CN103923306A - Liquid crystal polyester and liquid crystal polyester composition consisting of liquid crystal polyester and application of liquid crystal polyester composition - Google Patents
Liquid crystal polyester and liquid crystal polyester composition consisting of liquid crystal polyester and application of liquid crystal polyester composition Download PDFInfo
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- CN103923306A CN103923306A CN201410137929.9A CN201410137929A CN103923306A CN 103923306 A CN103923306 A CN 103923306A CN 201410137929 A CN201410137929 A CN 201410137929A CN 103923306 A CN103923306 A CN 103923306A
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Abstract
The invention relates to liquid crystal polyester which comprises the following repetitive units: FORMULAES (I-V) shown in the specification, wherein the monomers corresponding to the repetitive units (I-V) are respectively FORMULAES (A-E) shown in the specification. Based on all repetitive units, the molar percentage of the formula (I) is 50-64%, the sum of the molar percentages of the formulae (II and III) is 18-25%, the molar percentage of the formula (II) accounts for 0-25% of the sum of the molar percentages of the formulae (II and III), the sum of the molar percentages of the formulae (IV and V) is 18-25%, and the molar percentage of the formula (V) accounts for 24-60% of the sum of the molar percentages of the formulae(IV and V). A liquid crystal polyester composition consisting of the liquid crystal polyester comprises the following components in percentage by weight: 45-70wt% of liquid crystal polyester, 25-50wt% of inorganic filler and 0.1-5wt% of fluorine-containing polymers. The liquid crystal polyester composition has excellent high-temperature-resisting foaming characteristic and flatness and is suitable for workpieces of thin-wall electrical and electronic connectors with the thickness being less than 0.15mm.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of liquid crystal polyester and consisting of liquid-crystalline polyester composition and application thereof.
Background technology
Liquid crystal polyester (LCP) has excellent thermotolerance, dimensional stability, electrical property and processing fluidity, in field widespread uses such as junctors.
Along with miniaturization, the thin-walled property of electronic apparatus product, promote the development of electronic component densification, microminiaturization and high density packaging technique, the temperature tolerance of LCP material used is required also to improve constantly.Particularly adopt surface mounting technique (Surface Mount Technology is called for short SMT), the temperature tolerance of LCP material used is had higher requirement, conventionally require its heat-drawn wire (HDT) to be greater than 270 DEG C.
In order to improve the HDT of LCP material, United States Patent (USP) 5037939 has disclosed derived from P-hydroxybenzoic acid, Resorcinol, two parts, biphenyl, terephthalic acid/or the LCP resin of m-phthalic acid monomeric unit, in the time that the mol ratio of m-phthalic acid monomer and terephthalic acid monomers is 0.24:1 to 0.68:1, the HDT of its composition can exceed 275 DEG C.7304121 of United States Patent (USP)s have disclosed derived from P-hydroxybenzoic acid, '-biphenyl diphenol, terephthalic acid, 2, the LCP resin of 6-naphthalic acid monomeric unit, when 2, the mole number of 6-naphthalic acid accounts for 2, between 6-naphthalic acid and 0.05 to 0.3 of terephthalic acid mole number sum time, the HDT of gained LCP resin is greater than 280 DEG C.
But, in improving the HDT of LCP material, the mobility of LCP material is subject to certain impact also, planar connector taking CPU slot as representative is example, its contact pin quantity is along with the densification of junctor requires also increasing, and the spacing of contact pin reduces accordingly, keeps the resin width of pin holes also to reduce accordingly, traditional LCP material is during by this type of junctor of injection moulding, may due to its illiquidity occur local fill bad.
In order to improve the mobility of LCP material, United States Patent (USP) 6656386 has disclosed the LCP material that adopts the LCP resin of two kinds of different melt temperatures and the composition of glass fibre blend formation can obtain good fluidity.
Therefore, develop a kind of have the gas generated liquid crystal polyester of low melting glass and low levels and consisting of liquid-crystalline polyester composition seem very important.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of gas generated liquid crystal polyester with low melting glass and low levels.
Another object of the present invention is to provide the liquid-crystalline polyester composition that comprises above-mentioned liquid crystal polyester.
A further object of the present invention is to provide the purposes of above-mentioned liquid-crystalline polyester composition.
The present invention is achieved through the following technical solutions:
A kind of liquid crystal polyester, comprises following repeating unit:
（Ⅰ）；
（Ⅱ）；
（Ⅲ）；
（Ⅳ）；
（Ⅴ）；
Described repeating unit (I), (II), (III), (IV), monomer corresponding to (V) are respectively
(A),
(B),
(C),
(D) and
(E);
Wherein, based on whole repeating units, the molar percentage of the repeating unit shown in formula I is 50-64%, the molar percentage sum of the repeating unit shown in formula II, (III) is 18-25%, and formula II accounts for the 0-25% of the molar percentage sum of the repeating unit shown in (II), (III); The molar percentage sum of the repeating unit shown in formula IV, (V) is 18-25%, and formula (V) accounts for the 24-60% of the molar percentage sum of the repeating unit shown in formula IV, (V).
Wherein, the melt temperature that described liquid crystal polyester is measured by differential scanning calorimeter is 326-353 DEG C.
A kind of preparation method of above-mentioned liquid crystal polyester:
A) by monomer (A), (B), (C), (D) with (E) by under proportioning and acylating agent and catalyst action, at 120-150 DEG C of acetylize 1-6 hour, be warming up to the above 0-25 DEG C of this prepolymer melt temperature with the speed of 10-60 DEG C/h, and insulation reaction 10 minutes to 4 hours; The pressure-controlling of reaction system is 133-101080Pa, and melt polymerization prepares prepolymer;
B) prepolymer of molten state is discharged to cooling rear granulation by reaction container bottom under the impressed pressure of 0.05-0.6MPa, obtain prepolyer granule;
C) by gained prepolyer granule temperature of reaction of 10-80 DEG C below prepolymer melt temperature, pressure≤1000 Pa, under the condition of reaction times 1-24 hour, heating solid state polymerization obtains expecting the liquid crystal polyester of viscosity.
Monomer in described step a) (D), (E) both feed intake mole number sum with (B), the ratio of (C) both mole number sums that feeds intake is 1.05-1:1.
In described step a), acylating agent is acetic anhydride, and the consumption of described acylating agent is 1-1.5 times of monomer hydroxyl mole number, and preferably 1.02-1.2 doubly.
In described step a), catalyzer comprises the lewis acid of dialkyl tin oxide, diaryltin oxide compound, titan-alkoxide class, alkali and alkaline-earth metal salt and BF3 and so on, wherein the acetate of the preferred Zn of catalyzer, K, Mg, Ca or Co or fragrant hydrochlorate are catalyzer, be preferably magnesium acetate, the consumption of described catalyzer is the 0.001-1% based on total monomer weight, preferably 0.05-0.2%.
Prepolymer in described step a) is higher than 10 DEG C of its melt temperatures, 1000s
-1under shearing rate, be 3-6Pa.s by the melt viscosity of capillary rheometer determining.
The cross-sectional area of the prepolyer granule in described step b) is 7-24mm
2, length is 3-6mm; Spherical or ellipticity particle volume is 15-65mm
3.
Wherein, the liquid crystal polyester preparing by aforesaid method is higher than 20 DEG C of its melt temperatures, 1000s
-1under shearing rate, be 15-100Pa.s by the melt viscosity of capillary rheometer determining, preferably 20-50Pa.s.
The present invention further provides the liquid-crystalline polyester composition that comprises above-mentioned liquid crystal polyester, can be used for multiple fields by the liquid-crystalline polyester composition that adds one or more additives to obtain.
A composition for liquid crystal polyester, percentage ratio meter by weight, comprises following component:
Liquid crystal polyester 45 ~ 70wt%;
Mineral filler 25 ~ 50wt%;
Fluoropolymer 0.1 ~ 5wt%.
Described mineral filler is selected from one or more in wollastonite, mica, barium sulfate, calcium carbonate, silicon-dioxide, titanium dioxide, talcum powder; Be preferably mica; The mica that more preferably median size is 0.8 ~ 105um; Wherein, mica can be phlogopite, can be also white mica.
Described fluoropolymer is selected from one or more in tetrafluoroethylene, fluorinated ethylene propylene copolymer, polyvinylidene difluoride (PVDF); Be preferably tetrafluoroethylene; More preferably melt temperature is not higher than the tetrafluoroethylene of 330 DEG C, and wherein, the melt temperature of tetrafluoroethylene is measured by DSC.
A preparation method for above-mentioned liquid-crystalline polyester composition, comprises the steps:
A) join forcing machine from twin-screw extrusion owner spout after 45 ~ 70wt% liquid crystal polyester is mixed with 0.1 ~ 5%wt% fluoropolymer, 25-50wt% mineral filler is joined forcing machine from twin-screw extrusion pusher side spout;
B) melting mixing under the screw speed of 350RPM, barrel temperature is 290-355 DEG C, extrudes, cooling, granulation obtains liquid-crystalline polyester composition.
Wherein, the melt temperature of described liquid-crystalline polyester composition is 325-353 DEG C.
Wherein, the heat-drawn wire that described liquid-crystalline polyester composition is measured taking the heating rate of 2 DEG C/min under 1.82MPa load is as 275 ~ 300 DEG C.
Wherein, the length of flow that described liquid-crystalline polyester composition adopts helicoidal flow length characterizing method to measure is 860-960mm.
Above-mentioned liquid-crystalline polyester composition is applied to the purposes of electronic apparatus junctor product, and being more suitable for thickness is the thin-walled electronic apparatus junctor product below 0.15mm.
The present invention compared with prior art, has following beneficial effect:
1) melt temperature of the liquid crystal polyester that the present invention obtains is less than 355 DEG C, and gas generated content is low;
2) melt temperature of the liquid-crystalline polyester composition that the present invention obtains is less than 355 DEG C, HDT >=275 DEG C, mobility excellence;
3) liquid-crystalline polyester composition that the present invention obtains has excellent high temperature resistant whipability and excellent crosses planeness after high temperature;
4) it is the thin-walled electronic apparatus junctor product below 0.15mm that the liquid-crystalline polyester composition that the present invention obtains is applicable to thickness.
Embodiment
Further illustrate the present invention below by embodiment, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
The testing method of the melt temperature of liquid crystal polyester/liquid-crystalline polyester composition: adopt the resistance to DSC of speeding 200 F3 to measure, at 40mL/min nitrogen atmosphere, under, sample is heated to 400 DEG C and keep 2min from room temperature with the temperature rise rate of 20 DEG C/min, again sample is cooled to room temperature with the rate of temperature fall of 20 DEG C/min, recording exothermic peak (Tc) is Tc; And then sample is heated to 400 DEG C with the temperature rise rate of 20 DEG C/min, the endotherm(ic)peak recording on this heating curve is melt temperature (Tm).
The melt viscosity of liquid crystal polyester: adopt DyniscoLCR7001 type capillary rheometer to test, port mould diameter is 1mm, and length is 20mm, described liquid crystal polyester is at its more than melt temperature 20 DEG C, and shearing rate is 1000s
-1viscosity under condition is melt viscosity.
The gas generated testing method of liquid crystal polyester: get 0.5g liquid crystal polyester in airtight vial, then heat 3h under 220 DEG C of conditions, measure the gas gross producing by head space-gas-chromatography (7697A/7890A Agilent).
The testing method of the heat-drawn wire (HDT) of liquid-crystalline polyester composition: the sample that is 80mm × 10mm × 4mm by liquid-crystalline polyester composition injection moulding, uses this sample to measure heat-drawn wire according to ISO 75-2 standard heating rate with 2 DEG C/min under 1.82MPa load.
The appraisal procedure of the mobility of liquid-crystalline polyester composition: be called helicoidal flow characterizing method, after the liquid-crystalline polyester composition that will evaluate is dried to 4 hours at 150 DEG C, moulding on the injection moulding machine of mould of moulding spirrillum sample is housed in use, barrel temperature more than liquid crystal polyester melt temperature 5 DEG C, obtain wide 5mm, thick 1.5mm spirrillum sample, read sample length and weigh the mobility of liquid-crystalline polyester composition.
The thermotolerance appraisal procedure of liquid-crystalline polyester composition: with injection moulding machine (Kraussmaffei, 80 tons) more than liquid crystal polyester melt temperature under the injection speed of 5 DEG C and 60mm/s, liquid-crystalline polyester composition is shaped to thickness 0.5mm, the laminar sample that length and width are 60mm.10 samples in these samples are put into the baking oven 5min of 260 DEG C, then sample is taken out.Then, observe the Bubble formation situation of each specimen surface.
The testing flatness method of liquid-crystalline polyester composition: with injection moulding machine (Kraussmaffei, 80 tons) more than liquid crystal polyester melt temperature under the injection speed of 15 DEG C and 40mm/s, being injected into diameter is 100mm, thickness is the circular slab of 1.5mm, then the sample of 260 DEG C of high bake 5min of 10 mistakes is taken out and be placed on Quadratic Finite Element fiber Microscopic observation distortion vertex and plane ultimate range, finally average.
Mica, model is HYC500, and manufacturer is that Jiangmen essence reaches, and median size is at 18um, and wherein, median size records by particle size analyzer.
Tetrafluoroethylene, model is S131, manufacturer is Solvay CO., LTD., melt temperature is 327 DEG C;
Structure and the abbreviation of the monomer that repeating unit (I) that described liquid crystal polyester contains, (II), (III), (IV), (V) are corresponding are as follows respectively:
: P-hydroxybenzoic acid (HBA);
: '-biphenyl diphenol (BP);
: Resorcinol (HQ);
: terephthalic acid (TPA);
: NDA (NDA);
: acetic anhydride (AA).
embodiment 1: the preparation of liquid crystal polyester
In the 100L reactor of the agitator of being furnished with nitrogen inlet, show with power of agitator, add 6.906kg(50mol) HBA, 0.93kg(5mol) BP, 2.202kg(20mol) HQ, 1.678kg(10.1mol) TPA, 3.246kg(15mol) NDA, 11.23kg(110mol) AA and 3g magnesium acetate; After displacement nitrogen, temperature of reaction is elevated at 145 DEG C to back flow reaction under nitrogen atmosphere 2 hours; Be warming up to 330 DEG C (prepolymerization maximum temperature) with 60 DEG C/h of speed afterwards, remain at this temperature and react after 30 minutes, in 30min, be evacuated to 200Pa and continue to react to power of agitator and reach preset value.Then be 0.2MPa by adding nitrogen to pressure in reactor, discharge cooling rear granulation by still bottom valve;
Above-mentioned 10kg prepolyer granule is added in the reactor of 50L with agitator, and then at 245 DEG C, vacuum tightness is that under 100Pa condition, solid state polycondensation obtains expecting the liquid crystal polyester of viscosity for 8 hours.Melt temperature, melt viscosity and gas generated the listing in table 1 of gained liquid crystal polyester.
embodiment 2 ~ 12 and comparative example 1 ~ 3: the preparation of liquid crystal polyester
By the formula of table 1, HBA, BP, HQ, TPA, NDA and AA and magnesium acetate are fed intake, the consumption of described AA is 1.1 times of monomer hydroxyl total mole number, and the consumption of described magnesium acetate is based on 0.02% of total monomer weight, and its preparation method is with embodiment 1; Melt temperature, melt viscosity and gas generated the listing in table 1 of gained liquid crystal polyester.
Table 1
embodiment 13: the preparation of liquid-crystalline polyester composition
Join forcing machine from twin-screw extrusion owner spout being prepared by embodiment 1 after the liquid crystal polyester of gained and fluoropolymer mix by the proportioning of table 2, proportionally mineral filler is joined forcing machine from twin-screw extrusion pusher side spout; Melting mixing under the screw speed of 350RPM, barrel temperature is 290-355 DEG C, extrudes, and obtains liquid-crystalline polyester composition; Melt temperature, heat-drawn wire, mobility, high temperature resistant whipability and the planeness of testing respectively liquid-crystalline polyester composition, its test result is listed in table 2.
embodiment 14 ~ 24 and comparative example 4 ~ 8: the preparation of liquid-crystalline polyester composition
Join forcing machine from twin-screw extrusion owner spout being prepared by embodiment 2 ~ 12 after the liquid crystal polyester of gained and fluoropolymer mix by the proportioning of table 2, proportionally mineral filler is joined forcing machine from twin-screw extrusion pusher side spout; Melting mixing under the screw speed of 350RPM, barrel temperature is 290-355 DEG C, extrudes, and obtains liquid-crystalline polyester composition.Melt temperature, heat-drawn wire, mobility, high temperature resistant whipability and the planeness of testing respectively liquid-crystalline polyester composition, its test result is listed in table 2.
Table 2
From the embodiment 13 ~ 24 of table 2 and relatively can finding out of comparative example 4 ~ 8, the melt temperature of the liquid-crystalline polyester composition that the embodiment of the present application prepares is less than 355 DEG C, and gas generated content is low; Compared to comparative example, the liquid-crystalline polyester composition that the present invention obtains has higher heat-drawn wire and more excellent mobility; And by the interpolation of fluoropolymer, the thin wall parts of preparing the liquid-crystalline polyester composition institute moulding of gained has excellent high temperature resistant whipability and more excellent planeness, being specially adapted to thickness is the thin-walled electronic apparatus junctor product below 0.15mm.
Claims (10)
1. a liquid crystal polyester, is characterized in that, comprises following repeating unit:
（Ⅰ）；
（Ⅱ）；
（Ⅲ）；
（Ⅳ）；
（Ⅴ）；
Described repeating unit (I), (II), (III), (IV), monomer corresponding to (V) are respectively
(A),
(B),
(C),
(D) and
(E);
Wherein, based on whole repeating units, the molar percentage of the repeating unit shown in formula I is 50-64%, the molar percentage sum of the repeating unit shown in formula II, (III) is 18-25%, and formula II accounts for the 0-25% of the molar percentage sum of the repeating unit shown in (II), (III); The molar percentage sum of the repeating unit shown in formula IV, (V) is 18-25%, and formula (V) accounts for the 24-60% of the molar percentage sum of the repeating unit shown in formula IV, (V).
2. a preparation method for liquid crystal polyester as claimed in claim 1, comprises the steps:
A) by monomer (A), (B), (C), (D) with (E) by under proportioning and acylating agent and catalyst action, at 120-150 DEG C of acetylize 1-6 hour, be warming up to the above 0-25 DEG C of this prepolymer melt temperature with the speed of 10-60 DEG C/h, and insulation reaction 10 minutes to 4 hours; The pressure-controlling of reaction system is 133-101080Pa, and melt polymerization prepares prepolymer;
B) prepolymer of molten state is discharged to cooling rear granulation by reaction container bottom under the impressed pressure of 0.05-0.6MPa, obtain prepolyer granule;
C) by gained prepolyer granule temperature of reaction of 10-80 DEG C below prepolymer melt temperature, pressure≤1000 Pa, under the condition of reaction times 1-24 hour, heating solid state polymerization obtains expecting the liquid crystal polyester of viscosity.
3. the preparation method of liquid crystal polyester according to claim 2, is characterized in that, monomer in described step a) (D), (E) both feed intake mole number sum with (B), the ratio of (C) both mole number sums that feeds intake is 1.05-1:1.
4. a liquid-crystalline polyester composition that comprises the liquid crystal polyester described in claim 1 ~ 3 any one, percentage ratio meter by weight, comprises following component:
Liquid crystal polyester 45 ~ 70wt%;
Mineral filler 25 ~ 50wt%;
Fluoropolymer 0.1 ~ 5wt%.
5. liquid crystal polyester polymkeric substance according to claim 4, is characterized in that, described mineral filler is selected from one or more in wollastonite, mica, barium sulfate, calcium carbonate, silicon-dioxide, titanium dioxide, talcum powder; Be preferably mica; The mica that more preferably median size is 0.8 ~ 105um.
6. liquid-crystalline polyester composition according to claim 4, is characterized in that, described fluoropolymer is selected from one or more in tetrafluoroethylene, fluorinated ethylene propylene copolymer, polyvinylidene difluoride (PVDF); Be preferably tetrafluoroethylene; More preferably melt temperature is not higher than the tetrafluoroethylene of 330 DEG C.
7. liquid-crystalline polyester composition according to claim 4, is characterized in that, the melt temperature of described liquid-crystalline polyester composition is 325-353 DEG C.
8. liquid-crystalline polyester composition according to claim 4, is characterized in that, the heat-drawn wire that described liquid-crystalline polyester composition is measured taking the heating rate of 2 DEG C/min under 1.82MPa load is as 275 ~ 300 DEG C.
9. liquid-crystalline polyester composition according to claim 4, is characterized in that, the length of flow that described liquid-crystalline polyester composition adopts helicoidal flow length characterizing method to measure is 860-960mm.
10. liquid-crystalline polyester composition as claimed in claim 4 is applied to and has the purposes that thickness is the thin-walled electronic apparatus junctor product below 0.15mm.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542135A (en) * | 2015-12-30 | 2016-05-04 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
| CN105837804A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN105837806A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN105837803A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN106633705A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Liquid crystal polyester compound as well as preparation method and application thereof |
| CN106675021A (en) * | 2016-12-29 | 2017-05-17 | 江苏沃特特种材料制造有限公司 | Modified wholly-aromatic liquid crystal polyester resin composite and preparation method thereof |
| WO2017114160A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN107022171A (en) * | 2016-12-29 | 2017-08-08 | 江苏沃特特种材料制造有限公司 | Liquid-crystal polyester resin compound and preparation method and application |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| WO2021249409A1 (en) * | 2020-06-09 | 2021-12-16 | 华为技术有限公司 | Plastic for antenna element |
| CN114787285A (en) * | 2019-12-11 | 2022-07-22 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and camera module |
| WO2023276902A1 (en) * | 2021-06-28 | 2023-01-05 | 住友化学株式会社 | Resin composition and molded body |
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| CN103665354A (en) * | 2012-09-06 | 2014-03-26 | 金发科技股份有限公司 | Liquid crystal polyester, preparation method and composition thereof as well as application of composition thereof |
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| CN105542135A (en) * | 2015-12-30 | 2016-05-04 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of same |
| WO2017114160A1 (en) * | 2015-12-30 | 2017-07-06 | 金发科技股份有限公司 | Liquid crystal polyester composition |
| CN105837803B (en) * | 2016-02-01 | 2017-05-31 | 金发科技股份有限公司 | A kind of liquid crystal polyester and the moulding compound being made from it and its application |
| CN105837803A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN105837806A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN105837804A (en) * | 2016-02-01 | 2016-08-10 | 金发科技股份有限公司 | Liquid crystal polyester and its molded composition and use |
| CN106633705A (en) * | 2016-12-29 | 2017-05-10 | 江苏沃特特种材料制造有限公司 | Liquid crystal polyester compound as well as preparation method and application thereof |
| CN106675021A (en) * | 2016-12-29 | 2017-05-17 | 江苏沃特特种材料制造有限公司 | Modified wholly-aromatic liquid crystal polyester resin composite and preparation method thereof |
| CN107022171A (en) * | 2016-12-29 | 2017-08-08 | 江苏沃特特种材料制造有限公司 | Liquid-crystal polyester resin compound and preparation method and application |
| CN114787285A (en) * | 2019-12-11 | 2022-07-22 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and camera module |
| CN114787285B (en) * | 2019-12-11 | 2023-10-20 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and camera module |
| WO2021249409A1 (en) * | 2020-06-09 | 2021-12-16 | 华为技术有限公司 | Plastic for antenna element |
| CN112608461A (en) * | 2020-12-17 | 2021-04-06 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| CN112608461B (en) * | 2020-12-17 | 2021-08-17 | 上海思涛新材料科技有限公司 | Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof |
| WO2023276902A1 (en) * | 2021-06-28 | 2023-01-05 | 住友化学株式会社 | Resin composition and molded body |
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Effective date of registration: 20161130 Address after: Guangdong province Zhuhai City Road nine South Town Jinwan District Petrochemical 177 Building No. 1 Patentee after: ZHUHAI WANTONG SPECIAL ENGINEERING PLASTICS CO., LTD. Address before: Ke Feng Lu Science City high tech Industrial Development Zone of Guangzhou City, Guangdong Province, No. 33 Patentee before: Kingfa Technology Co., Ltd. |