CN107057321A - Excellent weatherable polycarbonate material of a kind of color and preparation method thereof - Google Patents
Excellent weatherable polycarbonate material of a kind of color and preparation method thereof Download PDFInfo
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- CN107057321A CN107057321A CN201710261533.9A CN201710261533A CN107057321A CN 107057321 A CN107057321 A CN 107057321A CN 201710261533 A CN201710261533 A CN 201710261533A CN 107057321 A CN107057321 A CN 107057321A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- 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
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- 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
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Abstract
The invention discloses a kind of excellent weatherable polycarbonate material of color, include the raw material of following parts by weight：Makrolon：100 parts；Antioxidant：0.5 1 parts；Releasing agent：3 parts；Ultra-violet absorber：24 parts；Light stabilizer：0.5 2 parts；Colouring agent：0.05 0.1 parts；Dispersed lubricant：0.1 1 parts；Colouring agent is at least one of the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.It solves existing weatherability polycarbonate resin the problem of colourity turns yellow, brightness declines after adding raising weatherability auxiliary agent to a certain extent, with the color of weatherable polycarbonate is improved, reduces yellow colour index, improves the advantage of its brightness.
Description
Technical field
The present invention relates to technical field of polymer materials, the excellent weatherable polycarbonate material of more particularly to a kind of color and
Its preparation method.
Background technology
Makrolon is the family macromolecule compound containing carbonate group in molecular structure, at present only fragrant adoption carbon
Acid esters obtains industrialization, using also most extensive.PC is due to extensive with excellent mechanical performance, heat resistance, optical property
For fields such as automobile making, optical lens, CD, building materials, packaging, medicine equipment and electronic apparatus, since industrialization
PC has turned into growth rate most fast engineering plastics.But PC is to notch sensitive, the high not easy mold release of not wear-resistant, melt melting means, no
Resistance to highly basic and ultraviolet etc..Especially when the ester bond of makrolon can be broken by the ultraviolet irradiation of daylight, cause product face
Color change and hydraulic performance decline, so needing to be modified it raising to broadening makrolon application field out of doors, its is weather-proof
Property.
Authorization Notice No. is CN1223278, and authorized announcement date disclosed one kind for the Chinese patent of on 07 21st, 1999
Makrolon (PC) resin combination, this PC resin composition contains (A) 100 parts by weight polyphosphate resin and (B) 0.0001
Parts by weight or more but less than 0.1 parts by weight sulfonic acid phosphonium salt, also contain (C) 0.01 to 10 parts by weight ultra-violet absorber PC
Resin combination.
At present, the preparation of weatherability PC resin is mainly by adding various light stabilizers and ultra-violet absorber, but purple
Outer light absorber generally white or ecru, due to the ultraviolet light of a part itself can be absorbed so that modified is weather-proof poly-
The colourity of carbonic ester sample turns yellow, and brightness declines, and PC particles are presented slightly yellow in itself so that the overall color shades of product
Turn yellow, brightness declines.
The content of the invention
The first object of the present invention is to provide a kind of excellent weatherable polycarbonate material of color, and it is solved to a certain extent
Existing weatherability polycarbonate resin determined the problem of colourity turns yellow, brightness declines after adding raising weatherability auxiliary agent, has had
Improve the color of weatherable polycarbonate, reduce yellow colour index, improve the advantage of its brightness.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of excellent weatherable polycarbonate material of color, a kind of excellent weatherable polycarbonate material of color, it is characterised in that
Include the raw material of following parts by weight：
Makrolon：100 parts；
Antioxidant：0.5-1 parts；
Releasing agent：3 parts；
Ultra-violet absorber：2-4 parts；
Light stabilizer：0.5-2 parts；
Colouring agent：0.04-0.1 parts；
Dispersed lubricant：0.1-1 parts；
Colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.
Using such scheme, there is phenolic hydroxyl group on the organic transparency dye molecule of Anthraquinones, can be with the terminal hydroxy group on PC and PET
Or end carboxyl reacts, therefore with good compatibility, the organic transparency dye of Anthraquinones has with PET/PC composites
There is good compatibility, it is dispersedly visibly homogeneous in PET/PC composites, the color to PET/PC composites is modified
With excellent effect.
More preferably：Include the raw material of following parts by weight：
Makrolon：100 parts；
Antioxidant：1.0 part；
Releasing agent：3.0 part；
Ultra-violet absorber：3.0 part；
Light stabilizer：1.0 part；
Colouring agent：0.1 part；
Dispersed lubricant：1.0 part；
Colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.
More preferably：Colouring agent is the organic transparent blue dyestuff A1 of Anthraquinones, the organic transparent cudbear of Anthraquinones
One or more in the organic transparent cudbear A3 of A2, Anthraquinones；A1, A2, A3 correspond to Germany Lang Shengmagaoliesisheng respectively
The Violet 3R of Violet B, Germany the Lang Shengmagaoliesi production of Blue RR, Germany the Lang Shengmagaoliesi production of production.
More preferably：Colouring agent is the 1 of A1 and A3:1 compounding.
More preferably：Yellow colour index before and after the makrolon material aging prepared is respectively -1.8 and 5.2；
Lightness L values before aging are 95.6, and colourity b values are 0.3；Elongation at break before and after aging is 118 and 100, and aging condition is
Ultra violet lamp 1000h.
More preferably：Antioxidant is that weight compares 1：2 Hinered phenols antioxidant 1010 and phosphite ester kind antioxidant
626 compoundings are formed.
More preferably：Ultraviolet absorber is one kind or many in benzotriazole, triazines, group-substituted acrylonitrile
Kind.
More preferably：Light stabilizer is salicylic acid lipid, benzophenone, benzotriazole, triazines, substitution third
One or more in alkene nitrile, Oxamides, organo-nickel compounds class, hindered amine (HAL) class.
The second object of the present invention is the preparation method for providing a kind of excellent weatherable polycarbonate material of color.
The above-mentioned technical purpose of the present patent application is achieved by technical scheme once：
A kind of preparation method of the excellent weatherable polycarbonate material of color, comprises the following steps：
S1：Makrolon is dried 3~4 hours at a temperature of 120 DEG C~130 DEG C；
S2：Weigh process step (1) the dried makrolon and antioxidant of formula ratio, ultra-violet absorber, releasing agent,
Light stabilizer, dispersed lubricant and colouring agent, the reaction raw materials weighed are stirred 10-30 minutes, are discharged after stirring；S3：
Compound in step S2 is added into double screw extruder, extruded under 260~280 DEG C of temperature conditionss by melting mixing,
Cooling granulation；The temperature conditionss of wherein described double screw extruder are：One 220~240 DEG C of area's temperature, two area's temperature 240~260
DEG C, 260~280 DEG C of three area's temperature, 260~280 DEG C of four area's temperature, 260~280 DEG C of five area's temperature, six area's temperature 260~280
DEG C, seven 260~280 DEG C of area's temperature, eight 260~280 DEG C of area's temperature, 270~280 DEG C of head temperature.
More preferably：The draw ratio of screw rod is 36:1, engine speed is 200~300r/min, and vacuum is -0.2
~-0.5kPa.
In summary, the invention has the advantages that：1st, ultra-violet absorber and light stabilizer are added in PC, it is purple
Ultraviolet absorbers and light stabilizer are salicylic acid lipid, benzophenone, benzotriazole, triazines, group-substituted acrylonitrile, grass
Amide-type, organo-nickel compounds class, the one or more of hindered amine (HAL) class, the good dispersion in matrix resin are easy to shape
Into mixed system, it can improve the performance of PC UV resistant, slow down the xanthochromia process of PC products, improve its long-term use
Colour brightness, improves the color of polycarbonate article after being used for a long time, and reduces yellow colour index；2nd, used on the basis of modified PC
One or more in tri- kinds of toners of A1, A2, A3 are mixed colours, and can improve material modified appearance color, it is in certain journey
Solved on degree existing weatherability polycarbonate resin add improve weatherability auxiliary agent after colourity turn yellow, brightness decline ask
Topic, with the color of weatherable polycarbonate is improved, reduces yellow colour index, improves the advantage of its brightness；3rd, antioxidant is hindered phenol
Kind antioxidant 1010 is formed with the compounding of phosphite ester kind antioxidant 626, it is only necessary to which a small amount of, the two compounding just can delay or suppress PC
The progress of macromolecular oxidizing process, prevents PC agings in external environment condition, reduces the xanthochromia effect that aging is brought, and extend product
Service life.
Embodiment
The present invention is described in further detail below.
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification without creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected in the protection domain of invention by Patent Law.
A kind of embodiment 1-4, the excellent weatherable polycarbonate material of color, is prepared as follows, formula and component
Referring to table 1：
S1：PC is positioned over after being dried 4 hours in 120 DEG C of blast drier according to each material component and its weight in table 1
Proportioning, is weighed by dried PC, light stabilizer, dispersed lubricant, antioxidant, colouring agent, and all reactions weighed are former
Material is stirred 30 minutes in high-speed mixer, obtains well mixed material；
S2：By the mixed material prepared in above-mentioned steps feeding double screw extruder, (draw ratio is 36：1) in, at 260-280 DEG C
Temperature conditionss under by melting mixing extrusion, cooling granulation, obtain the weather-proof makrolon material finished product of the demoulding.
Wherein, the process conditions of double screw extruder are：One 220 DEG C of area's temperature, two 240 DEG C of area's temperature, three area's temperature 260
DEG C, 280 DEG C of four area's temperature, 280 DEG C of five area's temperature, 280 DEG C of six area's temperature, seven 280 DEG C of area's temperature, eight 280 DEG C of area's temperature, head
270 DEG C of temperature, engine speed is 250r/min, vacuum -0.3kPa.
The embodiment 1-4 of table 1 raw material components and content table
Wherein, antioxidant is that weight compares 1：2 Hinered phenols antioxidant 1010 and phosphite ester kind antioxidant 626 compound and
Into；Releasing agent is pentaerythritol stearate PETS；Ultraviolet absorber is 2-hydroxy-4-n-octoxybenzophenone；Colouring agent
It is two kinds of toners of A1 and A3 with mass ratio 1:1 compounding；Dispersed lubricant is TAS-2A；Light stabilizer be decanedioic acid it is double (2,2,6,
6- tetramethyl -4- hydroxy piperidines) ester.
Embodiment 5：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, releasing agent contains
Measure as 2 parts.
Embodiment 6：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, releasing agent contains
Measure as 4 parts.
Embodiment 7：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, ultraviolet radiation absorption
The content of agent is 4 parts.
Embodiment 8：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, light stabilizer
Content for 2 parts.
Embodiment 9：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
0.1 part of A1.
Embodiment 10：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
0.1 part of A2.
Embodiment 11：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
0.1 part of A3.
Embodiment 12：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
The 1 of A1 and A2:1 compounding, A1 and A2 total amount are 0.1 part.
Embodiment 13：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
The 1 of A2 and A3:1 compounding, A2 and A3 total amount are 0.1 part.
Embodiment 14：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that colouring agent is
The 4 of A1, A2 and A3:3:3 compoundings, A1, A2 and A3 total amount are 0.1 part.
Embodiment 15-17：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, adopts respectively
Pentaerythritol stearate PETS is replaced with the monoglyceride, silicone oil or paraffin of equivalent.
Embodiment 18：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that antioxidant is
1.0 parts of Hinered phenols antioxidant 1076.
Embodiment 19：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that antioxidant is
1.0 parts of phosphite ester kind antioxidant 626.
Embodiment 20：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is, the length of screw rod
Footpath ratio is 50:1.
Embodiment 21：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that twin-screw is squeezed
The process conditions for going out machine are：One 220 DEG C of area's temperature, two 240 DEG C of area's temperature, 260 DEG C of three area's temperature, 260 DEG C of four area's temperature, 5th area
260 DEG C of temperature, 280 DEG C of six area's temperature, seven 280 DEG C of area's temperature, eight 280 DEG C of area's temperature, 270 DEG C of head temperature, engine speed is
300r/min, vacuum -0.5kPa.
Embodiment 22：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that twin-screw is squeezed
The process conditions for going out machine are：One 240 DEG C of area's temperature, two 260 DEG C of area's temperature, 280 DEG C of three area's temperature, 280 DEG C of four area's temperature, 5th area
280 DEG C of temperature, 260 DEG C of six area's temperature, seven 260 DEG C of area's temperature, eight 260 DEG C of area's temperature, 270 DEG C of head temperature, engine speed is
200r/min, vacuum -0.2kPa.
Embodiment 23：A kind of excellent weatherable polycarbonate material of color, the difference with embodiment 3 is that twin-screw is squeezed
The process conditions for going out machine are：One 240 DEG C of area's temperature, two 260 DEG C of area's temperature, 280 DEG C of three area's temperature, 280 DEG C of four area's temperature, 5th area
280 DEG C of temperature, 270 DEG C of six area's temperature, seven 270 DEG C of area's temperature, eight 270 DEG C of area's temperature, 270 DEG C of head temperature, engine speed is
200r/min, vacuum -0.2kPa.
Performance test and evaluation
For the performance of the embodiment of testing and evaluate the present patent application, following comparative example is prepared for as control sample.Comparative example
1-3 preparation method such as embodiment 3, each component and content are referring to table 2.
The comparative example 1-3 of table 2 raw material components and content table
Wherein, antioxidant is that weight compares 1：2 Hinered phenols antioxidant 1010 and phosphite ester kind antioxidant 626 compound and
Into；Releasing agent is pentaerythritol stearate PETS；Ultraviolet absorber is 2-hydroxy-4-n-octoxybenzophenone；Colouring agent
It is two kinds of toners of A1 and A3 with mass ratio 1:1 compounding；Dispersed lubricant is TAS-2A；Light stabilizer be decanedioic acid it is double (2,2,6,
6- tetramethyl -4- hydroxy piperidines) ester.
Test object is：Embodiment 1-4, embodiment 9-14 and comparative example 1-3；Test event, testing standard and test-strips
Part is as shown in table 3；Test result is as shown in table 4 and table 5.
The performance test conditions of table 3 and standard
The embodiment 1-4 of table 4, comparative example 1-3 the performance test results
Results showed that from embodiment 1-4 is with antioxidant and the increase of ultraviolet radiation absorption agent content, and xenon lamp aging is surveyed
Yellow colour index in examination is gradually reduced, and the elongation at break of sample is improved after heat ageing, illustrates the resistance to ultraviolet and ageing-resistant of sample
Performance is obviously improved.The colouring agent of compounding is with the addition of in the present invention to improve the appearance colour of product, from embodiment 1 to implementation
Example 4 component proportioning understand, with compound colorant addition increase, although the lightness L values of sample have to a certain degree decline,
But sample initial stage yellow colour index and colourity b values be then decreased obviously.The effect of synergy is served by the cooperation between various auxiliary agents,
Finally give a kind of makrolon material of the excellent weatherability of color.
The embodiment 3 of table 5, embodiment 9-14 the performance test results
It is excellent that results showed that according to 3 and embodiment 9-14 is implemented individually carries out color using colouring agent A1, A2 or A3
Change, the effect when effect of optimization of its color to PC products is compounded than colouring agent is poor.Specific result is embodied in yellow and referred to
It is on number：It is individually maximum using the yellow colour index before and after colouring agent A1, A2 or A3 PC product agings, A2 and A3 compoundings time
It, third, yellow colour index is minimum when A1 and A3 are compounded for A1, A2, A3 compounding and A1, A2 compounding.Although after addition compounding
Toner has certain decline in lightness L values, but colourity b values have obvious reduction, and colourity b values are most when wherein A1, A3 are compounded
It is low.Result above shows that the colouring agent obtained during A1 and A3 compoundings is optimal to the color modified effect of PC products.
Claims (10)
1. a kind of excellent weatherable polycarbonate material of color, it is characterized in that, include the raw material of following parts by weight：
Makrolon：100 parts；
Antioxidant：0.5-1 parts；
Releasing agent：3 parts；
Ultra-violet absorber：2-4 parts；
Light stabilizer：0.5-2 parts；
Colouring agent：0.04-0.1 parts；
Dispersed lubricant：0.1-1 parts；
The colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.
2. a kind of excellent weatherable polycarbonate material of color according to claim 1, it is characterized in that：Including following weight
The raw material of part：
Makrolon：100 parts；
Antioxidant：1.0 part；
Releasing agent：3.0 part；
Ultra-violet absorber：3.0 part；
Light stabilizer：1.0 part；
Colouring agent：0.1 part；
Dispersed lubricant：1.0 part；
The colouring agent is the one or more in the organic transparent blue dyestuff of Anthraquinones and the organic transparent cudbear of Anthraquinones.
3. a kind of excellent weatherable polycarbonate material of color according to claim 1, it is characterized in that：The colouring agent is
In the organic transparent cudbear A2 of the organic transparent blue dyestuff A1 of Anthraquinones, Anthraquinones, the organic transparent cudbear A3 of Anthraquinones
One or more；A1, A2, A3 correspond to Blue RR, the Germany Lang Shengmagaoliesisheng of Germany Lang Shengmagaoliesi productions respectively
The Violet 3R of Violet B, Germany the Lang Shengmagaoliesi production of production.
4. a kind of excellent weatherable polycarbonate material of color according to claim 3, it is characterized in that：The colouring agent is
The 1 of A1 and A3:1 compounding.
5. a kind of excellent weatherable polycarbonate material of color according to claim 4, it is characterized in that：What is prepared is poly-
Yellow colour index before and after carbonate material aging is respectively -1.8 and 5.2；Lightness L values before aging are 95.6, and colourity b values are
0.3；Elongation at break before and after aging is 118 and 100, and aging condition is ultra violet lamp 1000h.
6. a kind of excellent weatherable polycarbonate material of color according to claim 1, it is characterized in that：The antioxidant is
Weight compares 1：2 Hinered phenols antioxidant 1010 is formed with the compounding of phosphite ester kind antioxidant 626.
7. a kind of excellent weatherable polycarbonate material of color according to claim 1, it is characterized in that：The UV absorption
Agent is the one or more in benzotriazole, triazines, group-substituted acrylonitrile.
8. a kind of excellent weatherable polycarbonate material of color according to claim 1, it is characterized in that：The light stabilizer
For salicylic acid lipid, benzophenone, benzotriazole, triazines, group-substituted acrylonitrile, Oxamides, organo-nickel compounds
One or more in class, hindered amine (HAL) class.
9. a kind of a kind of preparation side of the excellent weatherable polycarbonate material of color in 1-8 such as claim as described in any one
Method, it is characterized in that, comprise the following steps：S1：Makrolon is dried 3~4 hours at a temperature of 120 DEG C~130 DEG C；S2：Claim
Take process step (1) the dried makrolon and antioxidant of formula ratio, ultra-violet absorber, releasing agent, light stabilizer,
Dispersed lubricant and colouring agent, the reaction raw materials weighed are stirred 10-30 minutes, are discharged after stirring；S3：By in step S2
Compound add double screw extruder, under 260~280 DEG C of temperature conditionss by melting mixing extrusion, cooling granulation；Its
Described in the temperature conditionss of double screw extruder be：One 220~240 DEG C of area's temperature, two 240~260 DEG C of area's temperature, three area's temperature
260~280 DEG C, four 260~280 DEG C of area's temperature, five 260~280 DEG C of area's temperature, six 260~280 DEG C of area's temperature, seven area's temperature
260~280 DEG C, eight 260~280 DEG C of area's temperature, 270~280 DEG C of head temperature.
10. a kind of preparation method of the excellent weatherable polycarbonate material of color according to claim 9, it is characterized in that：
The draw ratio of the screw rod is 36:1, engine speed is 200~300r/min, and vacuum is -0.2~-0.5kPa.
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| 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 |
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Application publication date: 20170818 |