CN105175924A - Antistatic master batch, PC alloy with the same and preparing method of PC alloy - Google Patents
Antistatic master batch, PC alloy with the same and preparing method of PC alloy Download PDFInfo
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Abstract
The invention relates to an antistatic master batch, PC alloy with the same and a preparing method of the PC alloy. The antistatic master batch is prepared from, by weight, 55 parts to 80 parts of AS resin, 15 parts to 35 parts of antistatic agents, 5 parts to 10 parts of carbon black, 0.5 part to 3 parts of dispersing assistants, 0.1 part to 1 part of antioxidants and 0.1 part to 1 part of lubricating agents. The PC alloy with the master batch is prepared from, by weight, 60 parts to 90 parts of polycarbonate resin, 20 parts to 30 parts of the antistatic master batch, 2 parts to 5 parts of flexibilizers, 0.1 part to 2 parts of antioxidants and 0.1 part to 2 parts of lubricating agents. The preparing method of the PC alloy includes the steps that antistatic agents are dispersed in PC alloy materials through secondary extruding, a conductive network is formed, and therefore the antistatic effect is better achieved. Compared with the prior art, the PC alloy prepared with the preparing method has the advantages of being resistant to static electricity, free of spraying, black, bright and the like.
Description
Technical field
The present invention relates to technical field of macromolecules, especially relate to a kind of antistatic master granule and spray the black PC Alloy And Preparation Method of high light containing antistatic the exempting from of this master batch.
Background technology
In recent years, the interior exterior trim that high light piano was black becomes and is being applied to the stylishness promoting automobile class and meet young consumers demand more and more.At present, the main complete processing of the black inside gadget of high light is that plastic component spray piano is pitch-dark, can improve product scrape resistant and ageing-resistant performance while realizing black decorative effect bright again.Another mode adopts to exempt to spray the black plastics of high light, can reduce operation, improve product yield, reduce and pollute and cost.
At present, the plastics that exempting from market sprays high light black mainly contain ABS, ASA, PMMA, PA, PC and ABS/PMMA alloy, PC/ABS alloy etc., there is heat-resisting lower shortcoming in ABS resin, and the impact resistance of PMMA resin is poor, and PC resin and alloy thereof are widely used in automotive upholstery due to the thermotolerance of its excellence and impact resistance.
PC resin and alloy thereof are all electrically insulating materials, and surface resistivity is higher, in use easily produce accumulation of static electricity, thus cause dust suction.Dust drops on exempts to spray the black plastic part surface of high light and seems comparatively obvious, must carry out continually cleaning and cleaning, thus cause surface scratch, affect attractive in appearance.
The antistatic ageing-resistant Masterbatch of Chinese patent CN104725809A PC, its component by mass percent proportioning is: vector resin 15% ~ 30%, static inhibitor 20% ~ 30%, antiaging agent 20% ~ 30%, carbon black 15% ~ 30%, oxidation inhibitor 2% ~ 6%, dispersion agent 2% ~ 5%, and described vector resin is bisphenol A-type aromatic copolycarbonate (PC).Each component is taken by weight ratio during preparation, and add in high-speed mixing and stir 5 ~ 30 minutes together, make fully mixing and dispersed after, discharging adds in twin screw extruder, extrude through melting mixing at 230 DEG C ~ 260 DEG C, cooling granulation, and dry rear packaging, get product, the vector resin PC of high molecular due to what use in the antistatic master granule in this patent, melt viscosity is larger, be unfavorable for the dispersion of static inhibitor and carbon black, easily cause pit, and can not be used in the black system of high light.
Chinese patent CN104788932A antistatic PC/ASA alloy material disclosing a kind of excellent heat stability and preparation method thereof; Described PC/ASA alloy material comprises following component PC resin, ASA resin, static inhibitor, toughner, oxidation inhibitor, lubricant by certainweight number.After the preparation method of described alloy comprises the steps: various resin and auxiliary agent to add and mixes in mixing and blending machine, by the main spout feeding of twin screw extruder, feed mouth by high-pressure inert gas from the side of forcing machine to inject, blended granulation, through melt extruding, namely granulation obtains product, the antistatic PC/ASA resin of obtained excellent heat stability.This patent, in order to promote that the dispersion of static inhibitor adopts high-pressure inert gas both to add cost, also improves requirement to production safety management and control.
Summary of the invention
Object of the present invention is exactly provide a kind of antistatic master granule to overcome defect that above-mentioned prior art exists and exempt to spray the black PC alloy of high light and preparation method containing the antistatic of this master batch, the PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again.
Object of the present invention can be achieved through the following technical solutions:
A kind of antistatic black masterbatch, this master batch comprises the component of following weight part content:
Described AS resin is the acrylonitritrile-styrene resin of molecular weight 1000 ~ 2000.
Described static inhibitor is permanent antistatic agent, preferably has the static inhibitor of polyether block structure.
Described dispersing auxiliary is the amphiphilic silicone composite with block structure.
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid Octadecane alcohol ester, three (2,4-di-t-butyl) phenyl-phosphites or distearyl pentaerythritol diphosphite;
Described lubricant is one or more in silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleylamide or ethylene bis stearamide.
PC alloy containing described antistatic black masterbatch, this alloy comprises the component of following weight part content:
Described polycarbonate (PC) resin is bisphenol A polycarbonate resin, and its melting index under 300 DEG C/1.2kg condition is 8 ~ 20g/10min.
Described toughner is one or more in methyl methacrylate, divinyl, styrene copolymer or CALCIUM ACRYLATE analog copolymer;
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid Octadecane alcohol ester, three (2,4-di-t-butyl) phenyl-phosphites or distearyl pentaerythritol diphosphite;
Described lubricant is one or more in silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleylamide or ethylene bis stearamide.
The preparation method of PC alloy, the method comprises the following steps:
(1) AS resin, carbon black, static inhibitor, dispersing auxiliary, oxidation inhibitor, lubricant are mixed at high-speed mixer according to proportioning;
(2) mixture of step (1) gained is added twin screw extruder melt blending to extrude, controlling extrusion temperature is 170 ~ 230 DEG C, screw speed is 200 ~ 500rpm, and pressure is 2 ~ 3MPa, after underwater cutpellet is dried, obtain antistatic black masterbatch;
(3) polycarbonate resin, antistatic black masterbatch, toughner, oxidation inhibitor, lubricant are mixed in high-speed mixer according to proportioning;
(4) mixture of step (3) gained is added twin screw extruder melt blending to extrude, controlling extruder temperature is 180 ~ 270 DEG C, and screw speed 300 ~ 600rpm, pressure is 2 ~ 3MPa.Obtain antistatic exempting from through water-cooled granulation and spray the black PC alloy of high light.
(5) the described twin screw extruder length-to-diameter ratio of step (2) is 40:1 ~ 50:1, and the described twin screw extruder length-to-diameter ratio of step (4) is 32:1 ~ 40:1.
The present invention utilizes lower molecular weight AS resin to provide the mobility of the black plastics indispensability of high light, and less to material monolithic material properties affect.And carbon black is as Absorbable rod UV-light while tinting material, improve the weathering resistance of goods.In addition, permanent antistatic agent is tentatively dispersed in high flowing AS through long bolt and more weak shearing, and the Strong shear extruded through secondary carries out redispersion at PC melt, form conductive network, reduce surface resistivity, reach dust-proof object, and then reduce the surface scratch caused because of scouring dust.
Compared with prior art, the present invention has the following advantages: make antistatic black masterbatch by the AS resin that static inhibitor and carbon black dispersion flowed at height, make carbon black and static inhibitor be dispersed in PC base material better, obtain antistatic property excellence exempt from spray the black PC alloy material of high light.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
The raw material used in embodiment 1 ~ 3 and comparative example 1 ~ 3 is specially:
Polycarbonate (PC) resin is 2400 of Bayer company;
AS resin is the EMI200 of Shanghai Zhi Sheng company;
Static inhibitor is the P18 of BASF AG;
Toughner is the EM500 of LG company;
Oxidation inhibitor is IRGANOX1010 and the IRGANOX168 mixture of BASF AG, and ratio is 1:1;
Carbon black is the Black9550WA of Cabot Co., Ltd;
Dispersing auxiliary is the TEGOMERP121 of goldschmidt chemical corporation;
Lubricant is commercially available silicone powder.
Comparative example 1
This comparative example antistatic is exempted to spray the black PC alloy of high light and is prepared by the following method and obtain:
1) take each component by weight: PC resin 80, AS resin 21, static inhibitor 7.5, carbon black 1.5, dispersing auxiliary 1, oxidation inhibitor 0.2, lubricant 0.3, mixes 20min in high mixing machine.
2) join twin screw extruder by said mixture from main spout, melt extrude at 240 ~ 260 DEG C, screw speed is 500rpm, through underwater cutpellet, obtains product through water-cooled granulation.
Comparative example 2
This comparative example antistatic is exempted to spray the black PC alloy of high light and is prepared by the following method and obtain:
1) take each component by weight: PC resin 100, carbon black 1.5, dispersing auxiliary 1, oxidation inhibitor 0.2, lubricant 0.3, in high mixing machine, mix 20min.
2) join twin screw extruder by said mixture from main spout, melt extrude at 240 ~ 270 DEG C, screw speed is 500rpm, through underwater cutpellet, obtains product through water-cooled granulation.
Comparative example 3 and embodiment 1 ~ 3
Comparative example 3 and embodiment 1 ~ 3 antistatic is exempted to spray the black PC alloy material of high light and is prepared by the following method and obtain, table 1 is comparative example 3 and each component of the antistatic black masterbatch of embodiment 1 ~ 3 and parts by weight thereof, and table 2 is comparative example 3 and each component of embodiment 1 ~ 3 and parts by weight thereof.
(1) take each component according to the component shown in table 1 and weight, in high mixing machine, mix 20min.
(2) join twin screw extruder by the mixture that step (1) obtains from main spout, melt extrude at 180 ~ 240 DEG C, screw speed is 450rpm, through underwater cutpellet, obtains antistatic black masterbatch after oven dry.
(3) take each component according to the component shown in table 2 and weight, in high-speed mixer, mix 20min.
(4) join twin screw extruder by the mixture that step (3) obtains from main spout, melt extrude at 200 ~ 260 DEG C, screw speed is 500rpm, obtains product through water-cooled granulation.
Table 1
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 3 |
| AS resin | 55 | 70 | 80 | 93 |
| Static inhibitor | 35 | 25 | 15 | / |
| Carbon black | 10 | 5 | 5 | 7 |
| Dispersing auxiliary | 3 | 2 | 2 | 2 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant | 0.3 | 0.3 | 0.3 | 0.3 |
Table 2
| Component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 3 |
| PC resin | 90 | 60 | 80 | 80 |
| Antistatic black masterbatch | 20 | 35 | 30 | 22.5 |
| Static inhibitor | / | / | / | 7.5 |
| Toughner | 3 | 5 | 4 | 4 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant | 0.3 | 0.3 | 0.3 | 0.3 |
Note: in table 1 and table 2, "/" represents not containing this component.
Performance Detection
After the abundant drying of composition particle prepared by above-mentioned comparative example and embodiment, be injection molded into the high tabula rasa of 140*90*3mm, carry out properties contrast test.Table 3 comparative example 1 ~ 3 and embodiment 1 ~ 3 product test result.
Table 3
Note: ★ more multilist shows that pit is more serious, and ☆ more multilist shows to fall that ash is more serious.
Embodiment 4
The present embodiment is substantially the same manner as Example 1, difference is that the molecular weight of the AS resin used is 1000, used toughner is CALCIUM ACRYLATE analog copolymer, and oxidation inhibitor used is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 5
The present embodiment is substantially the same manner as Example 1, and difference is that the molecular weight of the AS resin used is 2000, and used oxidation inhibitor is 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane alcohol ester.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 6
The present embodiment is substantially the same manner as Example 1, and difference is that used oxidation inhibitor is the mixture of three (2,4-di-t-butyl) phenyl-phosphites and distearyl pentaerythritol diphosphite.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 7
The present embodiment is identical with the concrete material used by embodiment, and difference is,
(1) take AS resin 70 parts by weight, 20 parts, static inhibitor, carbon black 8 parts, dispersing auxiliary 3 parts, 0.1 part, oxidation inhibitor, lubricant 0.1 part, mixes 20min in high mixing machine.
(2) mixture of step (1) gained is added twin screw extruder melt blending to extrude, twin screw extruder length-to-diameter ratio is 40:1, and controlling extrusion temperature is 170 DEG C, and screw speed is 200rpm, pressure is 2MPa, after underwater cutpellet is dried, obtain antistatic black masterbatch.
(3) take PC resin 75 parts by weight, antistatic black masterbatch 30 parts, toughner 2 parts, 2 parts, oxidation inhibitor, lubricant 2 parts, mixes 20min in high-speed mixer.
(4) mixture that step (3) obtains is joined twin screw extruder from main spout, twin screw extruder length-to-diameter ratio is 32:1, and controlling extruder temperature is 180 DEG C, screw speed 300rpm, pressure is 2MPa, obtains product through water-cooled granulation.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 8
The present embodiment is identical with the concrete material used by embodiment, and difference is,
(1) take AS resin 70 parts by weight, 20 parts, static inhibitor, carbon black 8 parts, dispersing auxiliary 0.5 part, 1 part, oxidation inhibitor, lubricant 1 part, mixes 20min in high mixing machine.
(2) mixture of step (1) gained is added twin screw extruder melt blending to extrude, twin screw extruder length-to-diameter ratio is 50:1, and controlling extrusion temperature is 230 DEG C, and screw speed is 500rpm, pressure is 3MPa, after underwater cutpellet is dried, obtain antistatic black masterbatch.
(3) take PC resin 75 parts by weight, antistatic black masterbatch 30 parts, toughner 5 parts, 0.1 part, oxidation inhibitor, lubricant 0.1 part, mixes 20min in high-speed mixer.
(4) mixture that step (3) obtains is joined twin screw extruder from main spout, twin screw extruder length-to-diameter ratio is 40:1, and controlling extruder temperature is 270 DEG C, screw speed 600rpm, pressure is 3MPa, obtains product through water-cooled granulation.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 9
The present embodiment is substantially the same manner as Example 2, and difference is that used lubricant is silicone oil.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 10
The present embodiment is substantially the same manner as Example 2, and difference is that used lubricant is paraffin.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 11
The present embodiment is substantially the same manner as Example 2, and difference is that used lubricant is the mixture of stearic acid and butyl stearate.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 12
The present embodiment is substantially the same manner as Example 2, and difference is that used lubricant is oleylamide.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Embodiment 13
The present embodiment is substantially the same manner as Example 2, and difference is that used lubricant is ethylene bis stearamide.The PC alloy prepared have antistatic, exempt from spraying, the black feature such as bright again, antistatic black masterbatch is uniformly dispersed in system.
Claims (10)
1. an antistatic black masterbatch, is characterized in that, this master batch comprises the component of following weight part content:
2. antistatic black masterbatch according to claim 1, is characterized in that, described AS resin is the acrylonitritrile-styrene resin of molecular weight 1000 ~ 2000.
3. antistatic black masterbatch according to claim 1, is characterized in that, described static inhibitor is permanent antistatic agent, comprises the static inhibitor with polyether block structure.
4. antistatic black masterbatch according to claim 1, is characterized in that, described dispersing auxiliary is the amphiphilic silicone composite with block structure.
5. antistatic black masterbatch according to claim 1, is characterized in that,
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid Octadecane alcohol ester, three (2,4-di-t-butyl) phenyl-phosphites or distearyl pentaerythritol diphosphite;
Described lubricant is one or more in silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleylamide or ethylene bis stearamide.
6. the PC alloy containing the antistatic black masterbatch according to any one of Claims 1 to 5, it is characterized in that, this alloy comprises the component of following weight part content:
7. PC alloy according to claim 6, is characterized in that, described polycarbonate resin is bisphenol A polycarbonate resin, and the melting index under 300 DEG C/1.2kg condition is 8 ~ 20g/10min.
8. PC alloy according to claim 6, is characterized in that,
Described toughner is one or more in methyl methacrylate, divinyl, styrene copolymer or CALCIUM ACRYLATE analog copolymer;
Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 3-(3,5-di-tert-butyl-hydroxy phenyl) one or more in propionic acid Octadecane alcohol ester, three (2,4-di-t-butyl) phenyl-phosphites or distearyl pentaerythritol diphosphite;
Described lubricant is one or more in silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleylamide or ethylene bis stearamide.
9. the preparation method of PC alloy as claimed in claim 6, it is characterized in that, the method comprises the following steps:
(1) AS resin, carbon black, static inhibitor, dispersing auxiliary, oxidation inhibitor, lubricant are mixed at high-speed mixer according to proportioning;
(2) mixture of step (1) gained is added twin screw extruder melt blending to extrude, controlling extrusion temperature is 170 ~ 230 DEG C, screw speed is 200 ~ 500rpm, and pressure is 2 ~ 3MPa, after underwater cutpellet is dried, obtain antistatic black masterbatch;
(3) polycarbonate resin, antistatic black masterbatch, toughner, oxidation inhibitor, lubricant are mixed in high-speed mixer according to proportioning;
(4) mixture of step (3) gained is added twin screw extruder melt blending to extrude, controlling extruder temperature is 180 ~ 270 DEG C, and screw speed 300 ~ 600rpm, pressure is 2 ~ 3MPa.Obtain antistatic exempting from through water-cooled granulation and spray the black PC alloy of high light.
10. the preparation method of PC alloy according to claim 9, is characterized in that, the described twin screw extruder length-to-diameter ratio of step (2) is 40:1 ~ 50:1, and the described twin screw extruder length-to-diameter ratio of step (4) is 32:1 ~ 40:1.
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| CN108329673A (en) * | 2018-01-05 | 2018-07-27 | 上海阿莱德实业股份有限公司 | A kind of highly conductive polycarbonate composite material of high tenacity and preparation method thereof |
| CN109438867A (en) * | 2018-11-13 | 2019-03-08 | 上海博怀化工有限公司 | High glaze, the dedicated master batch of high blackness applied to PC |
| CN111251494A (en) * | 2020-01-21 | 2020-06-09 | 天津利安隆新材料股份有限公司 | Preparation method of low-melting-point weather-resistant auxiliary agent master batch |
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