CN102002206A - High-glossiness high-toughness scratch resistant molding composition - Google Patents
High-glossiness high-toughness scratch resistant molding composition Download PDFInfo
- Publication number
- CN102002206A CN102002206A CN2010105975705A CN201010597570A CN102002206A CN 102002206 A CN102002206 A CN 102002206A CN 2010105975705 A CN2010105975705 A CN 2010105975705A CN 201010597570 A CN201010597570 A CN 201010597570A CN 102002206 A CN102002206 A CN 102002206A
- Authority
- CN
- China
- Prior art keywords
- quality
- butadiene
- acrylonitrile
- copolymer
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a high-glossiness high-toughness scratch resistant molding composition. The composition comprises at least two acrylonitrile-butadiene-styrene graft copolymers with specific rubber phase grain diameter, rubber content and fondant flowing characteristics, at least one of an acrylonitrile-styrene copolymer with specific fondant flowing characteristics, polymethylmethacrylate, polycarbonate and acrylonitrile-styrene-acrylate copolymer, a polymethylmethacrylate-butadiene-styrene copolymer with nuclear shell structure, an oil soluble dye system and an antioxidant system. A molding product has excellent impact resistant toughness, improved surface high glossiness and proper scratch resistant effect.
Description
Technical field
The present invention relates to the anti-zoned trace moulding compound of a kind of high smooth high-ductility, belong to polymer processing field.
Background technology
Acrylonitrile-butadiene-styrene copolymer (ABS, Acrylonitrile-Butadiene-Styrene) owing to rationally utilized each copolymerization component advantage, but thereby have good processing fluidity, low-temperature impact toughness and excellent characteristics such as dyeability concurrently, be household electrical appliances with using maximum resin kinds in the engineering plastics, be mainly used in the housing of liner, video and audio recording machine, air-conditioning, suction cleaner, telephone set, mellotron and other small household appliances of making televisor, computer, refrigerator and inner structural members etc.Parameters such as the ratio by changing ABS three components, polymerization process, rubber phase grain size can be produced a series of ABS kinds with different shock strengths, flow characteristics, satisfy different application demands.
Along with the fast development of household electric appliances and the continuous lifting of people's consumers demand, in some Application Areas, require injection-molded item not only to have excellent toughness, also require to have high surface luster and good scratch resistance ability, for example be applied to frame, the base of dull and stereotyped LCD TV, goods such as notebook computer casing and sound equipment housing, people always wish that again material has good superiority of effectiveness on the other hand.Single ABS resin system is low owing to the desired rubber phase content of high-surface gloss, particle diameter is little contradicts greatly with the desired rubber phase content of high impact-resistant toughness height, particle diameter, be difficult to meet the demands simultaneously, and the general surface hardness of ABS goods is on the low side, the scratch resistance performance is poor, can't satisfy the special applications demand.Traditional solution is the processing of spraying paint on the surface of common injection-molded item, thereby satisfy requirement to its surface luster and scratch resistance performance, but spray paint to handle and not only increased manufacturing procedure, material cost is risen, the organic solvent contaminate environment of spraying paint and adopting, and the operator is worked the mischief, and simultaneously, heat cured top coat has also brought disadvantageous effect to the recycling of thermoplastic articles.
CN101058623 discloses a kind of preparation method of the high gloss injection moulding level abs polymer based on continuous bulk, by improvement to synthesis technique, reaction obtains to have the graft copolymer of different rubber sizes and distribution thereof under given conditions, obtain the good high glossiness injection grade abs polymer of over-all properties, because foremost from the material synthetic, the suitable handiness of this method is lower, and is limited to the surface luster lifting of goods simultaneously, improves very little to goods scratch resistance performance; CN1404506 discloses a kind of the have workability of improvement and the ABS moulding compound of high glossiness, said composition contains the butadiene polymer latices of 3 kinds of regulation particle diameters, size distribution and gel contents from synthetic angle preparation, wherein at least a polybutadiene latex makes by seeding polymerization, but this method can't be taken into account high gloss, high tenacity and the scratch resistance performance of material simultaneously.CN101531801 discloses a kind of preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze, this method is by the melt flow control phase structure of multi-phase ingredients, acquisition has high gloss and excellent toughness ABS moulding compound concurrently, and its over-all properties and surface effect also can further promote.
We further discover, a kind of have a particular core shell structure, rubber phase unit with polyhutadiene is a nuclear, polymethylmethacrylate-butadiene-styrene copolymer the component that constitutes shell with the polystyrene-methyl methacrylate copolymer unit of vitreous state is introduced the high-light ABS alloy system, not only can significantly improve the impelling strength of ABS alloy, and very little to the intensity and the modulus influence of material.Simultaneously, the introducing of polymethylmethacrylate-butadiene-styrene copolymer, can play the effect of regulating each disperse phase refractive index of resin to opaque ABS system, thereby can to a certain degree improve the transparency of resin system, the component that dyes in the resin combination is more effectively played a role, demonstrate more stable and have more the dyeing form and aspect of expressive force, thereby improve the high light effect of resin system.
Nucleocapsid structure polymethylmethacrylate-butadiene-styrene copolymer is synthetic with emulsion polymerization usually, as grafted monomer, grafting forms the nucleocapsid structure polymkeric substance on the butadiene polymer latices particle by a certain proportion of vinylbenzene and methyl methacrylate.
We further discover, moulding compound system that and if only if comprises the ABS component of rubber phase particle diameter and flow characteristics graded, and be characterized as and contain the greater particle size rubber phase and have less melt flow index, contain than the small particle size rubber phase and have the higher melt flow index, and comprise the polymethylmethacrylate-butadiene-styrene copolymer that possesses nucleocapsid structure simultaneously, and acrylonitritrile-styrene resin, polymethylmethacrylate, polycarbonate, at least a in the acrylonitrile-styrene-acrylic ester copolymer can have best high light effect with the moulding compound of its formation.
Discover that further this system cooperates the dyestuff with oily molten characteristic black, can obtain deep more penetrating black phase, makes its injection-molded item surface effect obtain more significant lifting.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, anti-zoned trace moulding compound of a kind of high smooth high-ductility and preparation method thereof is provided, said composition is by the ABS with different structure performance characteristic and melt flow characteristics, acrylonitritrile-styrene resin, polymethylmethacrylate, polycarbonate, at least a in the acrylonitrile-styrene-acrylic ester copolymer, polymethylmethacrylate-butadiene-styrene copolymer with nucleocapsid structure, oil-soluble colourant system and antioxidant system constitute, and its moulded parts has the surperficial high gloss effect of enhanced toughness and improvement.
Purpose of the present invention is realized by following technical measures.Wherein said raw material umber is parts by weight except that specified otherwise.
The anti-zoned trace moulding compound of a kind of high smooth high-ductility, said composition comprises:
A) acrylonitrile-butadiene-phenylethene grafted copolymer (A)
B) acrylonitrile-butadiene-phenylethene grafted copolymer (B)
C) at least a (C) in acrylonitritrile-styrene resin, polymethylmethacrylate, polycarbonate, the acrylonitrile-styrene-acrylic ester copolymer
D) be the polymethylmethacrylate-butadiene-styrene copolymer with nucleocapsid structure (D) that nuclear, vinylbenzene and methyl methacrylate polymer unit constitute shell with the polyhutadiene unit
E) dye system
F) antioxidant systems
Wherein said graft copolymer A for the rubber phase median size that adopts the emulsion polymerization preparation less than 200nm, rubber phase content less than the 30%(mass percent, down with) acrylonitrile-butadiene-phenylethene grafted copolymer.
Wherein said graft copolymer B for the rubber phase median size that adopts the emulsion polymerization preparation greater than 200nm, rubber phase content greater than 30% acrylonitrile-butadiene-phenylethene grafted copolymer.
Wherein said acrylonitritrile-styrene resin, polymethylmethacrylate, polycarbonate, acrylonitrile-styrene-acrylic ester copolymer are relevant powdery or granular resin product, such material is the high gloss effect of Lifting Modules molding composition further, and gives resin combination suitable anti-zoned trace effect.
Wherein said is the polymethylmethacrylate-butadiene-styrene copolymer with nucleocapsid structure that nuclear, vinylbenzene and methyl methacrylate polymer unit constitute shell with the polyhutadiene unit, such material is synthetic with emulsion polymerization, by vinylbenzene and methyl methacrylate is grafted monomer, grafting forms the nucleocapsid structure acquisition on the butadiene polymer latices particle, can synthesize voluntarily or buy from market usually.
Wherein the melt flow index magnitude relationship of acrylonitrile-butadiene-phenylethene grafted copolymer A, acrylonitrile-butadiene-phenylethene grafted copolymer B and component C is component C＞graft copolymer A＞graft copolymer B, and the melt flow index of component C is greater than the melt flow index of component D.
Wherein said dye system is made of the black oil soluble dye and the colour carbon black of heatproof greater than 260 ℃.
Wherein said antioxidant system is the general antioxidant systems of ABS.
Each set of dispense ratio of the anti-zoned trace moulding compound of wherein said high light high-ductility is: graft copolymer A accounts for 10 quality %-80 quality %, graft copolymer B accounts for 10 quality %-quality 80%, component C accounts for 5 quality %-50 quality %, component D accounts for 5 quality %-40 quality %, dye system accounts for 0.5 quality %-8 quality %, and oxidation inhibitor accounts for 0.05 quality %-1 quality %.
Present method has following obvious advantage:
1. each component of composition is the resins for universal use kind, need not synthetic system and technology are changed, and can adjust flexibly at concrete application demand;
2. more excellent impact toughness and outstanding surperficial high gloss and form and aspect effect;
3. composition can be directly used in injection moulding, need not to spray paint to handle promptly to have splendid surface luster and good scratch resistance performance, more environmental protection.
Embodiment
Below be the present invention to be specifically described by embodiment; be necessary to be pointed out that at this following examples can only be used for the present invention is further specified; can not be interpreted as limiting the scope of the invention; the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above, and described umber is mass parts.
Embodiment 1:With 40 parts of rubber phase content is 25%, the about 150nm of rubber phase median size, melting index is 1.8 ABS, 35 parts of rubber phase content are 35%, the about 450nm of rubber phase median size, melting index is 1.2 ABS, 20 parts of melting index are 4.2 acrylonitritrile-styrene resin, 5 parts of polymethylmethacrylate-butadiene-styrene nucleocapsid structure multipolymers, 3 parts of look mothers and oxidation inhibitor black by the molten type dye of oil and that high-carbon black pigment constitutes mix for 0.1 part, melt extrude granulation by twin screw extruder, the extruding pelletization thing is made sample through injection molding, carry out the correlated performance test.
Embodiment 2:With 30 parts of rubber phase content is 20%, the about 130nm of rubber phase median size, melting index is 2.5 ABS, 30 parts of rubber phase content are 35%, the about 400nm of rubber phase median size, melting index is 1.2 ABS, 30 parts of melting index are 3.6 polymethylmethacrylate, 10 parts of polymethylmethacrylate-butadiene-styrene nucleocapsid structure multipolymers, 4 parts of look mother and 0.5 part of oxidation inhibitor black by the molten type dye of oil and that high-carbon black pigment constitutes mix, melt extrude granulation by twin screw extruder, the extruding pelletization thing is made sample through injection molding, carry out the correlated performance test.
Embodiment 3:With 25 parts of rubber phase content is 20%, the about 130nm of rubber phase median size, melting index is 2.5 ABS, 30 parts of rubber phase content are 35%, the about 450nm of rubber phase median size, melting index is 1.0 ABS, 25 parts of melting index are 3.2 acrylonitrile-styrene-acrylic ester copolymer, 20 parts of polymethylmethacrylate-butadiene-styrene nucleocapsid structure multipolymers, 3 parts of look mothers and oxidation inhibitor black by the molten type dye of oil and that high-carbon black pigment constitutes mix for 0.1 part, melt extrude granulation by twin screw extruder, the extruding pelletization thing is made sample through injection molding, carry out the correlated performance test.
Embodiment 4:With 50 parts of rubber phase content is 20%, the about 130nm of rubber phase median size, melting index is 2.5 ABS, 10 parts of rubber phase content are 35%, the about 450nm of rubber phase median size, melting index is 1.0 ABS, 5 parts of melting index are 3.2 acrylonitrile-styrene-acrylic ester copolymer, 35 parts of polymethylmethacrylate-butadiene-styrene nucleocapsid structure multipolymers, 2 parts of look mothers and oxidation inhibitor black by the molten type dye of oil and that high-carbon black pigment constitutes mix for 0.2 part, melt extrude granulation by twin screw extruder, the extruding pelletization thing is made sample through injection molding, carry out the correlated performance test.
Comparison example:Is 30% with 100 parts of general injection mouldings with ABS(rubber phase content, and melting index is 1.8) mix for 0.2 part with 5 parts of middle colour carbon black look mothers and oxidation inhibitor, make sample through injection molding, carry out the correlated performance test.
Table 1. scratch-resistant lacquer-free ABS moulding composition with high glaze relevant test data
| Foam sample | Notched Izod impact strength (kJ/m 2） | Surface gloss (MPa) | The surface pencil hardness |
| 1 | 22.2 | 101 | HB |
| Embodiment 2 | 25.6 | 105 | H |
| Embodiment 3 | 23.5 | 103 | HB |
| Embodiment 4 | 22.3 | 103 | HB |
| Comparison example | 12.7 | 83 | B |
Claims (6)
1. one kind high anti-zoned trace moulding compound of smooth high-ductility, said composition comprises:
A) acrylonitrile-butadiene-phenylethene grafted copolymer (A)
B) acrylonitrile-butadiene-phenylethene grafted copolymer (B)
C) at least a (C) in acrylonitritrile-styrene resin, polymethylmethacrylate, polycarbonate, the acrylonitrile-styrene-acrylic ester copolymer
D) be the polymethylmethacrylate-butadiene-styrene copolymer with nucleocapsid structure (D) that nuclear, vinylbenzene and methyl methacrylate polymer unit constitute shell with the polyhutadiene unit
E) dye system
F) antioxidant systems.
2. according to the anti-zoned trace moulding compound of the described a kind of high smooth high-ductility of claim 1, wherein said acrylonitrile-butadiene-phenylethene grafted copolymer A for the rubber phase median size that adopts the emulsion polymerization preparation less than 200nm, rubber phase content acrylonitrile-butadiene-phenylethene grafted copolymer less than 30 quality %.
3. according to the anti-zoned trace moulding compound of the described a kind of high smooth high-ductility of claim 1, wherein said acrylonitrile-butadiene-phenylethene grafted copolymer B for the rubber phase median size that adopts the emulsion polymerization preparation greater than 200nm, rubber phase content acrylonitrile-butadiene-phenylethene grafted copolymer greater than 30 quality %.
4. according to the anti-zoned trace moulding compound of the described a kind of high smooth high-ductility of claim 1, wherein the melt flow index magnitude relationship of acrylonitrile-butadiene-phenylethene grafted copolymer A, acrylonitrile-butadiene-phenylethene grafted copolymer B and component C is component C＞graft copolymer A＞graft copolymer B, and the melt flow index of component C is greater than the melt flow index of component D.
5. according to the anti-zoned trace moulding compound of the described a kind of high smooth high-ductility of claim 1, wherein dye system is made of the black oil soluble dye and the colour carbon black of heatproof greater than 260 ℃.
6. according to the anti-zoned trace moulding compound of the described a kind of high smooth high-ductility of claim 1, its composition proportioning is: graft copolymer A accounts for 10 quality %-80 quality %, graft copolymer B accounts for 10 quality %-quality 80%, component C accounts for 10 quality %-50 quality %, component D accounts for 5 quality %-40 quality %, dye system accounts for 0.5 quality %-8 quality %, and oxidation inhibitor accounts for 0.05 quality %-1 quality %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105975705A CN102002206A (en) | 2010-12-21 | 2010-12-21 | High-glossiness high-toughness scratch resistant molding composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105975705A CN102002206A (en) | 2010-12-21 | 2010-12-21 | High-glossiness high-toughness scratch resistant molding composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102002206A true CN102002206A (en) | 2011-04-06 |
Family
ID=43809928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105975705A Pending CN102002206A (en) | 2010-12-21 | 2010-12-21 | High-glossiness high-toughness scratch resistant molding composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102002206A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658713A (en) * | 2013-09-16 | 2016-06-08 | 英力士苯领集团股份公司 | Deep black thermoplastic molding compositions having high gloss and production thereof |
| CN106433064A (en) * | 2015-08-13 | 2017-02-22 | 三星Sdi株式会社 | Thermoplastic resin composition and article comprising the same |
| CN112795161A (en) * | 2020-12-30 | 2021-05-14 | 广州辰东新材料有限公司 | PC/ABS polymer alloy for improving weld marks of digital product shell and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282762A (en) * | 1999-07-29 | 2001-02-07 | 上海杰事杰新材料股份有限公司 | High-flowability, impact-resistant and electrically conductive temary acrylonitrile-butadiene-styrene copolymer and its preparing process |
| CN101531801A (en) * | 2009-04-20 | 2009-09-16 | 四川长虹模塑科技有限公司 | Preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze |
| CN101671470A (en) * | 2009-10-13 | 2010-03-17 | 青岛国恩科技发展有限公司 | Fire-retardant high-ductility composite material and manufacturing method thereof |
| CN101759980A (en) * | 2008-12-23 | 2010-06-30 | 上海普利特复合材料股份有限公司 | PC / ABS composite material with stable color and preparation method thereof |
| CN101875766A (en) * | 2009-10-29 | 2010-11-03 | 深圳市科聚新材料有限公司 | Special low-warpage composite material for notebook computer and preparation method thereof |
-
2010
- 2010-12-21 CN CN2010105975705A patent/CN102002206A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1282762A (en) * | 1999-07-29 | 2001-02-07 | 上海杰事杰新材料股份有限公司 | High-flowability, impact-resistant and electrically conductive temary acrylonitrile-butadiene-styrene copolymer and its preparing process |
| CN101759980A (en) * | 2008-12-23 | 2010-06-30 | 上海普利特复合材料股份有限公司 | PC / ABS composite material with stable color and preparation method thereof |
| CN101531801A (en) * | 2009-04-20 | 2009-09-16 | 四川长虹模塑科技有限公司 | Preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze |
| CN101671470A (en) * | 2009-10-13 | 2010-03-17 | 青岛国恩科技发展有限公司 | Fire-retardant high-ductility composite material and manufacturing method thereof |
| CN101875766A (en) * | 2009-10-29 | 2010-11-03 | 深圳市科聚新材料有限公司 | Special low-warpage composite material for notebook computer and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658713A (en) * | 2013-09-16 | 2016-06-08 | 英力士苯领集团股份公司 | Deep black thermoplastic molding compositions having high gloss and production thereof |
| CN106433064A (en) * | 2015-08-13 | 2017-02-22 | 三星Sdi株式会社 | Thermoplastic resin composition and article comprising the same |
| CN106433064B (en) * | 2015-08-13 | 2019-08-30 | 乐天尖端材料株式会社 | Thermoplastic resin composition and product comprising it |
| CN112795161A (en) * | 2020-12-30 | 2021-05-14 | 广州辰东新材料有限公司 | PC/ABS polymer alloy for improving weld marks of digital product shell and preparation method and application thereof |
| CN112795161B (en) * | 2020-12-30 | 2022-06-21 | 广州辰东新材料有限公司 | PC/ABS polymer alloy for improving weld marks of digital product shell and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101531801A (en) | Preparation method of scratch-resistant lacquer-free ABS moulding composition with high glaze | |
| CN102250413B (en) | Modified polypropylene composite material of high gloss and low shrinkage and preparation method thereof | |
| CN102952362B (en) | Metallic super-toughened PMMA (polymethyl methacrylate) composite material and preparation method thereof | |
| CN101659766B (en) | Low-shrinkage sprayable PP/PS blend alloy and preparation method thereof | |
| CN102838828B (en) | Bright-black functional black masterbatch for ABS engineering plastics and preparation method thereof | |
| CN101787158B (en) | Directly sprayed polypropylene material and preparation method thereof | |
| CN101649102B (en) | High-gloss composite material and preparation method thereof | |
| CN106519530B (en) | A kind of composite material and preparation method | |
| CN111978673B (en) | High-gloss high-surface-hardness spraying-free ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof | |
| CN101508817A (en) | High-light ABS alloy and method for producing the same | |
| CN101445638A (en) | PMMA/ABS modified resin and method for forming particles thereof | |
| CN103030743A (en) | Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin | |
| CN110218432A (en) | A kind of high tenacity PC/PMMA alloy material and preparation method thereof | |
| CN107011614A (en) | A kind of bumper metal-like exempts from spray coating polypropylene composite and preparation method thereof | |
| CN102532737B (en) | Transparent high-hardness impact-resistant acrylonitrile butadiene styrene (ABS) plastic alloy composition | |
| CN106589584B (en) | Lightweight, scratch-resistant, high luster materials and preparation method thereof and preparing the application in automobile instrument panel | |
| CN106751313A (en) | A kind of PETG and AS blended compound materials and preparation method thereof | |
| CN102002206A (en) | High-glossiness high-toughness scratch resistant molding composition | |
| CN102863731B (en) | Acrylonitrile-butadiene-styrene (ABS) composite plastic, and preparation method and application thereof | |
| KR101555085B1 (en) | Method for producing a Rubber Modified Styrene Resin Using Styrene-Butadiene Copolymer | |
| CN111440409A (en) | Spraying-free plastic and preparation method thereof | |
| CN102181121B (en) | High-fatigue-resistance ABS (Acrylonitrile Butadiene Styrene) resin composition and preparation method thereof | |
| CN112442251B (en) | ABS composite material and preparation method and application thereof | |
| CN102875949B (en) | Toughening filler master batch grain and preparation method thereof | |
| CN104725755A (en) | PMMA (polymethyl methacrylate)/ABS (acrylonitrile-butadiene-styrene) alloy material with high blackness and brightness and preparation method of PMMA/ABS alloy material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110406 |