CN106589768A - PC/ABS free-spraying resin composition improving silver wire problem in injection molding and preparation method of PC/ABS free-spraying resin composition - Google Patents
PC/ABS free-spraying resin composition improving silver wire problem in injection molding and preparation method of PC/ABS free-spraying resin composition Download PDFInfo
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- CN106589768A CN106589768A CN201611110299.1A CN201611110299A CN106589768A CN 106589768 A CN106589768 A CN 106589768A CN 201611110299 A CN201611110299 A CN 201611110299A CN 106589768 A CN106589768 A CN 106589768A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
Abstract
The invention relates PC/ABS free-spraying resin composition improving a silver wire problem in injection molding and a preparation method of the PC/ABS free-spraying resin composition. The PC/ABS free-spraying resin composition comprises components in parts by weight as follows: 20-95 parts of PC, 5-80 parts of ABS, 0.1-20 parts of toner master batches with a special effect, 0.05-1 part of an antioxidant, and 0.1-2 parts of a lubricant. The toner master batches with the special effect are artificially synthesized pigment with pearly luster, which is formed through coating treatment of an acrylonitrile-styrene-GMA (glycidyl methacrylate) copolymer (AS-GMA). During preparation, a screw extruder is adopted to prepare toner master batches with the special effect, and then the screw extruder is adopted to prepare a PC/ABS free-spraying resin composition product, wherein the toner master batches are added in a side feeding manner. Compared with the prior art, the PC/ABS free-spraying resin composition and the preparation method well solve the problems of material degradation, physical property downgrade, silver wire in injection molding when the PC/ABS free-spraying resin composition is prepared in the prior art.
Description
Technical field
The present invention relates to macromolecular material is received, and in particular to the PC/ABS for improving injection filamentary silver problem exempts to spray resin group
Compound and preparation method thereof.
Background technology
As consumer is to product appearance quality requirements more and more higher, the decoration technique of automotive interior material is more and more richer
Richness, use of the high-end texture appearance having in automotive trim are increasingly popularized.Wherein with the high-end matter of metal effect
Sense is most commonly seen in automotive trim.At present the metal effect material of main flow is reaching metal-like, flicker by painting
Deng aesthetic effect, but spray painting has the complicated procedures of forming such as pretreatment, application, transhipment, relatively costly；Painting process pollution environment, and easily
The disease such as " Pericarpium Citri tangerinae " spraying paint is produced, yields is not high；Because containing thermosetting spray-on coating, making that plastics are not recyclable, making in finished product
Into a large amount of wastes；There is depainting in use.
Exempt from spraying aesthetic plastics, the beautiful particular color effect of outward appearance be capable of achieving by one-shot forming, eliminate spraying,
The rear manufacturing procedure such as silk-screen, production efficiency height, low cost, non-environmental-pollution, low energy consumption, 100% recoverable.With metal
The PC/ABS of effect exempts from spraying resin material and has many merits such as heat-resisting, high tenacity, high texture, low VOC concurrently, applies in automobile
The embarrassment that interior material is faced in composite requests such as high texture, low cost and green productions can be solved with perfect in decorations.By U.S.
Learn plastics and water transfers the innovation scheme being combined together and more can cover the defects such as weld mark and current mark in appearance, and in work(
The scraping and weather-proof problem for solving the problems, such as aesthstic plastics can be gone up.
However, the PC/ABS with metal effect exempts from spraying resin is frequently encountered filamentary silver problem in injection.This be by
The pearlescent effect pigment such as mica sheet, sheet glass, these effect pigments will be often added to be typically by low in the material Jing of metal effect
The substrate surface of refractive index coats the metal-oxide such as TiO of high index of refraction2、Fe2O3Deng.Rutile TiO2With anatase titanium dioxide TiO2
PC is had significantly promote Degradation.It is likely due to Nano titanium dioxide surface and is also easy to produce chemisorbed-OH [2],
Under hot conditionss, TiO2- OH is possible to the degraded for producing that free radical promotes PC of rupturing.It could also be possible that due to Ti4+In PC
Ester group be mutually coordinated, cause the ester exchange of PC to be degraded.Further, since the metal-oxide on these effect pigment surfaces is all logical
Calcining after crossing chemical deposition is formed, and various chemical substances can be introduced during chemical deposition.Such as TiO2Deposition process, it is first
Before this by TiCl4Add reaction system in, Muscovitum with Electrostatic Absorption liquid phase in [Ti (H2O)6]4+, [the Ti on electric double layer
(H2O)6]4+It is hydrolyzed in the way of closing titanium complex ion more and growing：TiCl4+4H2O=Ti (OH)4+4HCl.Hydrolyze to form
Ti(OH)4Jing calcinings just define multiple structure again to be adsorbed onto mica surface.Course of reaction can also add the chemical inductions such as SnCl4
Other materials such as agent, PH buffer agents.Degraded of the various metals chloride to PC has facilitation.Therefore, these pearlescent effects
The introducing of pigment can cause greater risk to the stability of PC/ABS so that PC parts occur serious degraded, during injection easily
Produce filamentary silver.
In prior art, the method for suppressing metal ion to act on plastics mainly adopts chelating agen, and a certain
The chelating agen of type is often just for one or more metals.In addition, common chelating agen is in use, required environment
Acid-base value is different, therefore, sometimes can not use simultaneously.Chelating agen itself has certain Acidity of Aikalinity, is likely to
Promote PC to degrade, add the low characteristic of its molecular weight, have certain impact on material property, so can not use in a large number.The present invention
Using technology then do not have the problems referred to above.There is the extraordinary compatibility with PC/ABS using AS-GMA copolymers, molecular weight is high,
A large amount of additions will not obvious physical property.The polar functional group of the sense and effect pigment of AS-GMA produces good adsorption, makes
AS-GMA strands can be effective be coated on around effect pigment, the various active factorses that screen effect pigment is carried
Rush Degradation to PC, while the effect of the several different metal ions in suppressing material.Mode is fed by side will be special
Effect toner master batch can effectively shorten the time of contact of effect pigment and base material in being added to PC/ABS melts, further reduce base
The possibility of material degraded.
The content of the invention
The purpose of the present invention is exactly to provide a kind of improvement and be molded filamentary silver to overcome the defect of above-mentioned prior art presence
The PC/ABS of problem exempts to spray resin combination and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions：A kind of PC/ABS for improving injection filamentary silver problem exempts from
Spraying resin combination, it is characterised in that including the component of following weight portion：PC 20-95 parts, ABS 5-80 parts, special-effect
Toner master batch 0.1-20 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts；Described special-effect toner master batch is Jing propylene
The pearlescent effect pigment of the synthetic that nitrile-styrene-t glycidyl ester copolymer (AS-GMA) cladding is processed.
In described AS-GMA copolymers, GMA functional group contents are 0.2-0.8wt%, and AS-GMA weight average molecular weight used is
80000-120000g/mol。
Described special-effect toner master batch includes following parts by weight of component pearlescent effect pigment 0.1-25 parts, and AS-GMA is common
Polymers 75-99.9 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts；The particle diameter of pearlescent effect pigment is 1 μm -500 μm.
Described pearlescent effect pigment includes bismuth oxychloride crystal metal pigment, Muscovitum coated metal pigments, silicon dioxide
Coated metal pigments, boric acid aluminium salt coated metal pigments, artificial mica coated metal pigments, aluminium sesquioxide coating metal face
The mixture of one or more in material, bismuth oxide coated metal pigments.
It is 10000-35000g/mol that described PC is weight average molecular weight；The equal average molecular matter of weight of described ABS resin
Measure as 80000-200000g/mol, in described ABS resin, rubber content is 10-30%, and the number average bead diameter of rubber is 0.2-
3.0μm。
Described antioxidant is selected from aromatic amine antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant, monothioester
One or more in kind antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.
Described lubricant is selected from silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, polyethylene
Wax, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, virtue
One or more in race's phosphate ester.
The PC/ABS of above-mentioned improvement injection filamentary silver problem exempts to spray the preparation method of resin combination, it is characterised in that bag
Include following steps：
(1) prepared by special-effect toner master batch
By weight by AS-GMA copolymer 75-99.9 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts are in mixer
Interior pre- mixing, then premix material Jing double screw extruders extrusion, while by pearlescent effect pigment 0.1-25 by way of side is fed
Part is added in described melt, is carried out extrusion and is obtained special-effect toner master batch；
(2) PC/ABS for improving injection filamentary silver problem exempts to spray resin combination preparation
By weight by PC 20-95 parts, ABS 5-80 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts are in mixer
Interior pre- mixing, then premix material Jing double screw extruders extrusion, while by special-effect toner master batch by way of side is fed
0.1-20 parts are added in described melt, are carried out a kind of PC/ABS for improving injection filamentary silver problem of extrusion acquisition and are exempted to spray resin
Compositionss.
The temperature of the double screw extruder described in step (1) is 190-250 DEG C, and screw slenderness ratio is 25-45, screw speed
For 400-600 rev/min.
The temperature of the double screw extruder described in step (2) is 190-230 DEG C, and screw slenderness ratio is 25-45, screw speed
For 400-600 rev/min.
The antioxidant that above-mentioned steps (1) and step (2) are adopted is selected from aromatic amine antioxidant, Hinered phenols antioxidant, Asia
One or more in phosphoric acid ester antioxidant, monothioester kind antioxidant, aromatic phosphate acid ester, pentaerythritol ester, auxiliary antioxidant.
The lubricant that above-mentioned steps (1) and step (2) are adopted selected from silicone oil, white mineral oil, fatty acid amide, barium stearate,
Magnesium stearate, paraffin, Tissuemat E, ethylene bis stearic acid amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate,
One or more in ethylene-acrylic acid copolymer, aromatic phosphate acid ester.
The present invention has the extraordinary compatibility with PC/ABS using AS-GMA copolymers, and molecular weight is high, and a large amount of additions will not
Obvious physical property.The polar functional group of the sense and effect pigment of AS-GMA produces good adsorption, the AS-GMA molecules for making
Chain can be effective be coated on around effect pigment, the various active factorses that screen effect pigment is carried are degraded to the rush of PC
Effect, while the effect of the several different metal ions in suppressing material.Mode is fed by special-effect toner master batch by side
The time of contact of effect pigment and base material can effectively be shortened in being added to PC/ABS melts, what further reduction base material was degraded can
Energy.
Compared with prior art, when in the more preferable solution prior art of the present invention, preparation PC/ABS exempts to spray resin combination
The problems such as material degradation, physical property decline, are molded with filamentary silver.
Specific 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 the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention
Protection domain.
Embodiment 1～5 and comparative example 1～2
Each component that each embodiment and comparative example are used and its content as shown in table 1, respectively according to each embodiment in table 1 and
The component and content of comparative example is got the raw materials ready.
Special-effect toner master batch is prepared first：By except other raw materials of the above-mentioned master batch in addition to pearlescent effect pigment are mixed
Mixed in conjunction machine in advance, then premix material Jing double screw extruders extrusion, while pressing pearlescent effect pigment by way of side is fed
Proportioning is added in described melt, is carried out extrusion and is obtained special-effect toner master batch.Extruder temperature wherein used is 190-
230 DEG C, screw slenderness ratio is 25-45, and screw speed is 400-600 rev/min.
Then according to PC/ABS is exempted from spraying resin combination raw material and does not include effect toner master batch by the proportioning in table 1
Mixture is mixed in mixer in advance, then the blending of premix material Jing twin screw, by way of side is fed is added effect toner master batch
It is added in melt.Extruder temperature wherein used be 190～250 DEG C, screw slenderness ratio be 25～45, screw speed be 400～
600 revs/min, cooling granulation, the PC/ABS for obtaining improving injection filamentary silver problem exempt to spray resin combination.
It is related to component in above example and comparative example and characteristic is as follows：
PC1：Weight average molecular weight 10000；
PC2：Weight average molecular weight 22000；
PC3：Weight average molecular weight 35000；
ABS1：Butadiene rubber content 30%, number average bead diameter is 0.2um, weight average molecular weight 80000；
ABS2：Butadiene rubber content 17%, number average bead diameter is 1.5um, weight average molecular weight 100000；
ABS3：Butadiene rubber content 10%, number average bead diameter is 3um, weight average molecular weight 200000；
ABS4：Butadiene rubber content 20%, number average bead diameter is 0.6um, weight average molecular weight 140000；
Special-effect toner master batch 1：Pearlescent effect pigment be 15 parts of boric acid aluminium salt coated metal pigments, particle diameter 100-500 μ
85 parts of m, AS-GMA, weight average molecular weight 80000, GMA 0.6wt%, 0.2 part of irgasfos 168；Lubricant aromatic phosphate acid ester 0.5
Part；
Special-effect toner master batch 2：Pearlescent effect pigment be 25 parts of silica-coating metallic pigments, 20-70 μm of particle diameter,
75 parts of AS-GMA, weight average molecular weight 100000, GMA 0.8wt%, 0.2 part of antioxidant 1076；Lubricant pentaerythritol ester 0.5
Part；
Special-effect toner master batch 3：Pearlescent effect pigment be 0.5 part of Muscovitum coated metal pigments, 1-50 μm of particle diameter, AS-
95.5 parts of GMA, weight average molecular weight 120000, GMA 0.2wt%, 0.2 part of antioxidant 1076；Lubricant pentaerythritol ester 0.5
Part；
Pearlescent effect pigment 1 be silica-coating metallic pigments, 20-70 μm of particle diameter；Antioxidant：1076 0.2 parts；Profit
0.5 part of lubrication prescription aromatic phosphate acid ester.
1 component of table and content table
Quantitative measurement method：
Colour table heat stops filamentary silver：It is molded the colour table of 8cm × 12cm × 3mm and carries out 5min clocks by is moulded at 260 DEG C
Heat stop experiment come observe material colour table stop after filamentary silver situation.
IZOD notch shock IS：Test according to ISO 180, unit kJ/m2.
Melt index MI：Test according to ISO 1133,260 DEG C × 5kg, unit g/10min.
By the Comparative result of table 1, the invention has the advantages that：Have very good with PC/ABS using AS-GMA copolymers
The compatibility, molecular weight is high, and a large amount of additions will not obvious physical property.The polar functional group of the sense and effect pigment of AS-GMA is produced
Good adsorption, the AS-GMA strands for enabling are effective to be coated on around effect pigment, screen effect pigment
Rush Degradation of the various active factorses for carrying to PC, while the effect of the several different metal ions in suppressing material.
Mode is fed by side special-effect toner master batch is added in PC/ABS melts and can effectively shorten connecing for effect pigment and base material
The tactile time, further reduce the possibility of base material degraded.Compare
Invention solves well and prepares material degradation when PC/ABS exempts to spray resin combination, physical property decline, is molded with asking for filamentary silver
Topic, compared with prior art (addition chelating agen ethylenediaminetetraacetic acid comparative example 2), the present invention more has when the problems referred to above are improved
Effect.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, on the premise of without departing from the inventive method, can also make some improvement and supplement, and these improve and supplement also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of PC/ABS for improving injection filamentary silver problem exempts to spray resin combination, it is characterised in that including following weight portion
Component：PC 20-95 parts, ABS 5-80 parts, special-effect toner master batch 0.1-20 parts, antioxidant 0.05-1 parts, lubricant
0.1-2 parts；Described special-effect toner master batch is Jing acrylonitrile-styrenes-glycidyl methacrylate copolymer
(AS-GMA) the pearlescent effect pigment of the synthetic that cladding is processed.
2. the PC/ABS for improving injection filamentary silver problem according to claim 1 exempts to spray resin combination, it is characterised in that
In described AS-GMA copolymers, GMA functional group contents are 0.2-0.8wt%, and AS-GMA weight average molecular weight used is 80000-
120000g/mol。
3. the PC/ABS for improving injection filamentary silver problem according to claim 1 exempts to spray resin combination, it is characterised in that
Described special-effect toner master batch includes following parts by weight of component pearlescent effect pigment 0.1-25 parts, AS-GMA copolymer 75-
99.9 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts；The particle diameter of pearlescent effect pigment is 1 μm -500 μm.
4. the PC/ABS of the improvement injection filamentary silver problem according to claim 1 or 3 exempts to spray resin combination, and its feature exists
In described pearlescent effect pigment includes bismuth oxychloride crystal metal pigment, Muscovitum coated metal pigments, silica-coating gold
Category pigment, boric acid aluminium salt coated metal pigments, artificial mica coated metal pigments, aluminium sesquioxide coated metal pigments, oxidation
The mixture of one or more in bismuth coated metal pigments.
5. the PC/ABS for improving injection filamentary silver problem according to claim 1 exempts to spray resin combination, it is characterised in that
It is 10000-35000g/mol that described PC is weight average molecular weight；The average weight-molecular mass of described ABS resin is
80000-200000g/mol, in described ABS resin, rubber content is 10-30%, and the number average bead diameter of rubber is 0.2-3.0 μm.
6. the PC/ABS for improving injection filamentary silver problem according to claim 1 exempts to spray resin combination, it is characterised in that
Described antioxidant is selected from aromatic amine antioxidant, Hinered phenols antioxidant, phosphite ester kind antioxidant, thio esters antioxygen
Agent, aromatic phosphate acid ester, pentaerythritol ester, one or more in auxiliary antioxidant.
7. the PC/ABS for improving injection filamentary silver problem according to claim 1 exempts to spray resin combination, it is characterised in that
Described lubricant is double selected from silicone oil, white mineral oil, fatty acid amide, barium stearate, magnesium stearate, paraffin, Tissuemat E, ethylene
Stearic amide, ethylene-vinyl acetate copolymer, pentaerythritol stearate, ethylene-acrylic acid copolymer, aromatic phosphate acid ester
In one or more.
8. a kind of PC/ABS for improving injection filamentary silver problem as claimed in claim 1 exempts to spray the preparation side of resin combination
Method, it is characterised in that comprise the steps：
(1) prepared by special-effect toner master batch
By weight by AS-GMA copolymer 75-99.9 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts are pre- in mixer
Mix, then premix material Jing double screw extruders extrusion, while adding pearlescent effect pigment 0.1-25 parts by way of side is fed
Enter in described melt, carry out extrusion and obtain special-effect toner master batch；
(2) PC/ABS for improving injection filamentary silver problem exempts to spray resin combination preparation
By weight by PC 20-95 parts, ABS 5-80 parts, antioxidant 0.05-1 parts, lubricant 0.1-2 parts are pre- in mixer
Mix, then premix material Jing double screw extruders extrusion, while by special-effect toner master batch 0.1-20 by way of side is fed
Part is added in described melt, is carried out a kind of PC/ABS for improving injection filamentary silver problem of extrusion acquisition and is exempted to spray resin combination
Thing.
9. the PC/ABS for improving injection filamentary silver problem according to claim 8 exempts to spray resin combination, it is characterised in that
The temperature of the double screw extruder described in step (1) is 190-250 DEG C, and screw slenderness ratio is 25-45, and screw speed is 400-
600 revs/min.
10. the PC/ABS for improving injection filamentary silver problem according to claim 8 exempts to spray resin combination, and its feature exists
It it is 190-230 DEG C in the temperature of, the double screw extruder described in step (2), screw slenderness ratio is 25-45, screw speed is
400-600 rev/min.
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| CN201611110299.1A CN106589768B (en) | 2016-12-06 | 2016-12-06 | The PC/ABS for improving injection molding filamentary silver problem exempts to spray resin combination and preparation method thereof |
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| CN201611110299.1A CN106589768B (en) | 2016-12-06 | 2016-12-06 | The PC/ABS for improving injection molding filamentary silver problem exempts to spray resin combination and preparation method thereof |
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Cited By (8)
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| CN106977895A (en) * | 2017-04-28 | 2017-07-25 | 三阳机车工业有限公司 | Motor vehicle body is cladded with part bloom and exempts from spray painting alloy material and preparation method thereof |
| CN107629432A (en) * | 2017-09-22 | 2018-01-26 | 广东国立科技股份有限公司 | One kind is self-cleaning to be exempted to spray injected plastics material and preparation method thereof |
| CN109957207A (en) * | 2019-04-02 | 2019-07-02 | 清远市绚淳环保新材料有限公司 | It is a kind of to exempt from spraying metal aluminium pigment and preparation method thereof with brittle performance |
| CN111234443A (en) * | 2020-01-20 | 2020-06-05 | 上海锦湖日丽塑料有限公司 | Yellowing-resistant PMMA/ABS spraying-free resin and preparation method thereof |
| CN112251007A (en) * | 2020-09-22 | 2021-01-22 | 太仓市华鼎塑料有限公司 | PC-ABS resin composition capable of solving flow mark problem of injection molding silver wire and preparation method thereof |
| CN114525010A (en) * | 2022-03-16 | 2022-05-24 | 成都金发科技新材料有限公司 | ABS composition and preparation method and application thereof |
| CN115850937A (en) * | 2022-11-28 | 2023-03-28 | 青岛海泰科新材料科技有限公司 | High-gloss high-toughness spraying-free PC/ABS composite material and preparation method thereof |
| CN115926420A (en) * | 2022-12-30 | 2023-04-07 | 宁波福天新材料科技有限公司 | Polycarbonate composite material and preparation method thereof |
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| CN106977895A (en) * | 2017-04-28 | 2017-07-25 | 三阳机车工业有限公司 | Motor vehicle body is cladded with part bloom and exempts from spray painting alloy material and preparation method thereof |
| CN106977895B (en) * | 2017-04-28 | 2019-07-09 | 三阳机车工业有限公司 | Motor vehicle body is cladded with part bloom and exempts from the alloy material and preparation method thereof that paints |
| CN107629432A (en) * | 2017-09-22 | 2018-01-26 | 广东国立科技股份有限公司 | One kind is self-cleaning to be exempted to spray injected plastics material and preparation method thereof |
| CN107629432B (en) * | 2017-09-22 | 2019-04-30 | 广东国立科技股份有限公司 | One kind is self-cleaning to be exempted to spray injected plastics material and preparation method thereof |
| CN109957207A (en) * | 2019-04-02 | 2019-07-02 | 清远市绚淳环保新材料有限公司 | It is a kind of to exempt from spraying metal aluminium pigment and preparation method thereof with brittle performance |
| CN111234443A (en) * | 2020-01-20 | 2020-06-05 | 上海锦湖日丽塑料有限公司 | Yellowing-resistant PMMA/ABS spraying-free resin and preparation method thereof |
| CN111234443B (en) * | 2020-01-20 | 2022-09-20 | 上海锦湖日丽塑料有限公司 | Yellowing-resistant PMMA/ABS spraying-free resin and preparation method thereof |
| CN112251007A (en) * | 2020-09-22 | 2021-01-22 | 太仓市华鼎塑料有限公司 | PC-ABS resin composition capable of solving flow mark problem of injection molding silver wire and preparation method thereof |
| CN114525010A (en) * | 2022-03-16 | 2022-05-24 | 成都金发科技新材料有限公司 | ABS composition and preparation method and application thereof |
| CN115850937A (en) * | 2022-11-28 | 2023-03-28 | 青岛海泰科新材料科技有限公司 | High-gloss high-toughness spraying-free PC/ABS composite material and preparation method thereof |
| CN115926420A (en) * | 2022-12-30 | 2023-04-07 | 宁波福天新材料科技有限公司 | Polycarbonate composite material and preparation method thereof |
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