EP0998506A1 - Process for the preparation of low-gloss abs resins - Google Patents

Process for the preparation of low-gloss abs resins

Info

Publication number
EP0998506A1
EP0998506A1 EP98935370A EP98935370A EP0998506A1 EP 0998506 A1 EP0998506 A1 EP 0998506A1 EP 98935370 A EP98935370 A EP 98935370A EP 98935370 A EP98935370 A EP 98935370A EP 0998506 A1 EP0998506 A1 EP 0998506A1
Authority
EP
European Patent Office
Prior art keywords
abs
butadiene
latex
resins
accordance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98935370A
Other languages
German (de)
French (fr)
Inventor
Jin-Nyoung Yoo
Se-Woo Yang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Corp
Original Assignee
LG Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chemical Co Ltd filed Critical LG Chemical Co Ltd
Publication of EP0998506A1 publication Critical patent/EP0998506A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00Compositions 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
    • C08L25/02Homopolymers or copolymers of hydrocarbons
    • C08L25/04Homopolymers or copolymers of styrene
    • C08L25/08Copolymers of styrene
    • C08L25/12Copolymers of styrene with unsaturated nitriles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular 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
    • C08F279/02Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02Copolymers with acrylonitrile

Definitions

  • the present invention relates to a process for the preparation of an acrylonit ⁇ le- butad ⁇ ene-styrene(ABS) thermoplastic resin or resins comprising latex-blending ABS and butadiene-based rubber latices in the coagulation step, to form a polvme ⁇ c gloss modifier containing polybutad ⁇ ene(PBD) rubber, styrene-butadiene rubber(SBR) oi acrylonit ⁇ le-butadiene rubber(NBR) latices in an amount of 25 weight percent or less of the total resin based on the solid content
  • Vanous attempts have been made to develop a process to satisfacto ⁇ lv reduce the surface gloss of an article molded from a thermoplastic resin
  • Some of the proposed solutions may include a method of improving processing techniques, and a method of incorporating inorganic fillers such as silica into the thermoplastic resin Howevei these methods tend to adversely affect the mechanical properties of the final products and further result in a high production cost
  • a method has been developed wherein control of the surface gloss is achieved through incorporating an organic additive such as a polymeric gloss modifier ha ⁇ ing a lower thermal shrinkage than the thermoplastic base resin
  • the particle size of the polymeric modifier distributed on the molded surface is considered as a ke factor for reducing the surface gloss
  • Japanese Pat No 58-93711 there is disclosed a process for preparing low- gloss ABS thermoplastic resins which comprises incorporating polystyrene into the ABS latex This method, however, is not effecti e in reducing the surface gloss of the resins and degrades the impact
  • the surface gloss is lowered using another method preparing thermoplastic resins more specificallv. ABS thermoplastic resins using emulsion polymerization
  • This piocesb compnses introducing carboxy c acids during emulsion polymerization and inducing a condensation reaction between the carboxyhc acids in the compounding step to achieve particle sizes that can effect a lowered surface gloss
  • This method does not provide an appreciable gloss reduction due to the low yield of the condensation reaction, and further shows poor reproducibility.
  • Korean Pat. Publication No. 93-6912 discloses processes for producing low-gloss ABS resins by using suspension polymerization or two-step of bulk and suspension polymerization. While the low-gloss ABS resins produced thereby meet the aforementioned requirements, the products molded therefrom suffer from other problems such as severe shrinkage, nonuniform gloss distribution and reduced hardness to an extent that varies greatly depending upon injection conditions, making the range of applications very limited.
  • An object of the present invention is to provide a novel process for the preparation of an ABS thermoplastic resin or resins comprising latex-blending in the coagulation step, to form a polymeric gloss modifier for ABS resins and products therefrom that overcomes many of the problems and disadvantages of the aforementioned prior art.
  • Another object of the present invention is to provide a process for the preparation of an ABS thermoplastic resin or resins comprising mixing and coagulating ABS and butadiene-based rubber latices. to form an ABS thermoplastic resin or resins which can be used as a surface gloss modifier for thermoplastic resins.
  • the present invention provides, in embodiments, a process for the preparation of an ABS thermoplastic resin or resins comprising blending ABS and butadiene-based rubber latices in the coagulation step, to form a gloss modifier resin 01 resins containing a butadiene-based rubber latex in an amount of 25 percent or less b ⁇ weight of the total resin based on the solid content
  • ABS thermoplastic resins and butadiene-based rubber compounds for use in the piesent invention may be prepared by any known polymerization processes
  • One class of butadiene-based rubber compounds suitable for use in the present invention includes PBD(polybutad ⁇ ene) rubber, SBR(styrene-butad ⁇ ene rubber) and NBR
  • the invention provides a process for the preparation of a low-gloss ABS lesin oi resins which allows a simple production process and thus reduces the production cost compared to the prior art processes wherein a polymeric modifier is prepared in a separate process and incorporated into the ABS base resin as an additive, without undermining the gloss characteristics and mechanical properties of molded parts produced therefrom
  • the polymer product of the present invention may be blended under normal processing conditions with other thermoplastic resins, for example, SAN (stv i ene- acrylonitrile copolymer) and poly carbonate(PC)/ABS blends, without compromising low gloss and mechanical properties for their expected uses such as auto inte ⁇ oi parts
  • thermoplastic resins for example, SAN (stv i ene- acrylonitrile copolymer) and poly carbonate(PC)/ABS blends
  • NBR latex with an acrylonitrile content of 30 parts by weight (solid content 29 percent) and an ABS latex with a butadiene content of 40 parts by weight (solid content 39 percent) were used.
  • the diameter of the NBR latex particles was about 150 nm.
  • 0.3 parts by weight of -methyl styrene dimer 0.05 parts by weight of sodium hydrosulfide.
  • 40 parts by weight of acrylonitrile. and 0.2 parts by weight of potassium persulfate were charged into a clean reactor.
  • the reactor as well as the reaction mixture was purged under an argon or nitrogen atmosphere.
  • NBR latex To 294 g of the NBR latex thus prepared were added 1965 g of ABS latex in a 5 L coagulation reactor at 50°C. which was followed by the addition of 3.5 parts by weight of potassium chloride as a coagulating agent. The resulting mixture was mixed together and aged until the temperature reached 80°C.
  • Example I was repeated with the exception that 1921 g of ABS latex and 352 g of NBR latex were used. The results are given in Table 1.
  • Example I was repeated with the exception that 1878 g of ABS latex and 41 1 g of NBR latex were used. The results are given in Table 1.
  • Example I was repeated with the exception that 1834 g of ABS latex and 470 g of NBR latex were used. The results are given in Table 1.
  • Example I was repeated with the exception that 1790 g of ABS latex and 528 g of NBR latex were used. The results are given in Table 1.
  • Example VI Example I was repeated with the exception that 1747 g of ABS latex and 587 g of
  • NBR latex were used. The results are given in Table 1.
  • a PBD latex (solid content 41 percent) with a particle diameter of 100 nm was prepared by a well-known method.
  • Example I was repeated with the exception that 2919 g of ABS latex and 86 g of the aforementioned PBD latex were used. The results are given in Table 1.
  • Example VII was repeated with the exception that 2757 g of ABS latex and 138 g of PBD latex were used. The results are given in Table 1.
  • Example IX Example VII was repeated with the exception that 2595 g of ABS latex and 186 g of PBD latex were used. The results are given in Table 1.
  • SBR latex solid content 33 percent
  • Example I was repeated with the exception that 2235 g of ABS latex and 82 g of the aforementioned SBR latex were used. The results are given in Table 1.
  • Example XI was repeated with the exception that 1978 g of ABS latex and 149 g of SBR latex were used. The results are given in Table 1.
  • Example XI was repeated with the exception that 1721 g of ABS latex and 201 g of SBR latex were used. The results are given in Table 1.
  • Example I was repeated with the exception that no NBR latex was used. The results are given in Table 1. Table 1

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The present invention relates to a process for the preparation of an ABS thermoplastic resin or resins comprising latex-blending ABS and butadiene-based rubber latices in the coagulation step, to form a polymeric gloss modifier containing PBD, SBR, or NBR latices in an amount of 25 weight percent or less of the total resin based on the solid content.

Description

PROCESS FOR THE PREPARATION OF LOW-GLOSS ABS RESINS
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a process for the preparation of an acrylonitπle- butadιene-styrene(ABS) thermoplastic resin or resins comprising latex-blending ABS and butadiene-based rubber latices in the coagulation step, to form a polvmeπc gloss modifier containing polybutadιene(PBD) rubber, styrene-butadiene rubber(SBR) oi acrylonitπle-butadiene rubber(NBR) latices in an amount of 25 weight percent or less of the total resin based on the solid content
Description of the Related Art
Vanous attempts have been made to develop a process to satisfactoπlv reduce the surface gloss of an article molded from a thermoplastic resin Some of the proposed solutions may include a method of improving processing techniques, and a method of incorporating inorganic fillers such as silica into the thermoplastic resin Howevei these methods tend to adversely affect the mechanical properties of the final products and further result in a high production cost In order to overcome the drawbacks mentioned abov e a method has been developed wherein control of the surface gloss is achieved through incorporating an organic additive such as a polymeric gloss modifier ha\ ing a lower thermal shrinkage than the thermoplastic base resin In this method, the particle size of the polymeric modifier distributed on the molded surface is considered as a ke factor for reducing the surface gloss In Japanese Pat No 58-93711 there is disclosed a process for preparing low- gloss ABS thermoplastic resins which comprises incorporating polystyrene into the ABS latex This method, however, is not effecti e in reducing the surface gloss of the resins and degrades the impact resistance of the products therefrom
The surface gloss is lowered using another method preparing thermoplastic resins more specificallv. ABS thermoplastic resins using emulsion polymerization This piocesb compnses introducing carboxy c acids during emulsion polymerization and inducing a condensation reaction between the carboxyhc acids in the compounding step to achieve particle sizes that can effect a lowered surface gloss This method however, does not provide an appreciable gloss reduction due to the low yield of the condensation reaction, and further shows poor reproducibility.
Korean Pat. Publication No. 93-6912 discloses processes for producing low-gloss ABS resins by using suspension polymerization or two-step of bulk and suspension polymerization. While the low-gloss ABS resins produced thereby meet the aforementioned requirements, the products molded therefrom suffer from other problems such as severe shrinkage, nonuniform gloss distribution and reduced hardness to an extent that varies greatly depending upon injection conditions, making the range of applications very limited.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a novel process for the preparation of an ABS thermoplastic resin or resins comprising latex-blending in the coagulation step, to form a polymeric gloss modifier for ABS resins and products therefrom that overcomes many of the problems and disadvantages of the aforementioned prior art.
Another object of the present invention is to provide a process for the preparation of an ABS thermoplastic resin or resins comprising mixing and coagulating ABS and butadiene-based rubber latices. to form an ABS thermoplastic resin or resins which can be used as a surface gloss modifier for thermoplastic resins.
It is a further object of this invention to provide a process for the preparation of an ABS resin or resins as a gloss modifier which allows a simple production process and thus reduces the production cost compared to the prior art processes which adopt an emulsion or a 2-step bulk-suspension polymerization, without undermining the gloss characteristics and mechanical properties of the resulting polymer resins therefrom.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides, in embodiments, a process for the preparation of an ABS thermoplastic resin or resins comprising blending ABS and butadiene-based rubber latices in the coagulation step, to form a gloss modifier resin 01 resins containing a butadiene-based rubber latex in an amount of 25 percent or less b\ weight of the total resin based on the solid content
In other embodiments of the present invention, there are provided a process foi the preparation of a low-gloss ABS thermoplastic resin or resins of which surface structure is reminiscent of clusters of grapes, wherein the clustered particles aie made oi the butadiene-based rubber compound
In still other embodiments of the present invention, there are provided a process for the preparation of low-gloss ABS thermoplastic resins which does not undermine the mechanical properties of the resulting polymer resins therefrom, by forming strongl) bound clusters of butadiene-based rubber latex particles on the surfaces of relatively biggei ABS latex particles through partial miscibihty between the butadiene-based rubber latex particles and the rubbery component of the ABS latex particles during the aforementioned coagulation step The ABS thermoplastic resins and butadiene-based rubber compounds for use in the piesent invention may be prepared by any known polymerization processes One class of butadiene-based rubber compounds suitable for use in the present invention includes PBD(polybutadιene) rubber, SBR(styrene-butadιene rubber) and NBR
(aciylonitπle-butadiene rubber) The preferred diameter of the butadiene-based rubbei latex particles is in the range of about 90 to about 400 nm.
The present invention provides some specific advantages in embodiments as follows
The invention provides a process for the preparation of a low-gloss ABS lesin oi resins which allows a simple production process and thus reduces the production cost compared to the prior art processes wherein a polymeric modifier is prepared in a separate process and incorporated into the ABS base resin as an additive, without undermining the gloss characteristics and mechanical properties of molded parts produced therefrom
The polymer product of the present invention may be blended under normal processing conditions with other thermoplastic resins, for example, SAN (stv i ene- acrylonitrile copolymer) and poly carbonate(PC)/ABS blends, without compromising low gloss and mechanical properties for their expected uses such as auto inteπoi parts
The surface gloss of the polymer resins of the current invention was e aluated as follows In a Henschell mixer. 30 to 80 parts by weight of PW-601 (a
- J - styrene-acrylonitrile copolymer containing 69 parts by weight of -methv i stvrene commercially available from LG Chemical Ltd., Korea), 0.4 parts by weight of ethylene bisstearamide, 0.2 parts by weight of cyclic neopentane tetraalkyl bisbutyl phenyl phosphite. 0.2 parts by weight of butylidine bisbutyl methyl phenol, and 20 to 70 parts by weight of the polymer resin of the current invention were blended and dispersed. The resulting mixture was extruded into the form of pellets by using a single scre extruder at 220°C, and then the resulting pellets were injection-molded into a specimen preferrably plate-like in shape. The surface gloss of the samples was determined at a degree of 60° using a Glossometer (Toyo Seiki. Japan). The following Examples are being supplied to further define various species of the present invention, it being noted that these Examples are intended to illustrate and not limit the scope of the present invention. Parts and percentages are by weight unless otherwise indicated.
Example I
An NBR latex with an acrylonitrile content of 30 parts by weight (solid content 29 percent) and an ABS latex with a butadiene content of 40 parts by weight (solid content 39 percent) were used. The diameter of the NBR latex particles was about 150 nm. 120 parts by weight of aqueous anionic emulsifier, 0.7 parts by weight of sodium chloride. 0.3 parts by weight of -methyl styrene dimer, 0.05 parts by weight of sodium hydrosulfide. 40 parts by weight of acrylonitrile. and 0.2 parts by weight of potassium persulfate were charged into a clean reactor. The reactor as well as the reaction mixture was purged under an argon or nitrogen atmosphere. 60 parts by weight of butadiene were then added to the reactor and the resulting mixture was stirred and heated at a temperature of 65°C. At a conversion of 40 percent, 1.0 parts by weight of anionic emulsifier was added to the reactor over a time span of 30 minutes. When a conversion of 90 percent was reached, the reaction was terminated by adding diethyl hydroxv amine as an effective polymerization terminator, and the reaction mixture was cooled. Throughout the aforementioned reaction, the temperature within the reactor was maintained at 65°C. The pressure within the reactor was also maintained at under 6.0 kgf/cnr through a conversion of 50 percent. To 294 g of the NBR latex thus prepared were added 1965 g of ABS latex in a 5 L coagulation reactor at 50°C. which was followed by the addition of 3.5 parts by weight of potassium chloride as a coagulating agent. The resulting mixture was mixed together and aged until the temperature reached 80°C.
In a Henschell mixer. 20 to 70 parts by weight of the polymer resin of the current invention, 30 to 80 parts by weight of PW-601 (a styrene-acrylonitrile copolymer containing 69 parts by weight of -methyl styrene commercially available from LG Chemical Ltd.. Korea), 0.4 parts by weight of ethylene bisstearamide. 0.2 parts by weight of cyclic neopentane tetraalkyl bisbutyl phenyl phosphite, and 0.2 parts by weight of butylidine bisbutyl methyl phenol were blended and dispersed. The resulting mixture was extruded into the pellet form by using a single screw extruder at 220°C. and then the resulting pellets were injection-molded into a specimen of a desired shape. Measurements were made of the surface gloss and impact strength on the samples thus prepared, and the results are shown in Table 1.
Example II
Example I was repeated with the exception that 1921 g of ABS latex and 352 g of NBR latex were used. The results are given in Table 1.
Example III
Example I was repeated with the exception that 1878 g of ABS latex and 41 1 g of NBR latex were used. The results are given in Table 1.
Example IV
Example I was repeated with the exception that 1834 g of ABS latex and 470 g of NBR latex were used. The results are given in Table 1.
Example V
Example I was repeated with the exception that 1790 g of ABS latex and 528 g of NBR latex were used. The results are given in Table 1.
Example VI Example I was repeated with the exception that 1747 g of ABS latex and 587 g of
NBR latex were used. The results are given in Table 1.
Example VII
A PBD latex (solid content 41 percent) with a particle diameter of 100 nm was prepared by a well-known method. Example I was repeated with the exception that 2919 g of ABS latex and 86 g of the aforementioned PBD latex were used. The results are given in Table 1.
Example VIII
Example VII was repeated with the exception that 2757 g of ABS latex and 138 g of PBD latex were used. The results are given in Table 1.
Example IX Example VII was repeated with the exception that 2595 g of ABS latex and 186 g of PBD latex were used. The results are given in Table 1.
Example X
Example VII was repeated with the exception that 2435 g of ABS latex and 257 g of PBD latex were used. The results are given in Table 1.
Example XI
An SBR latex (solid content 33 percent) with a particle diameter of 100 nm and a styrene content of 20 parts by weight was prepared by a well-known method. Example I was repeated with the exception that 2235 g of ABS latex and 82 g of the aforementioned SBR latex were used. The results are given in Table 1.
Example XII
Example XI was repeated with the exception that 1978 g of ABS latex and 149 g of SBR latex were used. The results are given in Table 1.
Example XIII
Example XI was repeated with the exception that 1721 g of ABS latex and 201 g of SBR latex were used. The results are given in Table 1.
Comparative Example I
Example I was repeated with the exception that no NBR latex was used. The results are given in Table 1. Table 1
(Test Method)
Impact Strength: ASTM D-256 6.4 mm notched

Claims

WHAT IS CLAIMED IS
1. A process foi the preparation of an acrylon╬╣trile-butad╬╣ene-styrene(ABS) resin thermoplastic resin or resins comprising mixing ABS and butadiene-based rubbei latices in the coagulation step to form a polymeric gloss modifier
2. A process in accordance with claim 1 wherein the butadiene-based rubber latex is in an amount of 25 weight percent or less of the total resin on the basis of the solid content
3. A process in accordance with claim 1 wherein the butadiene-based rubber contains 50 weight percent or less of acrylonitrile monomers.
4. A process in accordance with claim 1 wherein the butadiene-based rubber contains 50 weight percent or less of styrene monomers.
5. A process in accordance with claim 1 wherein the butadiene-based rubbei has a particle diameter ranging from 90 to 400 nm.
6. A thermoplastic resin prepared by blending a polymeric gloss modifier resin prepared in accordance with any one of the claims 1 to 5 with any thermoplastic resins
7. A thermoplastic resin in accordance with claim 6 wherein the thermoplastic resin is prepared by blending with a styrene-acrylonitrile copolymer
EP98935370A 1997-07-19 1998-07-20 Process for the preparation of low-gloss abs resins Withdrawn EP0998506A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1019970033861A KR100235464B1 (en) 1997-07-19 1997-07-19 Process for preparing abs resins
KR9733861 1997-07-19
PCT/KR1998/000219 WO1999003904A1 (en) 1997-07-19 1998-07-20 Process for the preparation of low-gloss abs resins

Publications (1)

Publication Number Publication Date
EP0998506A1 true EP0998506A1 (en) 2000-05-10

Family

ID=19515064

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98935370A Withdrawn EP0998506A1 (en) 1997-07-19 1998-07-20 Process for the preparation of low-gloss abs resins

Country Status (4)

Country Link
EP (1) EP0998506A1 (en)
JP (1) JP2001510213A (en)
KR (1) KR100235464B1 (en)
WO (1) WO1999003904A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8764820B2 (en) 2005-11-16 2014-07-01 Edwards Lifesciences Corporation Transapical heart valve delivery system and method
US8222350B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
US8222351B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
US8475522B2 (en) 2009-07-14 2013-07-02 Edwards Lifesciences Corporation Transapical delivery system for heart valves
US9381082B2 (en) 2011-04-22 2016-07-05 Edwards Lifesciences Corporation Devices, systems and methods for accurate positioning of a prosthetic valve
US10149757B2 (en) 2013-03-15 2018-12-11 Edwards Lifesciences Corporation System and method for transaortic delivery of a prosthetic heart valve
US9687345B2 (en) 2014-05-29 2017-06-27 Edwards Lifesciences Cardiaq Llc Prosthesis, delivery device and methods of use
CN105601769A (en) * 2016-03-03 2016-05-25 天津大沽化工股份有限公司 Graft latex coagulation method for improving primary color of ABS resin
CN114933774A (en) * 2022-05-30 2022-08-23 安庆会通新材料有限公司 Low-gloss permanent antistatic ABS composite material and preparation method and application thereof
KR102618826B1 (en) * 2023-05-31 2023-12-29 회명산업 주식회사 The Method for Producing Organic Solvent Dispersion solution of Styrene Butadiene Rubber

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US4169869A (en) * 1977-11-03 1979-10-02 Abtec Chemical Company Low gloss abs extrusion compositions
DE3805057A1 (en) * 1988-02-18 1989-08-31 Bayer Ag HIGH PERFORMANCE ABS MOLDS WITH MATTER SURFACE
KR920011031B1 (en) * 1990-08-28 1992-12-26 주식회사 럭키 Process for preparing thermoplastic resin composition

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Title
See references of WO9903904A1 *

Also Published As

Publication number Publication date
WO1999003904A1 (en) 1999-01-28
JP2001510213A (en) 2001-07-31
KR970065576A (en) 1997-10-13
KR100235464B1 (en) 1999-12-15

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