CN106589880A - Transparent low-temperature-resistant scuffing-resistant polycarbonate composite material - Google Patents
Transparent low-temperature-resistant scuffing-resistant polycarbonate composite material Download PDFInfo
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- CN106589880A CN106589880A CN201611007124.8A CN201611007124A CN106589880A CN 106589880 A CN106589880 A CN 106589880A CN 201611007124 A CN201611007124 A CN 201611007124A CN 106589880 A CN106589880 A CN 106589880A
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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
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Abstract
The invention relates to the field of polymer composite materials, in particular to a transparent low-temperature-resistant scuffing-resistant polycarbonate composite material. The polycarbonate composite material is prepared from, by weight, 300-800 parts of bisphenol A polycarbonate resin, 100-500 parts of siloxane copolymerized PC resin, 10-50 parts of organosilicone flexibilizer, 50-200 parts of surface hardness improving agent, 10-100 parts of nanometer scuffing-resistant master batch and 5-15 parts of additive. The siloxane copolymerized PC, the surface hardness improving agent and the nanometer scuffing-resistant master batch are composited for use, on the basis that the luminousness and the basic mechanical properties of PC are uninfluenced, the surface hardness and the low-temperature properties of the material are improved, the surface hardness can be increased to 2 H, the abrasion resistance of the surface of a product is obviously improved, and the surface glossiness and the weather resistance are also improved. Moreover, the surface tension of the product can be increased, and the product is easier to clean; the composite material is good in mechanical property, high temperature impact property and low temperature impact property.
Description
Technical field
The present invention relates to field of polymer composite material, is a kind of transparent low temperature resistant scratch resistance Merlon specifically
Composite and preparation method thereof.
Background technology
Merlon is a kind of plastics with good transparency, and its excellent combination property, purposes is extremely wide, its 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 the cut produced in product surface also results in stress concentration, PC material products at ordinary times, in order to protect outward appearance, typically
Do coating processing.In order to improve the adhesion strength of Merlon, there is patent report to pass through addition PMMA, carbon fiber, glass
Fiber, wollastonite, talcum powder etc. are modified, although case hardness can reach 2H, sacrifice HI high impact, the height of PC materials
Transparent characteristic, application is 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, comprising the following components counted by weight：700～850 parts of polycarbonate resin, 100～250 parts have
Machine silicon copolymerization PC, 0～30 part of low temperature impact modifiers, 10～40 parts of fire retardant；Wherein described low temperature impact modifiers are
One or two mixing in silicone toughener, esters of acrylic acid toughener；The fire retardant is TDE, gathers
One or more mixing in bromo carbonic ester, perfluorobutyl potassium sulfonate or diphenyl sulfone sulfonate；The organosilicon copolymerization PC
For bisphenol-A and the polycarbonate resin of organosilicon copolymerization, its relative molecular weight is 20000～30000.But it is transparent with regard to one kind
Low temperature resistant scratch resistance polycarbonate composite material and preparation method thereof yet there are no report.
The content of the invention
It is an object of the invention to provide a kind of intensity height, good toughness, good cryogenic property, high surface hardness and scratch resistant
PC materials, and also the preparation method of this material is provided.
A first aspect of the present invention, there is provided a kind of transparent low temperature resistant scratch resistance polycarbonate composite material, comprising by weight
The following components of number meter：Bisphenol A polycarbonate resin 300-800 parts, copolymeric siloxane PC resin 100-500 part, organosilicon
Class toughener 10-50 parts, case hardness improver 50-200 parts, nanometer anti-scratch master batch 10-100 parts, auxiliary agent 5-15 parts.
Wherein, described polycarbonate resin is bisphenol A-type aromatic polycarbonate resin, and its relative molecular weight is 20000
～30000；
Described copolymeric siloxane PC resin is bisphenol-A and the polycarbonate resin of copolymeric siloxane, its relative molecular weight
For 20000～30000, content of siloxane is 5～20%；
Described silicone toughener is that silicon rubber-acrylate is core, and polymethyl methacrylate is the core-shell structure copolymer of shell
The graft copolymer of structure；
Described case hardness improver is being total to for the acrylate that has high-compatibility with PC and methyl methacrylate
Polymers, molecular weight is 10000～20000；
Described nanometer anti-scratch master batch is micro-size silica powder of the particle diameter in 10～30nm；
Described auxiliary agent includes the following components counted by weight：3 parts of antioxidant, 4 parts of antiultraviolet additive,
5 parts of processing aid and 1 part of toner.
Described antioxidant is phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, receives
Resistance phenol antioxidant 1076 in one or two.The more preferably mixing of irgasfos 168 and antioxidant 1076.
Described antiultraviolet additive is the compound of light stabilizer and ultra-violet absorber.It is furthermore preferred that the light
The weight ratio of stabilizer and the ultra-violet absorber is 1:1.It is further preferred that the light stabilizer is stable for light
770th, light stablizes the one kind in 622；The ultra-violet absorber is the one kind in UV234, UV-328, UV-320.More preferably
Light stablizes 770 and UV-234 compound.
Described processing aid is Tissuemat E, OPE, pentaerythritol stearate, many officials of LCFA
One or more mixing in ester can be rolled into a ball.More preferably pentaerythritol stearate.
Described toner is mainly made up of pigment and spread powder.
A second aspect of the present invention, there is provided the preparation side of above-mentioned transparent low temperature resistant scratch resistance polycarbonate composite material
Method, comprises the following steps：Raw material mixes 2～3 minutes in high-speed mixer, then the Jing twin-screw extrusions at 260～280 DEG C
Machine extrusion, cooling, granulation, gained pellet is molded into standard sample bar after 4 hours Jing 120 DEG C of dryings at 260～280 DEG C, obtains final product.
The invention has the advantages that：
1st, copolymeric siloxane PC, case hardness improver, nanometer anti-scratch master batch compound use, in the printing opacity for not affecting PC
On the basis of rate and basic mechanical performance, the case hardness and cryogenic property of material is improved, case hardness can be improved to 2H, shown
Work improves the scratch-resistant performance of product surface, surface gloss and weatherability, and can increase product surface tension force, be more easy to clearly
It is clean；
2nd, due to copolymeric siloxane PC, case hardness improver, nanometer anti-scratch master batch, the splendid phase in PC base materials
Capacitive and dispersiveness, it is ensured that good light transmittance；Copolymeric siloxane PC, the addition of silicone toughener be ensure that normal temperature and
Low temperature impact properties；
3rd, composite of the invention has good mechanical property, and good normal temperature and low temperature impact properties.
Specific embodiment
The specific embodiment that the present invention is provided is elaborated with reference to embodiment.
In following each embodiment, each raw material adopts following compositions：
Polycarbonate resin：The bisphenol A-type aromatic polycarbonate resin that company is created in Cohan is purchased from, its 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；
Silicone toughener：From Mitsubishi Li Yang companies, model S2030；
Case hardness improver：From Mitsubishi Li Yang companies, model H881；
Nanometer anti-scratch master batch：From Na Linwei nanosecond science and technology (Shanghai) Co., Ltd., particle diameter in 10-30nm ultra-fine two
Silica powder；
Irgasfos 168 and antioxidant 1076 are from BASF AG；
Light stablizes 770 and ultra-violet absorber UV-234 from BASF AG.
Processing flow promortor：Tissuemat E, OPE are manufactured by BASF AG, and pentaerythritol stearate is by U.S.
Guo Longsha companies manufacture, and LCFA polyfunctional group ester is manufactured by German Kening Co., Ltd.
Embodiment 1
By following component (1 part=100g) in parts by weight：The PC of 637 parts of models 2805,300 parts of copolymeric siloxanes
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 ultra-violet absorber UV-234 and 1 part of toner in high-speed mixer and mixing 2～3 minutes, then at 260～280 DEG C
Double-screw extruding pelletizing, gained pellet is molded into standard sample bar after 4 hours Jing 120 DEG C of dryings at 260～280 DEG C.
Embodiment 2
By following component (1 part=100g) in parts by weight：The PC of 537 parts of models 2805,300 parts of copolymeric siloxanes
PC, 100 parts of case 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 ultra-violet absorber 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 is Jing after 120 DEG C of dryings 4 hours at 260～280 DEG C
Under be molded into standard sample bar.
Embodiment 3
By following component (1 part=100g) in parts by weight：The PC of 507 parts of models 2805,300 parts of copolymeric siloxanes
PC, 100 parts of case hardness improver H881,30 parts of silicone toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of antioxygens
168,1 part of antioxidant 1076 of agent, 5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultra-violet absorber UV-234 and 1
Part toner in high-speed mixer and mixing 2～3 minutes, the then double-screw extruding pelletizing at 260～280 DEG C, 120 DEG C of gained pellet Jing
Standard sample bar is molded at 260～280 DEG C after being dried 4 hours.
Embodiment 4
By following component (1 part=100g) in parts by weight：The PC of 487 parts of models 2805,300 parts of copolymeric siloxanes
PC, 100 parts of case hardness improver H881,50 parts of silicone toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of antioxygens
168,1 part of antioxidant 1076 of agent, 5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultra-violet absorber UV-234 and 1
Part toner in high-speed mixer and mixing 2～3 minutes, the then double-screw extruding pelletizing at 260～280 DEG C, 120 DEG C of gained pellet Jing
Standard sample bar is molded at 260～280 DEG C after being dried 4 hours.
Embodiment 5
By following component (1 part=100g) in parts by weight：The PC of 537 parts of models 2805,300 parts of copolymeric siloxanes
PC, 50 parts of silicone 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 ultra-violet absorber 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 is Jing after 120 DEG C of dryings 4 hours at 260～280 DEG C
Under be molded into standard sample bar.
Embodiment 6
By following component (1 part=100g) in parts by weight：The PC of 787 parts of models 2805,100 parts of case hardnesses change
Kind agent H881,50 parts of silicone toughener S2030,50 parts of nanometer anti-scratch master batches, 2 parts of irgasfos 168s, 1 part of antioxidant
1076th, 5 parts of pentaerythritol stearates, 2 parts of light stablize 770,2 parts of ultra-violet absorber 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 Jing after 120 DEG C of dryings 4 hours
Standard sample bar 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, fire resistance is according to UL94 standard testings, and test result is as shown in the table：
The component and proportioning of the embodiment of table 1
The performance test results of the embodiment of table 2
The test performance result of table 2 shows：
(1) compounding 100 parts of case hardness improver H881 and 50 parts of nanometer anti-scratch master batches can make the case hardness of PC
Grade reaches 2H；
(2) PC of copolymeric siloxane PC, low temperature impact modifiers, case hardness improver, nanometer anti-scratch mother etc. is added
Composite improves low-temperature impact-resistant performance, case hardness, and with preferable light transmittance.
Below the preferred embodiment to the invention is illustrated, but the invention be not limited to it is described
Embodiment, those of ordinary skill in the art can also make a variety of equivalents on the premise of without prejudice to the invention spirit
Modification or replacement, the modification of these equivalents or replacement are all contained in the application claim limited range.
Claims (8)
1. a kind of transparent low temperature resistant scratch resistance polycarbonate composite material, it is characterised in that following comprising what is counted by weight
Component：Bisphenol A polycarbonate resin 300-800 parts, copolymeric siloxane PC resin 100-500 part, silicone toughener 10-50
Part, case hardness improver 50-200 parts, nanometer anti-scratch master batch 10-100 parts, auxiliary agent 5-15 parts；Described auxiliary agent include by
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.
2. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, it is characterised in that described is poly-
Carbonate resin is bisphenol A-type aromatic polycarbonate resin, and its relative molecular weight is 20000～30000.
3. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, it is characterised in that described silicon
Oxygen alkane copolymerization PC resin is the polycarbonate resin of bisphenol-A and copolymeric siloxane, and its 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, it is characterised 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
Thing.
5. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, it is characterised in that described table
Surface hardness improver is the copolymer of the acrylate and methyl methacrylate for having high-compatibility with PC, and molecular weight is
10000～20000.
6. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, it is characterised in that described receives
Rice anti-scratch master batch is micro-size silica powder of the particle diameter in 10～30nm.
7. transparent low temperature resistant scratch resistance polycarbonate composite material according to claim 1, it is characterised in that described is anti-
Oxygen agent is in phosphite antioxidant 168, hindered phenol antioxygen 1010, hindered phenol antioxygen 1098, hindered phenol antioxygen 1076
One or two；Described antiultraviolet additive is the compound of light stabilizer and ultra-violet absorber；The light is stablized
Agent is that light stablizes one kind that 770, light is stablized in 622；The ultra-violet absorber is in UV234, UV-328, UV-320
Kind；Described processing aid is Tissuemat E, OPE, pentaerythritol stearate, LCFA polyfunctional group
One or more mixing in ester；Described toner is made up of pigment and spread powder.
8. a kind of preparation method of the transparent low temperature resistant scratch resistance polycarbonate composite material as described in claim 1-7 is arbitrary,
Characterized in that, comprising the following steps：Raw material mixes 2～3 minutes in high-speed mixer, and then Jing is double at 260～280 DEG C
Screw extruder extrusion, cooling, granulation, gained pellet is molded into standard sample after 4 hours Jing 120 DEG C of dryings at 260～280 DEG C
Bar, obtains final product.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163537A (en) * | 2017-06-22 | 2017-09-15 | 上海长伟锦磁工程塑料有限公司 | A kind of clear scratch-resistant anti-electrostatic fire retardant polycarbonate composite material |
| CN109486149A (en) * | 2018-10-29 | 2019-03-19 | 广东聚钛新材料有限公司 | A kind of PC composite material |
| CN110157174A (en) * | 2019-05-30 | 2019-08-23 | 深圳华力兴新材料股份有限公司 | A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement |
| CN110283444A (en) * | 2019-07-05 | 2019-09-27 | 咖法科技(上海)有限公司 | A kind of compound polycarbonate of coffee grounds and preparation method thereof |
| CN110358277A (en) * | 2019-06-21 | 2019-10-22 | 东莞市广正模具塑胶有限公司 | A kind of enhancing is flexible to exempt to spray makrolon material, mobile phone shell and preparation method thereof |
| WO2019219615A1 (en) | 2018-05-17 | 2019-11-21 | Covestro Deutschland Ag | Filled polycarbonate compositions having good scratch resistance and reduced yellowing behavior |
| CN110951229A (en) * | 2019-11-28 | 2020-04-03 | 江林（贵州）高科发展股份有限公司 | High-toughness high-hardness PC material and preparation method thereof |
| CN111073248A (en) * | 2019-12-16 | 2020-04-28 | 上海长伟锦磁工程塑料有限公司 | Hydrolysis-resistant, illumination-resistant and low-temperature-resistant halogen-free flame-retardant polycarbonate composite material and preparation method thereof |
| CN111117262A (en) * | 2019-12-26 | 2020-05-08 | 浙江佳华精化股份有限公司 | Scratch-resistant agent for highlight spraying-free PC/ABS alloy and preparation method thereof |
| CN111423732A (en) * | 2020-04-08 | 2020-07-17 | 重庆兴勇实业有限公司 | Nano reinforced polycarbonate composite material and preparation method thereof |
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| CN111925548A (en) * | 2020-08-31 | 2020-11-13 | 东莞市亚仑塑料原料有限公司 | Polycarbonate material with high surface hardness and preparation method thereof |
| CN112430386A (en) * | 2019-08-26 | 2021-03-02 | 汉达精密电子(昆山)有限公司 | Ultraviolet absorbent master batch, transparent polycarbonate material and product thereof |
| CN112708253A (en) * | 2020-12-25 | 2021-04-27 | 上海长伟锦磁工程塑料有限公司 | Sound-insulation antistatic halogen-free flame-retardant polycarbonate composite material and preparation method thereof |
| CN112940477A (en) * | 2020-12-21 | 2021-06-11 | 胡梦蝶 | Scratch-resistant UV-resistant flame-retardant photodiffusion polycarbonate composition and preparation method thereof |
| CN114276666A (en) * | 2022-01-25 | 2022-04-05 | 贵州凯科特材料有限公司 | High-gloss high-surface-hardness polycarbonate composite material and preparation method thereof |
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| CN107163537A (en) * | 2017-06-22 | 2017-09-15 | 上海长伟锦磁工程塑料有限公司 | A kind of clear scratch-resistant anti-electrostatic fire retardant polycarbonate composite material |
| WO2019219615A1 (en) | 2018-05-17 | 2019-11-21 | Covestro Deutschland Ag | Filled polycarbonate compositions having good scratch resistance and reduced yellowing behavior |
| CN109486149A (en) * | 2018-10-29 | 2019-03-19 | 广东聚钛新材料有限公司 | A kind of PC composite material |
| CN110157174A (en) * | 2019-05-30 | 2019-08-23 | 深圳华力兴新材料股份有限公司 | A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement |
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| CN111423732A (en) * | 2020-04-08 | 2020-07-17 | 重庆兴勇实业有限公司 | Nano reinforced polycarbonate composite material and preparation method thereof |
| CN111690244A (en) * | 2020-05-25 | 2020-09-22 | 上海长伟锦磁工程塑料有限公司 | High-gloss scratch-resistant chemical-resistant PC/polyester alloy material and preparation method thereof |
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