WO2006059819A1 - Thermoplastic abs resin composition with improved impact resistance, dimensional stability and blow molding property - Google Patents

Thermoplastic abs resin composition with improved impact resistance, dimensional stability and blow molding property Download PDF

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Publication number
WO2006059819A1
WO2006059819A1 PCT/KR2005/000955 KR2005000955W WO2006059819A1 WO 2006059819 A1 WO2006059819 A1 WO 2006059819A1 KR 2005000955 W KR2005000955 W KR 2005000955W WO 2006059819 A1 WO2006059819 A1 WO 2006059819A1
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Prior art keywords
weight
parts
document
graft copolymer
vinyl aromatic
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PCT/KR2005/000955
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French (fr)
Inventor
Bang Duk Kim
Jae Ho Yang
Tae Uk Kim
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Cheil Industries Inc
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Cheil Industries Inc
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Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Priority to US11/720,441 priority Critical patent/US7776964B2/en
Priority to DE602005016301T priority patent/DE602005016301D1/en
Priority to EP05789552A priority patent/EP1828272B1/en
Priority to JP2007544252A priority patent/JP2008521997A/en
Publication of WO2006059819A1 publication Critical patent/WO2006059819A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a thermoplastic resin composition with improved impact resistance, dimensional stability and heat resistance as well as excellent extrusion and blow molding property. More particularly, the present invention relates to a thermoplastic ABS resin composition that comprises graft copolymer particles having rubbers with different range of particle sizes and two kinds of vinyl cyanide- vinyl aromatic copolymer.
  • ABS resin thermoplastic acrylonitrile-butadiene-styrene (hereinafter ABS) resin has been employed to materials for electric/electronic appliances, automobile parts and so on.
  • the requirements which the materials have to meet include heat resistance, mechanical strength and dimensional stability.
  • the materials when the resin is molded through extrusion or blow molding process, the materials further require high melt modulus and elongation ratio and should not cause a phenomenon of draw-down of parrison.
  • N-substituted maleimide copolymer confers improved heat resistance and low coefficient of linear thermal expansion, the use of N-substituted maleimide cannot provide sufficient impact resistance, so the application has been restricted.
  • thermoplastic ABS resin composition having improved impact resistance, dimensional stability and heat resistance as well as excellent extrusion and blow molding property by introducing ABS copolymer particles having different rubber particle size to vinyl cyanide- vinyl aromatic copolymer in a specific ratio.
  • An object of the present invention is to provide a thermoplastic ABS resin composition having good impact strength, dimensional stability and heat resistance.
  • Another object of the present invention is to provide a thermoplastic ABS resin composition having excellent extrusion blow molding property.
  • Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims. [13]
  • the thermoplastic ABS resin composition according to the present invention comprises (a) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D; (b) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D; (c) 2 to 18 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D; (d) 10 to 70 parts by weight of a branched vinyl cyanide- vinyl aromatic copolymer; and (e) 1 to 60 parts by weight of a long-chain linear vinyl cyanide- vinyl aromatic copolymer.
  • the branched vinyl cyanide- vinyl aromatic copolymer is prepared by copolymerizing 15-50 parts by weight of a vinyl cyanide compound and 85-50 parts by weight of a vinyl aromatic compound in the presence of less than 1 part by weight of a polyfunctional compound and has a weight average molecular weight of 100,000-2,000,000.
  • the branched vinyl cyanide- vinyl aromatic copolymer (d) can be used alone or in combination.
  • (b) is 5-35 parts by weight, and preferably (a)+(b)+(c) is 10-50 parts by weight.
  • the detailed descriptions of the resin composition according to the present invention are as follows.
  • the graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D(a) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
  • Monomer mixture to be used for the preparation of the graft copolymer particle (a) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
  • the rubber to be used for the preparation of the graft copolymer particle (a) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used.
  • the average rubber particle size of the graft copolymer particle is from 0.05 D to less than 0.18 D, preferably from 0.1 D to less than 0.15 D. In the present invention, two or more types of the rubbers having different average particle size can be used within the above range.
  • (a) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
  • Examples of the vinyl aromatic compound for preparing the graft copolymer particle (a) include styrene, ⁇ -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
  • the graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D (b) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
  • Monomer mixture to be used for the preparation of the graft copolymer particle (b) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
  • the rubber to be used for the preparation of the graft copolymer particle (b) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used.
  • the average rubber particle size of the graft copolymer particle is from 0.18 D to less than 0.4 D, preferably from 0.2 D to less than 0.35 D. In the present invention, two or more types of the rubber having different average particle size can be used within the above range.
  • (b) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
  • Examples of the vinyl aromatic compound for preparing the graft copolymer particle (b) include styrene, ⁇ -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
  • the graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D (c) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
  • Monomer mixture to be used for the preparation of the graft copolymer particle (c) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
  • the rubber to be used for the preparation of the graft copolymer particle (c) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used.
  • the average rubber particle size of the graft copolymer particle is from 0.4 D to 4 D, preferably from 0.5 D to 0.3 D. In the present invention, two or more types of the rubber having different average particle size can be used within the above range.
  • (c) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
  • Examples of the vinyl aromatic compound for preparing the graft copolymer particle (c) include styrene, ⁇ -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
  • the branched vinyl cyanide- vinyl aromatic copolymer (d) of the present invention is prepared by copolymerizing 100 parts by weight of a monomer mixture consisting of 15-50 parts by weight of a vinyl cyanide compound and 85-50 parts by weight of a vinyl aromatic compound with less than 1 part by weight of a polyfunctional compound.
  • the weight average molecular weight of the branched vinyl cyanide- vinyl aromatic copolymer (d) is preferably in the range of 100,000-2,000,000. It is preferable to have many long branches in the molecular structure.
  • Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in co mbination.
  • Examples of the vinyl aromatic compound include styrene, ⁇ - methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination.
  • the vinyl cyanide- vinyl aromatic copolymer (d) of the present invention can be prepared by emulsion, suspension, solution and bulk polymerization.
  • the polyfunctional compound is selected from the group consisting of polyfunctional vinyl aromatic compound, triallyl isocyanurate, polyfunctional mercaptan, polyfunctional peroxide or derivatives thereof and a mixture thereof.
  • polyfunctional vinyl aromatic compound divinylbenzene is most preferred.
  • the branched vinyl cyanide- vinyl aromatic copolymer (d) of the present invention can be used in an amount of 10-70 parts by weight. If the amount is more than 70 parts by weight, the impact strength of the resin composition is decreased. If the amount is less than 10 parts by weight, blow and extrusion molding properties are decreased.
  • the branched vinyl cyanide- vinyl aromatic copolymer (d) can be used alone or in combination.
  • the long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention is prepared by copolymerizing 10 ⁇ 50 parts by weight of a vinyl cyanide compound and 90—50 parts by weight of a vinyl aromatic compound.
  • the weight average molecular weight of the long-chain linear vinyl cyanide-vinyl aromatic copolymer (e) is in the range of 50,000—2,000,000.
  • Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in combination.
  • Examples of the vinyl aromatic compound include styrene, di- vinylbenzene, ⁇ -methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination.
  • the long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and so on.
  • the graft copolymer particles (a), (b) and (c) are prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization.
  • the long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) can be prepared together with the above graft copolymer particles, and can be also used in the present invention.
  • the long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention can be used in an amount of 1-60 parts by weight. If the amount is more than 60 parts by weight, blow and extrusion molding properties are decreased. If the amount is less than 1 part by weight, the mold surface of blow and extrusion mold becomes rough.
  • the amount of graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D (a) is 2-25 parts by weight
  • graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D(b) is 2-25 parts by weight
  • graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D (c) is 2-18 parts by weight based on 100 parts by weight of total resin composition.
  • the sum of (a), (b) and (c) is 10-50 parts by weight.
  • the sum of (a), (b) and (c) is 10-50 parts by weight.
  • the additives include an impact modifier, an oxidation inhibitor, a lubricant, a light stabilizer, a filler, an inorganic additive, pigment and/or dye.
  • ABS resin containing graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D [77]
  • ABS resin contained not only graft copolymer particle but also long-chain linear vinyl cyanide- vinyl aromatic copolymer (26 % by weight of graft copolymer particle and 74 % by weight of long-chain linear vinyl cyanide- vinyl aromatic copolymer).
  • the volume average diameter of rubber of the graft copolymer particle was 0.52 D.
  • the long-chain linear vinyl cyanide- vinyl aromatic copolymer contained 25 % by weight of acrylonitrile and had a weight average molecular weight of 140,000.
  • Comparative Example 1 was conducted in the same manner as in Example 1 except that ABS resin(c) which contains graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D was not used, but made the total content of rubber same as that of Example 1.
  • Comparative Example 2 was conducted in the same manner as in Example 1 except that ABS resin (c) which contains graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D was not used, and increase the total content of rubber.
  • Comparative Example 3 was conducted in the same manner as in Example 3 except that a styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ) was used instead of branched vinyl cyanide- vinyl aromatic copolymer(d). The total amount of long-chain linear vinyl cyanide- vinyl aromatic copolymer of Comparative Example 3 exceeded 60 parts by weight.
  • Comparative Example 4 was conducted in the same manner as in Example 4 except that a PMI-based vinyl cyanide- vinyl aromatic copolymer(f) was used instead of styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ).
  • the unit of rubber content is %, and the unit of each component is part by weight;
  • ( ) * is the amount of graft copolymer particle containing rubber having a volume average particle diameter range from 0.4 D to 4 D contained in ABS resin(c);
  • ( ) is the amount of long-chain linear vinyl cyanide- vinyl aromatic copolymer contained in ABS resin(c))
  • Notch Izod Impact Strength The notch Izod impact strength was measured in accordance with ASTM D256(l/4" notched, 23 °C).
  • Elongation Ratio The elongation ratio was calculated by measuring the increased value after biaxial drawing at 200 °C and compared the increased value to that of Example 1.
  • Strain-Hardening The strain-hardening was evaluated with naked eye. O means that the strain-hardening effect is string, ⁇ means that the strain-hardening effect is weak, x means that the strain-hardening effect is none.
  • Comparative Example 1 shows lower impact strength than Example 1. This illustrates that the usage of distinct groups of rubber particles having a different average particle is effective to increase the impact strength pf the resin composition.
  • Comparative Example 2 which contains larger amount of rubber content by increasing the amount of (a) and (b) shows extremely high melt index and low heat resistance, which means that the resin composition is inadequate for blow molding and that the materials therefrom is unfit for automobile parts. Further, Comparative Example 2 exhibits high coefficient of linear thermal expansion due to high content of rubber, which causes poor dimensional stability.
  • Comparative Example 3 in which a styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ) was used instead of branched vinyl cyanide- vinyl aromatic copolymer(d), shows low elongation ratio and poor strain hardening, which results in bad moldability.

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Abstract

The thermoplastic ABS resin composition according to the present invention comprises (a) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D; (b) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D; (c) 2 to 18 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to less than 4 D; (d) 10 to 70 parts by weight of a branched vinyl cyanide- vinyl aromatic copolymer; and (e) 1 to 60 parts by weight of a long-chain linear vinyl cyanide- vinyl aromatic copolymer.

Description

Description
THERMOPLASTIC ABS RESIN COMPOSITION WITH
IMPROVED IMPACT RESISTANCE, DIMENSIONAL
STABILITY AND BLOW MOLDING PROPERTY
Technical Field
[1] The present invention relates to a thermoplastic resin composition with improved impact resistance, dimensional stability and heat resistance as well as excellent extrusion and blow molding property. More particularly, the present invention relates to a thermoplastic ABS resin composition that comprises graft copolymer particles having rubbers with different range of particle sizes and two kinds of vinyl cyanide- vinyl aromatic copolymer.
[2]
Background Art
[3] Recently, thermoplastic acrylonitrile-butadiene-styrene (hereinafter ABS) resin has been employed to materials for electric/electronic appliances, automobile parts and so on. The requirements which the materials have to meet include heat resistance, mechanical strength and dimensional stability. In particular, when the resin is molded through extrusion or blow molding process, the materials further require high melt modulus and elongation ratio and should not cause a phenomenon of draw-down of parrison.
[4] It has been proposed to increase the amount of rubber content to improve the impact resistance of ABS resin. However, the molding compositions produced therefrom have inordinately high coefficient of linear thermal expansion, so that the dimensional stability of the resin is deteriorated. On the other hand, decreasing the amount of rubber content may cause crack formation due to poor impact resistance at low temperature. Inorganic fillers such as glass fiber may be used to improve dimensional stability, but this method is inadequate for the resins to be prepared by extrusion or blow molding process.
[5] In order to improve impact strength, it is also known to blend polymer particles produced by different polymerization process, that is, to blend polymer particles produced in an emulsion polymerization process with particles produced in a continuous polymerization process (c.f. U.S. Pat. Nos. 4,430,478 , 5,605,963 and 5,696,204). However, the resultant products exhibit low dimensional stability and poor extrusion and blow molding properties.
[6] That is, in order to obtain good extrusion and blow molding property, it is important that the resin compositions have high melt modulus and elongation ratio, and exhibit high strain hardening effect and no parrison phenomenon occurs. However, the exacting requirements are not fulfilled by these compositions produced from the above references.
[7] It is commonly known a method to minimize the rubber content and add N- substituted maleimide copolymer in order to provide good characteristics of heat resistance and dimensional stability to ABS resin. Though N-substituted maleimide copolymer confers improved heat resistance and low coefficient of linear thermal expansion, the use of N-substituted maleimide cannot provide sufficient impact resistance, so the application has been restricted.
[8] Accordingly, the present inventors have developed a thermoplastic ABS resin composition having improved impact resistance, dimensional stability and heat resistance as well as excellent extrusion and blow molding property by introducing ABS copolymer particles having different rubber particle size to vinyl cyanide- vinyl aromatic copolymer in a specific ratio.
[9]
Disclosure of Invention Technical Problem
[10] An object of the present invention is to provide a thermoplastic ABS resin composition having good impact strength, dimensional stability and heat resistance. [11] Another object of the present invention is to provide a thermoplastic ABS resin composition having excellent extrusion blow molding property. [12] Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims. [13]
Technical Solution
[14] The thermoplastic ABS resin composition according to the present invention comprises (a) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D; (b) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D; (c) 2 to 18 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D; (d) 10 to 70 parts by weight of a branched vinyl cyanide- vinyl aromatic copolymer; and (e) 1 to 60 parts by weight of a long-chain linear vinyl cyanide- vinyl aromatic copolymer.
[15] The branched vinyl cyanide- vinyl aromatic copolymer is prepared by copolymerizing 15-50 parts by weight of a vinyl cyanide compound and 85-50 parts by weight of a vinyl aromatic compound in the presence of less than 1 part by weight of a polyfunctional compound and has a weight average molecular weight of 100,000-2,000,000. The branched vinyl cyanide- vinyl aromatic copolymer (d) can be used alone or in combination.
[16] The sum of the amount of graft copolymer particle (a) and graft copolymer particle
(b) is 5-35 parts by weight, and preferably (a)+(b)+(c) is 10-50 parts by weight. The detailed descriptions of the resin composition according to the present invention are as follows.
[17]
Best Mode for Carrying Out the Invention
[18] (a) graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D
[19]
[20] The graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D(a) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
[21] Monomer mixture to be used for the preparation of the graft copolymer particle (a) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
[22] The rubber to be used for the preparation of the graft copolymer particle (a) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used. The average rubber particle size of the graft copolymer particle is from 0.05 D to less than 0.18 D, preferably from 0.1 D to less than 0.15 D. In the present invention, two or more types of the rubbers having different average particle size can be used within the above range.
[23] Examples of the vinyl cyanide compound for preparing the graft copolymer particle
(a) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
[24] Examples of the vinyl aromatic compound for preparing the graft copolymer particle (a) include styrene, α-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
[25]
[26] (b) graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D [27]
[28] The graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D (b) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
[29] Monomer mixture to be used for the preparation of the graft copolymer particle (b) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
[30] The rubber to be used for the preparation of the graft copolymer particle (b) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used. The average rubber particle size of the graft copolymer particle is from 0.18 D to less than 0.4 D, preferably from 0.2 D to less than 0.35 D. In the present invention, two or more types of the rubber having different average particle size can be used within the above range.
[31] Examples of the vinyl cyanide compound for preparing the graft copolymer particle
(b) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
[32] Examples of the vinyl aromatic compound for preparing the graft copolymer particle (b) include styrene, α-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
[33]
[34] (c) graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D
[35]
[36] The graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D (c) of the present invention may prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization or conventional emulsion graft polymerization.
[37] Monomer mixture to be used for the preparation of the graft copolymer particle (c) comprises 15-35 % by weight of a vinyl cyanide compound and 85-65 % by weight of a vinyl aromatic compound.
[38] The rubber to be used for the preparation of the graft copolymer particle (c) includes polybutadiene, polyisoprene, polychloroprene, a butadiene-styrene copolymer, a butadiene-acrylonitrile copolymer and so forth. Among them, polybutadiene, a butadiene-styrene copolymer, and a butadiene-acrylonitrile copolymer may be preferably used. The average rubber particle size of the graft copolymer particle is from 0.4 D to 4 D, preferably from 0.5 D to 0.3 D. In the present invention, two or more types of the rubber having different average particle size can be used within the above range.
[39] Examples of the vinyl cyanide compound for preparing the graft copolymer particle
(c) include acrylonitrile, methacrylonitrile and the like. These vinyl cyanide compounds can be used alone or in combination.
[40] Examples of the vinyl aromatic compound for preparing the graft copolymer particle (c) include styrene, α-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the like. These vinyl aromatic compounds can be used alone or in combination.
[41]
[42] (d) branched vinyl cyanide- vinyl aromatic copolymer
[43]
[44] The branched vinyl cyanide- vinyl aromatic copolymer (d) of the present invention is prepared by copolymerizing 100 parts by weight of a monomer mixture consisting of 15-50 parts by weight of a vinyl cyanide compound and 85-50 parts by weight of a vinyl aromatic compound with less than 1 part by weight of a polyfunctional compound.
[45] The weight average molecular weight of the branched vinyl cyanide- vinyl aromatic copolymer (d) is preferably in the range of 100,000-2,000,000. It is preferable to have many long branches in the molecular structure.
[46] Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in co mbination. Examples of the vinyl aromatic compound include styrene, α- methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination. The vinyl cyanide- vinyl aromatic copolymer (d) of the present invention can be prepared by emulsion, suspension, solution and bulk polymerization.
[47] The polyfunctional compound is selected from the group consisting of polyfunctional vinyl aromatic compound, triallyl isocyanurate, polyfunctional mercaptan, polyfunctional peroxide or derivatives thereof and a mixture thereof. As the polyfunctional vinyl aromatic compound, divinylbenzene is most preferred.
[48] The branched vinyl cyanide- vinyl aromatic copolymer (d) of the present invention can be used in an amount of 10-70 parts by weight. If the amount is more than 70 parts by weight, the impact strength of the resin composition is decreased. If the amount is less than 10 parts by weight, blow and extrusion molding properties are decreased. The branched vinyl cyanide- vinyl aromatic copolymer (d) can be used alone or in combination.
[49]
[50] (e) long-chain linear vinyl cyanide- vinyl aromatic copolymer
[51]
[52] The long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention is prepared by copolymerizing 10~50 parts by weight of a vinyl cyanide compound and 90—50 parts by weight of a vinyl aromatic compound.
[53] The weight average molecular weight of the long-chain linear vinyl cyanide-vinyl aromatic copolymer (e) is in the range of 50,000—2,000,000.
[54] Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the mixture thereof. These vinyl cyanide compounds can be used alone or in combination. Examples of the vinyl aromatic compound include styrene, di- vinylbenzene, α-methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene, vinyltoluene and the mixture thereof. These vinyl aromatic compounds can be used alone or in combination. The long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization and so on.
[55] Besides, when the graft copolymer particles (a), (b) and (c) are prepared by continuous polymerization such as bulk-suspension, bulk-solution polymerization, conventional bulk polymerization., the long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) can be prepared together with the above graft copolymer particles, and can be also used in the present invention.
[56] The long-chain linear vinyl cyanide- vinyl aromatic copolymer (e) of the present invention can be used in an amount of 1-60 parts by weight. If the amount is more than 60 parts by weight, blow and extrusion molding properties are decreased. If the amount is less than 1 part by weight, the mold surface of blow and extrusion mold becomes rough.
[57] In the thermoplastic ABS resin composition of the present invention, the amount of graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D (a) is 2-25 parts by weight, graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D(b) is 2-25 parts by weight, and graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D (c) is 2-18 parts by weight based on 100 parts by weight of total resin composition.
[58] Further, the sum of (a), (b) and (c) is 10-50 parts by weight. Preferably the sum of
(a) and (b) is 5-35 parts by weight.
[59] In case that the amounts of graft copolymer particles (a), (b) and (c) exceed the above ranges, the coefficient of linear thermal expansion is increased, and heat resistance is lowered. On the other hand, if the amounts of graft copolymer particles (a), (b) and (c) are less than the above ranges, the impact strength of the resin composition is reduced so that the product therefrom is of no practical use.
[60] Other additives may be contained in the resin composition of the present invention.
The additives include an impact modifier, an oxidation inhibitor, a lubricant, a light stabilizer, a filler, an inorganic additive, pigment and/or dye.
[61]
[62] The invention may be better understood by reference to the following examples which are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto. In the following examples, all parts and percentage are by weight unless otherwise indicated.
[63]
Mode for the Invention
[64] EXAMPLES
[65]
[66] Each component used in Examples and Comparative Examples was prepared as follow:
[67]
[68] (a) graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D
[69]
[70] To 40 parts by weight of butadiene rubber was added a monomer mixture consisting of 20 % by weight of acrilonitrile and 80 % by weight of styrene to make 100 parts by weight, followed by grafting in emulsion polymerization to obtain graft copolymer particle of which the volume average diameter of rubber was 0.11 D.
[71]
[72] (b) graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D
[73]
[74] To 45 parts by weight of butadiene rubber was added a monomer mixture consisting of 18 % by weight of acrilonitrile and 82 % by weight of styrene to make 100 parts by weight, followed by grafting in emulsion polymerization to obtain graft copolymer particle of which the volume average diameter of rubber was 0.21 D.
[75]
[76] (c) ABS resin containing graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D [77]
[78] To 15 parts by weight of butadiene rubber was added a monomer mixture consisting of 25 % by weight of acrilonitrile and 75 % by weight of styrene to make 100 parts by weight, followed by continuous polymerization to obtain ABS resin. The resultant ABS resin contained not only graft copolymer particle but also long-chain linear vinyl cyanide- vinyl aromatic copolymer (26 % by weight of graft copolymer particle and 74 % by weight of long-chain linear vinyl cyanide- vinyl aromatic copolymer). The volume average diameter of rubber of the graft copolymer particle was 0.52 D. And the long-chain linear vinyl cyanide- vinyl aromatic copolymer contained 25 % by weight of acrylonitrile and had a weight average molecular weight of 140,000.
[79]
[80] (d) branched vinyl cyanide- vinyl aromatic copolymer
[81]
[82] Both styrene-acrylonitrile copolymer containing 0.05 parts by weight of di- vinylbenzene and 100 parts by weight of monomer mixture consisting of 17 parts by weight of acrylonitrile and 83 parts by weight of styrene and having a weight average molecular weight of 150,000 and styrene-acrylonitrile copolymer containing 0.05 parts by weight of divinylbenzene and 100 parts by weight of monomer mixture consisting of 20 % by weight of acrylonitrile and 80 % by weight of styrene and having a weight average molecular weight of 1,500,000 were used simultaneously.
[83]
[84] (e) long-chain linear vinyl cyanide- vinyl aromatic copolymer
[85]
[86] (e ) The long-chain linear vinyl cyanide- vinyl aromatic copolymer prepared from the production of the above graft copolymer particle(c) was used.
[87] (e ) A styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000 was used.
[88]
[89] (f) PMI-based vinyl cyanide- vinyl aromatic copolymer
[90]
[91] A styrene-acrylonitrile copolymer resin containing 50 parts by weight of N- phenylmaleimide(PMI) and 100 parts by weight of monomer mixture consisting of 20 parts by weight of acrylonitrile and 80 parts by weight of styrene, and having a weight average molecular weight of 200,000 was used.
[92]
[93] Examples 1-4
[94]
[95] The components as shown in Table 1 were mixed and the mixture was extruded through a twin screw extruder with L/D=29 and Φ=45 mm in pellets. The cylinder temperature of the extruder was kept at 250 °C. Test specimens for flowability and physical properties were prepared. Test specimens for measuring the coefficient of linear thermal expansion were prepared in a size of 1.0x1.0x0.6 cm. The test specimens were subjected to biaxial drawing to inspect the strain-hardening and compare the elongation ratio.
[96]
[97] Comparative Example 1
[98]
[99] Comparative Example 1 was conducted in the same manner as in Example 1 except that ABS resin(c) which contains graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D was not used, but made the total content of rubber same as that of Example 1.
[100]
[101] Comparative Example 2
[102]
[103] Comparative Example 2 was conducted in the same manner as in Example 1 except that ABS resin (c) which contains graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D was not used, and increase the total content of rubber.
[104]
[ 105] Comparative Example 3
[106]
[107] Comparative Example 3 was conducted in the same manner as in Example 3 except that a styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ) was used instead of branched vinyl cyanide- vinyl aromatic copolymer(d). The total amount of long-chain linear vinyl cyanide- vinyl aromatic copolymer of Comparative Example 3 exceeded 60 parts by weight.
[108]
[ 109] Comparative Example 4
[HO]
[111] Comparative Example 4 was conducted in the same manner as in Example 4 except that a PMI-based vinyl cyanide- vinyl aromatic copolymer(f) was used instead of styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ).
[112]
[113] Table 1
Figure imgf000011_0001
[114] (The unit of rubber content is %, and the unit of each component is part by weight; ( )* is the amount of graft copolymer particle containing rubber having a volume average particle diameter range from 0.4 D to 4 D contained in ABS resin(c); ( )is the amount of long-chain linear vinyl cyanide- vinyl aromatic copolymer contained in ABS resin(c))
[115] [116] For the test specimens prepared according to the above examples, physical properties were measured as follow:
[117] [118] (1) Notch Izod Impact Strength : The notch Izod impact strength was measured in accordance with ASTM D256(l/4" notched, 23 °C).
[119] (2) Melt Flow Index : The melt flow index was determined in accordance with ISO 1133 (10 D, 220 °C). [120] (3) Heat Distortion Temperature (HDT) : The heat distortion temperature was measured according to ASTM D648 (1/4", 120 °C/hr) under 18.5 kgf/cm2. [121] (4) Coefficient Of Linear Thermal Expansion : The coefficient of linear thermal expansion was measured by thermomechanical analyzer (TMA), varying the temperature from 30 to 80 °C at the rate of 10 °C/min.
[122] (5) Elongation Ratio: The elongation ratio was calculated by measuring the increased value after biaxial drawing at 200 °C and compared the increased value to that of Example 1. [123] (6) Strain-Hardening: The strain-hardening was evaluated with naked eye. O means that the strain-hardening effect is string, Δ means that the strain-hardening effect is weak, x means that the strain-hardening effect is none.
[124] [125] The test results of Examples 1~4 and Comparative Examples 1~4 are shown in Table 2.
[126] [127] Table 2
Figure imgf000012_0001
[128] [129] As shown in Table 2, the compositions in Examples 1-4 show improved impact strength, coefficient of linear thermal expansion and heat resistance in comparison to Comparative Examples 1-4. The melt flow indexes of all Examples except Comparative Example 2 fell within the range of 1-5 which is a necessary value in normal blow molding.
[130] Though the resin compositions of Example 1 and Comparative Example 1 contain the same amount of rubber, Comparative Example 1 shows lower impact strength than Example 1. This illustrates that the usage of distinct groups of rubber particles having a different average particle is effective to increase the impact strength pf the resin composition.
[131] Comparative Example 2 which contains larger amount of rubber content by increasing the amount of (a) and (b) shows extremely high melt index and low heat resistance, which means that the resin composition is inadequate for blow molding and that the materials therefrom is unfit for automobile parts. Further, Comparative Example 2 exhibits high coefficient of linear thermal expansion due to high content of rubber, which causes poor dimensional stability.
[132] Comparative Example 3 in which a styrene-acrylonitrile copolymer resin containing 20 % by weight of acrylonitrile and having a weight average molecular weight of 150,000(e ) was used instead of branched vinyl cyanide- vinyl aromatic copolymer(d), shows low elongation ratio and poor strain hardening, which results in bad moldability.
[133] Comparative Example 4 in which PMI-based vinyl cyanide- vinyl aromatic copolymer(f) was used instead of styrene-acrylonitrile copolymer resin (e ) shows considerably low impact strength, which illustrates that the resin composition of the present invention has sufficient heat resistance, so that the PMI-based vinyl cyanide- vinyl aromatic copolymer which adversely affect the impact strength of the resin is not required in the present invention.
[134] The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be with the scope of the present invention as defined in the following claims.
[135]
[136]

Claims

Claims
[1] A thermoplastic ABS resin composition comprising:
(a) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.05 D to less than 0.18 D;
(b) 2 to 25 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.18 D to less than 0.4 D;
(c) 2 to 18 parts by weight of a graft copolymer particle containing rubbers having a volume average particle diameter range from 0.4 D to 4 D;
(d) 10 to 70 parts by weight of a branched vinyl cyanide- vinyl aromatic copolymer; and
(e) 1 to 60 parts by weight of a long-chain linear vinyl cyanide- vinyl aromatic copolymer.
[2] The thermoplastic ABS resin compositions as defined in claim 1, wherein said branched vinyl cyanide- vinyl aromatic copolymer(d) is prepared by copolymerizing 100 parts by weight of a monomer mixture consisting of 15-50 parts by weight of a vinyl cyanide compound and 85-50 parts by weight of a vinyl aromatic compound with less than 1 part by weight of a polyfunctional compound and has a weight average molecular weight of 100,000-2,000,000.
[3] The thermoplastic ABS resin compositions as defined in claim 1, wherein the sum of the amount of graft copolymer particles (a) and (b) is 5-35 parts by weight, and the sum of the amount of graft copolymer particles (a), (b) and (c) is 10-50 parts by weight.
[4] The thermoplastic ABS resin compositions as defined in claim 1, wherein said graft copolymer particle(a) contains rubbers having a volume average particle diameter range from 0.1 D to less than 0.15 D, said graft copolymer particle(b) contains rubbers having a volume average particle diameter range from 0.2 D to less than 0.35 D and said graft copolymer particle(c) contains rubbers having a volume average particle diameter range from 0.5 D to 3 D.
[5] The thermoplastic ABS resin compositions as defined in claim 1, wherein all or part of said graft copolymer particles (a), (b) and (c) has two or more types of the rubbers having different average particle size.
[6] The thermoplastic ABS resin compositions as defined in claim 1, wherein monomer mixture to be used for the preparation of said graft copolymer particles (a), (b) and (c) comprises a vinyl cyanide compound and a vinyl aromatic compound.
[7] The thermoplastic ABS resin compositions as defined in claims 1 or 6, wherein said vinyl cyanide compound is acrylonitrile or methacrylonitrile; and said vinyl aromatic compound is selected from the group consisting of styrene, α- methylstyrene, p-t-butylstyrene, 2,4-dimethylstyrene and vinyltoluene. [8] The thermoplastic ABS resin compositions as defined in claim 1, wherein said branched vinyl cyanide- vinyl aromatic copolymer (d) is prepared by using poly- functional compound selected from the group consisting of polyfunctional vinyl aromatic compound, triallyl isocyanurate, polyfunctional mercaptan, polyfunctional peroxide or derivatives thereof and a mixture thereof.
A. CLASSIFICATION OF SUBJECT MATTER
IPC7 C08F 279/04, C08L 51/04, C08L 25/12
According to International Patent Classification (IPC) or to both national classification and IPC
B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols) IPC7 C08F 279/04, C08L 51/04, C08L 25/12
Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched Korean Patents and applications for inventions since 1975 Korean Utility models and applictions for Utility models since 1975 Japanese Utility models and application for Utility models since 1975
Electronic data base consulted during the intertnational search (name of data base and, where practicable, search terms used) KIPASS, PAJ
C. DOCUMENTS CONSIDERED TO BE RELEVANT
Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.
KR 396402 Bl (Cheil Industries Inc.) 02 September 2003 1-8 see the whole document
WO 89/05836 Al (The Dow Chemical Co.) 29 June 1989 1-8 see the whole document
KR 2002-77501 A (Bayer Aktiengesellschaft) 11 October 2002 1-8 see the whole document
US 4430478 A (Burghard Schmitt et al) 07 February 1984 1-8 see the whole document, cited in application
KR 1994-3476 Bl (The Dow Chemical Co.) 22 April 1994 1-8 see the whole document
KR 2004-6120 A (Hyundai Motors Co.) 24 January 2004 1-8 see the whole document
Further documents are listed in the continuation of Box C. See patent family annex.
* Special categories of cited documents: "T" later document published after the international filing date or priority
"A" document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention 1E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot be filing date considered novel or cannot be considered to involve an inventive 'L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of citation or other "Y" document of particular relevance; the claimed invention cannot be special reason (as specified) considered to involve an inventive step when the document is "O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later "&" document member of the same patent family than the priority date claimed
Date of the actual completion of the international search Date of mailing of the international search report 31 AUGUST 2005 (31.08.2005) 31 AUGUST 2005 (31.08.2005)
Name and mailing address of the ISA/KR Authorized officer
Korean Intellectual Property Office
920 Dunsan-dong, Seo-gu, Daejeon 302-701, BAHN, Yong Byung
Republic of Korea
Figure imgf000016_0001
Facsimile No. 82-42-472-7140 Telephone No. 82-42-481-5539
Figure imgf000016_0002
Form PCT/ISA/210 (second sheet) (January 2004) Patent document Publication Patent family Publication cited in search report date members) date
KR 396402 B1 02.09.2003 NONE
WO 89/05836 A1 29.06.1989 DE3751728C0 11.04.1996
EP390781A1 10.10.1990
EP390781A4 28.08.1991
EP390781B1 06.03.1996
JP03501626 11.04.1991
JP2799327B2 17.09.1998
KR 2002-77501 A 11.10.2002 AU200144131A1 03.09.2001
BR200108555A 29.04.2003
CA2400685A1 30.08.2001
CN1153811C 16.06.2004
CN1404505A 19.03.2003
DE10008420A1 30.08.2001
EP1268662A1 02.01.2003
JP 15-528170A 24.09.2003
US2003092836A 15.05.2003
W0200162848A1 30.08.2001
US 4430478 A 07.02.1984 DE3044110A1 24.06.1982
EP52732A1 02.06.1982
EP52732B1 02.05.1985
KR 1994-3476 B1 22.04.1994 AU5271686A1 07.08.1986
CA1266732A1 13.03.1990
DE3670498C0 23.05.1990
EP190884A2 13.08.1986
EP190884B1 18.04.1990
EP190884A3 27.01.1988
J P61203158 A 09.09.1986
US4874815A 17.10.1989
W08905836A1 29.06.1989
KR 2004-6120 A 24.01.2004 NONE
Form PCT/ISA/210 (patent family annex) (January 2004)
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JP2008521997A (en) 2008-06-26
DE602005016301D1 (en) 2009-10-08
TW200619309A (en) 2006-06-16
US20080167426A1 (en) 2008-07-10
CN100562533C (en) 2009-11-25
EP1828272B1 (en) 2009-08-26
CN101065413A (en) 2007-10-31
EP1828272A4 (en) 2008-09-03

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