics such as polyvinyl chloride.
- Such a rubber-containing graft copolymer powder is obtained by recovering a rubber-containing graft copolymer as a dry powder from a rubber-containing graft copolymer latex obtained by emulsion polymerization. It is used as an impact strength modifier by melting and mixing.
- One method of recovering the rubber-containing graft copolymer as a powder is to spray the rubber-containing graft copolymer latex produced by emulsion polymerization into hot air and recover the rubber-containing graft copolymer as dry particles. There is a spray drying method.
- the rubber-containing graft copolymer powder has adhesiveness on the particle surface, the powder adheres and accumulates at various places in the manufacturing equipment in each manufacturing process including spray drying. Cause problems.
- a processing aid for example, there is a method of mixing a processing aid with the rubber-containing graft copolymer.
- the rubber-containing graft copolymer and the processing aid hard inelastic copolymer
- the processing aid hard inelastic copolymer
- spray-drying or co-aggregation and then encapsulating with a final seal and spray-drying for example, JP-A-8-176385, JP-A-5-224) No. 7313).
- the hard inelastic copolymer is contained inside the rubber-containing graft copolymer powder. They are taken in, and the surface modification of the sticky rubber-containing graft copolymer powder cannot be performed efficiently. Therefore, the effect of improving the powder properties of the rubber-containing graft copolymer and preventing adhesion to the inside of the dryer can hardly be expected.
- the rubber-containing graft copolymer powder produced by the method described in Japanese Patent Application Laid-Open No. H08-118369 is characterized in that calcium carbonate and silicon dioxide are contained in a resin obtained by adding the powder. Since they disperse without melting, the physical properties of the final molded product are affected. Therefore, the amount to which calcium carbonate, silica, and the like can be added is limited, and the addition of these alone may not be enough to improve the powder properties at the product level. Also, since calcium carbonate and silicon dioxide are added after the rubber-containing graft copolymer is spray-dried, it is not possible to prevent adhesion to the spray-dryer and to reduce coarse powder generated during drying. .
- the present invention has been made in order to solve the above-mentioned problems, and improves the powder properties of a rubber-containing graft copolymer powder recovered by spray drying without affecting the physical properties of a molded article.
- An object of the present invention is to provide a rubber-containing graft copolymer mixed resin powder capable of preventing adhesion to the inside of a dryer and piping during drying and a method for producing the same.
- the present inventors have conducted studies to solve the above problems, and as a result, have come to invent the rubber-containing daraft copolymer mixed resin powder of the present invention and a method for producing the same.
- One embodiment of the present invention is to independently spray-dry a rubber-containing graft copolymer latex and a hard inelastic copolymer lattetus having a glass transition temperature of 60 ° C to 150 ° C, respectively.
- the rubber-containing graft copolymer mixed resin powder obtained has a rubber-containing daraft copolymer / hard inelastic copolymer mass ratio of 90 to 99.9 Z10 to 0.1.
- Another aspect of the present invention is a method for producing a rubber-containing graft copolymer mixed resin powder obtained by spraying a rubber-containing graft copolymer latex in a dryer and drying with a heating gas for drying.
- the rubber-containing graft copolymer latex and the rigid inelastic copolymer latex having a glass transition temperature of 60 ° C. to 150 ° C. are combined in a rubber-containing graft copolymer / hard inelastic copolymer mass ratio.
- the rubber-containing graft copolymer mixed resin powder of the present invention contains a rubber-containing graft copolymer and a hard inelastic copolymer having a glass transition temperature of 60 ° C to 150 ° C.
- the rubber-containing graft copolymer used in the present invention refers to a rubber-like polymer having a glass transition temperature (hereinafter, T g) of 20 ° C. or lower as a trunk polymer, and a polymerizable monomer graft-polymerized thereto. Things.
- the content of the rubbery polymer in the rubber-containing graft copolymer is preferably not less than 40% by mass, more preferably not less than 50% by mass, as long as it is such a material. is there.
- the rubber-like polymer examples include, for example, an acryl-based rubber-like polymer containing n-butyl acrylate, 2-ethylhexyl acrylate, or the like as a main component, butadiene, isoprene, or chloroprene.
- a rubber-based polymer such as a silicone rubber-based polymer, a silicone rubber-based polymer containing organosiloxane as a main component, and a silicone acryl composite rubber-based polymer obtained by polymerizing acrylate in the presence of a silicone rubber-based polymer. No. Also, two or more of these rubbery polymers may be combined. Further, it may be a rubber-like polymer containing a glass-like polymer in a core.
- the polymerization method of the rubber-containing graft copolymer is not particularly limited, the polymerization of the rubbery polymer and the graft polymerization may be performed using two or more stirring devices, or may be continuously performed using the same stirring device. You can go,
- the rigid inelastic copolymer used in the present invention has a Tg of 60 to 150 ° C. This can improve the powder properties of the rubber-containing graft copolymer. If the Tg of the hard inelastic copolymer is less than 60 ° C, the effect of improving the powder properties is low, which is not preferable. If the T g of the rigid inelastic copolymer is higher than 150 ° C, the rigid inelastic copolymer powder may be crushed by shearing in the dryer and piping, and the fine powder may increase. I don't like it because of it.
- the T g of the rigid inelastic copolymer in the present invention is calculated from the ratio of the T g of the polymer of each monomer used in the emulsion polymerization to the charged ratio of each monomer, such as the formula of Fox, etc. It may be calculated by an equation, or may be measured using various measuring devices.
- the powder particle size of the hard inelastic copolymer used in the present invention after spray drying is 45 ⁇ The following is preferred. If the powder particle size after spray drying is larger than 45 m, the coverage of the rubber-containing graft copolymer latex with the hard inelastic copolymer latex will decrease, and the effect of improving the powder properties tends to decrease. It is in.
- the molecular weight of the hard inelastic copolymer used in the present invention is preferably 500,000 to 500,000, more preferably 800,000 to 300,000.
- the rigid inelastic copolymer used in the present invention is produced as a rigid inelastic copolymer latex containing a rigid inelastic copolymer by emulsion polymerization.
- the solid content in the hard inelastic copolymer latex is preferably at most 20%, more preferably at most 10%.
- the rigid inelastic copolymer used in the present invention is not particularly limited, but is usually produced by emulsion polymerization.
- the addition of monomers, a polymerization initiator and an emulsifier at the time of polymerization may be added all at once, continuously added, or dividedly added. It can be performed by multi-stage addition or the like. Also, these may be performed in combination.
- a monomer usually used for emulsion polymerization can be used as a component to be graft-polymerized to the rubbery polymer and a component of the hard inelastic copolymer.
- a monomer usually used for emulsion polymerization can be used.
- the aromatic butyl monomer is not particularly limited, and examples thereof include styrene, a-methinolestyrene, methinole- ⁇ -methinolestyrene, vinylinolenolene, and divininolebenzene. Of these, styrene is particularly preferred. These aromatic vinyl monomers may be used alone or in combination of two or more.
- the vinyl cyanide-based monomer is not particularly limited, and examples thereof include atarilonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -ethylacrylonitrile. Among these, acrylo-tolyl is particularly preferred. Even if only one type of these cyanide-based monomers is used, two or more types of May be used in combination.
- the ethylenically unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid. These ethylenically unsaturated carboxylic acid monomers may be used alone or in combination of two or more.
- unsaturated boronic acid alkyl ester-based monomer there are no particular restrictions on the unsaturated boronic acid alkyl ester-based monomer, but, for example, methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, acryl acrylate, and gly acrylate
- examples include sidyl acrylate, methyl methacrylate, ethyl methacrylate, ptynolemethacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, aryl methacrylate, and glycidyl methacrylate.
- unsaturated carboxylic acid alkyl ester monomers may be used alone or in combination of two or more.
- the vinyl halide monomer is not particularly limited, and examples thereof include vinyl chloride and vinylidene chloride. These vinyl halide monomers may be used alone or in combination of two or more.
- the maleimide-based monomer is not particularly limited, and examples thereof include maleimide, N-phenylenoleimide, N-cyclohexinolemalide, N-methinolemalide, and the like. These maleimide monomers may be used alone or in combination of two or more.
- monomers capable of emulsion polymerization such as ethylene, propylene, vinyl acetate, and butyl pyridine can also be used.
- dibutylbenzene, 13-butylene methacrylate, aryl methacrylate, and glycidyl may be used as needed during the polymerization of the rubbery polymer or the subsequent graft polymerization.
- a cross-linking agent such as metathalylate and a chain transfer agent such as mercaptans may be used in combination.
- the polymerization initiator used in the production of the rubber-containing graft copolymer and the rigid inelastic copolymer of the present invention is not particularly limited.
- persulfuric acid potassium, sodium persulfate, ammonium persulfate Such as water-soluble persulfuric acid, diisopropyl Benzene peroxide peroxide, p-menthane hydride peroxide, cumene hydride peroxide, t-butyl hydride peroxide, methylcyclohexyl hydride peroxide, 1,1,3,3-tetramethylbutyl hydride
- Organic peroxides such as peroxide, 1,1,3,3-tetramethylbutylperoxy-1-ethylhexanoate and t-butylperoxy-1,3,5,5-trimethylhexanoate as one component Redox initiators can be used.
- the emulsifier is not particularly limited.For example, only one kind of alkali metal salt of sulfonic acid such as disproportionated rosin acid, oleic acid, stearic acid, etc., or sulfonic acid such as dodecylbenzene sulfonic acid They may be used, or two or more types may be used in combination.
- sulfonic acid such as disproportionated rosin acid, oleic acid, stearic acid, etc.
- sulfonic acid such as dodecylbenzene sulfonic acid
- the emulsion-polymerized latex may be spray-dried after adding an appropriate antioxidant, additive or the like.
- the mass ratio of the rubber-containing graft copolymer to the hard inelastic copolymer in the rubber-containing graft copolymer mixed resin powder of the present invention is 90 to 99.9 to 10 to 0.1. . If the amount of the hard inelastic copolymer exceeds 10% by mass, it is not preferable because physical properties such as impact resistance of molded articles are reduced and fine powder generated is increased. If the amount of the hard inelastic copolymer is less than 0.1%, the effect of improving the powder properties cannot be sufficiently obtained, which is not preferable. More preferably, the mass ratio of the rubber-containing graft copolymer to the rigid inelastic copolymer is from 95 to 99.5 to 5 to 0.5.
- the rubber-containing daraft copolymer mixed resin powder of the present invention it is preferable to further add an inorganic fine powder.
- the inorganic fine powder is added in an amount of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the mixed powder obtained by spray-drying the rubber-containing graft copolymer and the rigid inelastic copolymer. Thereby, the powder characteristics such as blocking resistance in the rubber-containing graft copolymer mixed resin powder can be further improved.
- the amount of the inorganic fine powder is less than 0.01 part by mass, the effect of improving the powder properties is reduced, and when it is more than 5.0 parts by mass, the transparency of the molded product is apt to be reduced.
- the inorganic fine powder may be used alone or in combination of two or more.
- the inorganic fine powder used in the present invention includes silicon dioxide fine powder and / or charcoal. It is preferably a calcium acid fine powder.
- silicon dioxide fine powder any kind of silicon dioxide fine powder such as hydrophobic silica and hydrophilic silica can be used.
- Spray drying in the present invention is a method of spraying (atomizing) a latex containing a polymer into a drying gas (hot air) and collecting it as a dry powder.
- a drying gas hot air
- the shape of a dryer, a spraying device and the like are known. Spray dryers and spray devices can be used.
- the capacity of the spray dryer is not particularly limited, and any capacity from a small scale used in a laboratory to a large scale used industrially can be used. .
- the production method of the present invention comprises simultaneously spraying a rubber-containing graft copolymer latex containing a rubber-containing graft copolymer and a hard non-elastic copolymer latex containing a hard non-elastic copolymer, independently of each other.
- the mixed resin powder is obtained by spray drying with an apparatus. At this time, it is preferable that the inorganic fine powder is continuously charged into the dryer.
- the rubber-containing graft copolymer having adhesiveness is obtained by simultaneously spray-drying the rubber-containing graft copolymer latex and the hard non-conductive copolymer latex with independent spraying devices to obtain a mixed resin powder.
- the hard inelastic copolymer powder which is a hard component, is fixed to the surface of the copolymer powder, and the surface modification of the rubber-containing graft copolymer powder becomes possible. As a result, it is possible to efficiently improve powder characteristics and prevent adhesion.
- At least one spraying device for spraying the rubber-containing graft copolymer latex is installed above the dryer.
- the spraying method can be any of a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, and a pressurized two-fluid nozzle type. May be.
- At least one device for spraying the hard inelastic copolymer is provided on the upper part or side wall of the dryer, and the spraying method is preferably a nozzle method such as a pressure nozzle method, a two-fluid nozzle method, and a pressurized two-fluid nozzle method.
- the inorganic fine powder it is preferable to continuously feed the inorganic fine powder into a dryer for spraying each latex.
- a dryer for spraying each latex.
- powder adhesion can be more effectively prevented in each step, such as in the cone at the bottom of the dryer, piping to the separator, and inside the separator, and the powder characteristics are further improved.
- Connect the inorganic fine powder to the dryer As a method of continuously introducing the dryer, the powder may be directly introduced into the dryer from the ceiling and side surfaces of the dryer by using various powder feeders, or the inside of the dryer may be suctioned at a negative pressure.
- inorganic fine powder is mixed with dry gas, a gas for atomizing latex sprayed from nozzles such as a two-fluid nozzle or a pressurized two-fluid nozzle, or a gas for cooling a disk atomizer. It may be continuously charged into the dryer.
- a device for separating and recovering the rubber-containing graft copolymer mixed fine powder obtained by spray drying from the dry gas is not particularly limited, but a centrifugal cyclone filtration method and a bag filter are preferred.
- the powder properties of the rubber-containing graft copolymer powder can be improved without affecting the physical properties of the molded article. Further, the adhesion of the rubber-containing graft copolymer mixed resin powder of the present invention to the inside of the production apparatus in the powder production process is suppressed. Therefore, the contamination (contamination) through the production equipment can be reduced, and the quality can be improved. In addition, the yield can be improved and frequent cleaning is not required, so that productivity can be improved.
- the increase in cost can be suppressed, blockage at the time of powder transportation, blocking during storage or at the time of automatic weighing can be avoided, and the manufacturing apparatus can be enlarged.
- the measurement was performed using a laser diffraction type particle size distribution analyzer LA-9110 (manufactured by Horiba, Ltd.). .
- Blocking resistance 20 g of the rubber-containing graft copolymer powder was placed in a cylindrical container, and a pressure of 17.5 KPa was applied at 50 ° C. for 6 hours. Vibration was applied to the obtained block using a Miku mouth type electromagnetic vibrating sieve (manufactured by Tsutsui Rika), and the time (sec) for breaking the block by 60% was measured. The shorter this time, the better the blocking resistance.
- a reactor equipped with a stirrer was charged with 699 parts of rubber-like polymer (A-1) latex (233 parts as solids), 85 parts of water, and 1.0 part of sodium dodecylbenzenesulfonate. Then, 0.3 parts of sodium formaldehyde sulfoxyle monotonihydrate was added to the mixture, and the internal temperature was raised to 70 ° C. Then, a mixture of 28 parts of methyl methacrylate, 7 parts of ethyl acrylate, 0.15 parts of t-butyl hydroperoxide (trade name: Perbutyl (registered trademark) H-69, manufactured by NOF CORPORATION) was added continuously over 30 minutes. Cultivated and kept for 100 minutes.
- Emulsified and dispersed triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] was added to the graft copolymer (rubber content 70%) latex thus obtained. 0.21 part per 100 parts of the graft copolymer and 0.63 parts of emulsified and dispersed dilauryl 1,3,3,1-thiodipropionate per 100 parts of the graft copolymer were added, and the rubber-containing graft was added. A copolymer (A-2) latex was obtained.
- a reactor equipped with a stirrer was charged with 300 parts of deionized water, 1.2 parts of sodium lauryl sulfate, 69 parts of methyl methacrylate, 24 parts of butyl methacrylate, 7 parts of butyl acrylate, and 0.005 part of n-octyl mercaptan, and stirred. And the temperature was raised to 50 ° C.
- siloxane mixture Two parts of tetraethoxysilane, 0.5 part of ⁇ -methacryloyloxypropyl dimethoxymethylsilane and 97.5 parts of otatamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane mixture. 100 parts of the mixed siloxane was added to 200 parts of distilled water in which 1 part of sodium dodecylbenzenesulfonate and 1 part of dodecylbenzenesulfonic acid were respectively dissolved, and the mixture was preliminarily stirred at 10,000 rpm with a homomixer, and then homogenized.
- the mixture was emulsified and dispersed at a pressure of 3 OMPa to obtain an organosiloxane latex.
- the mixture was transferred to a separable flask equipped with a condenser and stirring blades, heated at 80 ° C for 5 hours with mixing and stirring, and then left at 20 ° C. After 48 hours, the pH of this latex was adjusted with an aqueous sodium hydroxide solution. Was neutralized to 7.4 to complete the polymerization, yielding a polyorganosiloxane latex.
- the polymerization rate of the obtained polyorganosiloxane was 89.5% by mass, and the average particle size of the polyorganosiloxane was 0.1.
- This latex was coagulated and dried with isopropanol to obtain a solid, which was extracted with toluene at 90 ° C for 12 hours, and the gel content was measured to be 90.6% by mass.
- Example 1 Production of Rubber-Containing Graft Copolymer Mixed Resin Powder (Spray Drying) Using a spray dryer (manufactured by Okawara Kakoki Co., Ltd.) having a straight body diameter of 350 Omm and a straight body height of 480 Omm, the amount of dry gas was 30 Nm.
- the rubber-containing graft copolymer (A-2) latex was flowed at a flow rate of 90 kg / hr (36 kg as solids). / hr) and spray drying was performed using a pressurized two-fluid nozzle at a processing speed of.
- a rigid inelastic copolymer (B-1) latex having a solid content adjusted to 10% was spray-dried with a two-fluid nozzle at a processing rate of 7.2 kg / hr. Each nozzle was installed so that it could be sprayed downward from the ceiling of the dryer.
- silica fine powder AEROSIL (registered trademark) # 50 manufactured by Nippon AEROSIL Co., Ltd. is spray-dried with a rubber-containing graft copolymer latex and a hard inelastic copolymer latex, and simultaneously with a side wall at a speed of 108 g Zhr. It was continuously charged into the dryer.
- the dry powder was separated from the dry gas by a cyclone and extracted. Table 1 shows the results of various evaluations of the recovered powder.
- Example 2 The procedure was performed in the same manner as in Example 1 except that the hard inelastic copolymer (B-1) latex was diluted so that the solid content was 5%, and the spray amount was 14.4 kgZhr.
- the rubber-containing graft copolymer (C-1) latex was used, and the weight ratio between the rubber-containing graft copolymer and the hard inelastic copolymer (B-1) was the same as in Examples 1-3.
- the procedures were performed in the same manner as in Examples 1 to 3, except that the amount of fog in B-1 was adjusted so as to obtain the following conditions, and that the addition amount of AEROSIL # 50 was 75 gZhr. Table 2 shows the results.
- the time required for the powder block to fracture 60% was as short as 36 to 47 seconds, and the blocking resistance was reduced. It turned out to be excellent and the powder properties were sufficiently improved.
- the time required for the powder block to break 60% was as long as 350 to 400 seconds, and the blocking resistance was extremely poor. It was found that the characteristics were not sufficiently improved.
- a rubber-containing graft copolymer resin that can improve the powder properties of the rubber-containing graft copolymer powder recovered by spray drying and prevent it from adhering to the inside of the dryer and piping during powder drying.
- a method for producing a powder and a rubber-containing graft copolymer mixed resin powder can be provided.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2004570940A JP4536521B2 (ja) | 2003-05-14 | 2004-05-14 | ゴム含有グラフト共重合体混合樹脂粉末およびその製造方法 |
EP04733144A EP1650252A4 (en) | 2003-05-14 | 2004-05-14 | RESIN POWDERS FROM A POWDERED PEPPOPOPOLYMIC MIXTURE AND PRODUCTION PROCESS THEREFOR |
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JP2003136086 | 2003-05-14 | ||
JP2003-136086 | 2003-05-14 |
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WO2004101658A1 true WO2004101658A1 (ja) | 2004-11-25 |
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PCT/JP2004/006858 WO2004101658A1 (ja) | 2003-05-14 | 2004-05-14 | ゴム含有グラフト共重合体混合樹脂粉末およびその製造方法 |
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EP (1) | EP1650252A4 (ja) |
JP (1) | JP4536521B2 (ja) |
KR (1) | KR20060022653A (ja) |
CN (1) | CN100404592C (ja) |
TW (1) | TW200513492A (ja) |
WO (1) | WO2004101658A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10639506B2 (en) | 2013-08-20 | 2020-05-05 | 3M Innovative Properties Company | Personal respiratory protection device |
US11154735B2 (en) | 2013-08-20 | 2021-10-26 | 3M Innovative Properties Company | Personal respiratory protection device |
US11241595B2 (en) | 2013-08-20 | 2022-02-08 | 3M Innovative Properties Company | Personal respiratory protection device |
US11247079B2 (en) | 2013-08-20 | 2022-02-15 | 3M Innovative Properties Company | Personal respiratory protection device |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100805505B1 (ko) | 2004-02-16 | 2008-02-20 | 미츠비시 레이온 가부시키가이샤 | 수지용 개질제 및 이것을 이용한 수지 조성물, 및 성형품 |
KR100694460B1 (ko) * | 2004-09-21 | 2007-03-12 | 주식회사 엘지화학 | 고무 함유 그라프트 공중합체 분체의 제조 방법 |
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JPH08176385A (ja) * | 1994-12-27 | 1996-07-09 | Kanegafuchi Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
JP2002226595A (ja) * | 2001-02-06 | 2002-08-14 | Mitsubishi Rayon Co Ltd | ジエン系グラフト重合体粉体の製造方法 |
Family Cites Families (4)
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US3985704A (en) * | 1975-06-19 | 1976-10-12 | Rohm And Haas Company | Methacrylate-butadiene-styrene graft polymers and process for their production |
JP3314881B2 (ja) * | 1992-09-18 | 2002-08-19 | 電気化学工業株式会社 | 粉状ポリマー組成物の製造方法 |
JPH06192483A (ja) * | 1992-12-24 | 1994-07-12 | Denki Kagaku Kogyo Kk | アクリル系粉末ゴム組成物及びその製造方法 |
JPH08231729A (ja) * | 1995-02-22 | 1996-09-10 | Mitsubishi Rayon Co Ltd | 再分散可能な樹脂の製造方法及びそれで得られる再分散可能な樹脂 |
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2004
- 2004-05-13 TW TW093113405A patent/TW200513492A/zh unknown
- 2004-05-14 WO PCT/JP2004/006858 patent/WO2004101658A1/ja not_active Application Discontinuation
- 2004-05-14 CN CNB2004800125425A patent/CN100404592C/zh not_active Expired - Lifetime
- 2004-05-14 EP EP04733144A patent/EP1650252A4/en not_active Withdrawn
- 2004-05-14 JP JP2004570940A patent/JP4536521B2/ja not_active Expired - Lifetime
- 2004-05-14 KR KR1020057021408A patent/KR20060022653A/ko not_active Application Discontinuation
Patent Citations (2)
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JPH08176385A (ja) * | 1994-12-27 | 1996-07-09 | Kanegafuchi Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
JP2002226595A (ja) * | 2001-02-06 | 2002-08-14 | Mitsubishi Rayon Co Ltd | ジエン系グラフト重合体粉体の製造方法 |
Non-Patent Citations (1)
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US10639506B2 (en) | 2013-08-20 | 2020-05-05 | 3M Innovative Properties Company | Personal respiratory protection device |
US11154735B2 (en) | 2013-08-20 | 2021-10-26 | 3M Innovative Properties Company | Personal respiratory protection device |
US11241595B2 (en) | 2013-08-20 | 2022-02-08 | 3M Innovative Properties Company | Personal respiratory protection device |
US11247079B2 (en) | 2013-08-20 | 2022-02-15 | 3M Innovative Properties Company | Personal respiratory protection device |
Also Published As
Publication number | Publication date |
---|---|
EP1650252A1 (en) | 2006-04-26 |
CN100404592C (zh) | 2008-07-23 |
JP4536521B2 (ja) | 2010-09-01 |
JPWO2004101658A1 (ja) | 2006-07-13 |
EP1650252A4 (en) | 2006-06-14 |
CN1784456A (zh) | 2006-06-07 |
KR20060022653A (ko) | 2006-03-10 |
TW200513492A (en) | 2005-04-16 |
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