CN107043516B - With the dark heat-proof ABS resin composition for improving weatherability - Google Patents
With the dark heat-proof ABS resin composition for improving weatherability Download PDFInfo
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- CN107043516B CN107043516B CN201611221990.7A CN201611221990A CN107043516B CN 107043516 B CN107043516 B CN 107043516B CN 201611221990 A CN201611221990 A CN 201611221990A CN 107043516 B CN107043516 B CN 107043516B
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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 with the dark heat-proof ABS resin composition for 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, and 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, it is sent into double screw extruder through metering device, under the conveying, shearing and mixing of the screw rod, it is material melting, compound, again through extrusion, tie rod, cooling, pelletizing step, obtain with the dark heat-proof ABS resin composition for improving weatherability.Heat-proof ABS resin composition provided by the invention not only has excellent weatherability, but also has 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, are related to a kind of suitable for the material of automotive upholstery and its preparation side
Method, and in particular to be a kind of with the dark heat-proof ABS resin composition for improving weatherability.
Background technique
Acrylonitrile-butadiene-styrene terpolymer (ABS) is a kind of high gloss, resistant to chemical etching, high heat resistance,
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 trims such as rearview mirror, grid, license plate, taillight field.
Heat-proof ABS as automobile interior decoration application is other than the requirements such as gloss, VOC, mechanical strength, and most important there are also resistance to
The requirement of light aging.With the especially deep stream by the favorite black interior trim for embodying sports style of young consumers of dark interior trim
Row, also just proposes very high requirement to the weatherability of black ABS resin.
Usually, the weatherability of black ABS due to carbon black to the absorption and shielding action of ultraviolet light better than cream-coloured, brown
This kind of light ABS resin of color, grey.When being exposed to the sun outdoors, also the light fastness aging of usually black ABS behaves oneself best.However
Some automobile interior decoration weathering protocols with very high blackboard temperature such as SAE J2412, masses PV1303 weather-proof test in, it is black
Color ABS resin is often difficult through this kind of weather resistant experiment.Show as the dark ABS product dermatoglyph with dermatoglyph surface texture after illumination
It loses, shinny, blackening leads to declining to a great extent for color fastness.As conventional black pigments carbon black have very high coloring and
Light absorptive, so the easily extinction yield heat under the irradiation of natural sunlight and the common xenon arc lamp of artificial accelerated aging, leads
Surface temperature is caused to increase, black material even can be higher by 30 DEG C or more than same white material surface temperature.So in blackboard
Temperature reaches 100 DEG C of public PV1303 weather resistant experiment standard, and the surface temperature of ABS is even up to 100 DEG C or more, black ABS
L value can often decline 5 units or more after the illumination in 5 periods, the glossiness in dermatoglyph face improves 100% or more so that
3 grades are usually less than in color fastness.And same time or irradiation energy of the dark ABS of same material in SAE J2412 weathering protocol
After measuring comparable illumination, the decline of L value can be within 1.Visible black color ABS resin at high temperature weather-proof sharply deteriorates, and this
The deterioration of a little photooxidation aging properties is cannot to be realized by simply increasing the content of light stabilizer.
Infrared reflecting paint is inorganic pigment, and by metal oxide, nitrate passes through after acetate or even oxide mixing
Reaction takes place in 1000 DEG C or more high-temperature calcinations, reaction, raw material solid itself, and the metal ion and oxonium ion in raw material are again
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 generally 25~40%.
In addition, increasing the content of heat-resistant agent, the heat resistance for improving ABS can improve dark ABS shinny change after light aging
Black problem improves weatherability.But generally heat-resistant agent is not high to the efficiency of the heat-resisting raising of ABS, the even resistance to thermal efficiency
Highest N-PMI-St-MAH class heat-resistant agent still needs more large content of addition, so will lead to mobility and impact strength
Deteriorate.
Summary of the invention
For the technological deficiency of existing dark heat-proof ABS weatherability difference, having the object of the present invention is 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.
It, must using the compound scheme in infrared emission pigment and a small amount of titanium dioxide in ABS resin system of the invention
Upgrading can just achieve the object of the present invention while both sides technology path must be passed through, i.e., on the one hand, reduce tree as much as possible
Rouge surface temperature is to reduce the required amount of heat-resistant agent, thus guarantee 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, improved dermatoglyph and lost, send out
Bright problem, and since the tinting strength, tinting power of infrared reflecting paint is relatively low, caused by the variation to illumination front and rear surfaces material
Color difference it is relatively small, to reduce whole color difference.On the other hand, the increasing of blackness is offset using titanium dioxide xanthochromia itself is allowed
Add, to guarantee color fastness；In system of the invention, titanium dioxide is counteracted under L value since xanthochromia can occur after light aging
Drop, reduces the degree of entire surface blackening, is also achieved that the reduction of color difference.The present invention can be reduced by above-mentioned means
To meet ABS weatherability and required thermal level, that is, mean to reduce the additive amount of heat-resistant agent, therefore the dark color
Heat-proof ABS can have excellent mechanical property and weather resistance simultaneously.Such as it is using the embodiment for reducing resin surface temperature
Technical problem of the invention is not can solve.
The purpose of the present invention is be achieved through the following technical solutions:
The present invention relates to for a kind of dark heat-proof ABS resin composition with improvement weatherability, including following parts by weight
Several each components:
In system of the invention, the effect of titanium dioxide is not to be to reduce resin surface temperature, but adjusts weather-proof mistake
Form and aspect in journey are offset the raising of dark resin blackness by the xanthochromia of titanium dioxide itself, so that whole color fastness variation is less,
Wherein from the comparative example in specific embodiment it is also seen that titanium dioxide is very big to the contribution of control 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 styrene-acrylonitrile copolymer (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 one of oxide of iron, chromium, manganese, copper, nickel, cobalt, titanium, silver, zinc, 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 partial size is 200-2000nm.It is preferred that 500-1000nm.When partial size is less than 200nm, it is easy to happen agglomeration, generates fiber crops
Point；When partial size is greater than 2000nm, the impact strength of ABS resin can obviously deteriorate.The additive amount of infrared reflecting paint is 0.5-
3.0 parts by weight, preferably 1.0-2.0 parts by weight.In system of the invention, when additive amount is less than 0.5 parts by weight, tinting strength, tinting power is not
It enough can not achieve dark color, and when additive amount is greater than 3.0 parts by weight, the impact strength of ABS resin can be significantly affected.
The titanium dioxide be rutile type titanium white, partial size 200-400nm, surface layer can by silica, aluminium oxide or
The two combination cladding.The additive amount of titanium dioxide is 0.1-1.0 parts by weight, preferably 0.4-0.8 parts by weight.When the additive amount of titanium dioxide
When less than 0.1 parts by weight, it is difficult to play the role of improving weatherability.And the additive amount of titanium dioxide be greater than 1.0 parts by weight when, instead
The weatherability of ABS resin can be deteriorated.In system of the invention, the additive amount of titanium dioxide is 0.1-1.0 parts by weight, infrared external reflection
The additive amount of pigment is that 0.5-3.0 parts by weight Shi Caineng plays good synergistic effect, allows to reduce the addition of heat-resistant agent
It measures (5~15 parts), avoids result in the deterioration of resin system mobility and impact strength, so that dark color of the invention is heat-resisting
ABS can have excellent mechanical property and weather resistance simultaneously.
The light stabilizer is the UV absorbent and hindered amine of salicylate, benzophenone, triazines, benzotriazole
One of type free base agent for capturing or a variety of mixtures.The benzophenone UV absorber such as Cyasorb UV-53；Described three
Piperazine class UV absorbent 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 coupling agent, titanate coupling agent, Hinered phenols antioxidant, phosphite ester antioxidant,
One of ethylene bis stearic acid amide, pentaerythritol stearate, magnesium stearate, calcium stearate or a variety of mixtures.
The invention further relates to a kind of above-mentioned preparation sides with the dark heat-proof ABS resin composition for improving weatherability
Method, which comprises by the acrylonitrile-butadiene-styrene resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light
Stabilizer, auxiliary agent mixing are squeezed out through double screw extruder, are granulated to get 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, revolving speed be 200~
500 revs/min.
The double screw extruder is equipped with temperature control device and vacuum evacuation device.
Specific preparation process is as follows:
Step 1: stocking up by following components and parts by weight: 100 parts by weight of acrylonitrile-butadiene-styrene resin, first
5~15 parts by weight of heat-resistant agent, 0.5~3.0 parts by weight of infrared reflecting paint, 0.1~1.0 parts by weight of titanium dioxide, light stabilizer 0.2
~1.0 parts by weight, other 0.5~2.0 parts by weight of auxiliary agent；
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, it is sent into double screw extruder through metering device, under the conveying, shearing and mixing of the screw rod,
It is material melting, compound, then through extrusion, tie rod, cooling, pelletizing step, obtain with the dark heat-resisting ABS resin for improving weatherability
Composition.
Compared with prior art, the present invention have it is following the utility model has the advantages that
The method that the present composition mainly uses infrared reflecting paint and titanium dioxide to compound prepares dark heat-proof ABS tree
Rouge while so that having Good All-around Property, can also have excellent weather resistance, can especially pass through Volkswagen
The weather resistant experiment standard of PV1303, this is and adds a large amount of light stabilizers or acrylic resin these prior arts cannot
It realizes.This will greatly increase heat-proof ABS in the application range in automobile interior decoration field.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
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 scope.
The test method of each embodiment and comparative example is described below:
The test of tensile strength is carried out according to ASTM D638 standard, test speed 50mm/min.
The test of bending strength is carried out according to ASTM D790 standard, test speed 3mm/min.
The test of notch impact strength is carried out according to ASTM D256 standard.
Melt index test according to ASTM D1238 standard carry out, load 10kg, 220 DEG C of test temperature.
Vicat softening point temperature is carried out according to ASTM D1525 standard, loads 5kg, 50 DEG C/h of heating rate.
Weatherability test is carried out according to Volkswagen PV1303 inside gadget standard, irradiation level 1.2W/m2@420nm, when irradiation
Between be 5 periods.
The method that the test of glossiness uses ASTM D2457, uses 268 glossiness of Konica Minolta Multigloss
Instrument, is molded K31 dermatoglyph colour table, and test angle is 60 °.
Chromatism test uses Konica Minolta CR-10.
Embodiment and comparative example the preparation method is as follows:
Step 1: stocking up by following components and parts by weight: 100 parts by weight of acrylonitrile-butadiene-styrene resin, first
5~15 parts by weight of heat-resistant agent, 0.5~3.0 parts by weight of infrared reflecting paint, 0.1~1.0 parts by weight of titanium dioxide, light stabilizer 0.2
~1.0 parts by weight, 0.5~2.0 parts by weight of auxiliary agent；
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 has special requirement to dark color, can also add other dark pigments (non-infrared reflecting paint)) it is several
In high-speed mixer stirring be sufficiently mixed after, through metering device be sent into double screw extruder in, screw rod conveying, shearing and
It is material melting, compound under mixing, then through extrusion, tie rod, cooling, pelletizing step, obtain heat-resisting with the dark color for improving weatherability
ABS resin composition.Wherein the screw slenderness ratio of double screw extruder is 40, and has temperature control device and vacuum evacuation device.
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 are as shown in table 1, component involved in the present embodiment and comparative example and spy
Property is as follows:
ABS-1 resin, weight average molecular weight 90,000, butadiene content 18%；
ABS-2 resin, weight average molecular weight 110,000, butadiene content 16%；
ABS-3 resin, 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 oxide)；
Titanium dioxide, Du Pont, R-108；
UV absorbent, Tinuvin 326；
Hindered amine, Tinuvin 770；
Antioxidant, Irganox B900；
Lubricant, EBS；
ASA, South Korea Jin Hu, XC500A.
1 Examples 1 to 7 of table 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, meets PV1303 five weeks
The weather resistant experiment of phase is tested, but also has excellent mechanical property and processability.And it uses and improves (the comparison 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 implementation method (comparative example 6) of 102627828 A of patent CN can not achieve high-weatherability, can not pass through
The weather resistant experiment in five period of PV1303.Although and excellent weatherability may be implemented in comparative example 2, 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.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to 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 substantive content of the invention.
Claims (8)
1. a kind of with the dark heat-proof ABS resin composition for improving weatherability, which is characterized in that the composition includes following
The each component of parts by weight:
The infrared reflecting paint is one or more of iron, chromium, manganese, copper, nickel, cobalt, titanium, silver, zinc, the oxide of palladium；Institute
The partial size for stating infrared reflecting paint is 200-2000nm；
The titanium dioxide is rutile type titanium white, partial size 200-400nm.
2. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, which is characterized 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, which is characterized in that institute
Stating heat-resistant agent is 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, which is characterized in that institute
The surface layer for stating titanium dioxide coats the mixture of silica, aluminium oxide or silica and aluminium oxide.
5. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, which is characterized in that institute
Stating light stabilizer is that salicylate, benzophenone, triazines, the UV absorbent of benzotriazole and hindered amines free radical are caught
Catch one or more of agent.
6. according to claim 1 have the dark heat-proof ABS resin composition for improving weatherability, which is characterized in that institute
It states auxiliary agent and is selected from the double tristearin of silane coupling agent, titanate coupling agent, Hinered phenols antioxidant, phosphite ester antioxidant, ethylene
One or more of sour amide, pentaerythritol stearate, magnesium stearate, calcium stearate.
7. a kind of preparation method with the dark heat-proof ABS resin composition for improving weatherability according to claim 1,
It is characterized in that, described method includes following steps:
The acrylonitrile-butadiene-styrene resin, heat-resistant agent, infrared reflecting paint, titanium dioxide, light stabilizer, auxiliary agent are mixed
It closes, squeezes out, is granulated to get the dark heat-proof ABS resin composition for having and improving weatherability through double screw extruder.
8. the preparation method with the dark heat-proof ABS resin composition for improving weatherability according to claim 7, special
Sign is, the screw slenderness ratio of the double screw extruder is 36-44, and extrusion temperature is 200~250 DEG C, revolving speed is 200~
500 revs/min.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250661A (en) * | 2018-01-02 | 2018-07-06 | 合肥永健工贸有限公司 | A kind of heat-resisting weather-proof modified materials of ABS 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 |
| 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 |
| CN113897022B (en) * | 2020-07-06 | 2024-03-01 | 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 |
| 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 |
| 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 |
| 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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