WO2002053642A1 - Styrenic thermoplastic resin compositions with good vacuum-forming ability - Google Patents
Styrenic thermoplastic resin compositions with good vacuum-forming ability Download PDFInfo
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- WO2002053642A1 WO2002053642A1 PCT/KR2001/001662 KR0101662W WO02053642A1 WO 2002053642 A1 WO2002053642 A1 WO 2002053642A1 KR 0101662 W KR0101662 W KR 0101662W WO 02053642 A1 WO02053642 A1 WO 02053642A1
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- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 229920005992 thermoplastic resin Polymers 0.000 title abstract description 9
- 238000007666 vacuum forming Methods 0.000 title description 11
- 239000000178 monomer Substances 0.000 claims abstract description 25
- -1 vinyl cyanide compound Chemical class 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 17
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 9
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 8
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 6
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920001890 Novodur Polymers 0.000 claims 4
- 229920003244 diene elastomer Polymers 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 10
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 21
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 238000000071 blow moulding Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002825 nitriles Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- MAYCNCJAIFGQIH-UHFFFAOYSA-N buta-1,3-diene 5-phenylpenta-2,4-dienenitrile Chemical compound C=CC=C.N#CC=CC=CC1=CC=CC=C1 MAYCNCJAIFGQIH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920006164 aromatic vinyl copolymer Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007652 sheet-forming process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
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)
Abstract
The thermoplastic resin composition according to the present invention comprises (A) 20-50 % by weight of a graft copolymer prepared by grafting 70-30 % by weight of monomer mixture of a vinyl cyanide compound and a vinyl aromatic compound onto 30-70 % by weight of butadiene rubber, (B) 40-60 by weight of a styrene-acrylonitrile copolymer prepared by polymerizing 50-90 % by weigth of a vinyl aromatic monomer and 10-50 % by weigth of a vinyl cyniade monomer and (C) 0.1-30 % by weight of an ultramacronmolecular copolymer with a weight average molecular weight from about 1,000,000 to about 5,000,000 prepared by polymerizing 50-90 % by weight ofa vinyl aromatic monomer and 10-50 % by weight of a vinyl cyanide monomer and (C) 0.1-30 % by weight of an ultramacromolecular copolymer with a weight average molecular weight form about 1,000,000 to about 5,000,000 prepared by polymerizing 50-90 % by weight of a vinyl aromatic monomer and 10-50 % by weight of a vinyl cyanide monomer.
Description
STYRENIC THERMOPLASTIC RESIN COMPOSITIONS WITH GOOD VACUUM-FORMING ABILITY
Field of the Invention
The present invention relates to a styrenic thermoplastic resin composition having a good vacuum formability. More particularly, the present invention relates to a thermoplastic resin composition having an excellent vacuum formability by enhancing a drawing property by employing an ultra high molecular styrene- acrylonitrile copolymer (SAN).
Background of the Invention
Vacuum forming is one of the plastic molding methods and is commonly carried out by extruding a resin composition to prepare a flat sheet, heating the flat sheet in a vacuum forming machine to become softened and adhering the softened sheet closely to the mold to obtain a desired shape. Typically, the vacuum forming makes use of a drawing property of a resin. The term "drawing property" used herein means the degree of resistance of a resin when the resin is elongated or expanded by an external force at a high temperature to the extent that the resin become flowed. If a resin has a good drawing property, the wall thickness distribution of the resin is uniform and the rupture does not occur even though the resin contains a corner part or thin wall part. In general, the drawing property of a resin is closely connected with the chemical structure of the resin itself. In case of an olefinic resin such as polyolefin, drawing property of a branched olefinic resin is better than that of a linear olefinic resin, so the molded article of the branched olefinic resin can have a good mechanical strength and uniform thickness distribution in blow molding or film extrusion.
The vacuum forming has been commonly employed for preparation of the internal box of a refrigerator. Generally acrylonitrile-butadiene-styrene copolymer (ABS resin) has been used here, because the resin has a good balance of physical properties such as rigidity, impact resistance, easy formability and excellent glossy appearance. The above-mentioned ABS resin is generally prepared by blending a styrene-acrylonitrile copolymer (SAN) comprising 10-50 % by weight of acrylonitrile with a graft copolymer (g-ABS) obtained by grafting a monomer mixture comprising from 10 to 50% by weight of a acrylonitrile monomer and from 90 to 50% by weight of an styrene monomer in the presence of polybutadiene rubber. However, this conventional ABS resin has a drawback in vacuum-forming of large- sized articles in that uneven wall thickness tends to occur, thereby the formed articles produced therefrom reveal inferior appearance. To overcome this problem, it has been proposed to use SAN copolymer having a high molecular weight and broad molecular weight distribution to reduce the thickness deviation. This, however, results in decrease of fiowability, so that the stress of extrusion machine increases during compounding process and sheet forming process. Furthermore, the productivity becomes decreased and a color change occurs.
Meanwhile, blow molding is generally employed to produce a hollow article such as a plastic bottle, and the utilization field thereof has been expanded from a small bottle to a large-sized structural article. Blow molding has a lower mold cost than injection molding and makes it possible for the molded product to have a curved surface structure as well as a variety of design. Further, for a large-sized structural article, the molded products obtained by the blow molding process have little residual stress. As a result, the blow molding method is now expanding its application. In case of producing a large-sized article, polyolefin resin such as low density polyethylene (LDPE) has a good formability. However, the adhesive strength of the coating layer of polyolefin resin is low, which makes it difficult to be applied to the structural articles. Further, for a modified polyphenylene ether resin, it has a good adhesion property and heat resistance, but shows poor chemical resistance to cause a stress crack at the time of painting, so that the appearance of the
molded article is decreased. For acrylonitrile-butadiene-styrene copolymer (ABS resin), it has been use for injection molding and vacuum forming, because the resin has a good mechanical property, easy formability and excellent appearance. However, it has also several problems such as serious draw-down, an unevenness of thickness for the molded article, which makes it difficult to be applied for the blow molding.
Japanese Patent Publication No. 95-015039 discloses a resin composition for blow molding by use of an ABS-based resin which has good coating performance. Though the inclusion of the resin composition having specific molecular weight and molecular weight distribution may overcome the above-mentioned problem to some extent, but the blow moldability of the ABS resin is not improved sufficiently.
Japanese Patent Publication No. 95-005820 discloses a process for preparing a resin composition by using a copolymer produced by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound to an organic silane compound to increase a blow moldability. However, the above-mentioned process has a drawback that since the resin composition is prepared by a solution polymerization, it leads to an increase in the production cost and makes it difficult to produce in the large scale.
Accordingly, the present inventors have developed a resin composition which is capable of overcoming the above-described problems during vacuum forming, blow molding or other molding process substantially affected by drawing property by introducing a vinyl cyanide-aromatic vinyl copolymer with an ultra high molecular weight to enhance the drawing property of the resin composition.
Objects of the Invention
An object of this invention is to provide a styrenic thermoplastic resin composition having good vacuum formability. Another object of the invention is to provide a styrenic thermoplastic resin
composition having improved drawing ability by means of an ultra high molecular styrene-acrylonitrile copolymer (SAN).
A further object of the invention is to provide a styrenic thermoplastic resin composition in which degradation of flowability, draw-down and unevenness in thickness do not occur in vacuum forming, blow molding or other forming process. Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
Summary of the Invention
The resin composition according to the present invention comprises (A) 20- 50 % by weight of a graft copolymer prepared by graft polymerization of 30-70 % by weight of a butadiene rubber and 70-30 % by weight of monomer mixture comprising aromatic vinyl compound and vinyl cyanide compound, (B) 40-60 % by weight of styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000-500,000 prepared by copolymerization of 50-90 % by weight of aromatic vinyl compound and 50-10 % by weight of vinyl cyanide compound, and (C) 0.1-30 % by weight of a ultra high molecular weight SAN copolymer having a weight average molecular weight of 1 ,000,000-5,000,000 prepared by copolymerization of 50-90 % by weight of aromatic vinyl compound and 10-50 % by weight of vinyl cyanide compound.
The detailed descriptions of the present invention are as follows.
Detailed Description of the Invention
The resin composition according to the present invention comprises (A) a graft copolymer (B) a styrene-acrylonitrile (SAN) copolymer and (C) an ultra high molecular weight SAN copolymer. The detailed descriptions of the present
invention are as follows.
(A) Graft Copolymer
The graft polymer of the present invention can be prepared by graft polymerizing 70-30 % by weight of monomer mixture consisting of unsaturated nitrile monomer and aromatic vinyl monomer in the presence of 30-70 % by weight of butadiene rubber having a gel content of more than 50% wherein more than 90%
of butadiene rubber have an average rubber particle size of 500-3500 A. The unsaturated nitrile monomer is preferably vinyl cyanide monomer.
The graft copolymer has 50-100% of graft ratio and 50,000-100,000 of weight average molecular weight. It is preferable to use 20-50 % by weight of the graft copolymer based upon the total weight of the resin composition.
(B) SAN copoylmer
The SAN copolymer (B) of the present invention can be prepared by copolymerizing 50-90 % by weight of aromatic vinyl monomer and 10-50 % by weight of unsaturated nitrile monomer. A vinyl cyanide monomer is preferably used for the unsaturated nitrile monomer. The copolymer of the present invention is a commercially used SAN copolymer with 100,000-500,000 of a weight average molecular weight converted to that of polystyrene. And it is preferable to use 40- 60 % by weight of the SAN copoylmer based upon the total weight of the resin composition.
(C) Ultra high molecular SAN copolymer
The ultra high molecular weight SAN copolymer (C) according to the present invention can be prepared by copolymerizing 50-90 % by weight of an aromatic vinyl monomer and 10-50 % by weight of an unsaturated nitrile monomer.
A vinyl cyanide monomer is preferably used for the unsaturated nitrile monomer. The copolymer (C) of the present invention has a weight average molecular weight of 1,000,000-5,000,000 of converted to that of polystyrene. And it is preferable to use 0.1-30 % by weight of the ultra high molecular SAN copolymer based upon the total weight of the resin composition.
The styrene-containing graft copolymer (A), styrene-containing copolymer (B) and ultra high molecular SAN copolymer (C) may be prepared by a conventional polymerization process well known in the art, such as emulsion polymerization, bulk polymerization, suspension polymerization and solution polymerization.
The thermoplastic resin composition of the present invention may contain customary additives such as anti-dripping agents, impact modifiers, inorganic filler, heat stabilizers, anti-oxidants, light stabilizers, pigment and/or dye. The inorganic filler may include asbestos, glass fiber, and talc etc.
The invention may be better understood by reference to the following examples that 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.
Examples
Each component of (A), (B) and (C) used in Examples 1 ~3 and Comparative Examples 1 ~ 3 was prepared as follow:
(A) Graft copolymer
To a reactor, 50 parts by weight of polybutadiene latex having average
rubber particle size of 0.3 μm were charged and then 150 parts of deionized water,
0.9 part of rosin soap, 0.3 part of cumene hydroperoxide, 0.2 part of mercaptane- containing chain transfer agents and 0.3 part of glucose were added. The
temperature was maintained at 70 °C. 35 parts of styrene and 15 parts of acrilonitrile were dropped into the mixture for 3 hours and the polymerization was started by means of redox initiator to obtain styrene-acrylonitrile-butadiene graft copolymer latex. The resultant was coagulated by adding 1.5 % of magnesium sulfate aqueous solution and dried to produce styrene-acrylonitrile-butadiene graft copolymer resin powder.
(B) SAN copolymer
A SAN copolymer by Cheil Industries Inc. of Korea (Product name: SAN HR-5330) was used.
(C) Ultra high molecular weight SAN copolymer
71 % by weight of styrene monomer, 29 % by weight of acrylonitrile monomer, 150 parts of ion-exchanged water, 0.4 part of tricalciumphosphate, 0.03 part of carboxylic anionic surfactant, 0.01 part of polyoxyethylene alkyl ether phosphate and 0.001-1 part of 2,2'-azobisisobutylonitrile as an initiator were blended and added to a reactor. And the reactor was sealed completely. The mixture was
agitated sufficiently to disperse. The reaction temperature was heated up to 75 °C and polymerization was carried out for 3 hours. After the polymerization was terminated, the reactor was cooled to room temperature to terminate the reaction. The resultant was washed, dehydrated and dried to obtain a copolymer in the form of beads. The weight average molecular weight of the copolymer was 4,000,000.
The compositions of each component in Examples 1-3 and Comparative Examples 1-3 are shown in Table 1. The resin compositions in Examples 1-3 are prepared in accordance with the present invention and that of Comparative Examples 1-3 are prepared without using the ultra high molecular weight SAN copolymer. Each component were mixed by means of Henschel mixer and the mixture was extruded with a conventional twin screw extruder in pellets. The resin
pellets were molded into test specimens.
Table 1
(A) Graft (B) SAN (C) Ultra High Molecular
Copolymer Copolymer Weight SAN Copolymer
1 30 67 3
Example 2 40 57 3
3 50 47 3
1 30 70 0
Comparative
2 40 60 0
Example
3 50 50 0 *The unit of content is "% by weight".
The resin pellets prepared from the above were compressed into test
specimens in a size of 400 mm *400 mm x2 mm by means of a press machine. The pressed test specimens were marked by a lattice having a width of 50 mm and a
length of 50 mm and vacuum-molded in a size of 300 mm(L) *30 mm(W) *200 mm(H) by means of the vacuum molding machine to obtain a vacuum-formed product. The thickness of the lattice crossing was measured by using a thickness tester with an accuracy of 1/100 mm. If the minimum thickness has a large value and the standard deviation is small, the resin is considered to be excellent in vacuum formability and drawing property. The measured minimum thickness and standard deviation is shown in Table 2.
In addition, a tensile strength test is carried out with a test specimen which was extruded according to ASTM D236 using a pellet prepared from the above at room temperature and 150 °C respectively. If a tensile strength at high temperature and an elongation are high, the resin is considered to be excellent in vacuum formability and drawing property.
Table 2
Vacuum forming test Tensil strength test(l)
Minimum Standard Tensil strength
_, . , , . A. Tensil strength(kgf/cm2)/ thickness deviation v x Ejilonga ♦ti■on , (o%/ \) (kgf/cm2) '/
(mm) (mm) .. .. J Elongation (%) at 23°C at 150°C
1 0.55 0.10 460/30 7.7/1400
Example 2 0.52 0.12 400/40 7.4/1400
3 0.50 0.13 360/60 7.3/1400
1 0.3 0.23 460/30 4.7/800
Comp. 2 0.28 0.27 400/40 4.1/950
Example
3 0.22 0.25 360/60 3.7/1000
As shown in Table 2, since the test specimens in Examples 1-3 have a larger value of minimum thickness and a smaller value of standard deviation than Comparative examples, it showed good vacuum formability and drawing property. The results of the tensile strength test at room temperature showed that the tensile strength and elongation of Examples 1-3 were the same as in Comparative Examples 1-3. But, at a high temperature, Examples 1-3 showed higher tensile strength and elongation than Comparative Examples 1-3. Therefore, the resin composition of the present invention is considered to be excellent in vacuum formability and drawing property.
Claims
1. A styrenic resin composition comprising:
(A) 20-50 % by weight of a graft copolymer having a weight average molecular weight of 50,000-100,000 prepared by graft polymerization of 30-70 % by weight of a butadiene rubber and 70-30 % by weight of monomer mixture comprising aromatic vinyl compound and vinyl cyanide compound;
(B) 40-60 % by weight of styrene-acrylonitrile copolymer having a weight average molecular weight of 100,000-500,000 prepared by copolymering 50-90 % by weight of aromatic vinyl compound and 50-10 % by weight of vinyl cyanide compound; and
(C) 0.1-30 % by weight of a ultra high molecular weight SAN copolymer having a weight average molecular weight of 1,000,000-5,000,000 prepared by copolymerization of 50-90 % by weight of aromatic vinyl compound and 10-50 % by weight of vinyl cyanide compound.
2. The styrenic resin composition according to claim 1 wherein said graft polymer (A) has a graft ratio of 50- 100% of grafting the polymer matrix of vinyl cyanide monomers and aromatic vinyl monomers onto the conjugated diene rubber.
3. The styrenic resin composition according to claim 1 wherein said butadiene rubber has a gel content of more than 50% and more than 90% of butadiene rubber
has an average rubber particle size of 500-3500 A.
4. The styrenic resin composition of any of claims 1 to 3, which further comprises anti-dripping agents, impact modifiers, inorganic filler, heat stabilizers, anti-oxidants, light stabilizers, pigment and/or dye.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR2000/83855 | 2000-12-28 | ||
| KR10-2000-0083855A KR100408109B1 (en) | 2000-12-28 | 2000-12-28 | Styrenic Thermoplastic Resin Compositions with Good Vacuum-forming Ability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002053642A1 true WO2002053642A1 (en) | 2002-07-11 |
Family
ID=19703765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2001/001662 WO2002053642A1 (en) | 2000-12-28 | 2001-10-05 | Styrenic thermoplastic resin compositions with good vacuum-forming ability |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR100408109B1 (en) |
| CN (1) | CN1210347C (en) |
| WO (1) | WO2002053642A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9297944B2 (en) | 2011-10-05 | 2016-03-29 | Lg Chem, Ltd. | Resin composition for optical film and compensation film using the same |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100474830B1 (en) * | 2001-12-20 | 2005-03-08 | 제일모직주식회사 | Styrenic Thermoplastic Resin Composition with High Melt Strength |
| KR100450110B1 (en) * | 2001-12-22 | 2004-09-24 | 제일모직주식회사 | Thermoplastic Resin Compositions With Good Vacuum Formability |
| KR100488857B1 (en) * | 2002-07-09 | 2005-05-11 | 현대자동차주식회사 | Composition of thermoplastic resin having a high resistance |
| KR100581436B1 (en) * | 2004-05-13 | 2006-05-17 | 제일모직주식회사 | Low Linear Expansion Thermoplastic Composition |
| KR100665803B1 (en) * | 2004-12-28 | 2007-01-09 | 제일모직주식회사 | Thermoplastic resin composition for refrigerators excellent in environmental stress resistance |
| KR100665804B1 (en) | 2005-06-16 | 2007-01-09 | 제일모직주식회사 | Heat resistant ABS resin composition excellent in chemical resistance and crack resistance |
| KR100716563B1 (en) | 2006-02-08 | 2007-05-09 | 금호석유화학 주식회사 | Thermoplastic resin composition for extrusion excellent in vacuum forming and a method for producing the same |
| CN101921439B (en) * | 2010-06-29 | 2012-05-30 | 上海达凯塑胶有限公司 | ABS calendered substrate and preparation method thereof |
| WO2013051802A1 (en) * | 2011-10-05 | 2013-04-11 | 주식회사 엘지화학 | Resin composition for an optical film, and retardation film using same |
| KR101925728B1 (en) * | 2017-10-19 | 2018-12-05 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
| CN112210172B (en) * | 2020-10-13 | 2023-05-30 | 上海金发科技发展有限公司 | Creep-resistant glass fiber reinforced styrene compound and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02284906A (en) * | 1989-04-27 | 1990-11-22 | Mitsubishi Monsanto Chem Co | Thermoplastic resin composition resistant to fluorocarbons and its use |
| KR970021197A (en) * | 1995-10-09 | 1997-05-28 | 유현식 | ABS resin composition with excellent fluidity and vacuum forming |
| KR20000055398A (en) * | 1999-02-05 | 2000-09-05 | 유현식 | Thermoplastic resin composition with good chemical resistance and sheet extraction characteristics |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4110459A1 (en) * | 1991-03-30 | 1992-10-01 | Basf Ag | ABS MOLDING WITH BIMODAL RUBBER PARTICLE SIZE DISTRIBUTION |
| DE19627423A1 (en) * | 1996-07-08 | 1998-01-15 | Bayer Ag | High tenacity ABS molding compounds |
| DE19649249A1 (en) * | 1996-11-28 | 1998-06-04 | Bayer Ag | Improved thermoplastic molding compounds of the ABS type |
-
2000
- 2000-12-28 KR KR10-2000-0083855A patent/KR100408109B1/en not_active Expired - Fee Related
-
2001
- 2001-10-05 WO PCT/KR2001/001662 patent/WO2002053642A1/en active Application Filing
- 2001-10-05 CN CNB018214606A patent/CN1210347C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02284906A (en) * | 1989-04-27 | 1990-11-22 | Mitsubishi Monsanto Chem Co | Thermoplastic resin composition resistant to fluorocarbons and its use |
| KR970021197A (en) * | 1995-10-09 | 1997-05-28 | 유현식 | ABS resin composition with excellent fluidity and vacuum forming |
| KR20000055398A (en) * | 1999-02-05 | 2000-09-05 | 유현식 | Thermoplastic resin composition with good chemical resistance and sheet extraction characteristics |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9297944B2 (en) | 2011-10-05 | 2016-03-29 | Lg Chem, Ltd. | Resin composition for optical film and compensation film using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020054688A (en) | 2002-07-08 |
| KR100408109B1 (en) | 2003-12-01 |
| CN1210347C (en) | 2005-07-13 |
| CN1483060A (en) | 2004-03-17 |
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