CN107043516A - Dark heat-proof ABS resin composition with improvement weatherability - Google Patents
Dark heat-proof ABS resin composition with improvement weatherability Download PDFInfo
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- CN107043516A CN107043516A CN201611221990.7A CN201611221990A CN107043516A CN 107043516 A CN107043516 A CN 107043516A CN 201611221990 A CN201611221990 A CN 201611221990A CN 107043516 A CN107043516 A CN 107043516A
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- abs resin
- resin composition
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- proof abs
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of dark heat-proof ABS resin composition for having and improving weatherability;The composition includes each component of following parts by weight:100 parts of acrylonitrile butadiene styrene resin, 5~15 parts of heat-resistant agent, 0.5 3.0 parts of infrared reflecting paint, 0.1 1.0 parts of titanium dioxide, 0.2~1.0 part of light stabilizer, 0.5~2.0 part of other auxiliary agents.Above-mentioned raw material are stirred in high-speed mixer after being sufficiently mixed, through in metering device feeding double screw extruder, under conveying, shearing and mixing in screw rod, it is material melting, compound, extruded again, tie rod, cooling, pelletizing step, obtain the dark heat-proof ABS resin composition with improvement weatherability.The heat-proof ABS resin composition that the present invention is provided not only has excellent weatherability, and with excellent mechanical property;It is highly suitable to be applied for automotive upholstery field.
Description
Technical field
The present invention relates to technical field of polymer materials, it is related to a kind of material suitable for automotive upholstery and its preparation side
Method, and in particular to there is the dark heat-proof ABS resin composition for improving weatherability to be a kind of.
Background technology
Acrylonitrile-butadiene-styrene terpolymer (ABS) is a kind of high gloss, it is resistant to chemical etching, high it is heat-resisting,
The engineering plastics of the high comprehensive performances such as easy processing, superior dimensional stability, in electric, automobile, household electrical appliance, office etc.
Field has a wide range of applications.Wherein heat-proof ABS is the most universal in the application of automotive field, especially automobile door plate, secondary instrument
Disk, sunshading board, saucer, glove box, catch etc. have certain requirements inside gadget to heat resistance.In addition, heat-proof ABS can also be applied
In the exterior trim such as rearview mirror, grid, license plate, taillight field.
The heat-proof ABS applied as automotive trim is most important also resistance in addition to the requirement such as gloss, VOC, mechanical strength
The requirement of light aging.With flowing for the dark interior trim especially black interior trim for the embodiment sports style that depth is liked by young consumers
OK, the weatherability to black ABS resin also just proposes very high requirement.
As a rule, black ABS weatherability is better than cream-coloured, palm fibre due to carbon black to the absorption and shielding action of ultraviolet
This kind of light ABS resin of color, grey.When being exposed to the sun out of doors, also typically black ABS light fastness aging behaves oneself best.But
It is black in some automotive trim weathering protocols with very high blackboard temperature such as SAE J2412, masses PV1303 weather-proof test
Color ABS resin is difficult often by this kind of weather resistant experiment.Show as the dark ABS products dermatoglyph with dermatoglyph surface texture after illumination
Lose, shinny, blackening causes declining to a great extent for color fastness.As the carbon black of conventional black pigments have very high coloring and
Light absorptive, so the easily extinction yield heat under the irradiation of natural sunshine and the conventional xenon arc lamp of artificial accelerated aging, leads
Surface temperature increase is caused, black material even can be higher by more than 30 DEG C than equal white material surface temperature.So in blackboard
Temperature reaches 100 DEG C of popular PV1303 weather resistant experiments standard, and ABS surface temperature is even up to more than 100 DEG C, black ABS
L values can often decline more than 5 units after the illumination in 5 cycles, the glossiness in dermatoglyph face improves more than 100% so that
3 grades are typically smaller than in color fastness.And equal times or irradiation energy of the dark ABS of same material in SAE J2412 weathering protocols
After the suitable illumination of amount, the decline of L values can be within 1.Weather-proof in high temperature of visible black color ABS resin drastically deteriorates, and this
The deterioration of a little photooxidation aging properties is can not to be realized by simply increasing the content of light stabilizer.
Infrared reflecting paint is inorganic pigment, by metal oxide, and nitrate, acetate, or even oxide are passed through after mixing
Metal ion and oxonium ion in reaction, raw material takes place again in the calcining of 1000 DEG C of high temperature above, reaction, raw material solid in itself
Arrangement, formed it is more stable be similar to spinel structure or Rutile structure, a part of infrared light can be reflected.Such as BASF
(infrared reflecting paint of triumphant one hundred) and Shepherd (Xue Te) company is too by (BASF), Clariant (Clariant), Heubach
Sunlight reflectivity (TSR) is general 25~40%.
In addition, the content of increase heat-resistant agent, dark ABS shinny changes after light aging can be improved by improving ABS heat resistance
Black the problem of, improve weatherability.But typically heat-resistant agent is not high to the efficiency of ABS heat-resisting raising, the even resistance to thermal efficiency
Highest N-PMI-St-MAH class heat-resistant agents need for more large content of addition, so can cause mobility and impact strength
Deteriorate.
The content of the invention
For the technological deficiency of existing dark heat-proof ABS weatherability difference, having it is an object of the invention to provide one kind improves
The dark heat-proof ABS resin composition of weatherability, so as to solve it is above-mentioned prepare dark heat-resisting ABS resin in the prior art when exist
Mechanical property deteriorate, the problems such as weatherability is bad.
In the ABS resin system of the present invention, using the compound scheme in infrared emission pigment and a small amount of titanium dioxide, it must
The purpose of the present invention must could be realized by upgrading while both sides technology path, i.e., on the one hand, reduction as much as possible is set
Fat surface temperature is to reduce the required amount of heat-resistant agent, so that ensure that mechanical property loss is reduced to minimum level, specifically,
The surface temperature of ABS resin product in photo aging process can be reduced by infrared reflecting paint, improves dermatoglyph and loses, send out
Bright the problem of, and because the tinting strength, tinting power of infrared reflecting paint is relatively low, to caused by the change of illumination front and rear surfaces material
Aberration it is relatively small, so as to reduce overall aberration.On the other hand, the increasing of blackness is offset using titanium dioxide xanthochromia itself is allowed
Plus, so as to ensure color fastness;In the system of the present invention, titanium dioxide is counteracted under L values due to xanthochromia can occur after light aging
Drop, reduces the degree of the overall blackening in surface, is also achieved that the reduction of aberration.The present invention can be reduced by above-mentioned means
For meet ABS weatherabilities and needed for thermal level, that is, mean that the addition of heat-resistant agent, therefore the dark color can be reduced
Heat-proof ABS can have excellent mechanical property and weather resistance simultaneously.Such as it is using the embodiment of reduction resin surface temperature
The technical problem of the present invention can not be solved.
The purpose of the present invention is to be achieved through the following technical solutions:
The present invention relates to have the dark heat-proof ABS resin composition for improving weatherability, including following parts by weight for a kind of
Several each components:
In the system of the present invention, the effect of titanium dioxide is not, in order to reduce resin surface temperature, but to adjust weather-proof mistake
Form and aspect in journey, the raising of dark resin blackness is offset by the xanthochromia of titanium dioxide in itself so that overall color fastness change is little,
Wherein from the comparative example in embodiment it is also seen that titanium dioxide is very big to the contribution for controlling color fastness.
The weight average molecular weight of the ABS resin is 80000~150000;The quality of butadiene rubber in the ABS resin
Degree is 12%~18%.
The heat-resistant agent is N-phenylmaleimide-styrene-maleic anhydride copolymer (N-PMI-St-MAH), α-first
Base SAN (α-SAN), styrene-maleic anhydride copolymer (SMA), methyl methacrylate-benzene second
The composition of one or both of alkene-maleic anhydride (MMA-St-MAH).
The infrared reflecting paint is iron, chromium, manganese, copper, nickel, cobalt, titanium, silver, zinc, one kind in the oxide of palladium or several
Kind.As BASF (BASF), Clariant (Clariant), Heubach (triumphant one hundred) and Shepherd (Xue Te) company it is infrared anti-
Penetrate pigment.Such as Sicopal Black K0095, Paliogen Black L0086, Xfast Black 0095, Metaor
Plus 9875, Metaor Plus 9880, Metaor Plus 9889, Black 10C909, rutile-type Ti-Ni pigment etc..
Its particle diameter is 200-2000nm.It is preferred that 500-1000nm.When particle diameter is less than 200nm, easily occurs agglomeration, produce fiber crops
Point;When particle diameter is more than 2000nm, the impact strength of ABS resin can substantially deteriorate.The addition of infrared reflecting paint is 0.5-
3.0 parts by weight, preferably 1.0-2.0 parts by weight.In the system of the present invention, when addition is less than 0.5 parts by weight, tinting strength, tinting power is not
It can not enough realize dark color, and addition can significantly affect the impact strength of ABS resin when being more than 3.0 parts by weight.
The titanium dioxide is rutile type titanium white, and particle diameter is 200-400nm, top layer can by silica, aluminum oxide or
Both combination claddings.The addition of titanium dioxide is 0.1-1.0 parts by weight, preferably 0.4-0.8 parts by weight.When the addition of titanium dioxide
During less than 0.1 parts by weight, it is difficult to play a part of improving weatherability.And the addition of titanium dioxide be more than 1.0 parts by weight when, on the contrary
The weatherability of ABS resin can be deteriorated.In the system of the present invention, the addition of titanium dioxide is 0.1-1.0 parts by weight, infrared external reflection
The addition of pigment can just play good synergy when being 0.5-3.0 parts by weight so that can reduce the addition of heat-resistant agent
Measure (5~15 parts), it is to avoid cause the deterioration of resin system mobility and impact strength, and then cause the present invention's dark heat-resisting
ABS can have excellent mechanical property and weather resistance simultaneously.
The light stabilizer is salicylate, benzophenone, triazines, the UV absorbents and hindered amine of benzotriazole
One or more mixtures in type free base agent for capturing.The benzophenone UV absorber such as Cyasorb UV-53;Described three
Piperazine class UV absorbents such as Cyasorb UV-1164;The benzotriazole uv absorbers such as Tinuvin 326, Cyasorb UV-
5411;The hindered amines free radical scavenger such as Tinuvin 770, Cyasorb UV-3346.
The auxiliary agent be selected from silane coupler, titanate coupling agent, Hinered phenols antioxidant, phosphite ester kind antioxidant,
One or more mixtures in ethylene bis stearic acid amide, pentaerythritol stearate, magnesium stearate, calcium stearate.
The invention further relates to a kind of above-mentioned preparation side with the dark heat-proof ABS resin composition for improving weatherability
Method, methods described includes:By the acrylonitrile-butadiene-styrene resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light
Stabilizer, auxiliary agent mixing, extrude through double screw extruder, granulate, and produce the dark heat-proof ABS tree for having and improving weatherability
Oil/fat composition.
The screw slenderness ratio of the double screw extruder be 36-44, extrusion temperature be 200~250 DEG C, rotating speed be 200~
500 revs/min.
The double screw extruder is provided with temperature control device and vacuum extractor.
Specific preparation process is as follows:
Step 1: being got the raw materials ready by following components and parts by weight:The parts by weight of acrylonitrile-butadiene-styrene resin 100, first
The parts by weight of heat-resistant agent 5~15, the parts by weight of infrared reflecting paint 0.5~3.0, the parts by weight of titanium dioxide 0.1~1.0, light stabilizer 0.2
~1.0 parts by weight, other parts by weight of auxiliary agent 0.5~2.0;
Step 2: ABS resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light stabilizer, other auxiliary agents are mixed in high speed
After stirring is sufficiently mixed in conjunction machine, sent into through metering device in double screw extruder, under the conveying, shearing and mixing in screw rod,
It is material melting, compound, then extruded, tie rod, cooling, pelletizing step, obtain with improving the dark heat-resisting ABS resin of weatherability
Composition.
Compared with prior art, the present invention has following beneficial effect:
The method that the present composition is mainly compounded using infrared reflecting paint and titanium dioxide prepares dark heat-proof ABS tree
Fat so that while possessing Good All-around Property, can also have excellent weather resistance, especially can be by Volkswagen
PV1303 weather resistant experiment standard, this is can not with adding a large amount of light stabilizers or acrylic resin these prior arts
Realize.This will greatly increase application of the heat-proof ABS in automotive trim field.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
The method of testing of each embodiment and comparative example is described below:
The test of tensile strength is carried out according to ASTM D638 standards, and test speed is 50mm/min.
The test of bending strength is carried out according to ASTM D790 standards, and test speed is 3mm/min.
The test of notch impact strength is carried out according to ASTM D256 standards.
Melt index test is carried out according to ASTM D1238 standards, loads 10kg, 220 DEG C of test temperature.
Vicat softening point temperature is carried out according to ASTM D1525 standards, loads 5kg, 50 DEG C/h of programming rate.
Weatherability test is carried out according to Volkswagen PV1303 inside gadgets standard, irradiation level 1.2W/m2@420nm, during irradiation
Between be 5 cycles.
The test of glossiness uses the glossiness of Konica Minolta Multigloss 268 using ASTM D2457 method
Instrument, is molded K31 dermatoglyph colour tables, and test angle is 60 °.
Chromatism test uses Konica Minolta CR-10.
Embodiment and the preparation method of comparative example are as follows:
Step 1: being got the raw materials ready by following components and parts by weight:The parts by weight of acrylonitrile-butadiene-styrene resin 100, first
The parts by weight of heat-resistant agent 5~15, the parts by weight of infrared reflecting paint 0.5~3.0, the parts by weight of titanium dioxide 0.1~1.0, light stabilizer 0.2
~1.0 parts by weight, the parts by weight of auxiliary agent 0.5~2.0;
Step 2: by ABS resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light stabilizer and auxiliary agent (infrared external reflection
Pigment provides for dark color, such as there is special requirement to dark color, can also add other dark pigments (non-infrared reflecting paint)) it is some
After stirring is sufficiently mixed in high-speed mixer, sent into through metering device in double screw extruder, conveying in screw rod, shearing and
It is material melting, compound under mixing, then extruded, tie rod, cooling, pelletizing step, obtain with improving the dark heat-resisting of weatherability
ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 40, and with temperature control device and vacuum extractor.
The extrusion temperature of double screw extruder is 200~250 DEG C, and screw speed is 500 revs/min.
Specific embodiment and the component proportion of comparative example as shown in table 1, are related to component and spy in the present embodiment and comparative example
Property is as follows:
ABS-1 resins, weight average molecular weight 90,000, butadiene content 18%;
ABS-2 resins, weight average molecular weight 110,000, butadiene content 16%;
ABS-3 resins, weight average molecular weight 130,000, butadiene content 14%;
Heat-resistant agent, electrochemically, DENKAIP MS-NH (N-PMI-St-MAH)
Infrared reflecting paint, Sicopal Black K0095 (Cr/Fe oxides);
Titanium dioxide, Du Pont, R-108;
UV absorbents, Tinuvin 326;
Hindered amine, Tinuvin 770;
Antioxidant, Irganox B900;
Lubricant, EBS;
ASA, South Korea Jin Hu, XC500A.
The embodiment 1~7 of table 1 and comparative example 1~6
From each embodiment and comparative example of table 1 it is known that the present invention uses the infrared reflecting paint of 0.5-3.0 parts by weight
When being compounded with the titanium dioxide of 0.1-1.0 parts by weight, the weatherability of dark heat-proof ABS can be significantly improved, PV1303 is met five weeks
The weather resistant experiment test of phase, but also with excellent mechanical property and processability.And use and improve (the contrast of light stabilizer content
Example 1), excessive titanium white powder content (comparative example 3), free white powder when (comparative example 5), the ASA resin (comparative example using weatherability
4) and the similar implementations of the A of patent CN 102627828 (comparative example 6) can not realize high-weatherability, it can not pass through
The weather resistant experiment in the cycles of PV1303 five.And although comparative example 2 can realize excellent weatherability, its impact strength and processing
Performance but deteriorate drastically.It can be seen that the present invention can provide and a kind of have excellent processing characteristics, mechanical property and excellent weather-proof
The dark heat-resisting ABS resin of property.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that the composition includes following
The each component of parts by weight:
2. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
The weight average molecular weight for stating acrylonitrile-butadiene-styrene resin is 80000~150000;The acrylonitrile-butadiene-benzene second
The mass percentage content of butadiene rubber is 12%~18% in olefine resin.
3. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
Heat-resistant agent is stated for N-phenylmaleimide-styrene-maleic anhydride copolymer, α-methylstyrene-acrylonitrile copolymer, benzene
The composition of one or both of ethylene maleic acid anhydride copolymer, Methyl Methacrylate-Styrene-maleic anhydride.
4. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
It is the one or more in iron, chromium, manganese, copper, nickel, cobalt, titanium, silver, zinc, the oxide of palladium to state infrared reflecting paint.
5. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
Titanium dioxide is stated for rutile type titanium white, particle diameter is 200-400nm.
6. according to claim 5 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
State the mixture of top layer cladding silica, aluminum oxide or silica and the aluminum oxide of titanium dioxide.
7. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
Light stabilizer is stated to catch for salicylate, benzophenone, triazines, the UV absorbents of benzotriazole and hindered amines free radical
Catch the one or more in agent.
8. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, it is characterised in that institute
State auxiliary agent and be selected from the double tristearin of silane coupler, titanate coupling agent, Hinered phenols antioxidant, phosphite ester kind antioxidant, ethylene
One or more in sour acid amides, pentaerythritol stearate, magnesium stearate, calcium stearate.
9. a kind of preparation method according to claim 1 with the dark heat-proof ABS resin composition for improving weatherability,
Characterized in that, methods described comprises the following steps:
The acrylonitrile-butadiene-styrene resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light stabilizer, auxiliary agent are mixed
Close, extrude, granulate through double screw extruder, produce the dark heat-proof ABS resin composition for having and improving weatherability.
10. the preparation method according to claim 9 with the dark heat-proof ABS resin composition for improving weatherability, its
It is characterised by, the screw slenderness ratio of the double screw extruder is 36-44, extrusion temperature is 200~250 DEG C, rotating speed is 200~
500 revs/min.
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WO2021032827A1 (en) * | 2019-08-21 | 2021-02-25 | Ineos Styrolution Group Gmbh | Abs molding composition for sheet extrusion and thermoforming with high escr, high color and thermal stability and low tendency to delamination |
CN113897022A (en) * | 2020-07-06 | 2022-01-07 | 合肥杰事杰新材料股份有限公司 | Fiber-filled ABS resin with excellent weather resistance and preparation method thereof |
CN114644792A (en) * | 2022-02-25 | 2022-06-21 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
CN114656687A (en) * | 2022-03-30 | 2022-06-24 | 金发科技股份有限公司 | Coloring agent, coloring ABS resin, and preparation method and application thereof |
CN114752175A (en) * | 2022-03-15 | 2022-07-15 | 金发科技股份有限公司 | Thermal-oxidative-aging-resistant ABS (acrylonitrile butadiene styrene) resin composite material as well as preparation method and application thereof |
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CN109929214A (en) * | 2019-02-13 | 2019-06-25 | 金发科技股份有限公司 | A kind of ABS composition and preparation method thereof |
CN109929214B (en) * | 2019-02-13 | 2021-12-10 | 金发科技股份有限公司 | ABS composition and preparation method thereof |
CN114938651B (en) * | 2019-08-21 | 2023-12-26 | 英力士苯领集团股份公司 | ABS moulding compositions for sheet extrusion and thermoforming with high ESCR, high colour and thermal stability and low tendency to delamination |
WO2021032827A1 (en) * | 2019-08-21 | 2021-02-25 | Ineos Styrolution Group Gmbh | Abs molding composition for sheet extrusion and thermoforming with high escr, high color and thermal stability and low tendency to delamination |
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CN113897022A (en) * | 2020-07-06 | 2022-01-07 | 合肥杰事杰新材料股份有限公司 | Fiber-filled ABS resin with excellent weather resistance and preparation method thereof |
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CN114644792A (en) * | 2022-02-25 | 2022-06-21 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
CN114644792B (en) * | 2022-02-25 | 2023-11-03 | 金发科技股份有限公司 | Polypropylene composite material and preparation method and application thereof |
CN114752175A (en) * | 2022-03-15 | 2022-07-15 | 金发科技股份有限公司 | Thermal-oxidative-aging-resistant ABS (acrylonitrile butadiene styrene) resin composite material as well as preparation method and application thereof |
CN114752175B (en) * | 2022-03-15 | 2023-10-31 | 金发科技股份有限公司 | Thermal-oxidative aging-resistant ABS resin composite material and preparation method and application thereof |
CN114656687A (en) * | 2022-03-30 | 2022-06-24 | 金发科技股份有限公司 | Coloring agent, coloring ABS resin, and preparation method and application thereof |
CN114656687B (en) * | 2022-03-30 | 2023-08-29 | 金发科技股份有限公司 | Colorant, colored ABS resin, and preparation method and application thereof |
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