CN106589880B - A kind of transparent low temperature resistant scratch resistance polycarbonate composite material - Google Patents
A kind of transparent low temperature resistant scratch resistance polycarbonate composite material Download PDFInfo
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- CN106589880B CN106589880B CN201611007124.8A CN201611007124A CN106589880B CN 106589880 B CN106589880 B CN 106589880B CN 201611007124 A CN201611007124 A CN 201611007124A CN 106589880 B CN106589880 B CN 106589880B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The present invention relates to field of polymer composite material, specifically a kind of transparent low temperature resistant scratch resistance polycarbonate composite material, include following components according to parts by weight: 300-800 parts of bisphenol A polycarbonate resin, 100-500 parts of copolymeric siloxane PC resin, 10-50 parts of organic silicon toughener, 50-200 parts of surface hardness improver, 10-100 parts of nanometer anti-scratch master batch, 5-15 parts of auxiliary agent.Copolymeric siloxane PC, surface hardness improver, nanometer anti-scratch master batch are used in combination in the present invention, on the basis of not influencing the light transmittance and basic mechanical performance of PC, improve the surface hardness and cryogenic property of material, surface hardness can be improved to 2H, significantly improve the scratch-resistant performance of product surface, surface gloss and weatherability are also improved, and can increase product surface tension, more easy to clean；Composite material of the invention has good mechanical property and good room temperature and low temperature impact properties.
Description
Technical field
The present invention relates to field of polymer composite material, specifically, being a kind of transparent low temperature resistant scratch resistance polycarbonate
Composite material and preparation method.
Background technique
Polycarbonate is a kind of plastics with good transparency, and excellent combination property, purposes is extremely wide, product
It is widely used in the technical fields such as electronic apparatus, automobile, machine-building, computer.
However, the surface scratch resistance performance of makrolon material is poor, the aesthetic measure of product is largely reduced,
And also result in stress in the scratch that product surface generates and concentrate, PC material product usually, in order to protect appearance, generally
Do coating processing.In order to improve the adhesion strength of polycarbonate, there is patent report to pass through addition PMMA, carbon fiber, glass
Fiber, wollastonite, talcum powder etc. are modified, although surface hardness can achieve 2H, sacrifice HI high impact, the height of PC material
Transparent characteristic, using limited.
Chinese patent literature CN103788610A discloses a kind of high transparency low-temperature impact-resistant fire-retardant polycarbonate composite wood
Material and preparation method thereof, includes following components according to parts by weight: 700~850 parts of polycarbonate resin, 100~250 parts have
Machine silicon is copolymerized PC, 0~30 part of low temperature impact modifiers, 10~40 parts of fire retardant；Wherein the low temperature impact modifiers are
The mixing of one or both of organic silicon toughener, esters of acrylic acid toughener；The fire retardant is decabromodiphenylethane, gathers
The mixing of one or more of bromo carbonic ester, perfluorobutyl potassium sulfonate or diphenyl sulfone sulfonate；The organosilicon is copolymerized PC
For the polycarbonate resin that bisphenol-A and organosilicon are copolymerized, relative molecular weight is 20000~30000.But about a kind of transparent
Low temperature resistant scratch resistance polycarbonate composite material and preparation method thereof yet there are no report.
Summary of the invention
The purpose of the present invention is to provide a kind of intensity height, good toughness, cryogenic property be good, high surface hardness and scratch resistant
PC material, and the preparation method of this material is also provided.
The first aspect of the present invention provides a kind of transparent low temperature resistant scratch resistance polycarbonate composite material, comprising by weight
The following components of number meter: 300-800 parts of bisphenol A polycarbonate resin, 100-500 parts of copolymeric siloxane PC resin, organosilicon
10-50 parts of class toughener, 50-200 parts of surface hardness improver, 10-100 parts of nanometer anti-scratch master batch, 5-15 parts of auxiliary agent.
Wherein, the polycarbonate resin is bisphenol A-type aromatic polycarbonate resin, relative molecular weight 20000
~30000；
The copolymeric siloxane PC resin is the polycarbonate resin of bisphenol-A and copolymeric siloxane, relative molecular weight
It is 20000~30000, content of siloxane is 5~20%；
The organic silicon toughener is that silicon rubber-acrylate is core, and polymethyl methacrylate is the core-shell structure copolymer of shell
The graft copolymer of structure；
The surface hardness improver is to have the acrylate of high-compatibility and being total to for methyl methacrylate with PC
Polymers, molecular weight are 10000~20000；
The nanometer anti-scratch master batch is micro-size silica powder of the partial size in 10~30nm；
The auxiliary agent includes following components according to parts by weight: 3 parts of antioxidant, 4 parts of antiultraviolet additive,
5 parts of processing aid and 1 part of toner.
The antioxidant be phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, by
Hinder one or both of phenol antioxidant 1076.The more preferably mixing of irgasfos 168 and antioxidant 1076.
The antiultraviolet additive is the compound of light stabilizer and ultraviolet absorbing agent.It is furthermore preferred that the light
The weight ratio of stabilizer and the ultraviolet absorbing agent is 1:1.It is further preferred that the light stabilizer is stablized for light
770, light stablizes one of 622；The ultraviolet absorbing agent is one of UV234, UV-328, UV-320.More preferably
Light stablizes the compound of 770 and UV-234.
The processing aid is polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate, the more officials of long chain fatty acids
The mixing of one or more of ester can be rolled into a ball.More preferably pentaerythritol stearate.
The toner is mainly made of pigment and spread powder.
The second aspect of the present invention provides the preparation side of above-mentioned transparent low temperature resistant scratch resistance polycarbonate composite material
Method, comprising the following steps: raw material mixes 2~3 minutes in a high speed mixer, then through twin-screw extrusion at 260~280 DEG C
Machine squeezes out, is cooling, being granulated, gained pellet be molded at 260~280 DEG C after 120 DEG C 4 hours dry standard sample item to get.
The invention has the advantages that:
1, copolymeric siloxane PC, surface hardness improver, nanometer anti-scratch master batch are used in combination, in the light transmission for not influencing PC
On the basis of rate and basic mechanical performance, the surface hardness and cryogenic property of material are improved, surface hardness can be improved to 2H, show
The scratch-resistant performance for improving product surface, surface gloss and weatherability are write, and product surface tension can be increased, be easier to clearly
It is clean；
2, the splendid phase due to copolymeric siloxane PC, surface hardness improver, nanometer anti-scratch master batch, in PC substrate
Capacitive and dispersibility guarantee good light transmittance；The addition of copolymeric siloxane PC, organic silicon toughener be ensure that room temperature and
Low temperature impact properties；
3, composite material of the invention has good mechanical property and good room temperature and low temperature impact properties.
Specific embodiment
It elaborates below with reference to embodiment to specific embodiment provided by the invention.
In the following examples, each raw material uses following compositions:
Polycarbonate resin: being purchased from the bisphenol A-type aromatic polycarbonate resin of Cohan wound company, and relative molecular weight is
20000~30000, model 2405,2805 or 3105；
Copolymeric siloxane PC: it is purchased from Japan and goes out light RC1760, SABIC 1414T；
Organic silicon toughener: Mitsubishi Li Yang company, model S2030 are come from；
Surface hardness improver: Mitsubishi Li Yang company, model H881 are come from；
Nanometer anti-scratch master batch: come from Na Linwei nanosecond science and technology (Shanghai) Co., Ltd., partial size in 10-30nm ultra-fine two
Silica powder；
Irgasfos 168 and antioxidant 1076 come from BASF AG；
Light stablizes 770 and ultraviolet absorbing agent UV-234 from BASF AG.
Process flow promortor: polyethylene wax, oxidized polyethylene wax are manufactured by BASF AG, and pentaerythritol stearate is by beauty
The manufacture of Guo Longsha company, long chain fatty acids polyfunctional group ester are manufactured by German Kening Co., Ltd.
Embodiment 1
By following component (1 part=100g) in parts by weight: PC, the 300 parts of copolymeric siloxanes of 637 parts of models 2805
PC, 50 parts of nanometer anti-scratch master batches, 2 parts of irgasfos 168s, 1 part of antioxidant 1076,5 parts of pentaerythritol stearates, 2 parts of light are steady
Fixed 770,2 parts of ultraviolet absorbing agent UV-234 and 1 part of toner were at high-speed mixer and mixing 2~3 minutes, then at 260~280 DEG C
Double-screw extruding pelletizing, gained pellet are molded into standard sample item after 120 DEG C 4 hours dry at 260~280 DEG C.
Embodiment 2
By following component (1 part=100g) in parts by weight: PC, the 300 parts of copolymeric siloxanes of 537 parts of models 2805
PC, 100 parts of surface hardness improver H881,50 parts of nanometer anti-scratch master batches, 2 parts of irgasfos 168s, 1 part of antioxidant 1076,5 parts
Pentaerythritol stearate, 2 parts of light stablize 770,2 parts of ultraviolet absorbing agent UV-234 and 1 part of toner high-speed mixer and mixing 2~
3 minutes, the then double-screw extruding pelletizing at 260~280 DEG C, gained pellet was after 120 DEG C 4 hours dry at 260~280 DEG C
Under be molded into standard sample item.
Embodiment 3
By following component (1 part=100g) in parts by weight: PC, the 300 parts of copolymeric siloxanes of 507 parts of models 2805
PC, 100 parts of surface hardness improver H881,30 parts of organic silicon toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of antioxygens
168,1 parts of antioxidant 1076s of agent, 5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultraviolet absorbing agent UV-234 and 1
Part toner was at high-speed mixer and mixing 2~3 minutes, the then double-screw extruding pelletizing at 260~280 DEG C, and gained pellet is through 120 DEG C
Standard sample item is molded at 260~280 DEG C after 4 hours dry.
Embodiment 4
By following component (1 part=100g) in parts by weight: PC, the 300 parts of copolymeric siloxanes of 487 parts of models 2805
PC, 100 parts of surface hardness improver H881,50 parts of organic silicon toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of antioxygens
168,1 parts of antioxidant 1076s of agent, 5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultraviolet absorbing agent UV-234 and 1
Part toner was at high-speed mixer and mixing 2~3 minutes, the then double-screw extruding pelletizing at 260~280 DEG C, and gained pellet is through 120 DEG C
Standard sample item is molded at 260~280 DEG C after 4 hours dry.
Embodiment 5
By following component (1 part=100g) in parts by weight: PC, the 300 parts of copolymeric siloxanes of 537 parts of models 2805
PC, 50 parts of organic silicon toughener S2030,100 parts of nanometer anti-scratch master batches, 2 parts of irgasfos 168s, 1 part of antioxidant 1076,5 parts
Pentaerythritol stearate, 2 parts of light stablize 770,2 parts of ultraviolet absorbing agent UV-234 and 1 part of toner high-speed mixer and mixing 2~
3 minutes, the then double-screw extruding pelletizing at 260~280 DEG C, gained pellet was after 120 DEG C 4 hours dry at 260~280 DEG C
Under be molded into standard sample item.
Embodiment 6
By following component (1 part=100g) in parts by weight: the PC of 787 parts of models 2805,100 parts of surface hardnesses change
Kind agent H881,50 parts of organic silicon toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of irgasfos 168s, 1 part of antioxidant
1076,5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultraviolet absorbing agent UV-234 and 1 part of toner in high mixer
Middle mixing 2~3 minutes, the then double-screw extruding pelletizing at 260~280 DEG C, gained pellet after 120 DEG C 4 hours dry
Standard sample item is molded at 260~280 DEG C.
The evaluation of implementation result
The sample that above-described embodiment 1 is obtained to embodiment 5, mechanical property is according to American Society Testing and Materials (ASTM)
Standard testing, flame retardant property is according to UL94 standard testing, and test result is as follows shown in table:
The component and proportion of 1 embodiment of table
The performance test results of 2 embodiment of table
The test performance of table 2 the result shows that:
(1) the surface hardness improver H881 and 50 parts of nanometer anti-scratch master batches of 100 parts of compounding can make the surface hardness of PC
Grade reaches 2H；
(2) PC of copolymeric siloxane PC, low temperature impact modifiers, surface hardness improver, nanometer anti-scratch mother etc. is added
Composite material improves low-temperature impact-resistant performance, surface hardness, and with good light transmittance.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, these equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (7)
1. a kind of transparent low temperature resistant scratch resistance polycarbonate composite material, which is characterized in that below according to parts by weight
Component: 300-800 parts of bisphenol A polycarbonate resin, 100-500 parts of copolymeric siloxane PC resin, organic silicon toughener 10-50
Part, 50-200 parts of surface hardness improver, 10-100 parts of nanometer anti-scratch master batch, 5-15 parts of auxiliary agent；The auxiliary agent includes pressing
The following components of parts by weight meter: 3 parts of antioxidant, 4 parts of antiultraviolet additive, 5 parts of processing aid and 1 part of color
Powder；The surface hardness improver is the copolymer with the PC acrylate with high-compatibility and methyl methacrylate；
The nanometer anti-scratch master batch is micro-size silica powder of the partial size in 10~30nm.
2. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, which is characterized in that described is poly-
Carbonate resin is bisphenol A-type aromatic polycarbonate resin, and relative molecular weight is 20000~30000.
3. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, which is characterized in that the silicon
Oxygen alkane is copolymerized the polycarbonate resin that PC resin is bisphenol-A and copolymeric siloxane, and relative molecular weight is 20000~30000, silicon
Oxygen alkane content is 5~20%.
4. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, which is characterized in that described has
Machine silicon class toughener is that silicon rubber-acrylate is core, and polymethyl methacrylate is the graft copolymerization of the nucleocapsid structure of shell
Object.
5. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, which is characterized in that the table
Surface hardness improver molecular weight is 10000~20000.
6. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, which is characterized in that described is anti-
Oxygen agent is phosphite antioxidant 168, in hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, hindered phenol antioxygen 1076
One or two；The antiultraviolet additive is the compound of light stabilizer and ultraviolet absorbing agent；The light is stablized
Agent stablizes 770, light for light and stablizes one of 622；The ultraviolet absorbing agent is one in UV234, UV-328, UV-320
Kind；The processing aid is the mixing of one or more of polyethylene wax, oxidized polyethylene wax, pentaerythritol stearate；
The toner is made of pigment and spread powder.
7. a kind of preparation method of the transparent low temperature resistant scratch resistance polycarbonate composite material as described in claim 1-6 is any,
Characterized by comprising the following steps: raw material mixes 2~3 minutes in a high speed mixer, then through double at 260~280 DEG C
Screw extruder squeezes out, is cooling, being granulated, and gained pellet is molded into standard sample at 260~280 DEG C after 120 DEG C 4 hours dry
Item to get.
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| CN106589880B true CN106589880B (en) | 2019-04-16 |
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