CN101787164A - Scratch-resistant resin blend and preparation method thereof - Google Patents
Scratch-resistant resin blend and preparation method thereof Download PDFInfo
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- CN101787164A CN101787164A CN200910198475A CN200910198475A CN101787164A CN 101787164 A CN101787164 A CN 101787164A CN 200910198475 A CN200910198475 A CN 200910198475A CN 200910198475 A CN200910198475 A CN 200910198475A CN 101787164 A CN101787164 A CN 101787164A
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Abstract
The invention relates to scratch-resistant resin blend which comprises the following components and formula: 0 to 75 weight parts of SAN, 10 to 80 weight parts of polymer which contains methyl methacrylate, 10 to 100 weight parts of rubber modified copolymer which contains styrene, and 0.5 to 3 weight parts of anti-wear agent. Compared with the prior art, the invention has the advantages of low friction coefficient, high surface hardness, good processing performance, good toughness and the like.
Description
Technical field
The present invention relates to a kind of scratch-resistant resin blend and preparation method thereof, or rather, the present invention relates to a kind of blend of comparing with the resin of routine with higher surface hardness and lower skin friction coefficient.
Background technology
Current, indicating meter, especially in recent years popular LCD TV and plasm TV, its housing no longer has been simple housing, has more possessed the function of decorating, when the graft copolymer ABS material of acrylonitrile-butadiene-styrene (ABS) is used for display housing, because the anti-scratch property of ABS is bad, pencil hardness is not high yet, is easy to generate surface scratch, influence outward appearance, so often need surface lacquer when using ABS as housing.The spraying coating line investment is big, and seriously polluted, qualification rate is low, virtually, has just improved material cost greatly.
The ordinary method of improving the ABS scratch resistance is the content that increases vinyl cyanide in the ABS resin (being called for short AN) compound, the molecular weight that reduces rubber content, increase acrylonitrile-styrene (being called for short SAN) copolymer resin.Yet the content that increases acrylonitrile compound can cause the yellow of the course of processing and reduce material flowability.Reduce rubber content and can reduce toughness of material, cause material crisp partially.The molecular weight that increases SAN also can reduce the flowability of material, causes the relatively poor processibility of material.
Chinese patent publication number CN 1962749A has introduced the ABS/PMMA alloy that improves surface hardness.But this alloy material frictional coefficient does not improve, and wear resistance is improved very limited.
Chinese patent publication number CN 1986633A has introduced the ABS modified resin with high surface hardness, and the realization approach also is the PMMA by the interpolation high rigidity, on the one hand, frictional coefficient does not reduce, wear-resisting improvement is limited, and on the other hand, the resin shock strength that obtains in this patent is on the low side.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists that a kind of frictional coefficient is low, surface hardness is high, processibility is good, the scratch-resistant resin blend of good toughness and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions: a kind of scratch-resistant resin blend is characterized in that this blend comprises following component and prescription:
SAN 0-75 weight part;
Contain Polymerization of Methyl thing 10～80 weight parts;
Modified rubber contain cinnamic copolymer 1 0～100 weight part;
Anti-wear agent 0.5～3 weight part.
Described SAN is the multipolymer of vinylbenzene and vinyl cyanide, and wherein acrylonitrile content is 16-36wt%, and number-average molecular weight Mn is 9～150,000.
The number-average molecular weight Mn of described SAN is 10～120,000.
SAN select for use molecular weight be higher than 120,000 or AN content be higher than 30wt%, the mechanical property of materials, surface hardness can improve, but mobile can the reduction selects for use the SAN molecular weight to be lower than 100,000, mechanical strength can be on the low side.
The described multipolymer that contains methyl methacrylate is one or more in polymethylmethacrylate, the copolymer of methyl methacrylatestyrene.
The content of methyl methacrylate is 95-100% in the described polymethylmethacrylate.
The content of methyl methacrylate is 40-80% in the described copolymer of methyl methacrylatestyrene.
The described multipolymer that contains methyl methacrylate can be at least a in polymethylmethacrylate (be called for short PMMA), the copolymer of methyl methacrylatestyrene (being called for short MS).
Described PMMA is a polymethylmethacrylate, and its MMA content is 98-100%.
PMMA has high rigidity, high gloss, high weatherable characteristics.The introducing of PMMA when improving material hardness, has improved the weathering resistance of material, has prolonged the work-ing life of material, in some cases, can remove the technological process of product surface lacquer from, and reach same high rigidity, high weatherable characteristics.
PMMA can select Atofina, strange beautiful, any a PMMA product that companies such as LG is chemical, Degussa produce for use, selects hardness high, and the mechanical property of materials can improve, and flowability then can reduce.
Described MS is a copolymer of methyl methacrylatestyrene, and its MMA content is 40-80%.
Select the high MS of MMA content for use, material hardness, mechanical property can improve, but mobile can the reduction.
The cinnamic multipolymer that contains of described modified rubber comprises:
Styrene compound 30～75 weight parts;
Propene compound 10～35 weight parts;
Rubber 15～85 weight parts.
Described styrene compound is selected from one or more in vinylbenzene, alpha-methyl styrene, the p-methylstyrene; Described propene compound is selected from one or more in vinyl cyanide, the methyl methacrylate; Described rubber is selected from one or more in polybutadiene rubber, acrylic elastomer, the ethylene-propylene-diene ternary rubber.
Described rubber size is 0.05～2.3 micron.
Modified rubber contain the graft copolymer that cinnamic multipolymer can be an acrylonitrile-butadiene-styrene (ABS), be called for short the ABS rubber powder, butadiene content can be 40～70%, preferred 45-65%, rubber size can be 0.1～1 micron, preferred 0.2～0.4 micron.
Modified rubber contain the acrylonitrile-butadiene-styrene (ABS) particle that cinnamic multipolymer can be mass polymerization, butadiene content can be 10～20%, rubber size can be 0.05～2.3 micron, the preferred rubber particle diameter is the distribution of two peaks, as: 0.1～0.5 micron at peak, 1.0～2.0 microns at another peak.
Modified rubber contain the graft copolymer that cinnamic multipolymer can be an acrylonitrile-acrylate-styrene, be called for short the ASA rubber powder, acrylate content can be 40～70%, preferred 45-65%, rubber size can be 0.1～1 micron, preferred 0.2～0.6 micron.
Modified rubber contain the graft copolymer that cinnamic multipolymer can be vinyl cyanide-ethylene-propylene rubber-styrene-alkene, be called for short the AES rubber powder, ethylene-propylene rubber(EPR) content can be 40～80%, preferred 50-75%, rubber size can be 0.1～1 micron, preferred 0.2～0.4 micron.
Modified rubber contain the terpolymer that cinnamic multipolymer can be the butadiene-styrene-methyl methacrylate of emulsion grafting polymerization (be called for short MBS), butadiene content can be 50～80%, preferred 75%, rubber size can be 0.05～0.5, preferred 0.1～0.3 micron.
The cinnamic multipolymer that contains of modified rubber can be methyl methacrylate-acrylonitrile-butadiene-styrene resin (being called for short MABS), it has the cantilever-type impact strength of about 130～400J/m of the thickness of sample measurement that utilizes 1/8 inch, the MABS that preferably has 250～400J/m shock strength.
Described anti-wear agent is a polysiloxane, and the main chain of this polysiloxane is a polysiloxane, and two ends are organic groups.
Described organic group comprises alkyl, phenyl, styroyl.
A kind of method for preparing scratch-resistant resin blend is characterized in that: this method may further comprise the steps:
(1) takes by weighing raw material by weight ratio: the SAN0-75 weight part; Contain Polymerization of Methyl thing 10～80 weight parts; Modified rubber contain cinnamic copolymer 1 0～100 weight part; Anti-wear agent 0.5～3 weight part;
(2) all raw materials are put into high-speed mixer and mixing 2-5 minute;
(3) discharging;
(4) mixed raw material is put into the dual-screw-stem machine extruding pelletization, the rotating speed of screw rod machine is 180-600 rev/min, and temperature is 190-240 ℃.
Polysiloxane is an inorganic materials, incompatible with matrix resin, can move to material surface, reduce the material friction coefficient thereby play, improve the purpose of scratch resistance, and organic group in the modified polyorganosiloxane and matrix resin consistency are better, make polysiloxane can be retained in material surface for a long time, and can not move out of material, guaranteed the long-lasting of material scrape resistant.In addition, the polysiloxane of organic group modification, owing to matrix resin better consistency is arranged, the dispersion in material is fine, has guaranteed the homogeneity of material scrape resistant.
Except said components, described scratch-resistant resin blend can randomly also contain the various conventional additives of 0.01-3.0wt%, preferred 0.1-1wt%, for example following material, or their mixture.
Oxidation inhibitor, can be phenols (Irganox 1076, Irganox 1010, E-330), contain thioesters class (as DLTP, DSTP), phosphorous acid esters (TNP, Irganox 168), phosphiinic acid ester, cumarone, metal passivator (as MD 1024, MD 1025), the compound of preferred 0.1-0.3wt% hindered phenol antioxygen and 0.1-0.3wt% phosphite oxidation inhibitor, hindered phenol antioxygen can be Irganox 1076, phosphite oxidation inhibitor can be Irganox 168, and its effect is the thermostability that improves in materials processing and the use.
UV absorption agent and photostabilizer, can be benzotriazole (as UV-P, UV-327, UV-326), benzophenone (as UV-9, UV-531), hindered amine (as Tinuvin-770, Tinuvin-944), the compound of preferred 0.1-0.4wt% benzotriazole and 0.1-0.4wt% hindered amine, its effect are the weather resistances that improves material.
Lubricant can be low molecule ester class, amides, stearate, stearic acid complex ester class, PE wax, preferred 0.1-0.5wt% pentaerythritol stearate, and its effect is to improve Drawing abillity.
Compared with prior art, in order to improve the scratch resistance of resin, the present invention has developed and introduced the multipolymer raising material surface hardness that contains methyl methacrylate in ABS, adds silicone lubricant simultaneously and reduces the material friction coefficient, has comprehensively improved the scratch resistance of material.
Scratch-resistant resin blend of the present invention has been selected the multipolymer that contains methyl methacrylate of high surface hardness for use, give the material higher surface hardness, give material lower frictional coefficient by the polysiloxane anti-wear agent of selecting the organic group modification for use again, comprehensively improved the scratch resistance of resin, simultaneously owing to contain the adding of the multipolymer of methyl methacrylate, give material higher weathering resistance and surface luster, and kept original impact property of resin and good processibility.When being used to make the housing of household electrical appliance, office equipment, give that product is attractive in appearance, rub resistance, characteristics such as weather-proof, the technological process that can remove surface lacquer from can be that household electrical appliances manufacturers saves about 50% cost, economic benefit is big, market application foreground is wide.
Embodiment
The present invention is further detailed explanation below in conjunction with specific embodiment.
A is SAN in the present embodiment, and B1 is PMMA, and B2 is MS, C1 is that rubber content is 55% ABS rubber powder, and C2 is MBS, and C3 is that rubber content is 14% MABS pellet, C4 is that rubber content is 55% ASA powder, and C5 is that rubber content is 70% AES powder, and D is the anti-wear agent polysiloxane.
The prescription of embodiment 1～8 and Comparative Examples 1～4 sees Table one.
Table one
The whole components of embodiment 1～8 in the last table are joined in the high-speed mixer respectively in proportion mix, feed then and melt extrude granulation in the twin screw extruder, the barrel zone temperature of forcing machine is 190～240 ℃, and screw speed is 400rpm.
With the above ABS resin composition for preparing according to embodiment 1～8 and Comparative Examples 1～4, prepare test bars according to same injecting condition, concrete injecting condition is, injection temperature: 190-240 ℃, die temperature: 40-80 ℃, injection pressure: 40-90MPa, injection moulding speed: 30-70mm/s.Concrete physicals test item such as following table two:
| Project | Test condition | Testing standard | Unit |
| Tensile strength | ?50mm/min | ??ASTM?D638 | ?MPa |
| Flexural strength | ?3mm/min | ??ASTM?D790 | ?MPa |
| Modulus in flexure | ?3mm/min | ??ASTM?D790 | ?MPa |
| Melting index | ?220℃*10kg | ??ASTM?D1238 | ?g/10min |
| Notched izod intensity | ?3.2mm，23℃ | ??ASTM?D256 | ?J/m |
The properties of sample that sample that embodiment 1～8 makes and Comparative Examples 1～4 make sees Table three.
Table three
From table three as can be seen: on the one hand, along with the increase of methyl methacrylate (M) content, Rockwell hardness, the pencil hardness of material are improved, and scraping and wiping resistance performance also improves; On the other hand, compare with the Comparative Examples that does not contain anti-wear agent, the embodiment among the present invention but still relies on anti-wear agent to reduce the effect of frictional coefficient under the prerequisite that does not have higher Rockwell hardness, pencil hardness, obtains the excellent in scratching resistance energy.The present invention is the advantage of the two comprehensively, has both utilized M to improve the hardness of material, and the adding of passing through anti-wear agent again reduces the frictional coefficient of material, has greatly improved the scraping and wiping resistance performance of material.
Embodiment 9～13
A is SAN in the present embodiment, B1 is PMMA, B2 is MS, C1 is that rubber content is 55% ABS rubber powder, C2 is MBS, C3 is that rubber content is 14% MABS pellet, it has the cantilever-type impact strength of about 130～400J/m of the thickness of sample measurement that utilizes 1/8 inch, the MABS that preferably has 250～400J/m shock strength, C4 is that rubber content is 55% ASA powder, C5 is that rubber content is 70% AES powder, and C6 is the acrylonitrile-butadiene-styrene (ABS) particle of mass polymerization, and C7 is a styrene compound, propene compound, the modified rubber that rubber mix forms contain cinnamic multipolymer.
The formula material table four of embodiment 9～13.
Table four
Adopt the prescription of the scratch-resistant resin blend of above-mentioned raw materials preparation to see Table five:
| Raw material | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 |
| ??A | ??2 | ??10 | ??30 | ??50 | ??60 |
| ??B1 | ??10 | ??20 | ??50 | ??30 | ??30 |
| ??B2 | ??10 | ??30 | ??20 | ??12 | ??30 |
| ??C1 | ??0 | ??23 | ??0 | ??0 | ??22 |
| ??C2 | ??15 | ??0 | ??15 | ??0 | ??0 |
| ??C3 | ??0 | ??0 | ??0 | ??10 | ??0 |
| ??C4 | ??0 | ??10 | ??0 | ??10 | ??0 |
| ??C5 | ??0 | ??18 | ??20 | ??0 | ??0 |
| ??C6 | ??0 | ??0 | ??25 | ??20 | ??0 |
| ??C7 | ??10 | ??0 | ??0 | ??0 | ??30 |
| ??D | ??0.5 | ??2 | ??1.5 | ??0.8 | ??3 |
Take by weighing raw material by table five weight proportion; All raw materials were put into high-speed mixer and mixing 2-5 minute; Discharging; Mixed raw material is put into the dual-screw-stem machine extruding pelletization, and the rotating speed of screw rod machine is 180-600 rev/min, and temperature is 190-240 ℃.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (13)
1. a scratch-resistant resin blend is characterized in that, this blend comprises following component and prescription:
SAN 0-75 weight part;
Contain Polymerization of Methyl thing 10～80 weight parts;
Modified rubber contain cinnamic copolymer 1 0～100 weight part;
Anti-wear agent 0.5～3 weight part.
2. a kind of scratch-resistant resin blend according to claim 1 is characterized in that, described SAN is the multipolymer of vinylbenzene and vinyl cyanide, and wherein acrylonitrile content is 16-36wt%, and number-average molecular weight Mn is 9～150,000.
3. a kind of scratch-resistant resin blend according to claim 1 is characterized in that, the number-average molecular weight Mn of described SAN is 10～120,000.
4. a kind of scratch-resistant resin blend according to claim 1 is characterized in that, the described multipolymer that contains methyl methacrylate is one or more in polymethylmethacrylate, the copolymer of methyl methacrylatestyrene.
5. a kind of scratch-resistant resin blend according to claim 4 is characterized in that, the content of methyl methacrylate is 95-100% in the described polymethylmethacrylate.
6. a kind of scratch-resistant resin blend according to claim 4 is characterized in that, the content of methyl methacrylate is 40-80% in the described copolymer of methyl methacrylatestyrene.
7. a kind of scratch-resistant resin blend according to claim 1 is characterized in that, the cinnamic multipolymer that contains of described modified rubber comprises:
Styrene compound 30～75 weight parts;
Propene compound 10～35 weight parts;
Rubber 15～85 weight parts.
8. a kind of scratch-resistant resin blend according to claim 7 is characterized in that described styrene compound is selected from one or more in vinylbenzene, alpha-methyl styrene, the p-methylstyrene; Described propene compound is selected from one or more in vinyl cyanide, the methyl methacrylate; Described rubber is selected from one or more in polybutadiene rubber, acrylic elastomer, the ethylene-propylene-diene ternary rubber.
9. a kind of scratch-resistant resin blend according to claim 1, it is characterized in that the graft copolymer (ABS rubber powder) that to contain cinnamic multipolymer rubber be commercially available acrylonitrile-butadiene-styrene (ABS) of described modified rubber, the acrylonitrile-butadiene-styrene (ABS) particle of mass polymerization, the graft copolymer of acrylonitrile-acrylate-styrene (ASA rubber powder), the graft copolymer of vinyl cyanide-ethylene-propylene rubber-styrene-alkene (AES rubber powder), the terpolymer of the butadiene-styrene-methyl methacrylate of emulsion grafting polymerization (MBS) or methyl methacrylate-acrylonitrile-butadiene-styrene resin (being called for short MABS).
10. according to claim 7 or 8 or 9 described scratch-resistant resin blends, it is characterized in that described rubber size is 0.05～2.3 micron.
11. scratch-resistant resin blend according to claim 1 is characterized in that: described anti-wear agent is a polysiloxane, and the main chain of this polysiloxane is a polysiloxane, and two ends are organic groups.
12. scratch-resistant resin blend according to claim 11 is characterized in that: described organic group comprises alkyl, phenyl, styroyl.
13. a method for preparing scratch-resistant resin blend as claimed in claim 1 is characterized in that: this method may further comprise the steps:
(1) takes by weighing raw material by weight ratio: the SAN0-75 weight part; Contain Polymerization of Methyl thing 10～80 weight parts; Modified rubber contain cinnamic copolymer 1 0～100 weight part; Anti-wear agent 0.5～3 weight part;
(2) all raw materials are put into high-speed mixer and mixing 2-5 minute;
(3) discharging;
(4) mixed raw material is put into the dual-screw-stem machine extruding pelletization, the rotating speed of screw rod machine is 180-600 rev/min, and temperature is 190-240 ℃.
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