CN1060491C - Thermoplastic polycarbonate resin composition - Google Patents
Thermoplastic polycarbonate resin composition Download PDFInfo
- Publication number
- CN1060491C CN1060491C CN97104250A CN97104250A CN1060491C CN 1060491 C CN1060491 C CN 1060491C CN 97104250 A CN97104250 A CN 97104250A CN 97104250 A CN97104250 A CN 97104250A CN 1060491 C CN1060491 C CN 1060491C
- Authority
- CN
- China
- Prior art keywords
- weight
- polycarbonate resin
- methyl methacrylate
- parts
- copolymer
- 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.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a thermoplastic polycarbonate resin composition, which can reduce thermal discoloration during processing and has a small reduction rate of Izod impact strength during processing. The composition contains (1) 40 to 95 parts by weight of polycarbonate resin A, 5 to 60 parts by weight of acrylonitrile-rubber system graft copolymer B, 0 to 3 parts by weight of methyl methacrylate system copolymer C [The total amount of A, B and C is 100 parts by weight.], and (2) 0.05 to 5 parts by weight of anhydrous maleic acid system copolymer D with 800 to 25, 000 of weight average molecular weight.
Description
The invention relates to a kind of polycarbonate resin composition, refer to that especially a kind of moulding product that lower add and are heated man-hour and produce variable color (thermo-color), are adding the less resin combination of Ai Zuode in man-hour (Izod beam type) shock strength reduced rate simultaneously.
General polycarbonate-based resin is heated and produces variable color adding easily when mixing with acrylonitrile-butadiene-phenylethene grafted copolymer resin (ABS resin) for example man-hour, and its shock strength also descends easily, therefore, is very restricted on practicality; In order to improve above-mentioned disappearance, feasible mode is to add a large amount of antioxidants in ABS resin, perhaps fully clean ABS resin by materials such as acid, alkali, pure water, though above-mentioned processing mode is feasible, its production cost height, it is complicated that the process of production becomes, and it is very limited for preventing thermo-color and improving the effect of aspects such as shock strength reduction to add man-hour, therefore, above-mentioned puzzlement still is present in the constituent that this kind thermoplastic polycarbonate is a resin, and has to be solved.
Therefore, main purpose of the present invention is to provide a kind of the attenuating to process thermal time color change, and is adding the thermoplastic polycarbonate resin composition that reduces the Izod impact strength reduced rate man-hour.Thermoplastic polycarbonate resin composition of the present invention is characterized in that comprising: the polycarbonate resin A of (1) 40～95 weight part, the vinyl cyanide-rubber of 5～60 weight parts are that methyl methacrylate based copolymer C[A, B, the C of graft copolymer B, 0～30 weight part adds up to 100 weight parts]; And (2) 0.05～5 weight parts and weight average molecular weight are 800～25,000 Maleic Acid, Anhydrous based copolymer D;
It is less that the polycarbonate resin composition that the above-mentioned characteristics combination of mat forms has processing thermal time color change Izod impact strength reduced rate low, that add man-hour, and effect such as can conveniently reclaim, and be the very high resin combination of a practical value.
Contain the following formula composite unit on its main chain of polycarbonate resin A used in the present invention:
Wherein, X represents the functional group of phenol (phenol) based compound of divalence, and n represents the polymerization degree, the functional group of above-mentioned divalent phenol based compound, its concrete example has: dihydroxyphenyl propane (BisphenolA), bis-phenol (bisphenol), Resorcinol (resorcinol), 2,2-two (3,5-dimethyl-4-hydroxyl-phenyl) propane [2,2-bis (3,5-di-methyl-4-hydroxy phenyl) propane], 1, two (4-hydroxyl-phenyl) hexanaphthenes [1,1-bis (4-hydroxy phenyl) cyclohexane] of 1-etc., particularly use separately with dihydroxyphenyl propane or with the phenol system compound of other divalence also with being representative; The molecular weight of above-mentioned polycarbonate resin A, normally used scope are weighed average 10,000～200,000.
Vinyl cyanide-rubber used in the present invention is graft copolymer B, mean the compound that contains plural ethene (ethylene) unsaturated group, (weight average particle diameter of above-mentioned rubber polymer is between 0.1～1.0 μ m at the water system emulsified rubber polymkeric substance below-20 ℃ to aggregate into a kind of glass transfer temperature, size distribution can be unimodal or 2～3 peaks distribute, in the presence of above-mentioned water system emulsified rubber polymkeric substance, add vinyl cyanide and other polymerisable monomer copolymerizations, then add for example mineral acid of condensing agent, organic acid, calcium chloride, sal epsom etc. condense, and the moisture content in the polymkeric substance is removed in dehydration, can obtain graft copolymer, perhaps in addition with bulk, solution, outstanding turbid, polymerization methodses such as emulsification are made acrylic copolymer, join and get (for example ABS resin) and mix jointly with above-mentioned graft copolymer; Can be used as its typical example of rubber of the present invention has: the butadiene-based polymkeric substance, alkene (olefin) is rubber and acrylic ester rubber, wherein, the butadiene-based polymkeric substance is representative to be had: styrene-butadiene copolymer, acrylonitrile butadiene copolymer and polyhutadiene etc., and ethylene series can be for example: ethylene-propylene-ethylidene norbornene multipolymer (ethylene-propylene-ethylidene norbornene), acrylic ester rubber is for example: just-and butylacrylic acid ester-aromatic substituted acrylic acid methyl esters (n-butylacrylate-6arylmethacrylate), and the present invention's's " acrylonitrile copolymer of making in addition " noted earlier molecular weight, its weighed average is usually 50,000～250, between 000.
Adding vinyl cyanide and copolymerizable monomer are carried out graft polymerization in rubbery polymer, and employed in the manufacturing of " the acrylic co-polymer of making in addition " perhaps noted earlier can have with the monomer of copolymerization of acrylonitrile is representative: vinylbenzene, alpha-methyl styrene, methyl acrylate, methyl methacrylate, glycidyl methacrylate, hydroxyl-ethylacrylic acid methyl esters, phenyl maleimide, Vinylstyrene etc.; In the composition of aforesaid propylene nitrile and copolymerizable monomer, acrylonitrile monemer is generally 10～50 weight %, and styrene monomer is 40～90 weight %, and other copolymerizable monomers add up to 0～40 weight %; Above-mentioned rubbery polymer accounts for 12～85 weight % that vinyl cyanide-rubber is graft copolymer.
Methyl methacrylate based copolymer C used in the present invention, formed by the methyl methacrylate of 80～99 weight % and the copolymerizable monomer of 1～20 weight %, above-mentioned copolymerizable monomer for example is: methyl acrylate, vinylformic acid, methacrylonitrile, vinylbenzene, glycidyl methacrylate etc., its weight average molecular weight normally 50,000～300,000.
And Maleic Acid, Anhydrous multipolymer D used in the present invention, be to form by Maleic Acid, Anhydrous and copolymerizable vinyl compound copolymerization, wherein, Maleic Acid, Anhydrous accounts for 35～60 moles of %, especially be good with 45～55 moles of %, and copolymerizable vinyl compound accounts for 40～65 moles of %, above-mentioned copolymerizable vinyl compound can be: the alkene carbohydrate, vinyl ethers and aromatic hydroxy compound etc., wherein, olefin(e) compound can be for example: ethene, iso-butylene, the 1-octene, three-iso-butylene, the 1-laurylene, the 1-octadecylene, and the ethene ethers can be for example: butyl-vinyl ether, cyclohexyl-vinyl ether, divinyl ether etc., and aromatic hydroxy compound can be for example: hydroxyl-butyl ether, hydroxyl-phenyl ether, hydroxacetic acid, hydroxybenzene etc.; Other are for example: neodecanoic acid ethene (vinylversatate), just-vinyl pyrrolidone, vinylbenzene, methyl methacrylate, dimethyl maleic acid (being dimethyl maleate), dimethyl fumarate (being the dimethyl FUMARIC ACID TECH GRADE) etc. also can use.
The weight average molecular weight of Maleic Acid, Anhydrous based copolymer D of the present invention is 800～25,000, wherein, with 1,200～22,000 is good, when weight average molecular weight greater than 25,000 o'clock, the bad dispersibility of multipolymer did not reach at 800 o'clock and has the tendency that undermines the sight of shaping beyond the region of objective existence; In addition, the monomethyl ester (mono-methyl ester of maleic acid) of the toxilic acid in the substitute of use Maleic Acid, Anhydrous, single ethyl ester of toxilic acid, toxilic acid, oxalic acid, institute's polymerization such as fumaric acid and multipolymer, also can be used to and aforesaid polycarbonate resin A, vinyl cyanide-rubber is graft copolymer B, and composition such as methyl methacrylate based copolymer C is mixing together, remove methyl alcohol again, ethanol, materials such as water, aforementioned result also is the use occasion of Maleic Acid, Anhydrous multipolymer D, ought to be included in certainly in the scope that the present invention contains.
In the resin combination of the present invention again, polycarbonate resin A accounts for 40～95 weight parts, and vinyl cyanide-rubber is graft copolymer B is 5～60 weight parts, methyl methacrylate based copolymer C accounts for 0～30 weight part polymerization, in addition, the content of Maleic Acid, Anhydrous based copolymer D is with respect to 0.05～5 weight part that is added up to 100 weight parts by above-mentioned A, B, three kinds of compositions of C.
In resin combination of the present invention, can use phenol system compound, the diphenylamine based compound, the organophosphorus based compound, the organic thioether based compound, sequestrants etc. are as antioxidant, and can adopt higher fatty acid with and derivative as lubricant, for example: stearic acid, stearyl alcohol, tetradecanoic acid, dodecyl ester, palmitamide, the two oily alkene acid amides of ethylene, the two stearylamides of ethylene, the methylene bis stearylamide, Zinic stearas, aluminum stearate etc., in addition, what can be used as wax has: paraffin series wax, polyethylene wax, carnauba wax, montanin wax and derivative thereof, Viscotrol C wax materials such as (castor wax), can and as the silicon (oxygen alkane) of oilness material oil (silicone oil), polybutene, whiteruss wet goods material appropriate selection is used.
During with respect to resin combination 100 weight parts of the present invention, the usage quantity of above-mentioned antioxidant is usually at 0.02～2.0 weight part, and the usage quantity of lubricant is 0.05～7.0 weight part.Also can add incombustible agent and difficult combustion auxiliary agent in the resin combination of the present invention, and can be used as having of incombustible agent: halogen is incombustible agent and not halogen-containing phosphorus series flame-resisting agent etc., and wherein, the object lesson of halogen incombustible agent has:
*Ten bromine bis-phenol ethers (decabromodiphenylether).
*The two tetrabromo phosphorus Phthalimide (ethylene bistetrabromophthalimide) of ethidine.
*1, and the two penta-bromophenyl ethane of 2-(1,2-bispentabromophenylethane).
*Tetrabromobisphenol-A (tetrabromobisphenyl-A).
*The brominated epoxy resin oligomer.
*Three (tribromo phenyl) phosphoric acid ester [tris (tri-bromophenyl) phosphate].
*Israel, Bromine compound company makes, and the bromine of commodity FR-1808 by name is an incombustible agent.
*The U.S., Occidental chemical company makes, and the chlorine of commodity Decloraneplus by name is incombustible agent.
And the object lesson of phosphorus series flame-resisting agent has:
*Triphenyl (Triphenyl phosphate).
*In following formula structural formula [I], the biphosphonate of Y=Ya, Z=Za, Zb, Zc or Zd.
*The biphosphonate of Y=Yb, Z=Za in following formula structural formula [I].
*In following formula structural formula [I], the biphosphonate of Y=Yc, Z=Za, Zb, Zc or Zd.
Above shown in compound in [I] formula, the meaning of each symbology is as follows: Y ... the residual base of the reaction of monovalence phenolic compound.Z ... the residual base of the reaction of bivalent phenol compound.Ya ... phenol.Yb ... adjacent-,-or p-Cresol (cresol).Yc ... 2,6-dimethyl phenol or 2,4-dimethyl phenol.Za ... Resorcinol.Zb ... Resorcinol.Zc ... dihydroxyphenyl propane.Zd ... the residual base of the reaction of bis-phenol.
In addition, difficult combustion auxiliary agent used in the present invention can adopt the following various materials of putting down in writing, in following each material, the high molecular weight ptfe powder be drip to hang down prevent to use effective, especially in not halogen-containing phosphorus series flame-resisting agent and usefulness, its effect is pretty good, and the example of difficult combustion auxiliary agent has:
*The powder of trimeric cyanamide-isocyanuric acid hydrochloric acid complex compound.
*The red phosphorus powder.
*Foaminess carbon.
*The powder of aluminium hydroxide.
*The powder of ANTIMONY TRIOXIDE SB 203 99.8 PCT, four weisspiessglanzs, antimony pentaoxide.
*Chlorinatedpolyethylene.
*The high molecular weight ptfe powder.
*The powder of silicone resin.
In addition, when using halogen to be, incombustible agent can suitably add thermo-stabilizer.In resin combination of the present invention, can add the pigment such as carbon black, red, green, yellow look of fluidity amendment, light deterioration preventing agent, charged preventor, weighting agent, fibee reinforced dose, tinting material-for example again, and other suitable materials use together; The usage quantity of above-mentioned substance is usually with respect in resin combination 100 weight parts of the present invention, wherein, incombustible agent is 5～30 weight parts, difficult combustion auxiliary agent is 0.05～15 weight part, and thermo-stabilizer is 0.05～5 weight part, and fluidity amendment is 0.05～5 weight part, the light deterioration preventing agent is 0.05～3 weight part, tinting material is 0.0005～10 weight part, and it is suitably to add by various objectives, and the object lesson of fluidity amendment has:
*Two-phenylcyclohexane dioctyl phthalate, two-the tridecyl phthalic acid.
*The polyester oligomerization compound of hexanodioic acid-neo-pentyl ethylene glycol.
*The carboxylate of stearic acid and tetramethylolmethane.
*1, the dibenzoate of 4-dihydroxyl-methylcyclohexane.
*Phosphate trimethylbenzene phosphoric acid ester (tricresyl phosphate).
*Three-dimethylbenzene phosphoric acid ester.
*Three (2,6-dimethyl-phenyl) phosphoric acid ester.
And the object lesson of light deterioration preventing agent has:
*Benzophenone (benzophenone) is a UV light absorber.
*Benzotriazole (benzotriazole) is a UV light absorber.
*O-hydroxybenzoic acid (salicylate) is a UV light absorber.
*Alpha-cyanoacrylate (cyano acrylate) is a UV light absorber.
*Carbonamidine (formamidine) is a UV light absorber.
*Bulky amine (hinderedamine) is a UV light absorber.
*Nickel (nickel) mistakeization thing is a light absorber.
Resin combination of the present invention is a thermoplastic resin, is mainly used in the use of shaping things such as ejection formation, extrusion moulding, blowing.
In order further to describe the present invention in detail, be described as follows with embodiment and physical property measurement again, the composition unless specifically stated otherwise of following constituent, otherwise all represent with weight part.And record changes about thermochromism that adds man-hour and the shock strength that adds man-hour in following embodiment and the comparative example, is the following method test of mat:
*The thermochromism that adds man-hour: the resin combination of estimating usefulness is with biaxial extruder granulations of mixing, and makes via the male mechanical society of shake again, numbers the extrusion shaping machine of SM-90, in 260 ℃ of ejaculations of temperature, waiting to be detained institute must be after the time, extrusion moulding again, and the yellowness index of mensuration test piece.
*The shock strength that adds man-hour changes: the test piece that thermochromism test above-mentioned obtains, remake the Izod impact strength test, and it measures temperature is 23 ℃.
Embodiment
The polycarbonate resin that makes from dihydroxyphenyl propane, vinyl cyanide-rubber is graft copolymer, the methyl methacrylate based copolymer, and Maleic Acid, Anhydrous based copolymer, according to 1 shown constituent and the mixed of tabulating down, employed antioxidant can be that [octadecyl-3-(3 in this mixture, 5-two-tertiary butyl-4-hydroxyphenyl) propionic ester] 0.2 weight part, tetramethylolmethane four idols [(3,5-two-tertiary butyl-4-hydroxyphenyl) propionic ester] 0.2 weight part, it is phosphorous antioxidant 0.1 weight part of Sandostab PEPQ that Switzerland Sando company makes trade(brand)name, and U.S. GE company manufacturing trade(brand)name is phosphorous antioxidant 0.1 weight part of Weston 618, its lubricant can be used two stearylamide 0.1 weight parts of ethidine, above-mentioned raw materials is mixed with biaxial extruder, and extrude and make micelle.
Then, with " thermochromism that adds man-hour " and determination of test method such as " shock strength that adds man-hour change ", the result is stated from table 2 with above-mentioned micelle; Wherein, the Izod impact strength conservation rate is to represent with respect to the percentage of general condition shaping institute value.
＜table 1 〉
(unit: weight part)
| The experiment numbers combination ingredient | Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 4 | 1 | 2 | |
| Polycarbonate resin A | A 1 55 | A 1 55 | A 1 50 | A 2 50 | A 1 55 | A 2 50 |
| Vinyl cyanide one rubber is graft copolymer B | B 1 45 | B 1 45 | B 1/B 2 40/10 | B 1 40 | B 1 45 | B 1 40 |
| Methyl methacrylate based copolymer C | - | - | C 1 5 | C 2 10 | - | C 2 10 |
| Maleic Acid, Anhydrous based copolymer D | D 1 0.5 | D 1 0.2 | D 1 0.3 | D 2 0.3 | - | - |
Remarks:
A
1: weight average molecular weight is 23,000 polycarbonate.
A
2: weight average molecular weight is 27,000 polycarbonate.
B
1: the ABS resin of applicant company manufacturing, commodity are called polylac 747B, and its major ingredient comprises: vinyl cyanide 22 weight parts, vinylbenzene 57 weight parts, polybutadiene rubber 21 weight parts.
B
2: the ABS resin of applicant company manufacturing commodity polylac 777ED by name, contain N-phenylmaleimide (N-phenyl maleimide) in the above-mentioned resin, its major ingredient comprises: vinyl cyanide 21 weight %, vinylbenzene 47 weight %, N-phenylmaleimide 14 weight %, polybutadiene rubber 18 weight %.
C
1: methyl methacrylate methyl acrylate copolymer, wherein, methyl methacrylate is 99 weight %, and methyl acrylate is 1 weight %, its weight average molecular weight is 150,000.
C
2: methyl methacrylate-vinylbenzene-N-phenylmaleimide multipolymer, wherein, methyl methacrylate is 97 weight %, vinylbenzene 1 weight %, N-phenylmaleimide 2 weight %, its weight average molecular weight is 120,000.
D
1: Maleic Acid, Anhydrous-(1-octadecylene) multipolymer, wherein, Maleic Acid, Anhydrous is that 52 molar percentages, 1-octadecylene are 48 molar percentages, its weight average molecular weight is 15,000.
D2: Maleic Acid, Anhydrous-(butyl-vinyl ether) multipolymer, wherein, Maleic Acid, Anhydrous is that 51 molar percentages, butyl-vinyl ether are 49 molar percentages, its weight average molecular weight is 20,000.
＜table 2 〉
| The experiment numbers experimental project | Embodiment | Comparative example | |||||
| 1 | 2 | 3 | 4 | 1 | 2 | ||
| Yellowness index | Residence time is shaped usually | 11 | 12 | 10 | 12 | 14 | 15 |
| " 15 minutes | 11 | 13 | 11 | 13 | 20 | 21 | |
| " 30 minutes | 12 | 14 | 11 | 15 | 31 | 33 | |
| Izod impact strength conservation rate % | Residence time is shaped usually | 100 | 100 | 100 | 100 | 100 | 100 |
| " 15 minutes | 100 | 99 | 99 | 100 | 82 | 84 | |
| " 30 minutes | 100 | 98 | 97 | 99 | 59 | 60 | |
By the test-results of comparative example 1,2 as can be known, among the present invention if do not add Maleic Acid, Anhydrous based copolymer D, the poor heat stability during its heating, the reduced rate of Izod impact strength that adds man-hour is also bigger; See embodiment 1,2,3,4 again, the present invention is through aforementioned each composition and use quantitative limitation, can improve the thermostability that polycarbonate resin composition adds man-hour, the Izod impact strength reduced rate that adds man-hour is reduced, and can improve the shortcoming on polycarbonate resin composition processing and the finished product.And can utilize on the industry, so propose the application of patent of invention in accordance with the law.
Only the above only is several preferable possible embodiments of the present invention, is familiar with this skill personage such as, it is done in the category that technical solution of the present invention contained can think easily and equivalence modify or change, all ought to be included in the technical scheme of the present invention.
Claims (1)
1, a kind of thermoplastic polycarbonate resin composition is characterized in that comprising:
The polycarbonate resin A of (1) 40～95 weight part, the acrylic rubber of 5～60 weight parts are the methyl methacrylate based copolymer C of graft copolymer B, 0～30 weight part, and wherein A, B, C add up to 100 weight parts; And
(2) 0.05～5 weight parts and weight average molecular weight are 800～25,000 Maleic Acid, Anhydrous based copolymer D
4
Wherein, contain the following formula composite unit on its main chain of polycarbonate resin A:
X represents the functional group of the phenol system compound of divalence, and n represents the polymerization degree, and the common use range of the molecular weight of polycarbonate resin A is weighed average 10.000～200, and 000;
Vinyl cyanide-rubber is that graft copolymer B is meant the compound that contains plural ethene unsaturated group, aggregate into a kind of glass transfer temperature at the water system emulsified rubber polymkeric substance below-20 ℃, in the presence of above-mentioned water system emulsified rubber polymkeric substance, add vinyl cyanide and other polymerisable monomer copolymerization and get;
Methyl methacrylate based copolymer C is made up of the copolymerizable monomer of the methyl methacrylate of 80～99 weight % and 1～20 weight %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104250A CN1060491C (en) | 1997-05-07 | 1997-05-07 | Thermoplastic polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97104250A CN1060491C (en) | 1997-05-07 | 1997-05-07 | Thermoplastic polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172132A CN1172132A (en) | 1998-02-04 |
| CN1060491C true CN1060491C (en) | 2001-01-10 |
Family
ID=5167235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97104250A Expired - Fee Related CN1060491C (en) | 1997-05-07 | 1997-05-07 | Thermoplastic polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060491C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0488932A1 (en) * | 1990-11-29 | 1992-06-03 | Bayer Ag | ABS moulding compositions |
| EP0570797A1 (en) * | 1992-05-21 | 1993-11-24 | Bayer Ag | Polycarbonate-ABS moulding compositions |
| EP0728161A1 (en) * | 1994-09-09 | 1996-08-28 | General Electric Company | A polycarbonate resin composition |
-
1997
- 1997-05-07 CN CN97104250A patent/CN1060491C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0488932A1 (en) * | 1990-11-29 | 1992-06-03 | Bayer Ag | ABS moulding compositions |
| EP0570797A1 (en) * | 1992-05-21 | 1993-11-24 | Bayer Ag | Polycarbonate-ABS moulding compositions |
| EP0728161A1 (en) * | 1994-09-09 | 1996-08-28 | General Electric Company | A polycarbonate resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1172132A (en) | 1998-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1201050A (en) | Preparation for aqueous dispersion of fluoropolymer and thermoplastic resin composition of fluoropolymer | |
| CN104072648B (en) | Preparation method, onium bromide composition and the fire-retardant combination of brominated styrenic polymer dispersant | |
| CN1118795A (en) | Reduced gloss, flame retarded, high impact thermoplastic composition | |
| CN1137936C (en) | Impact-resistant thermoplastic resin composition | |
| CN1703450A (en) | Thermoplastic composition comprising an aromatic polycarbonate and/or a polyester with improved mould release behaviour | |
| CN1162474C (en) | Impact-resistant thermoplastic resin composition | |
| CN1060491C (en) | Thermoplastic polycarbonate resin composition | |
| CN1127762A (en) | Process thermoplastic compositions and emulsion graft copolymer utilizing a polyacid | |
| CN1235970C (en) | Thermoplastic molding compositions | |
| TWI225869B (en) | Polycarbonate having a low shear thinning behavior | |
| CN1125856C (en) | Low gloss thermoplastic resin composition | |
| CN1182448A (en) | Molding resin composition | |
| CN1026987C (en) | UV stable, impact resistant flame retarded ABS composition containing aliphatic resin | |
| EP0281779B1 (en) | Flame-retardant rubber-modified styrene resin composition | |
| CN1189129A (en) | Use of polymer molding compounds to produce partical color change using laser energy to generate high-contrast optical information | |
| CN1057105C (en) | High luster impact-resistance excellent processing fluidity styrene series resin composition | |
| CN1116636A (en) | Flame-retardancy styrene resin composition | |
| CN1082527C (en) | Flame-retarding styrene-series resin compositions | |
| CN1491257A (en) | Impact modifier for thermoplastic resin and resin composition containing the same | |
| CN1202504A (en) | Composition containing styrene polymers and copolymers and containing blends of these, and moulded articles, which are resistant to frictional make obtained from these compositions | |
| CN1257939C (en) | Polyamide composition and its preparing method | |
| CN1624039A (en) | Large bore dual-wall polyproplyene corrugated pipe composition | |
| CN1149255C (en) | Polycarbonate moulding materials with anti-static properties | |
| CN1049230C (en) | Phenylethylene resin composition for extrusion moulding | |
| CN1257218C (en) | Flame retardant polyolefin resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20010110 Termination date: 20160507 |