CN106349678A - Antistatic anti-flaming PC/ABS compound material and preparation method thereof - Google Patents
Antistatic anti-flaming PC/ABS compound material and preparation method thereof Download PDFInfo
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- CN106349678A CN106349678A CN201610899010.2A CN201610899010A CN106349678A CN 106349678 A CN106349678 A CN 106349678A CN 201610899010 A CN201610899010 A CN 201610899010A CN 106349678 A CN106349678 A CN 106349678A
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- ester
- fire retardant
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- abs composite
- electrostatic fire
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses an antistatic anti-flaming PC/ABS compound material and a preparation method thereof. The compound material contains 60-80 parts of PC resin, 8-15 parts of ABS resin, 8-12 parts of anti-flaming agent, 1-5 parts of flexibilizer, 8-25 parts of antistatic agent, 0.01-2 parts of antioxidant and 0.4-0.8 part of other auxiliaries. According to the invention, the optimal antistatic agent is selected, the influence on PC performance can be extremely reduced, and the emulsion method ABS is adopted so that the long-lasting antistatic effect of the antistatic agent is benefited.
Description
Technical field
The present invention relates to pc/abs field of compound material is and in particular to a kind of anti-electrostatic fire retardant pc/abs composite.
Background technology
Pc/abs resin is a kind of alloy material of function admirable, has excellent physical and mechanical property, case hardness, relatively
High intensity and mobility, and have certain thermostability, be widely used in electric/electronic device material, computer, mobile phone,
Printer, the part manufacture material of house material, automotive material and other industrial circles.But pc/abs resin shortcoming is fire-retardant
Poor-performing, and have very high electrical insulating property, so various modifying agent will be added at present in pc/abs alloy to improve its property
Can, fire-retardant pc/abs alloy is as the important modified direction of one of which.
In quasiconductor and auto industry, the accumulation of electrostatic charge can lead to the permanent damage to electronic unit and permissible
Lead to the situation of danger, the antistatic property of therefore fire-retardant pc/abs alloy becomes the demand in market.For improving the anti-quiet of material
Electrically it will usually add antistatic additive to go to improve the electrical conductance of material, to reduce the surface being formed when producing and when using
Electric charge.General antistatic additive is divided into inside and outside antistatic additive, and external anti-static agents are to be applied to the modern designs of plastics after the process
On thing processed, inner antistatic agent is added in the modern designs of plastics plastics as additive, and the inside antistatic using in Merlon
Agent can allow pc that degradation property degradation occurs, and the defects such as variable color occur.In ep1290106b1 in the plastic using perfluor alkane
The quaternary ammonium salt of base sulfonic acid is as antistatic additive, but this antistatic additive price is high, and pc heat stability declines, and seriously limits
The practical application of this invention.
Content of the invention
The purpose of the present invention it is simply that provide a kind of anti-electrostatic fire retardant pc/abs composite in order to solve the above problems
And preparation method thereof.
The object of the present invention is achieved like this:
A kind of anti-electrostatic fire retardant pc/abs composite of the present invention includes following components and parts by weight:
The viscosity-average molecular weight that described abs resin prepares gained for emulsion polymerization is 8000～150000 abs resin；Should
In abs resin, the content of the rubber that butadiene is formed is 5～30wt%, and the segment content that acrylonitrile is formed is 10～30wt%,
The segment content that styrene is formed is the number average bead diameter of the rubber that butadiene is formed in 40～70wt%, and this abs resin is 150
～800nm, preferably 200～500nm, the number average bead diameter of the rubber that butadiene is formed is by transmission electron microscope herein
(sem) measure.In the application, involved number average bead diameter is all in applied voltage using Hitachi's transmission electron microscope
2.0kv, amplification is 10000 times of particle diameters observing 300 rubber particles to measure gained.
Described toughener is MBS, methyl methacrylate-acrylic acid
Copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-methacrylic acid contracting
Water glyceride terpolymer, the ethylene-vinyl acetate copolymer of maleic anhydride functional, acrylic compounds toughener and propylene
At least one in acid-silicone rubber kinds toughener, particle diameter is 50～700nm.
Described antistatic additive is at least one in polyether ester amides, tristerin and copolyesteramide, wherein excellent
Elect polyether ester amides as.
The number of the rubber that butadiene is formed in the abs resin in a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite
All particle diameter is 150～800nm.
The number of the rubber that butadiene is formed in the abs resin in a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite
All particle diameter is 200～500nm.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite, toughener is to prepare gained by emulsion polymerization
MBS and this copolymer in butadiene formed rubber content be 40～
90wt%, the particle diameter of this MBS is 130～300nm.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite, MBS is common
The particle diameter of polymers is 140～260nm, the rubber that in this MBS, butadiene is formed
Content 50～70wt%.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite, pc resin is aromatic copolycarbonate, aliphatic poly
At least one in carbonic ester, aromatic-aliphatic Merlon and branching polycarbonate.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite pc resin for viscosity-average molecular weight be 13000～
40000 aromatic copolycarbonate, more preferably viscosity-average molecular weight are the aromatic copolycarbonate of 17000-24000.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite fire retardant be nitrogenous flame ratardant, phosphonium flame retardant and
At least one in metal organic sulfonate fire retardant.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite, phosphonium flame retardant is Triphenyl phosphate, tricresyl phosphate
Toluene base ester, tricresyl phosphate base diphenyl, tricresyl phosphate dimethylbenzene base ester, tricresyl phosphate (2,4,6- trimethylphenyl) ester, phosphoric acid
Double (diphenyl phosphate) ester of three (2,4- di-tert-butyl-phenyl) ester, tricresyl phosphate (2,6- di-tert-butyl-phenyl) ester, resorcinol, right
Double (diphenyl phosphate) ester of Benzodiazepiness, double (diphenyl phosphate) ester of bis-phenol a-, double (2,6- di-tert-butyl-phenyl) phosphorus of resorcinol
At least one in acid esters and double (2,6- 3,5-dimethylphenyl) phosphate ester of hydroquinone.
In a kind of above-mentioned anti-electrostatic fire retardant pc/abs composite, antioxidant includes the main anti-oxidant that proportioning is 1:1
And auxiliary antioxidant.The inclusion propionic ester of suitable antioxidant and phosphite ester, compositionss can comprise octadecyl -3-
(3,5- di-t-butyl -4- hydroxy phenyl) propionic ester, other suitable antioxidants also include but is not limited to organic phosphite
As three (nonyl phenyl) phosphite ester, double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl Ji Wusi
Alcohol diphosphites；Alkylating monophenols or polyphenols；Polyphenol and the alkylating product of diene, such as four [methylene (3,5-
Di-t-butyl -4- hydroxy hydrocinnamate)] methane；Paracresol or the butylated product of bicyclopentadiene；Alkylation
Hydroquinone；Hydroxylated thiodiphenyl ethers；Alkylidenebisphenols；Benzyl compounds；β-(3,5- di-t-butyl -4- hydroxy benzeness
Base)-propanoic acid and unitary or polyhydric alcohol ester；β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyl)-propanoic acid and unitary or polyhydric alcohol
Ester；Alkylthio or the ester of thioaryl compounds, such as distearyl thiopropionate, dilauryl thiopropionate, two
Tridecyl thiodipropionate, tetramethylolmethane base-four [3- (3,5- di-t-butyl 4- hydroxy phenyl) propionic ester；β-(3,5-
Di-t-butyl -4- hydroxy phenyl)-propanoic acid amide, or include above-mentioned antioxidant at least one combination.Wherein excellent
Elect the spiral shell phosphite ester (spiro phosphite) of high content of phosphorus as, this antioxidant has higher heat stability, can will be subject to
The dark intermediate that resistance phenol antioxidant oxidation is formed is changed into the form of relatively low colourity.
Other auxiliary agents can also be properly added in the present invention as needed and include anti-dripping agent, plasticizer, filler, coloring
At least one in agent.Anti-dripping agent is preferably fluorinated polyolefin, specifically can have including fluoride resin, tetrafluoroethene tree
Fat, tetrafluoroethylene/hexafluoropropylene copolymer resin, wherein preferred TFE.Lubricant is tristerin；Filler
Including mineral fillers such as titanium dioxide, Pulvis Talci, Muscovitum, barium sulfate；Coloring agent includes various pigment, dyestuff.
The present invention also provides a kind of preparation method of anti-electrostatic fire retardant pc/abs composite, comprises the following steps:
(1) according to following components and weight portion content preparation raw material:
(2) putting into above-mentioned raw materials is blended into uniformly in mixer, prepared pre-composition；
(3) pre-composition being obtained in step (2) is put in double screw extruder, the screw slenderness ratio of double screw extruder
Example is 40～45:1, and barrel temperature is 250～260 DEG C, and screw speed is 400～500rpm；Pre-composition is in double screw extruder
Middle melting mixing extruding pelletization, you can of the present invention high-weatherability fire-retardant pc/abs composite is obtained.
The present invention selects preferred antistatic additive, farthest reduces the impact to pc performance, coordinates emulsion method abs
Can be lasting using the performance being conducive to antistatic additive antistatic effect.Permissible using auxiliary antioxidant in processing and production process
Farthest stop the degraded to pc for the antistatic additive, and preferably bathochrome can be changed into the form antioxidation effect of light color
Really, decrease antistatic additive to fire-retardant pc/abs composite mechanics and thermal property impact.The preparation method of the present invention
Simply, safe operation, and prepare the composite of gained there is excellent antistatic behaviour, little to Effect on Mechanical Properties, especially suitable
Require higher occasion for use environment.
Specific embodiment
Below in conjunction with embodiment, the invention will be further described.
The material that the embodiment of the present invention and comparative example are adopted is as follows:
Pc resin: viscosity-average molecular weight is 25000, the trade mark is s-2000f, producer: Mitsubishi；
Abs resin: emulsion polymerization prepares gained, the trade mark is pa-757, producer: Taiwan is very beautiful；
Other abs resins: mass polymerization prepares gained, the trade mark is 8391, producer: Shanghai Gaoqiao petrochemical industry；
Fire retardant: the trade mark is phireguard bdp, producer: refined gram of Jiangsu；
Toughener: the trade mark is m-701, producer: Japanese clock deep pool chemistry；
Antistatic additive: the trade mark is pebax mh2030, producer: French A Ke agate；
Primary antioxidant: the trade mark is chinox 1076；Producer: Taiwan double bond chemical industry；
Auxiliary antioxidant: a kind of spiral shell phosphite ester of high content of phosphorus, the trade mark is revonox 228；Producer: the strange titanium in Taiwan
Chemical industry；
Lubricant: the trade mark is unister-m9676, producer: Japan Oil Co；
Anti-dripping agent: the trade mark is a3800, producer: the beautiful sun of Rhizoma Sparganii.
Embodiment 1～5 and comparative example 1～4:
Put into mixed by table 1 formula pc resin, abs resin, fire retardant, toughener, antistatic additive, antioxidant and other auxiliary agents
The blending of conjunction machine, until uniform, the pre-composition obtaining, puts in double screw extruder and carries out melting mixing, and extruding pelletization, obtains
The product anti-electrostatic fire retardant pc/abs composite of the present invention.The screw slenderness ratio of wherein double screw extruder is 40:1, barrel
Temperature is 260～280 DEG C, and screw speed is 400～500rpm.
The antistatic behaviour of pc/abs composite, anti-flammability and the notched Chalpy impact intensity of preparing gained are surveyed
Examination, test institute's reference standard or method are as described below:
(1) antistatic behaviour: the antistatic property of material is characterized with surface resistivity, by 2mm thick molding square plate, at 23 DEG C,
After 50% humidity regulation 24h, test the surface resistivity of square plate according to astm d257-93, material shows 106Ohm/sq is extremely
109During the surface resistivity of the scope of ohm/sq, just there is preferably antistatic behaviour.
(2) anti-flammability measures: according to " the flammable test of plastic material, the code of ul94 carries out flammable test.
(3) notched Chalpy impact intensity measures: under the conditions of 23 DEG C, using the molding notched izod punching that 3.2mm is thick
Hit rod and measure notched Chalpy impact intensity.Notched Chalpy impact intensity is measured according to astm d256, result is recorded with j/m.
Table 1 embodiment 1～5 and comparative example 1～4 component (weight portion) and the performance test results
As can be seen that compared with fire-retardant pc/abs composite obtained by with comparative example 1～4 for the embodiment 1～5, comparative example 1
The antistatic behaviour of fire-retardant pc/abs composite obtained by～4 and notched impact properties, all high or low variation it is impossible to
When meet preferable antistatic and mechanical property.Different from comparative example 1～4, the antistatic property obtained by the embodiment of the present invention
, after adding antistatic additive, antistatic property is excellent, and the choosing due to abs and antioxidant for excellent fire-retardant pc/abs composite
Selecting property is added, and the Toughness of material is not almost had yet.
Anti-electrostatic fire retardant pc/abs composite products obtained by the present invention can be widely applied to as electric/electronic device
Material, computer, mobile phone, printer, part manufacture material of house material, automotive material and other industrial circles etc..
Above example is used for illustrative purposes only, rather than limitation of the present invention, about the technology people of technical field
Member, without departing from the spirit and scope of the present invention, can also make various conversion or modification, therefore all equivalent
Technical scheme also should belong to scope of the invention, should be limited by each claim.
Claims (11)
1. a kind of anti-electrostatic fire retardant pc/abs composite is it is characterised in that include following components and parts by weight:
The viscosity-average molecular weight that described abs resin prepares gained for emulsion polymerization is 8000～150000 abs resin；
Described toughener is MBS, methyl methacrylate-acrylic acid copolymer
Thing, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-Glycidyl methacrylate are sweet
Grease terpolymer, the ethylene-vinyl acetate copolymer of maleic anhydride functional, acrylic compounds toughener and acrylic acid-silicon
At least one in rubber-like toughener, particle diameter is 50～700nm；
Described antistatic additive is at least one in polyether ester amides, tristerin and copolyesteramide.
2. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that in described abs resin
The number average bead diameter of the rubber that butadiene is formed is 150～800nm.
3. as claimed in claim 2 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that in described abs resin
The number average bead diameter of the rubber that butadiene is formed is 200～500nm.
4. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described toughener is logical
Cross emulsion polymerization and prepare butadiene shape in the MBS of gained and this copolymer
The content of the rubber becoming is 40～90wt%, the particle diameter of this MBS is 130～
300nm.
5. as claimed in claim 4 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described methacrylic acid
The particle diameter of methyl ester-BS is 140～260nm, this MBS copolymerization
Content 50～the 70wt% of the rubber that butadiene is formed in thing.
6. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described pc resin be virtue
At least one in fragrant adoption carbonic ester, fatty poly-ester carbonate, aromatic-aliphatic Merlon and branching polycarbonate.
7. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described pc resin is viscous
Average molecular weight is 13000～40000 aromatic copolycarbonate.
8. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described fire retardant be containing
At least one in nitrogen combustion inhibitor, phosphonium flame retardant and metal organic sulfonate fire retardant.
9. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described phosphonium flame retardant
For Triphenyl phosphate, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate dimethylbenzene base ester, tricresyl phosphate (2,4,
6- trimethylphenyl) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester, tricresyl phosphate (2,6- di-tert-butyl-phenyl) ester, isophthalic two
Double (diphenyl phosphate) ester of phenol, double (diphenyl phosphate) ester of hydroquinone, double (diphenyl phosphate) ester of bis-phenol a-, resorcinol are double
At least one in (2,6- di-tert-butyl-phenyl) phosphate ester and double (2,6- 3,5-dimethylphenyl) phosphate ester of hydroquinone.
10. as claimed in claim 1 a kind of anti-electrostatic fire retardant pc/abs composite it is characterised in that described antioxidant packages
Include the main anti-oxidant that proportioning is 1:1 and auxiliary antioxidant.
11. as claimed in claim 1 a kind of preparation method of anti-electrostatic fire retardant pc/abs composite it is characterised in that bag
Include following steps:
(1) according to following components and weight portion content preparation raw material:
(2) putting into above-mentioned raw materials is blended into uniformly in mixer, prepared pre-composition；
(3) pre-composition being obtained in step (2) is put in double screw extruder, the screw slenderness ratio example of double screw extruder is
40～45:1, barrel temperature is 250～260 DEG C, and screw speed is 400～500rpm；Pre-composition is molten in double screw extruder
Melt mixing extruding pelletization, you can of the present invention high-weatherability fire-retardant pc/abs composite is obtained.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107090168A (en) * | 2017-06-26 | 2017-08-25 | 宁波市特尔佳塑料科技有限公司 | A kind of anlistatig PC/ABS compositions |
| CN107177184A (en) * | 2017-06-26 | 2017-09-19 | 宁波市特尔佳塑料科技有限公司 | A kind of anlistatig fire retardation PC/ABS compositions |
| CN107236272A (en) * | 2017-06-16 | 2017-10-10 | 广东圆融新材料有限公司 | A kind of thin-walled anti-static halogen-free flame-retardant PC/ABS compositions and preparation method thereof |
| CN108976754A (en) * | 2018-08-08 | 2018-12-11 | 柏力开米复合塑料(昆山)有限公司 | A kind of anti-electrostatic fire retardant compound material and its preparation method and application |
| CN113136097A (en) * | 2021-05-12 | 2021-07-20 | 广东银禧科技股份有限公司 | Halogen-free flame-retardant antistatic natural-color PC/ABS alloy and preparation method thereof |
| CN114292510A (en) * | 2021-12-31 | 2022-04-08 | 广东圆融新材料有限公司 | PC-ABS alloy material and preparation method thereof |
| CN115627064A (en) * | 2022-11-08 | 2023-01-20 | 天津金发新材料有限公司 | Antistatic PC/ABS composition and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107236272A (en) * | 2017-06-16 | 2017-10-10 | 广东圆融新材料有限公司 | A kind of thin-walled anti-static halogen-free flame-retardant PC/ABS compositions and preparation method thereof |
| CN107090168A (en) * | 2017-06-26 | 2017-08-25 | 宁波市特尔佳塑料科技有限公司 | A kind of anlistatig PC/ABS compositions |
| CN107177184A (en) * | 2017-06-26 | 2017-09-19 | 宁波市特尔佳塑料科技有限公司 | A kind of anlistatig fire retardation PC/ABS compositions |
| CN108976754A (en) * | 2018-08-08 | 2018-12-11 | 柏力开米复合塑料(昆山)有限公司 | A kind of anti-electrostatic fire retardant compound material and its preparation method and application |
| CN108976754B (en) * | 2018-08-08 | 2020-11-24 | 柏力开米复合塑料(昆山)有限公司 | Antistatic flame-retardant composite material and preparation method and application thereof |
| CN113136097A (en) * | 2021-05-12 | 2021-07-20 | 广东银禧科技股份有限公司 | Halogen-free flame-retardant antistatic natural-color PC/ABS alloy and preparation method thereof |
| CN114292510A (en) * | 2021-12-31 | 2022-04-08 | 广东圆融新材料有限公司 | PC-ABS alloy material and preparation method thereof |
| CN114292510B (en) * | 2021-12-31 | 2024-01-12 | 广东圆融新材料有限公司 | PC-ABS alloy material and preparation method thereof |
| CN115627064A (en) * | 2022-11-08 | 2023-01-20 | 天津金发新材料有限公司 | Antistatic PC/ABS composition and preparation method and application thereof |
| CN115627064B (en) * | 2022-11-08 | 2024-03-19 | 天津金发新材料有限公司 | Antistatic PC/ABS composition, and preparation method and application thereof |
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Inventor after: Tian Zhengyu Inventor after: Wang Qiling Inventor after: Dong Xiangmao Inventor after: Liu Xianwen Inventor after: Cen Yin Inventor after: Ai Junwei Inventor after: Tong Wei Inventor before: Tian Zhengyu Inventor before: Wang Qiling Inventor before: Dong Xiangmao Inventor before: Liu Xianwen Inventor before: Cen Yin Inventor before: Ai Junwei Inventor before: Tong Wei |
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