WO2006016490A1 - Procédé de production de latex polyorganosiloxane, de copolymère obtenu du latex et de composition de résine contenant le copolymère greffé - Google Patents
Procédé de production de latex polyorganosiloxane, de copolymère obtenu du latex et de composition de résine contenant le copolymère greffé Download PDFInfo
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- WO2006016490A1 WO2006016490A1 PCT/JP2005/013981 JP2005013981W WO2006016490A1 WO 2006016490 A1 WO2006016490 A1 WO 2006016490A1 JP 2005013981 W JP2005013981 W JP 2005013981W WO 2006016490 A1 WO2006016490 A1 WO 2006016490A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
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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
- C08L21/00—Compositions of unspecified rubbers
Definitions
- the present invention relates to a method for producing a polyorganosiloxane latex in which the amount of emulsifier and particle diameter are controlled, the polyorganosiloxane graft copolymer, and a resin composition blended with the graft copolymer.
- Silicone has unique properties such as heat resistance, cold resistance, releasability, and water repellency. Polyorganosiloxane graft copolymers using this unique property are used in the market as a number of high-value-added products such as flame retardants, impact modifiers, impact modifiers, and release agents.
- Patent Document 1 As an emulsion polymerization method of polyorganosiloxane, a method by Hyde et al. Is well known (Patent Document 1). In this method, a polydimethylsiloxane precursor, a surfactant, water, and a polymerization catalyst were mixed, stirred, and heated to obtain a latex. However, latex particles of 0.1 ⁇ m or less were not obtained.
- Cekada has shown a method for producing a cissesquioxane colloidal suspension with three Si-O bonds per Sil, in which the ability to obtain particles of 0.001-0.
- a method for producing a polyorganosiloxane latex is shown (Patent Document 2).
- a method for producing a polyorganosiloxane latex having a small particle size includes cyclopolyorganosiloxane, a surfactant (0.15 to 5 times the weight of polyorganosiloxane), and an emulsion precursor consisting of water.
- cyclopolyorganosiloxane a surfactant (0.15 to 5 times the weight of polyorganosiloxane)
- an emulsion precursor consisting of water.
- Patent Document 1 U.S. Pat.No. 2891920
- Patent Document 2 U.S. Pat.No. 3,975,294
- Patent Document 3 Japanese Patent Application Laid-Open No. 62-141029
- Patent Document 4 Japanese Patent Laid-Open No. 5-194740
- a polyorganosiloxane having a small particle size can be produced by the disclosed technique, etc.
- an impact resistance improver and impact resistance are actually obtained by graft polymerization using polyorganosiloxane by these methods.
- a modifier such as a property-improving aid, a mold release agent or a flame retardant is synthesized, the amount of emulsifier and acid catalyst is too large, causing the final molded body to undergo thermal degradation during molding, Deterioration of mechanical properties occurs and becomes a big problem.
- solvent washing, etc. it is possible to prevent thermal deterioration during molding and deterioration of the mechanical properties of the final molded product.
- an aqueous solution containing a specific seed polymer and an acid catalyst is mixed with an organosiloxane and a bifunctional siloxane graft cross-linking agent.
- the present invention for producing a non-crosslinked polyorganosiloxane latex having a volume average particle diameter of 0.075 or less was completed by a method of continuously adding a mixture of the above and an emulsified liquid with an emulsifier.
- the present invention provides:
- the polyorganosiloxane latex (E) according to claim 1, characterized in that the ratio of the volume of the latex particles after the latex and the diameter of the latex particles before stirring is 3 to 50 times in terms of the swollen volume ratio.
- a method of manufacturing (Claim 2).
- the formula (1) is established between the weight average particle size of the obtained polyorganosiloxane latex (E), the amount of the emulsifier (D), and the amount of the acid catalyst (B). Item 1 or Item 2.
- volume average particle diameter of polyorganosiloxane latex (E)) ⁇ 0. 075-0. 01 (parts by weight of milky additive (D) + parts by weight of acid catalyst (B)) ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ (1) (Claim 3).
- a resin composition comprising 0.1 to 30 parts by weight of a polyorganosiloxane-containing graft copolymer according to claim 4 per 100 parts by weight of thermoplastic resin (claim) Five). About. The invention's effect
- a non-crosslinked polyorganosiloxane latex having a volume average particle diameter of 0.075 ⁇ or less could be produced with a small amount of emulsifier used of 5 parts by weight or less. Also this poly
- thermoplastic resin could be improved by the polyorganosiloxane-containing resin using the organosiloxane.
- the present invention relates to an aqueous solution containing a unique seed polymer ( ⁇ ) and an acid catalyst ( ⁇ ), a mixture (C) of an organosiloxane and a bifunctional siloxane-based graft crossing agent, an emulsifier (D), and
- a method of continuously adding an emulsion with water a non-crosslinked polyorganosiloxane latex ( ⁇ ) having a volume average particle size of 0.075 or less with a small amount of an emulsifier of 7.5 parts by weight or less is produced.
- the present invention relates to a method, a graft copolymer using the latex, and a resin composition containing the graft copolymer.
- the seed polymer ( ⁇ ) does not particularly limit the force synthesis method that can be obtained by ordinary emulsion polymerization.
- the seed polymer is not limited to rubber components such as butyl acrylate rubber and butadiene rubber, but butyl acrylate-styrene copolymer, butyl acrylate-butadiene copolymer, butyl acrylate-acrylonitrile copolymer.
- the glass transition point of the seed polymer is preferably -10 ° C or lower.
- the glass transition point can be obtained as a temperature at which the change of the specific gravity of the polymer is measured and the change is suddenly changed.
- the glass transition and glass transition point are behaviors and characteristics peculiar to amorphous polymers, and this behavior and characteristics are not seen for polymers with a molecular weight of 10,000 or less.
- the seed polymer As a method for improving the swelling property of the seed polymer with respect to the organosiloxane, it is important to first make the seed polymer suitable for the organosiloxane in terms of polarity, etc., followed by the use of a chain transfer agent and high polymerization. It is effective to significantly reduce the molecular weight of the seed polymer by selecting the temperature and the use of a large amount of initiator.
- the number average molecular weight of the seed polymer is preferably 10,000 or less, more preferably 7,000 or less. Number average molecular weight can be measured by GPC analysis (polystyrene equivalent).
- organosiloxane relating to the swelling property of the seed polymer refers to organosiloxane which is a monomer constituting polyorganosiloxane.
- organosiloxane is otamethylcyclotetrasiloxane.
- the hydrophilicity of the seed polymer can be measured by the extraction rate into water after adding 20 times the amount (weight) of water to the dried seed polymer and stirring at 23 ° C for 1 hour.
- the lower limit of the value should be 1% or more. Preferably it is 10% or more, more preferably 50% or more.
- the upper limit is 200% or less, preferably 100% or less, and more preferably 80% or less.
- the swelling property of the seed polymer with respect to the organosiloxane is determined by adding 50 times (by weight) of the organosiloxane to the seed polymer latex and stirring the mixture at 23 ° C for 1 hour. And the swelling volume ratio obtained from the ratio of the latex particle diameter before stirring.
- the seed polymer (A) which swells in the organosiloxane of the present invention is one having a swelling volume ratio of 2.1 times or more.
- the lower limit of the value is preferably 3 times or more, and the upper limit is preferably 80 times or less, more preferably 50 times or less, and particularly preferably 15 times or less.
- the volume average particle diameter of the polyorganosiloxane (E) in the latex state can be obtained from the light scattering method or the observation ability with an electron microscope, and is preferably 0.075 or less. Those exceeding 0.075 can also be synthesized by conventional methods.
- the polyorganosiloxane (E) is composed of an organosiloxane and a bifunctional siloxane-based graph crossing agent.
- the organosiloxane used in the present invention has the general formula RmSiO (4-m) Z2 (wherein R Is a substituted or unsubstituted monovalent hydrocarbon group, m is an integer of 0 to 3, and has a linear, branched or cyclic structure, An organosiloxane having a cyclic structure is preferred.
- Examples of the substituted or unsubstituted monovalent hydrocarbon group of the organosiloxane include a methyl group, an ethyl group, a propyl group, a full group, and a substituted hydrocarbon group obtained by substituting them with a cyano group. I can give it.
- organosiloxane examples include hexamethylcyclotrisiloxane (D3), otamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6),
- cyclic compounds such as trimethyltriphenylcyclotrisiloxane
- linear or branched organosiloxanes can be mentioned. These organosiloxanes can be used alone or in combination of two or more.
- the bifunctional siloxane grafting agent that can be used in the present invention includes, for example, p-Buylmethylmethyldimethoxysilane, p-Buyl-Fuylethyldimethoxysilane, 2- (p-Bulfuhel) Tylmethyldimethoxysilane, 3- (p-Bulbenzoyloxy) propylmethyldimethoxysilane, p-vinylphenylmethyldimethoxysilane, vinylmethyldimethoxysilane, arylmethyldimethoxysilane, mercaptopropylmethyldimethoxysilane, methacryloxypropyl And methyldimethoxysilane.
- the proportion of the grafting agent used is preferably 0.1 to 7% by weight based on the organosiloxane. If the amount of the grafting agent used is too large, the impact resistance of the final molded product containing the polyorganosiloxane-containing graft copolymer will be reduced, and if the amount of the grafting agent used is too small, the polyorganosiloxane-containing graft copolymer will be deteriorated. There is a tendency that a large lump is formed at the time of solidification / heat treatment, so that a decent resin powder cannot be obtained or the formability of the final molded body is lowered.
- the emulsifier (D) a key-on emulsifier is used.
- the cation emulsifier include forces such as sodium alkylbenzene sulfonate, sodium lauryl sulfonate, potassium oleate, and the like. Particularly, sodium dodecylbenzene sulfonate is often used.
- Specific examples of non-one emulsifiers include polyoxyesters. Examples include tylene nouryl ether and polyoxyethylene lauryl ether.
- the emulsifier (D) is mixed with a mixture (C) of organosiloxane and a bifunctional siloxane-based graft crossing agent and water, and is made into an emulsified liquid by a homogenizer, a line mixer, or the like.
- Examples of the acid catalyst (B) used in the present invention 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. .
- sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid
- mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid.
- n-dodecylbenzenesulfonic acid is particularly preferred, which is preferably an aliphatic substituted benzenesulfonic acid that is excellent in the emulsion stability of the organosiloxane.
- the volume average particle size of polyorganosiloxane latex (E), the amount of emulsifier (D), and the amount of acid catalyst (B) are preferably in the relationship of the following formula (1).
- the final molded body tends to be thermally deteriorated, and the mechanical properties of the final molded body tend to decrease.
- the weight part of the emulsifier (D) and the weight part of the acid catalyst (B) are 100 weights for the mixture (C) of the seed polymer (A), the organosiloxane and the bifunctional siloxane grafting agent. It is the number of parts by weight per part.
- the heating for the polymerization is preferably 60 to 120 ° C, more preferably 70 to 100 ° C in that an appropriate polymerization rate can be obtained.
- the Si—O—Si bond forming the polyorganosiloxane skeleton is in an equilibrium state of cleavage and formation, and this equilibrium changes with temperature.
- it is preferable to neutralize with an aqueous alkali solution such as sodium hydroxide, potassium hydroxide and sodium carbonate.
- an emulsion containing an organosiloxane, a siloxane-based graft crossing agent, and an emulsifier is continuously added.
- the addition when the addition is divided into 5 or more times, it is considered that they are added continuously. If the above emulsion is added all at once, or dividedly added four times or less, the properties of the organosiloxane latex (E) may be inferior.
- the Bulle monomer (F) is a component used to obtain a polyorganosiloxane-containing graft copolymer.
- the graft copolymer is added to a thermoplastic resin to give impact resistance.
- it is also a component used to ensure the compatibility of the graft copolymer and the thermoplastic resin and to uniformly disperse the graft copolymer in the thermoplastic resin.
- the monomer include, for example, aromatic butyl monomers such as styrene, ⁇ -methylstyrene, paramethylstyrene, and parabutylstyrene; -Cyanide butyl monomers such as tolyl, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxy acrylate (Meth) acrylic acid ester monomers such as butyl, methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, (meth) acrylic acid, Carboxyl group-containing beir monomers such as fumaric acid and maleic acid And the like.
- the polyorganosiloxane-containing graft copolymer is composed of 100 to 90 parts by weight of polyorganosiloxane ( ⁇ ) 40 to 90 parts by weight (solid content) and 10 to 60 parts by weight of vinyl monomer (F). It is obtained by polymerization so that If the amount of polyorganosiloxane ( ⁇ ⁇ ⁇ ) is too small or too large, the effect of improving impact resistance or the like tends to be small. In addition, when the amount of the buler monomer (F) is too small or too large, the improvement effect such as impact resistance tends to be small.
- Graft copolymer latex force obtained by emulsion polymerization As a method for separating the polymer, for example, the latex is calcium chloride, magnesium chloride, magnesium sulfate. Examples include a method of coagulating, separating, washing, dehydrating and drying the latex by adding a metal salt such as. A spray drying method can also be used. If necessary, the polyorganosiloxane-containing graft copolymer can be washed with an organic solvent such as methanol.
- radical initiator for polymerizing the vinyl monomer of the present invention include organic peroxides such as cumene hydroperoxide, t-butyl hydride peroxide, benzoyl peroxide, and t-butyl peroxyisopropyl carbonate.
- organic peroxides such as cumene hydroperoxide, t-butyl hydride peroxide, benzoyl peroxide, and t-butyl peroxyisopropyl carbonate.
- Inorganic peroxides such as acids, potassium persulfate, ammonium persulfate, 2, 2'-azobisisobutyryl-tolyl, 2,2'-azobis-2,4 dimethyl-bare-tolyl, etc. Compound etc. are mentioned.
- Redox such as ferrous sulfate, formaldehyde sulfoxylate, ethylene diamine, tetraacetic acid, 2Na salt, ferrous sulfate-darcose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate
- Redox such as ferrous sulfate, formaldehyde sulfoxylate, ethylene diamine, tetraacetic acid, 2Na salt, ferrous sulfate-darcose-sodium pyrophosphate, ferrous sulfate-sodium pyrophosphate-sodium phosphate
- the polyorganosiloxane-containing graft copolymer obtained in this way is blended with various types of thermoplastic resin to form a resin composition having excellent impact resistance, releasability, flame retardancy, and the like. Give things.
- thermoplastic resin examples include polycarbonate, polycarbonate Z polyethylene terephthalate mixed resin, polycarbonate Z polyester mixed resin such as polycarbonate Z polybutylene terephthalate mixed resin, and polycarbonate Z acrylonitrile styrene copolymer mixed resin.
- Fat polycarbonate z butadiene styrene copolymer
- HIPS resin polycarbonate / acrylonitrile-butadiene rubber-styrene copolymer
- ABS resin polycarbonate / acrylonitrile-butadiene rubber-styrene copolymer
- polycarbonate Z styrene butadiene rubber acrylonitrile N Blended resin of phenol-maleimide copolymer, polycarbonate Z acrylonitrile-acrylic rubber-styrene copolymer (AAS resin) mixed resin, styrene resin, styrene-methyl methacrylate copolymer resin, styrene Acrylonitrile copolymer resin can be used.
- the polyorganosiloxane-containing graft copolymer may be added in an amount of 0.01 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin. preferable. If the amount is less than 01 parts by weight, the effect of improving the final molded body, such as impact resistance, mold release and flame retardancy, will be reduced. If it exceeds 30 parts by weight, the moldability (particularly the fluidity) of the molded product may be greatly reduced.
- antioxidants antioxidants, anti-dripping agents, polymeric calorific aids, flame retardants, impact modifiers, plasticizers, lubricants, ultraviolet absorbers, pigments, glass Fibers, fillers, polymer lubricants and the like can be blended.
- a molding method used for molding a normal thermoplastic resin composition that is, an injection molding method, an extrusion molding method, a blow molding method, a calendar molding method, or the like is applied. can do.
- the use of the molded article that also provides the composition of the resin composition of the present invention is not particularly limited.
- a desktop computer a notebook computer, a tower computer, a server computer, a printer, and a copier. Uses such as.
- the obtained molded article is excellent in impact resistance, release properties, flame retardancy, and the like.
- the latex was dried with a hot air dryer at 120 ° C. for 1 hour to determine the amount of solid components, and the amount was calculated as 100 X solid-form amount Z charged monomer amount (%).
- the volume average particle size of the seed polymer, polyorganosiloxane particles, and graft copolymer was measured in the latex state.
- MICROTRAC manufactured by LEED & NORTHRUP INSTRUMENTS
- the seed polymer latex was converted to a solid content in an about 5 g beaker, completely dried with a 120 ° C. dryer, and precisely weighed. After adding lOOg of water to the dried seed polymer and stirring at 23 ° C for 1 hour using a stirrer, the filtrate was taken out using a filter paper, and the water-soluble component was dried with a 120 ° C dryer and weighed accurately. . The extraction rate (%) of the water-soluble component in the dry seed polymer was determined.
- the particle diameter of the seed polymer latex was measured by MICROTRAC UPA (particle diameter before swelling).
- the pellet-shaped resin composition obtained by the method described above was subjected to ASTM-1 dumbbell (thickness 3mm) with a cylinder temperature of 240 ° C and mold using an injection molding machine (FANUC, FAS-75D). After molding at a temperature of 40 ° C, an injection speed of 25 mmZ seconds, an injection time of 5 seconds, and a cooling time of 25 seconds, a molded body was formed at an ejector one forward speed of 50 mmZ seconds and an ejector one forward position of 35 mm. The state where the molded body was released from the mold was observed. Ejector pins are arranged in two places so that the molded product can be easily released from the mold.
- the holding pressure is low, the molded product is easily separated from the mold force by the protrusion of the ejector pin. Only However, as the holding pressure increases, the molded body becomes difficult to separate from the mold, and finally the mold force does not separate even if the ejector pin protrudes. Even if the ejector pin protrudes, the holding pressure when the molded product is not separated from the mold is clearly measured (hereinafter, this holding pressure is called “holding pressure that is difficult to release”). did. Then, the holding pressure, which is difficult to release, was compared between the resin composition containing the polyorganosiloxane-containing graft copolymer and the resin composition that was not added.
- the evaluation criteria for releasability are as follows.
- ⁇ The difference in holding pressure that is difficult to release is 200 kgZcm 2 f or more.
- ⁇ The difference in holding pressure that is difficult to release is 50 to 200 kg / cm 2 f.
- Tick acid '2Na salt was added in an amount of 0.005 parts by weight and 0.2 part by weight of formaldehyde sulfoxylate so that polymerization was continued for another hour.
- a polyorganosiloxane latex was obtained in the same manner as in Example 2 except that DBSA was added 20 minutes after the start of addition of the organosiloxane emulsion.
- Table 2 shows the volume average particle size of this lux.
- a homomixer is a mixture of 150 parts by weight of pure water, 5 parts by weight of SDBSO.
- DBSA dodecylbenzenesulfonic acid
- seed latex seed 2
- the volume average particle diameter, hydrophilicity, and swelling degree after synthesis were measured, and the results are shown in Table 1.
- a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer port, and thermometer 450 parts by weight of water (various dilutions)
- the total amount of water including water), 2 parts by weight of seed 2 (solid content) and dodecylbenzenesulfonic acid (DBSA) in the amount shown in Table 2 (solid content) were mixed and heated to 80 ° C. After the temperature reaches 80 ° C, nitrogen substitution is performed.
- a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, monomer inlet, thermometer, 450 parts by weight of water (total amount of water including various dilution water), 2 parts of seed 2 Part (solid content) and the amount of DBSA (solid content) shown in Table 2 are mixed and then heated to 80 ° C. After the liquid temperature reaches 80 ° C, nitrogen substitution is performed.
- 150 parts by weight of pure water, 5 parts by weight of SDBSO. (Solid content), 97 parts by weight of otamethylcyclotetrasiloxane, and 1 part by weight of methacryloxypropylmethyldimethoxysilane (DSMA) were mixed using a homomixer.
- a 5-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet, additional monomer port and thermometer, 240 parts by weight of water (total amount of water including various dilution water), and Table 4 70 parts by weight (solid content) of polyorganosiloxane was charged, and the temperature was raised to 40 ° C under a nitrogen stream while stirring. After reaching 40 ° C, 0.2 parts by weight of sodium formaldehyde sulfoxylate, 0.012 parts of diethylenediamineacetic acid, 0.01 parts by weight of sodium ferrous sulfate, and 0.225 parts by weight of ferrous sulfate were added, followed by 27 parts by weight of methyl methacrylate. , Add a mixture of 3 parts by weight of glycidyl methacrylate and 0.06 parts by weight of tamennoidropa monooxide dropwise over 1.5 hours. Stirring was continued to obtain a graft copolymer latex.
- Ion-exchanged water and swellable mica (trade name: Somasif ME100, manufactured by Co-op Chemical Co., Ltd.) were mixed. Then, a polyethery compound (trade name: Bisol 18EN, manufactured by Toho Chemical Co., Ltd.) was added, and the mixture was processed by continuing mixing for 15 to 30 minutes. Thereafter, it was pulverized to obtain an inorganic filler treated with a polyether compound.
- Thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A) 100 parts by weight, inorganic filler 10 parts by weight, and polyorganosiloxane-based graft copolymer shown in Table 4 7.5 parts by weight
- the polyester resin composition was obtained by melt kneading the part using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44) to evaluate the physical properties. The results are shown in Table 4. (Comparative Example 19)
- Polyester resin composition by melt-kneading 100 parts by weight of a thermoplastic polyester resin (manufactured by Kanebo Co., Ltd., trade name: Belpet EFG85A) using a twin screw extruder (manufactured by Nippon Steel Co., Ltd., TEX44). The physical properties were evaluated. The results are shown in Table 4.
- SDBS (parts by weight) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
- a polyorganosiloxane latex having a particle size of 0.075 ⁇ m or less was obtained without using a siloxane-based crosslinking agent with a small amount of an emulsifier and an acid catalyst.
- the polyorganosiloxane-containing graft polymer using it showed excellent thermal stability, heat resistance and releasability.
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Abstract
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000103804A (ja) * | 1998-09-30 | 2000-04-11 | Sekisui Chem Co Ltd | 単分散微粒子の製造方法、微粒子の製造方法及び液晶表示素子用スペーサの製造方法 |
JP2003105160A (ja) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
JP2003327635A (ja) * | 2002-05-08 | 2003-11-19 | Kanegafuchi Chem Ind Co Ltd | グラフト共重合体及びそれを含有する耐衝撃性、難燃性樹脂組成物 |
WO2005012392A1 (fr) * | 2003-08-02 | 2005-02-10 | Lg Chem. Ltd. | Anti-chocs hybrides en acryle-silicone, procede de preparation de ceux-ci et compositions de resine de chlorure de vinyle renfermant ceux-ci |
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- 2005-07-29 WO PCT/JP2005/013981 patent/WO2006016490A1/fr active Application Filing
- 2005-07-29 JP JP2006531445A patent/JPWO2006016490A1/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000103804A (ja) * | 1998-09-30 | 2000-04-11 | Sekisui Chem Co Ltd | 単分散微粒子の製造方法、微粒子の製造方法及び液晶表示素子用スペーサの製造方法 |
JP2003105160A (ja) * | 2001-09-28 | 2003-04-09 | Mitsubishi Rayon Co Ltd | 熱可塑性樹脂組成物 |
JP2003327635A (ja) * | 2002-05-08 | 2003-11-19 | Kanegafuchi Chem Ind Co Ltd | グラフト共重合体及びそれを含有する耐衝撃性、難燃性樹脂組成物 |
WO2005012392A1 (fr) * | 2003-08-02 | 2005-02-10 | Lg Chem. Ltd. | Anti-chocs hybrides en acryle-silicone, procede de preparation de ceux-ci et compositions de resine de chlorure de vinyle renfermant ceux-ci |
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