CN106893297B - One kind is exempted to spray PC/ASA composite material and preparation method - Google Patents

One kind is exempted to spray PC/ASA composite material and preparation method Download PDF

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Publication number
CN106893297B
CN106893297B CN201710136865.4A CN201710136865A CN106893297B CN 106893297 B CN106893297 B CN 106893297B CN 201710136865 A CN201710136865 A CN 201710136865A CN 106893297 B CN106893297 B CN 106893297B
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area
composite material
spray
exempt
asa
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CN106893297A (en
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刘春艳
孔抵柱
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SHANGHAI ZHONGLEI NEW MATERIAL TECHNOLOGY Co Ltd
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SHANGHAI ZHONGLEI NEW MATERIAL TECHNOLOGY Co Ltd
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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
    • 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
    • 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
    • B29C2948/9259—Angular 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

Exempt to spray PC/ASA composite material and preparation method the present invention provides one kind.The PC/ASA composite material according to the mass fraction, including following component: 60-95 parts PC, 5-40 parts ASA, 1-10 parts of compatilizers, 1-10 parts of optical brighteners, 1-5 parts of scratch resistance liniments and 0.1-1 parts of coupling agents.The PC/ASA composite material is by squeezing out to obtain through extruder after mixing each component of formula ratio.The present invention PC/ASA composite material made while having good wear-resisting property, mechanical performance and higher glossiness by selecting specific component and its proportion.

Description

One kind is exempted to spray PC/ASA composite material and preparation method
Technical field
The invention belongs to technical field of polymer composite materials, and in particular to one kind exempt from spray PC/ASA composite material and its Preparation method.
Background technique
Polycarbonate (PC) is with fastest developing speed, most widely used one of engineering plastics.Wherein yield is maximum, purposes is most wide It is bisphenol A polycarbonate.Bisphenol A polycarbonate has excellent impact resistant strength, creep resistant, heat resistance and resists cold Property, can use in -100 DEG C~140 DEG C temperature ranges, it is seen that the transmitance of light is up to 90% or so, anti-tensile with higher Intensity, bending strength, elongation and rigidity, resistance to ag(e)ing, excellent electrical properties and water absorption rate is low.PC material is widely used in vapour The fields such as vehicle, electric.But PC equally has the shortcomings that oil resistivity, wearability and processing performance be not good enough, and make its application by To limitation.
Acrylonitrile-styrene-acrylic ester copolymer (ASA), due to selecting acrylic ester unit instead of acrylic nitrile-butadiene Butadiene unit in diene-styrene copolymer (ABS) does not contain double bond in system, therefore the weatherability of material obtains It is greatly improved.ASA also retain simultaneously good mechanical property, thermal stability and it is easy to process the advantages that, be suitable for Outdoor decoration material, sports equipment and automobile decoration piece etc..
PC resin and ASA have certain compatibility, and the two is blended, the PC/ASA composite material of preparation combine PC and The excellent performance of ASA exempts to spray inside gadget commonly used in automobile.But automobile exempts from the wearability sprayed inside gadget to material, gloss Degree and weatherability requirement with higher.
By taking Volkswagen as an example, exempt from the wearability requirement for spraying inside gadget to automobile are as follows: it is tested through PV3.3.3 water mill, After 20 cyclic tests, material surface gloss percent retension is that (gloss percent retension of common PC/ASA material is lower than 50-60% 20%)；Glossiness requirement are as follows: under 20 ° of test angles, glossiness >=90% (under same test angle, common PC/ASA material Glossiness is 75-80%)；Weatherability requirement are as follows: tested through PV1303 light shine, material tonal gradation >=4 grade (phase after 5 periods With under test condition, tonal gradation≤2.5 grade of common PC/ASA material).
The performance of common PC/ASA composite material needs to carry out PC/ASA composite material far from above-mentioned requirements are met It is corresponding modified.CN 106084716A discloses a kind of weather-proof bloom and exempts to spray PC/ASA alloy material and preparation method thereof, although The weather resistance of material is improved by addition weather resisting agent and antioxidant, but this document is not related to change wear-resisting property Into.CN 105885379A discloses a kind of scratch-resistant bloom and exempts to spray PC/ASA alloy material and preparation method thereof, the PC/ASA Alloy material according to parts by weight, by 50-70 parts of PC resins, 10-40 parts of ASA resins, 5-20 parts of scratch resistance liniments, 0.1-1 parts of phases Hold agent, 0.1-1 parts of antioxidant, 0.1-1 parts of lubricants and 2-5 parts of black masterbatch compositions.In order to obtain enough scraping and wiping resistance performances, The scratch resistances liniments such as a large amount of polymethyl methacrylate (PMMA) are added in the PC/ASA alloy material.But scratch resistance liniment and base The compatibility of body material is poor, while improving scraping and wiping resistance performance, to the mechanical performance of PC/ASA alloy material also have compared with Big negative effect.
Therefore, it is expected to obtain in this field and a kind of have both exempting from for good wear-resisting property, mechanical performance and higher gloss degree Spray PC/ASA composite material.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide one kind exempt from spray PC/ASA composite material and Preparation method.The PC/ASA composite material has good wear-resisting property, mechanical performance and higher glossiness simultaneously.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention provides one kind and exempts to spray PC/ASA composite material, according to the mass fraction, including following component:
In the present invention, compatilizer and coupling agent have the compatibility improved between each component, improve interface binding intensity Effect；Optical brightener makes material have metallic luster, has the function of improving material surface glossiness；Scratch resistance liniment, which has, improves material Expect the effect of wear-resisting property.But above-mentioned each component not only plays respective effect independently of each other, each component is all Can have an impact the multiple performance of composite material (for example, glossiness of the optical brightener in addition to that can improve material surface, also will affect Wearability and mechanical performance).Therefore, each component needs to cooperate under specific proportion, can just be had simultaneously good Wear-resisting property, mechanical performance and higher glossiness exempt from spray PC/ASA composite material.
In the present invention, the mass fraction of the PC can be 60 parts, 62 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 Part, 80 parts, 82 parts, 85 parts, 88 parts, 90 parts, 92 parts or 95 parts etc..
The mass fraction of the ASA can be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 Part, 30 parts, 32 parts, 35 parts, 38 parts or 40 parts etc.
The mass fraction of the compatilizer can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts Deng.
The mass fraction of the optical brightener can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts Deng.
The mass fraction of the scratch resistance liniment can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts etc..
The mass fraction of the coupling agent can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part etc..
Preferably, described to exempt to spray PC/ASA composite material according to the mass fraction, including following component:
It is further preferred that described exempt to spray PC/ASA composite material according to the mass fraction, including following component:
Preferably, described to exempt to spray PC/ASA composite material according to the mass fraction, it further include 0.1-0.5 parts of lubricants；Profit The mass fraction of lubrication prescription can be 0.1 part, 0.2 part, 0.3 part, 0.4 part or 0.5 part etc..
Preferably, the lubricant is in pentaerythritol stearate, N, N '-ethylene bis stearamide or amide waxe It is a kind of or at least two combination；Such as it can be pentaerythritol stearate and N, the combination of N '-ethylene bis stearamide, season Combination, the N of penta tetrol stearate and amide waxe, the combination of N '-ethylene bis stearamide and amide waxe or pentaerythrite are stearic Acid esters, N, the combination of N '-ethylene bis stearamide and amide waxe three.
Preferably, described to exempt to spray PC/ASA composite material according to the mass fraction, it further include 1-5 parts of light stabilizers；Light is steady The mass fraction for determining agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts etc..
It is further preferred that the mass fraction of the light stabilizer is 1-3 parts.
Preferably, the light stabilizer is ultraviolet absorbing agent and/or radical scavenger.
Preferably, the ultraviolet absorbing agent is benzotriazole light stabilizer and/or triazines as light stabilizer.
Preferably, the radical scavenger is hindered amine light stabilizer.
Preferably, described to exempt to spray PC/ASA composite material according to the mass fraction, it further include 0.1-0.2 parts of antioxidant；It is anti- The mass fraction of oxygen agent can be 0.1 part, 0.12 part, 0.15 part, 0.18 part or 0.2 part etc..
Preferably, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxygens Agent 1010) and three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168) combination.
Preferably, described to exempt to spray PC/ASA composite material according to the mass fraction, it further include 0.05-0.1 parts of toners, toner Mass fraction can be 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part or 0.1 part etc..
Preferably, the number-average molecular weight of the PC is 1.5-3 ten thousand, for example, can be 1.5 ten thousand, 1.6 ten thousand, 1.7 ten thousand, 1.8 ten thousand, 1.9 ten thousand, 20,000,2.1 ten thousand, 2.2 ten thousand, 2.3 ten thousand, 2.4 ten thousand, 2.5 ten thousand, 2.6 ten thousand, 2.7 ten thousand, 2.8 ten thousand, 2.9 ten thousand or 30,000 etc.；Vitrifying Transition temperature is 140-150 DEG C, such as can be 140 DEG C, 141 DEG C, 142 DEG C, 143 DEG C, 144 DEG C, 145 DEG C, 146 DEG C, 147 DEG C, 148 DEG C, 149 DEG C or 150 DEG C etc..
Preferably, the mass percentage of acrylic ester unit is 30-60% in the ASA, such as can be 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60% etc..
Preferably, the compatilizer is selected from the acrylonitrile-styrene-acrylic ester copolymer (ASA- of maleic anhydride grafting G-MAH), the acrylonitrile-butadiene-styrene copolymer (ABS-g-MAH) or maleic anhydride of maleic anhydride grafting are grafted poly- One of styrene (PS-g-MAH) or at least two combination；Such as it can be the group of ASA-g-MAH and ABS-g-MAH Close, the combination of ASA-g-MAH and PS-g-MAH, the combination of ABS-g-MAH and PS-g-MAH or ASA-g-MAH, ABS-g-MAH with The combination of PS-g-MAH three.
Preferably, the optical brightener is silane-modified aluminium powder pigment.
Preferably, the scratch resistance liniment be selected from polytetrafluoroethylene (PTFE), organo montmorillonite or Shanghai Supreme Being's Renhua work LUBDE One of 305 scratch resistance liniments.
Organo montmorillonite refers to organically-modified montmorillonite in the present invention.
Preferably, the coupling agent is selected from gamma-aminopropyl-triethoxy-silane (KH550), γ-(2,3- the third oxygen of epoxy) third One of base trimethoxy silane (KH560) or N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH972) or extremely Few two kinds of combination；Such as can be the combination of KH550 and KH560, the combination of KH550 and KH972, KH560 and KH972 group Conjunction or the combination of KH550, KH560 and KH972 three.
On the other hand, the present invention provides a kind of above-mentioned preparation method for exempting to spray PC/ASA composite material, the preparation side Method are as follows: will formula ratio each component mix after squeezed out by extruder, obtain described exempting from spraying PC/ASA composite material.
Preferably, described to be combined by high-speed mixer realization.
Preferably, the revolving speed of the high-speed mixer is 350-400r/min, such as can be 350r/min, 360r/ Min, 370r/min, 380r/min, 390r/min or 400r/min etc.；The mixed time is 5-10min, such as be can be 5min, 6min, 7min, 8min, 9min or 10min etc..
Preferably, the extruder is double screw extruder.
Preferably, the double screw extruder includes the area, 2nd area, 3rd area, four being sequentially connected from feed opening to head Area, 5th area, 6th area, 7th area, 8th area and 9th area, the mixed material of each component successively pass through each area；
The temperature in one area is 185-195 DEG C, such as can be 185 DEG C, 186 DEG C, 187 DEG C, 188 DEG C, 189 DEG C, 190 DEG C, 191 DEG C, 192 DEG C, 193 DEG C, 194 DEG C or 195 DEG C etc.；
The temperature in 2nd area is 215-225 DEG C, such as can be 215 DEG C, 216 DEG C, 217 DEG C, 218 DEG C, 219 DEG C, 220 DEG C, 221 DEG C, 222 DEG C, 223 DEG C, 224 DEG C or 225 DEG C etc.；
The temperature in 3rd area is 225-235 DEG C, such as can be 225 DEG C, 226 DEG C, 227 DEG C, 228 DEG C, 229 DEG C, 230 DEG C, 231 DEG C, 232 DEG C, 233 DEG C, 234 DEG C or 235 DEG C etc.；
The temperature in 4th area is 235-245 DEG C, such as can be 235 DEG C, 236 DEG C, 237 DEG C, 238 DEG C, 239 DEG C, 240 DEG C, 241 DEG C, 242 DEG C, 243 DEG C, 244 DEG C or 245 DEG C etc.；
The temperature in 5th area is 245-255 DEG C, such as can be 245 DEG C, 246 DEG C, 247 DEG C, 248 DEG C, 249 DEG C, 250 DEG C, 251 DEG C, 252 DEG C, 253 DEG C, 254 DEG C or 255 DEG C etc.；
The temperature in 6th area is 255-265 DEG C, such as can be 255 DEG C, 256 DEG C, 257 DEG C, 258 DEG C, 259 DEG C, 260 DEG C, 261 DEG C, 262 DEG C, 263 DEG C, 264 DEG C or 265 DEG C etc.；
The temperature in 7th area is 265-275 DEG C, such as can be 265 DEG C, 266 DEG C, 267 DEG C, 268 DEG C, 269 DEG C, 270 DEG C, 271 DEG C, 272 DEG C, 273 DEG C, 274 DEG C or 275 DEG C etc.；
The temperature in 8th area is 265-275 DEG C, such as can be 265 DEG C, 266 DEG C, 267 DEG C, 268 DEG C, 269 DEG C, 270 DEG C, 271 DEG C, 272 DEG C, 273 DEG C, 274 DEG C or 275 DEG C etc.；
The temperature in 9th area be 260-270 DEG C, such as can be 260 DEG C, 261 DEG C, 262 DEG C, 263 DEG C, 2634 DEG C, 265 DEG C, 266 DEG C, 267 DEG C, 268 DEG C, 269 DEG C or 270 DEG C etc.；
The temperature of the head be 260-270 DEG C, such as can be 260 DEG C, 261 DEG C, 262 DEG C, 263 DEG C, 2634 DEG C, 265 DEG C, 266 DEG C, 267 DEG C, 268 DEG C, 269 DEG C or 270 DEG C etc..
Preferably, the screw speed of the double screw extruder is 350-450r/min；Such as can be 350r/min, 360r/min、370r/min、380r/min、390r/min、400r/min、410r/min、420r/min、430r/min、440r/ Min or 450r/min etc..
Preferably, residence time of the mixed material of each component in the double screw extruder is 1.5-2min； Such as can be 1.5min, 1.6min, 1.7min, 1.8min, 1.9min or 2min etc..
Compared with prior art, the invention has the following advantages:
In the present invention, compatilizer and coupling agent have the compatibility improved between each component, improve interface binding intensity Effect；Optical brightener makes material have metallic luster, has the function of improving material surface glossiness；Scratch resistance liniment, which has, improves material Expect the effect of wear-resisting property.But the effect of above-mentioned each component is not single, and each component will affect a variety of property of composite material Energy.The present invention makes each component cooperate by the specific proportion of selection, has obtained a kind of while having had good wearability Can, mechanical performance and higher glossiness exempt from spray PC/ASA composite material.
The tensile strength provided by the invention for exempting to spray PC/ASA composite material is 60-68MPa, elongation at break 80- 110%, impact strength 60-70kJ/m2, glossiness is 100-105% under 20 ° of test angles, coefficient of friction≤0.16, Gloss percent retension is 75-85% after the test of PV3.3.3 water mill.
By carrying out preferably, the comprehensive performance of PC/ASA composite material provided by the invention being made to obtain to dosage of each component It further increases.Its tensile strength is 65-68MPa, elongation at break 100-110%, impact strength 65-70kJ/m2, Glossiness is 103-105% under 20 ° of test angles, and gloss percent retension is after the test of coefficient of friction≤0.1, PV3.3.3 water mill 80-85%.
By addition light stabilizer and antioxidant, cooperate other components, PC/ASA composite material can be made to have good resistance to Hou Xing, tonal gradation reaches 4.8 grades after PV1303 illumination tested for 5 periods.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 10min under the revolving speed of 350r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 185 DEG C, and the temperature in 2nd area is 215 DEG C, and the temperature in 3rd area is 225 DEG C, the temperature in 4th area is 235 DEG C, and the temperature in 5th area is 245 DEG C, and the temperature in 6th area is 255 DEG C, and the temperature in 7th area is 265 DEG C, the temperature in 8th area is 265 DEG C, and the temperature in 9th area is 260 DEG C, and the temperature of head is 260 DEG C, screw speed 350r/min, Residence time of the mixed material of each component in double screw extruder is 2min.
Embodiment 2
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 5min under the revolving speed of 400r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of 195 DEG C of the temperature of Zhong-1 block, 2nd area is 225 DEG C, and the temperature in 3rd area is 235 DEG C, the temperature in 4th area is 245 DEG C, and the temperature in 5th area is 255 DEG C, and the temperature in 6th area is 265 DEG C, and the temperature in 7th area is 275 DEG C, the temperature in 8th area is 275 DEG C, and the temperature in 9th area is 270 DEG C, and the temperature of head is 270 DEG C, screw speed 450r/min, Residence time of the mixed material of each component in double screw extruder is 1.5min.
Embodiment 3
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 8min under the revolving speed of 380r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 190 DEG C DEG C, and the temperature in 2nd area is 220 DEG C, the temperature in 3rd area It is 230 DEG C, the temperature in 4th area is 240 DEG C, and the temperature in 5th area is 250 DEG C, and the temperature in 6th area is 260 DEG C, and the temperature in 7th area is 270 DEG C, the temperature in 8th area is 270 DEG C, and the temperature in 9th area is 265 DEG C, and the temperature of head is 265 DEG C, screw speed 400r/min, Residence time of the mixed material of each component in double screw extruder is 1.8min.
Embodiment 4
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 6min under the revolving speed of 360r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 188 DEG C, and the temperature in 2nd area is 218 DEG C, and the temperature in 3rd area is 228 DEG C, the temperature in 4th area is 238 DEG C, and the temperature in 5th area is 248 DEG C, and the temperature in 6th area is 258 DEG C, and the temperature in 7th area is 268 DEG C, the temperature in 8th area is 268 DEG C, and the temperature in 9th area is 268 DEG C, and the temperature of head is 268 DEG C, screw speed 280r/min, Residence time of the mixed material of each component in double screw extruder is 1.5min.
Embodiment 5
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 7min under the revolving speed of 370r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 192 DEG C, and the temperature in 2nd area is 222 DEG C, and the temperature in 3rd area is 232 DEG C, the temperature in 4th area is 242 DEG C, and the temperature in 5th area is 252 DEG C, and the temperature in 6th area is 262 DEG C, and the temperature in 7th area is 272 DEG C, the temperature in 8th area is 272 DEG C, and the temperature in 9th area is 270 DEG C, and the temperature of head is 266 DEG C, screw speed 420r/min, Residence time of the mixed material of each component in double screw extruder is 1.9min.
Embodiment 6
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 9min under the revolving speed of 390r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 185 DEG C, and the temperature in 2nd area is 216 DEG C, and the temperature in 3rd area is 230 DEG C, the temperature in 4th area is 235 DEG C, and the temperature in 5th area is 246 DEG C, and the temperature in 6th area is 260 DEG C, and the temperature in 7th area is 265 DEG C, the temperature in 8th area is 273 DEG C, and the temperature in 9th area is 270 DEG C, and the temperature of head is 270 DEG C, screw speed 430r/min, Residence time of the mixed material of each component in double screw extruder is 1.6min.
Embodiment 7
One kind is exempted to spray PC/ASA composite material, mass fraction meter, including following component:
The above-mentioned preparation method for exempting to spray PC/ASA composite material includes the following steps:
(1) each component of formula ratio is added in high-speed mixer, mixes 10min under the revolving speed of 350r/min；
(2) mixed material for each component for obtaining step (1) by double screw extruder squeeze out, double screw extruder from Feed opening to head include the area being sequentially connected, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area, each group The mixed material divided successively passes through each area, and the temperature of Zhong-1 block is 195 DEG C, and the temperature in 2nd area is 215 DEG C, and the temperature in 3rd area is 235 DEG C, the temperature in 4th area is 235 DEG C, and the temperature in 5th area is 245 DEG C, and the temperature in 6th area is 255 DEG C, and the temperature in 7th area is 265 DEG C, the temperature in 8th area is 275 DEG C, and the temperature in 9th area is 270 DEG C, and the temperature of head is 260 DEG C, screw speed 400r/min, Residence time of the mixed material of each component in double screw extruder is 1.5min.
Comparative example 1
The difference from embodiment 1 is that the mass fraction of PC is 55 parts.
Comparative example 2
The difference from embodiment 1 is that the mass fraction of PC is 105 parts.
Comparative example 3
The difference from embodiment 1 is that the mass fraction of ASA is 3 parts.
Comparative example 4
The difference from embodiment 1 is that the mass fraction of ASA is 45 parts.
Comparative example 5
The difference from embodiment 1 is that the mass fraction of compatilizer ASA-g-MAH is 0.5 part.
Comparative example 6
The difference from embodiment 1 is that the mass fraction of compatilizer ASA-g-MAH is 12 parts.
Comparative example 7
The difference from embodiment 1 is that the mass fraction of the silane-modified aluminium powder pigment of optical brightener is 0.5 part.
Comparative example 8
The difference from embodiment 1 is that the mass fraction of the silane-modified aluminium powder pigment of optical brightener is 12 parts.
Comparative example 9
The difference from embodiment 1 is that the mass fraction of scratch resistance liniment polytetrafluoroethylene (PTFE) is 0.5 part.
Comparative example 10
The difference from embodiment 1 is that the mass fraction of scratch resistance liniment polytetrafluoroethylene (PTFE) is 6 parts.
Comparative example 11
The difference from embodiment 1 is that the mass fraction of coupling agent KH550 is 0.05 part.
Comparative example 12
The difference from embodiment 1 is that the mass fraction of coupling agent KH550 is 1.5 parts.
The glossiness provided by the invention for exempting from spraying PC/ASA composite material is the glossiness under 20 ° of test angles；It is wear-resisting Property characterized by the gloss percent retension that PV3.3.3 water mill tests material after 20 circulations, gloss percent retension is bigger, it was demonstrated that material The wear-resisting property of material is better；Weatherability is characterized by the tonal gradation of material after PV1303 illumination 5 periods of test, and tonal gradation is got over Greatly, it was demonstrated that the weather resistance of material is better.
What above-described embodiment 1-7 and comparative example 1-12 was provided exempts to spray the performance data of PC/ASA composite material and test mark It is quasi- as shown in table 1 below.
Table 1
By the performance data of comparative example 1 and comparative example 4 it is found that when the dosage of PC is very few or the dosage of ASA is excessive, obtain Exempt from spray PC/ASA composite material glossiness declined, tensile strength and impact strength are then substantially reduced, and performance reaches Less than requiring.
By the performance data of comparative example 2 and comparative example 3 it is found that being obtained when the dosage of PC is excessive or the dosage of ASA is very few Exempt to spray the tensile strength of PC/ASA composite material and impact strength improves, but glossiness is lower, is unsatisfactory for requiring.
By the performance data of comparative example 5 and comparative example 6 it is found that when the dosage of compatilizer is very few, what is obtained exempts from spraying PC/ The glossiness of ASA composite material reduces, and coefficient of friction increases, and gloss percent retension is decreased obviously, and wear-resisting property is deteriorated；Work as phase Hold agent dosage it is excessive when, the obtained wear-resisting property for exempting to spray PC/ASA composite material decreases, and mechanical performance is then substantially Decline, is unsatisfactory for requiring.
By the performance data of comparative example 7 and comparative example 8 it is found that when the dosage of optical brightener is very few, what is obtained exempts from spraying PC/ The glossiness of ASA composite material is decreased obviously；When the dosage of optical brightener is excessive, exempting from of obtaining sprays PC/ASA composite material Mechanical performance is substantially reduced；In addition, the dosage of optical brightener is excessive or very few, it will lead to and obtained exempt to spray PC/ASA composite wood The wear resistance decrease of material.
By the performance data of comparative example 9 and comparative example 10 it is found that is obtained exempts to spray when the dosage of scratch resistance liniment is very few The mechanical performance of PC/ASA composite material decreases, and glossiness and wear-resisting property then decline to a great extent；When the dosage of scratch resistance liniment When excessive, the obtained mechanical performance for exempting to spray PC/ASA composite material is then substantially reduced, and is unsatisfactory for requiring.
By the performance data of comparative example 11 and comparative example 12 it is found that can be led when the dosage of coupling agent is excessive or very few Exempting from the mechanical performance for spraying PC/ASA composite material and scraping and wiping resistance performance made from cause reduces.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.

Claims (23)

1. one kind is exempted to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA composite material by mass fraction Meter, including following component:
The optical brightener is silane-modified aluminium powder pigment；
The scratch resistance liniment selected from polytetrafluoroethylene (PTFE), organo montmorillonite or Shanghai Supreme Being's Renhua work LUBDE305 scratch resistance liniment in One kind.
2. it is according to claim 1 exempt from spray PC/ASA composite material, which is characterized in that it is described exempt from spray PC/ASA it is compound Material according to the mass fraction, including following component:
3. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA Composite material further includes 0.1-0.5 parts of lubricants according to the mass fraction.
4. according to claim 3 exempt to spray PC/ASA composite material, which is characterized in that the lubricant is selected from Ji Wusi Alcohol stearate, N, one of N '-ethylene bis stearamide or amide waxe or at least two combination.
5. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA Composite material further includes 1-5 parts of light stabilizers according to the mass fraction.
6. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA Composite material further includes 1-3 parts of light stabilizers according to the mass fraction.
7. according to claim 5 exempt to spray PC/ASA composite material, which is characterized in that the light stabilizer is ultraviolet light Absorbent and/or radical scavenger.
8. according to claim 7 exempt to spray PC/ASA composite material, which is characterized in that the ultraviolet absorbing agent is benzene And triazole type light stabilizer and/or triazines as light stabilizer.
9. it is according to claim 7 exempt from spray PC/ASA composite material, which is characterized in that the radical scavenger be by Hindered amine light stabilizer.
10. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA Composite material further includes 0.1-0.2 parts of antioxidant according to the mass fraction.
11. according to claim 10 exempt to spray PC/ASA composite material, which is characterized in that the antioxidant is four [β- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4- di-tert-butyl-phenyl) phosphite esters combination.
12. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that described to exempt to spray PC/ASA Composite material further includes 0.05-0.1 parts of toners according to the mass fraction.
13. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that the equal molecule of the number of the PC Amount is 1.5-3 ten thousand, and glass transition temperature is 140-150 DEG C.
14. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that acrylic acid in the ASA The mass percentage of ester units is 30-60%.
15. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that the compatilizer is selected from One of ASA-g-MAH, ABS-g-MAH or PS-g-MAH or at least two combination.
16. according to claim 1 or 2 exempt to spray PC/ASA composite material, which is characterized in that the coupling agent is selected from One of KH550, KH560 or KH972 or at least two combination.
17. -16 described in any item preparation methods for exempting to spray PC/ASA composite material according to claim 1, which is characterized in that The preparation method is that: will formula ratio each component mix after squeezed out by extruder, obtain that described to exempt from spraying PC/ASA compound Material.
18. preparation method according to claim 17, which is characterized in that described to be combined by high-speed mixer realization.
19. preparation method according to claim 18, which is characterized in that the revolving speed of the high-speed mixer is 350- 400r/min, the mixed time are 5-10min.
20. preparation method according to claim 17, which is characterized in that the extruder is double screw extruder.
21. preparation method according to claim 20, which is characterized in that the double screw extruder is from feed opening to head Including an area, 2nd area, 3rd area, 4th area, 5th area, 6th area, 7th area, 8th area and 9th area being sequentially connected, the mixed material of each component Successively pass through each area, the temperature in an area is 185-195 DEG C, and the temperature in 2nd area is 215-225 DEG C, the temperature in 3rd area Degree is 225-235 DEG C, and the temperature in 4th area is 235-245 DEG C, and the temperature in 5th area is 245-255 DEG C, 6th area Temperature is 255-265 DEG C, and the temperature in 7th area is 265-275 DEG C, and the temperature in 8th area is 265-275 DEG C, 9th area Temperature be 260-270 DEG C, the temperature of the head is 260-270 DEG C.
22. preparation method according to claim 20, which is characterized in that the screw speed of the double screw extruder is 350-450r/min。
23. preparation method according to claim 20, which is characterized in that the mixed material of each component is in double spiral shells Residence time in bar extruder is 1.5-2min.
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