CN105907058A - Liquid crystal polyester composition - Google Patents
Liquid crystal polyester composition Download PDFInfo
- Publication number
- CN105907058A CN105907058A CN201610226651.1A CN201610226651A CN105907058A CN 105907058 A CN105907058 A CN 105907058A CN 201610226651 A CN201610226651 A CN 201610226651A CN 105907058 A CN105907058 A CN 105907058A
- Authority
- CN
- China
- Prior art keywords
- liquid
- polyester composition
- crystalline polyester
- repetitive
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
- C08G63/605—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds the hydroxy and carboxylic groups being bound to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2250/00—Compositions for preparing crystalline polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a liquid crystal polyester composition. The content of the metal strontium element in the liquid crystal polyester composition is 0.1-300ppm. A test method of the weight content of the metal strontium element comprises the following steps: drying the liquid crystal polyester composition at 120DEG C for 4h, taking 1g of a sample to be processed, adding nitric acid and hydrogen peroxide, heating the obtained mixture for 2h, and continuously adding nitric acid and hydrogen peroxide in the heating process; taking the obtained digested sample after digestion of the sample is completed, and analyzing the weight content of the metal strontium element in the sample through adopting a fully-automatic inductively coupled plasma atomic emission spectrometer 720ES from Agilent Technologies. 0.1-300Ppm of the metal strontium element is added to the formula of the liquid crystal polyester composition, so the obtained liquid crystal polyester composition has improved high temperature resisting stability and welding foam resistance.
Description
Technical field
The present invention relates to polymeric material field, particularly to a kind of liquid-crystalline polyester composition.
Background technology
Liquid crystal polyester (LCP), as a kind of special engineered class material, compared with resins for universal use, has higher fusing point and height
Heat-resistant stability, but thermally decompose or because of the strand by external force hot shearing when liquid crystal polyester remains at high temperature processing
Chain rupture, causes the phenomenon that various aspects of performance declines.On the other hand, liquid crystal polyester is commonly used to fabricate thin wall parts, and to carry out
Reflow Soldering is processed, and also has high requirement to foaming characteristic.In order to improve the heat-resistant stability of liquid crystal polyester, this area professional people
Member has done many trials.
US5397502 discloses the liquid-crystalline polymer composition that a kind of heat-resistant stability improves, and compositions comprises 15 ~
The alkali metal of 3000ppm or the magnesium of 50 ~ 3000ppm or calcium；Liquid crystal polymer contains P-hydroxybenzoic acid, hydroquinone, biphenyl
Diphenol, p-phthalic acid, NDA and biphenyl dicarboxylic acid repetitive.The introducing of metallics improves compositions
Fusing point and heat distortion temperature, make thermostability be improved.But patent is mentioned and makes liquid crystal polymer and functional compound exist
Under high temperature contact and long enough make its melt viscosity decline at least 10%.Professional and technical personnel in the field institute is public
Knowing, liquid crystalline resin processes for a long time under higher than its melt temperature, owing to thermal decomposition can cause melt viscosity and molecular weight
Reducing, the decline also having mechanical property thus brought, and the generation of side reaction, this may increase the wind that resin bubbles
Danger.
CN1234749 discloses a kind of liquid-crystal polyester resin, wherein contain 4 hydroxyisophthalic acid and/or salicylic acid and
The repetitive come is as copolymer composition, and the alkali metal compound containing 10 ~ 5000ppm, and claims the coloring of resin excellent
Good, thermostability is high, and mechanicalness is good.This invention mainly stresses the improvement of liquid crystal polyester degree of staining and impact property, not in reality
Execute other parts in example or patent and illustrate whether heat resistance changes.And whether this patent undeclared invention are applicable to liquid crystal
Polymer blend.
US6755991 discloses a kind of liquid-crystalline polyester composition, comprises at least one aromatic dicarboxylic acid, and at least one contains naphthalene
Ring carboxylic acid and at least one alkali metal of 1 ~ 1000ppm and at least one transition metal of 0 ~ 3000ppm.Liquid crystal prepared by this invention
Polymer blend has whiteness and the impact strength of improvement, and whether not mentioned high-temperature heat-resistance stability changes.
Up to the present, high to described liquid-crystalline polyester composition about adding Preparation of Metallic Strontium element in liquid-crystalline polyester composition
The impact of temperature heat-resistant stability and proper alignment foaming characteristic has no report.
The present inventor through great many of experiments surprisingly it has been found that, select in liquid-crystalline polyester composition formula add Preparation of Metallic Strontium unit
When the weight content gross weight based on liquid-crystalline polyester composition of element is 0.1ppm-300ppm, the liquid-crystalline polyester composition obtained
Heat-resistant stable and proper alignment foaming characteristic obtain beyond thought significantly improving.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of high-temperature heat-resistance stable
The liquid-crystalline polyester composition that property and proper alignment foaming characteristic significantly improve.
The present invention is achieved through the following technical solutions:
A kind of liquid-crystalline polyester composition, gross weight based on liquid-crystalline polyester composition, the weight content of Preparation of Metallic Strontium element is
0.1ppm-300ppm。
Being preferably based on the gross weight of liquid-crystalline polyester composition, the weight content of Preparation of Metallic Strontium element is preferably 0.5ppm-
100ppm, more preferably 1ppm-50ppm.
Wherein, the method for testing of the weight content of Preparation of Metallic Strontium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of strontium element.
Document is not yet had to be reported in liquid-crystalline polyester composition the introducing Preparation of Metallic Strontium element impact on composition properties at present,
Present inventors have unexpectedly found that and introduce appropriate strontium element in liquid-crystalline polyester composition, the high-temperature heat-resistance of liquid-crystalline polyester composition is stable
Property and proper alignment foaming characteristic are significantly improved.And work as the weight content of Preparation of Metallic Strontium element in liquid-crystalline polyester composition and exceed specific
During value, liquid-crystal composition contains higher metal residuals, will certainly affect its dielectricity as electronic apparatus type component
Can, it is substantially reduced its range, and mobility there will be significantly decline, affects its mouldability.
Introducing of Preparation of Metallic Strontium element contains what strontium compound realized typically by adding, and can be selected from second containing strontium compound
Acid strontium, strontium oxide, strontium nitrate, strontium sulfide, strontium sulfate, strontium carbonate, strontium phosphate, strontium oxalate, strontium fluoride, hydroxide
The inorganic chemical such as strontium, strontium chloride, strontium bromide, selenizing strontium, strontium monophosphate, strontium peroxide, strontium titanates, strontium tungstate, strontium zirconate
Thing, it is also possible to be isopropanol strontium, double (2,2,6,6-tetramethyl-3, the acid of 5-heptadione) strontium dihydrate, dipivaloylmethane
The organic compound such as acid strontium.The source of the Preparation of Metallic Strontium element pointed by the present invention is not limited only to the example above, no matter which kind of uses
Form containing strontium compound, atomic emission spectrometry can be used to detect.The weight content of Preparation of Metallic Strontium element is with metal
Strontium element itself rather than by add Preparation of Metallic Strontium element containing strontium compound on the basis of.The Preparation of Metallic Strontium element represented with ppm
Weight content is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
The liquid-crystalline polyester composition of the present invention can also include metallic antimony element, gross weight based on liquid-crystalline polyester composition
Amount, the weight content of metallic antimony element is 0.1ppm-300ppm, preferably 1ppm-50ppm.
Wherein, the method for testing of the weight content of metallic antimony element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of antimony element.
Introducing typically by adding what antimony containing compounds realized of metallic antimony element, antimony containing compounds can be selected from oxygen
Change antimony (III), stibium oxide (V), antimony trisulfide (III), antimony trisulfide (V), Antimonous sulfate, antimony acetate, antimony selenide (III), antimony iodide
(III) inorganic compound such as, it is also possible to selected from propanol antimony (III), antimony triphenyl (III), ethyoxyl antimony, isopropoxy antimony,
Methoxyl group antimony, 1-butyl-3-Methylimidazole. hexafluoro antimonate, three (4-bromophenyl) chlordene ammonium antimonate, triphenyl oxalic acid antimony
(V), the organic compound such as triphenyl antimony butter (V), tetraphenylphosphonibromide bromide antimony (V).Metallic antimony element pointed by the present invention
Source is not limited only to the example above, no matter uses the antimony containing compounds of which kind of form, atomic emission spectrometry can be used to examine
Measure.The weight content of metallic antimony element is with metallic antimony element itself rather than to add the antimony containing compounds of metallic antimony element
On the basis of.The weight content of the metallic antimony element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition
's.
Wherein, described liquid-crystalline polyester composition, by weight, including following component:
Liquid crystal polyester 100 parts；
Filler 5 parts-100 parts.
Wherein, the fusing point of described liquid-crystalline polyester composition is 150 DEG C-400 DEG C；The method of testing of described fusing point is: pass through
NETZSCH company DSC 200 F3 type differential scanning calorimeter DSC, is starting to survey with the Elevated Temperature Conditions of 20 DEG C/min from room temperature
Examination, observes endotherm peak temperature Tm1After, than Tm1Keep 5 minutes at a temperature of high 20 DEG C, then the cooling of 20 DEG C/min
Under the conditions of be cooled to room temperature, be the most again measured with the Elevated Temperature Conditions of 20 DEG C/min, the endotherm peak temperature now observed
Tm2It is the fusing point of liquid-crystalline polyester composition.
Wherein, described liquid crystal polyester, by mole meter, comprise following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-35mol% derived from aromatic diol；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
Preferably, described liquid crystal polyester, by mole meter, including following repetitive:
Repetitive 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-25mol% derived from aromatic diol；
Repetitive 0mol%-25mol% derived from aromatic dicarboxylic acid.
Wherein, the described repetitive derived from aromatic hydroxy-carboxylic is selected from the repetition list derived from 4-HBA
Unit and/or the repetitive of 2-hydroxyl-6-naphthoic acid；The described repetitive derived from aromatic diol is selected from hydroquinone
Repetitive and/or the repetitive of 4,4 '-dihydroxybiphenyl；The described repetitive derived from aromatic dicarboxylic acid is selected from right
The repetitive of phthalic acid, the repetitive of M-phthalic acid, 2,6-naphthalenedicarboxylic acid repetitive in one or more.
The preparation method of above-mentioned liquid crystal polyester, can use standard polycondensation techniques method well known to those skilled in the art,
Comprise the steps:
The reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device is separately added into according to proportioning
Repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and derived from aromatic dicarboxylic acid
Repetitive, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start
Stirring, is heated to 140 DEG C-160 DEG C by reactant mixture by room temperature in nitrogen stream, at this temperature backflow 1 hour-3 hours；
Hereafter continue to heat up, mixture was heated to 300 DEG C-350 DEG C through 2 hours-4 hours from 140 DEG C-160 DEG C, steams in the process
Go out unreacted acetic anhydride and side reaction product acetic acid；Whole polycondensation phase, reduces pressure to reaction system, and by observing moment of torsion
Raise the endpoint terminated as reaction；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Enter
Prepolymer is transferred to solid phase device by one step, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C,
At a temperature of this, insulation carries out solid-phase polymerization in 9 hours-11 hours；Product is derived after terminating by reaction, thus obtains liquid crystal and gather
Ester.
Wherein, described filler is selected from fibrous filler and/or tabular filler；Described fibrous filler is selected from glass
Glass fiber, asbestos fibre, silicon dioxide fibre, silica-alumina fiber, potassium titanate fibre, carbon or graphite fibre, metal
One or more in fiber；It is preferably glass fibre；Described tabular filler is in Talcum, Muscovitum, graphite, Kaolin
One or more；It is preferably Muscovitum.
Preferably, the equal fibre diameter of number of described glass fibre is 3 microns-30 microns, and the equal draw ratio of number is more than or equal to 5,
Number average fiber length is 50 microns-3000 microns；The mean diameter of described Muscovitum is 0.5 micron-200 microns.
When adding filler, relative to liquid crystal polyester 100 weight portion, adding the filler more than more than 100 parts, liquid crystal gathers
The mechanical strength of ester compositions may reduce.The method adding filler is not particularly limited, and can enumerate in the art
Known method.
Additionally, in addition to the foregoing, can be not damage the liquid crystal that the amount of the object of the invention uses in the present invention
Polymer blend adds known various additives；Various additives can be selected from plasticizer, stabilizer, coloring agent, lubrication
One or more in agent, releasing agent, antioxidant.
Suitably plasticizer is phthalic acid ester.
Suitably stabilizer includes organic phosphite, such as triphenyl phosphite, tricresyl phosphite-(2,6-3,5-dimethylphenyl)
Ester, tricresyl phosphite-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphate etc., organic phosphite, alkylating unitary
The butylation reaction of the alkylation reaction product of phenol or polyhydric phenols, polyhydric phenols and diene, paracresol or bicyclopentadiene is produced
Thing, alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters, benzene
And triazole type, one or more combinations of benzophenone.
Suitably releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, stone
Wax, lignite wax etc..
Suitably coloring agent includes various pigment, and dyestuff, such as metal-oxide and the mixed-metal oxides of inorganic pigment
Zinc oxide, titanium oxide, ferrum oxide, sulfide such as zinc sulfide etc.；Aluminate, silicate, ferrite etc., white carbon black, ultramarine；Organic
Pigment such as azo, diazonium class, Anthraquinones, phthalocyanine, quinolines, naphthalene, ketone, piperazine class etc..
Proper lubrication agent includes the slaine etc. of higher fatty acids, high-grade fatty ester, higher fatty acids.
Suitably antioxidant includes organic phosphite, alkylating monohydric phenol or polyhydric phenols, polyhydric phenols and diene
The butylation product of alkylation reaction product, paracresol or bicyclopentadiene, alkylating hydroquinones, hydroxylated sulfur
For diphenylether, alkylidene-bis-phenol, benzyl compounds, polyhydric alcohol esters etc..
Various additives are not limited to above-mentioned several, can optionally contain the heat stability to liquid crystal polyester and physical property is harmless
Other species components and thermoplastic compounds in common other material, such as the polypropylene, polyamide, poly-of one or more
Ester, polyphenylene sulfide, polyether-ketone, Merlon, polyether sulfone, polyphenyl ether and modified material thereof, thermoplastic resin such as polyetherimide
Amine, thermosetting resin such as phenolic resin, epoxy resin, polyimide resin and cyanide resin.
The method coordinating filler, various additives etc. in the liquid crystal polyester of embodiments of the present invention, the most specific
Limit, it is possible to use dry type blending, solution mixing method, the polymerization of liquid crystal polyester are interpolation, melting mixing etc., be wherein preferably molten
Melt mixing.Such as kneader, uniaxially or biaxially extruder, rubber-roller machine etc., biaxial extruder is wherein preferably used.The temperature of melting mixing
More than the degree fusing point for liquid crystal polyester, fusing point less than+50 DEG C.
As compounding process, it is possible to use put into liquid crystal polyester, filler, various additive in the lump from rear dress charger
Carry out mixing method；Liquid crystal polyester and various additive can also be penetrated from rear dress charger, add from side charger and fill
Agent carries out mixing method, can also prepare the liquid-crystalline polyester composition mother that high concentration comprises liquid crystal polyester and various additive
Grain, then carries out any one side of the method etc. of the mixing concentration to become regulation by liquid-crystalline polyester composition master batch and filler
Method.
The liquid-crystalline polyester composition of embodiments of the present invention, by carrying out injection moulding, injection compression molding, is compressed into
The known melt molding product such as type, extrusion molding, blow molding, compressing spinning.Products formed described here, can be note
Penetrate products formed, extrusion molding article, compressing product, sheet, pipe, non-stretched film, single axle drawn membrane, biaxially oriented film etc. each
Plant the various cellosilks etc. such as membrane product, undrawn yarn, super drawing silk.In the case of extrusion molding, can significantly obtain the present invention
Effect, the most preferably.
Wherein, the liquid-crystalline polyester composition obtained by extruding-out process, specifically comprise the following steps that liquid crystal according to proportioning
Polyester, filler, containing strontium compound and/or antimony containing compounds and/or various additive high-speed mixer mix homogeneously after,
Adding double screw extruder, melting mixing under the screw speed of 280RPM-320RPM, barrel temperature is 290 DEG C-355 DEG C, squeezes
Go out, cooling, pelletizing, obtain liquid-crystalline polyester composition.
Strontium acetate, strontium oxide, strontium nitrate, strontium sulfide, strontium sulfate, strontium carbonate, phosphoric acid can be selected from containing strontium compound
Strontium, strontium oxalate, strontium fluoride, Strontium hydrate., strontium chloride, strontium bromide, selenizing strontium, strontium monophosphate, strontium peroxide, metatitanic acid
The inorganic compound such as strontium, strontium tungstate, strontium zirconate, it is also possible to be isopropanol strontium, double (2,2,6,6-tetramethyl-3,5-heptadione
Acid) organic compound such as strontium dihydrate, dipivaloylmethane acid strontium.The source of the Preparation of Metallic Strontium element pointed by the present invention is not
Be only limitted to the example above, no matter use which kind of form containing strontium compound, atomic emission spectrometry can be used to detect.Gold
Belong to strontium element weight content be by Preparation of Metallic Strontium element itself rather than by interpolation Preparation of Metallic Strontium element containing strontium compound on the basis of
's.The weight content of the Preparation of Metallic Strontium element represented by ppm is to calculate on the basis of the gross weight of liquid-crystalline polyester composition.
Antimony containing compounds can be selected from stibium oxide (III), stibium oxide (V), antimony trisulfide (III), antimony trisulfide (V), Antimonous sulfate,
The inorganic compound such as antimony acetate, antimony selenide (III), antimony iodide (III), it is also possible to selected from propanol antimony (III), antimony triphenyl
(III), ethyoxyl antimony, isopropoxy antimony, methoxyl group antimony, 1-butyl-3-Methylimidazole. hexafluoro antimonate, three (4-bromobenzenes
Base) organic compound such as chlordene ammonium antimonate, triphenyl oxalic acid antimony (V), triphenyl antimony butter (V), tetraphenylphosphonibromide bromide antimony (V)
Thing.The source of the metallic antimony element pointed by the present invention is not limited only to the example above, no matter use which kind of form containing antimony chemical combination
Thing, can use atomic emission spectrometry to detect.The weight content of metallic antimony element is with metallic antimony element itself not
On the basis of being the antimony containing compounds to add metallic antimony element.The weight content of the metallic antimony element represented with ppm is with liquid
Calculate on the basis of the gross weight of brilliant polymer blend.
The products formed that the liquid-crystalline polyester composition that the present invention is obtained is formed can have following application, with various gears, respectively
Kind of housing, sensor, LED lamp, adapter, socket, resistor, casing of relay, relay base, relay roll,
Switch, coil axle, capacitor, variable condenser housing, optical pickup unit, resonator, various terminal board, transformator, plug, printing
Wiring plate, tuner, speaker, microphone, head type headphones, miniature motor, magnetic head base, power model, shell, partly lead
Body, liquid crystal display component, FDD bracket, FDD chassis, HDD parts, motor brush holder, parabola antenna, computer are correlated with
Electrical and electronic parts that parts etc. are representative, with VTR parts, TV part, flatiron, hair dryer, electric cooker parts, microwave oven
Speech ciphering equipment parts, illuminace component, parts of refrigerator, the air supply rates such as parts, sound part, audio frequency, laser disk, CD, beat
Family that word machine parts, word processor parts etc. are representative, enterprise's electric product parts, office computer associated components,
Telephone set associated components, facsimile machine associated components, photocopier associated components, washing fixture, oilless bearing, stern bearing, water
The various bearing such as middle (center) bearing, motor component, mechanical associated components with lighter, typewriter etc. as representative, with microscope, double
Optical device that tube telescope, photographing unit, clock and watch etc. are representative, precision optical machinery associated components；Alternating current generator terminal, exchange are sent out
Various valves, fuel association, exhaust system, the air-breathings such as motor connectors, IC actuator, dimmer potentiometer base, aerofluxus air valve
The various pipes of system, inlet jet breather, inlet manifold, petrolift, engine cool water swivel, carburator main body, vaporization
Device spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, TPS, crank position sensing
Device, mass air flow sensor, Brake pad abrasion sensor, idle call thermostat base, air conditioning electricity motivation insulator, motorized window etc.
On-vehicle motor insulator, warmer heated airflow control valve, radiator fan motor brush carrier, water pump vane, turbo blade,
Wiper motor associated components, ignition distributor, starter switch, starter relay, actuating device wire harness, window cleaning device
Nozzle, air-conditioning panel switch substrate, fuel association electromagnetic valve coil, electric fuse adapter, loudspeaker terminal, parts of electric are exhausted
Listrium, stepping motor rotor, lamp ring, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, electromotor oil strain
The automobile such as device, ignition housings, vehicle associated components etc., at printed wiring board, have in small-sized thin-walled electronic device etc. especially
With.
The present invention compared with prior art, has the advantages that
The present invention is by selecting the weight content adding Preparation of Metallic Strontium element in liquid-crystalline polyester composition formula based on liquid crystal polyester
When the gross weight of compositions is 0.1ppm-300ppm, heat-resistant stable and the proper alignment of the liquid-crystalline polyester composition obtained rise
Bubble property obtains beyond thought significantly improving.
Detailed description of the invention
Further illustrating the present invention below by detailed description of the invention, following example are the present invention preferably embodiment party
Formula, but embodiments of the present invention are not limited by following embodiment.
The method of testing of the weight content of described Preparation of Metallic Strontium element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of strontium element.
The method of testing of the weight content of described metallic antimony element: liquid-crystalline polyester composition is dried 4 hours at 120 DEG C,
Taking the pending sample of 1g, add nitric acid and hydrogen peroxide, heat 2 hours, period is continuously added nitric acid and hydrogen peroxide；Clearing up of sample
After completing, cancel the sample after solution, the full-automatic inductance coupled plasma-atomic using Agilent company model to be 720ES
Emission spectrometer is analyzed Gold Samples and is belonged to the weight content of antimony element.
The method of testing of the fusing point of described liquid-crystalline polyester composition: swept by the DSC 200 F3 type differential of NETZSCH company
Retouch calorimeter (DSC), starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, observing endotherm peak temperature Tm1After, than
Tm1Keep 5 minutes at a temperature of high 20 DEG C, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, the most again with 20
DEG C/min Elevated Temperature Conditions be measured, the endotherm peak temperature T now observedm2Fusing point for liquid-crystalline polyester composition.
Deflection temperature (HDT) method of testing under described liquid-crystalline polyester composition load: liquid-crystalline polyester composition is molded
Make long 127 mm, wide 12.7 mm and the sample of thick 6.4 mm, then according to ASTM D648 surveys under the load of 1.82MPa
Fixed.
The method of testing of the maximum resistant blister temperature of described liquid-crystalline polyester composition: liquid-crystalline polyester composition injection is made
Length 40 mm, width 40 mm, the model of thickness 0.8mm, evaluate as bubbling and use.By model in the silicone oil bath of arbitrary temp
After impregnating 5 minutes, observe its surface.Surface is not occurred, and the maximum temperature bubbled is set as maximum resistant blister temperature, this temperature
The highest explanation thermostability and proper alignment foaming characteristic are the best.
Title and the abbreviation of the monomer that the repetitive that contains of liquid crystal polyester that uses in the present invention is corresponding are as follows:
4-HBA (HBA)；
4,4 '-dihydroxybiphenyl (BP)；
P-phthalic acid (TA)；
M-phthalic acid (IA)；
2-hydroxyl-6-naphthoic acid (HNA)；
Hydroquinone (HQ)；
2,6-naphthalenedicarboxylic acid (NDA)；
In the present invention use containing strontium compound:
Strontium acetate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Strontium oxide: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Strontium carbonate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
Strontium sulfate: Sigma-Aldrich (Shanghai) trade Co., Ltd；
The antimony containing compounds used in the present invention:
Stibium oxide (III): Sigma-Aldrich (Shanghai) trade Co., Ltd；
The glass fibre used in the present invention: trade mark CS03JAPX-1, number equal fibre diameter 10 microns, the equal draw ratio 300 of number, number
All fibre length 3000 microns, Asahi Fiber Glass Co., Ltd.
Embodiment A1-A4: the preparation of liquid crystal polyester
The reactor being equipped with agitator, thermometer, nitrogen ingress pipe and reflux condensate device is separately added into according to proportioning
Repetitive derived from aromatic hydroxy-carboxylic, the repetitive derived from aromatic diol and derived from aromatic dicarboxylic acid
Repetitive, and to add a certain proportion of acetic anhydride be acylating agent；Then nitrogen is passed through in reactor and replaces；Start
Stirring, is heated to 140 DEG C-160 DEG C by reactant mixture by room temperature in nitrogen stream, at this temperature backflow 1 hour-3 hours；
Hereafter continue to heat up, mixture was heated to 300 DEG C-350 DEG C through 2 hours-4 hours from 140 DEG C-160 DEG C, steams in the process
Go out unreacted acetic anhydride and side reaction product acetic acid；Whole polycondensation phase, reduces pressure to reaction system, and by observing moment of torsion
Raise the endpoint terminated as reaction；Now the prepolymer of melt state is discharged through drain hole, and be cooled to room temperature；Enter
Prepolymer is transferred to solid phase device by one step, through 5 hours-7 hours, temperature from ambient is increased to 260 DEG C-280 DEG C,
At a temperature of this, insulation carries out solid-phase polymerization in 9 hours-11 hours；Product is derived after terminating by reaction, thus obtains liquid crystal and gather
Ester.
The concrete proportioning of table 1 embodiment A1-A4 and test performance result thereof
Embodiment 1-14 and comparative example 1-6: the preparation of liquid-crystalline polyester composition
By the proportioning of table 2 will by embodiment A1-A4 prepare gained liquid crystal polyester, filler, containing strontium compound and/or the chemical combination in antimony
After thing and/or various additive high-speed mixer mix homogeneously, add double screw extruder, at the spiral shell of 280RPM-320RPM
Melting mixing under bar rotating speed, barrel temperature is 290 DEG C-355 DEG C, extrusion, and cooling, pelletizing obtain liquid-crystalline polyester composition.Gained
The fusing point of liquid-crystalline polyester composition, maximum resistant blister temperature and HDT are shown in Table 2；
Wherein, the Preparation of Metallic Strontium element in liquid-crystalline polyester composition, metallic antimony constituent content are the preparations at liquid-crystalline polyester composition
During by being adjusted containing the actual addition of strontium compound, antimony containing compounds and record.
Table 2
Continued 2
Continued 2
From embodiment 1-14 of table 2 and the comparison of comparative example 1-6 it can be seen that the present invention is by selecting at liquid-crystalline polyester composition
When in formula, the weight content gross weight based on liquid-crystalline polyester composition of interpolation Preparation of Metallic Strontium element is 0.1ppm-300ppm,
To the high-temperature heat-resistance stability of liquid-crystalline polyester composition and proper alignment foaming characteristic obtain beyond thought significantly improving.
Claims (13)
1. a liquid-crystalline polyester composition, it is characterised in that gross weight based on liquid-crystalline polyester composition, the weight of Preparation of Metallic Strontium element
Amount content is 0.1ppm-300ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that the test of the weight content of Preparation of Metallic Strontium element
Method: be dried 4 hours at 120 DEG C by liquid-crystalline polyester composition, takes the pending sample of 1g, adds nitric acid and hydrogen peroxide, and heating 2 is little
Time, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancel the sample after solution, use Agilent company type
Number analyzing Gold Samples for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES belongs to the weight of strontium element and contains
Amount.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that gross weight based on liquid-crystalline polyester composition
Amount, the weight content of Preparation of Metallic Strontium element is preferably 0.5ppm-100ppm, more preferably 1ppm-50ppm.
Liquid-crystalline polyester composition the most according to claim 1, it is characterised in that also include metallic antimony element, based on liquid crystal
The gross weight of polymer blend, the weight content of metallic antimony element is 0.1ppm-300ppm, preferably 1ppm-50ppm.
Liquid-crystalline polyester composition the most according to claim 4, it is characterised in that the test of the weight content of metallic antimony element
Method: be dried 4 hours at 120 DEG C by liquid-crystalline polyester composition, takes the pending sample of 1g, adds nitric acid and hydrogen peroxide, and heating 2 is little
Time, period is continuously added nitric acid and hydrogen peroxide；After having cleared up of sample, cancel the sample after solution, use Agilent company type
Number analyzing Gold Samples for the full-automatic inductively coupled plasma atomic emission spectrometer of 720ES belongs to the weight of antimony element and contains
Amount.
6. according to the liquid-crystalline polyester composition described in any one of claim 1-5, it is characterised in that described liquid crystal polyester combines
Thing, by weight, including following component:
Liquid crystal polyester 100 parts；
Filler 5 parts-100 parts.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that the fusing point of described liquid-crystalline polyester composition is
150℃-400℃；The method of testing of described fusing point is: by NETZSCH company DSC 200 F3 type differential scanning calorimeter
DSC, is starting to test with the Elevated Temperature Conditions of 20 DEG C/min from room temperature, is observing endotherm peak temperature Tm1After, than Tm1High 20 DEG C
At a temperature of keep 5 minutes, then under the cooling conditions of 20 DEG C/min, be cooled to room temperature, the most again with 20 DEG C/min
Elevated Temperature Conditions is measured, the endotherm peak temperature T now observedm2It is the fusing point of liquid-crystalline polyester composition.
Liquid-crystalline polyester composition the most according to claim 6, it is characterised in that described liquid crystal polyester, by mole
Meter, comprises following repetitive:
Repetitive 30mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-35mol% derived from aromatic diol；
Repetitive 0mol%-35mol% derived from aromatic dicarboxylic acid.
Liquid-crystalline polyester composition the most according to claim 8, it is characterised in that described liquid crystal polyester, by mole
Meter, including following repetitive:
Repetitive 50mol%-100mol% derived from aromatic hydroxy-carboxylic；
Repetitive 0mol%-25mol% derived from aromatic diol；
Repetitive 0mol%-25mol% derived from aromatic dicarboxylic acid.
Liquid-crystalline polyester composition the most according to claim 8 or claim 9, it is characterised in that described derived from aromatic hydroxyl carboxylic
The repetitive of acid is selected from the repetitive derived from 4-HBA and/or the repetitive of 2-hydroxyl-6-naphthoic acid；Institute
State the repetitive derived from aromatic diol and be selected from repetitive and/or the repetition of 4,4 '-dihydroxybiphenyl of hydroquinone
Unit；The described repetitive derived from aromatic dicarboxylic acid is selected from the repetitive of p-phthalic acid, the weight of M-phthalic acid
Answer one or more in the repetitive of unit, 2,6-naphthalenedicarboxylic acid.
11. liquid-crystalline polyester compositions according to claim 6, it is characterised in that described filler is selected from fibrous filler
Agent and/or tabular filler；Described fibrous filler is selected from glass fibre, asbestos fibre, silicon dioxide fibre, titanium dioxide
One or more in silicon-alumina fibre, potassium titanate fibre, carbon or graphite fibre, metallic fiber；It is preferably glass fibre；
One or more in Talcum, Muscovitum, graphite, Kaolin of described tabular filler；It is preferably Muscovitum.
12. liquid-crystalline polyester compositions according to claim 11, it is characterised in that the equal fiber of number of described glass fibre is straight
Footpath is 3 microns-30 microns, and the equal draw ratio of number is more than or equal to 5, and number average fiber length is 50 microns-3000 microns；Described Muscovitum
Mean diameter is 0.5 micron-200 microns.
13. liquid-crystalline polyester compositions according to claim 6, it is characterised in that also comprise various additive；Described various
One or more in plasticizer, stabilizer, coloring agent, lubricant, releasing agent, antioxidant of additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226651.1A CN105907058B (en) | 2016-04-13 | 2016-04-13 | A kind of liquid-crystalline polyester composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610226651.1A CN105907058B (en) | 2016-04-13 | 2016-04-13 | A kind of liquid-crystalline polyester composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105907058A true CN105907058A (en) | 2016-08-31 |
| CN105907058B CN105907058B (en) | 2018-06-15 |
Family
ID=56746791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610226651.1A Active CN105907058B (en) | 2016-04-13 | 2016-04-13 | A kind of liquid-crystalline polyester composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105907058B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112126243A (en) * | 2020-09-09 | 2020-12-25 | 金发科技股份有限公司 | Liquid crystal polymer composition |
| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
| US12032272B2 (en) | 2019-03-20 | 2024-07-09 | Ticona Llc | Polymer composition for use in a camera module |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5397502A (en) * | 1993-06-10 | 1995-03-14 | E. I. Du Pont De Nemours And Company | Heat resistant liquid crsytalline polymers |
| CN1680486A (en) * | 2004-04-02 | 2005-10-12 | 住友化学株式会社 | Organic resin composition, solution of the same and shaped article of the same |
| CN101932654A (en) * | 2007-12-03 | 2010-12-29 | 住友化学株式会社 | Liquid crystalline polyester and molded article thereof |
| JP2013203993A (en) * | 2012-03-29 | 2013-10-07 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition and molded article |
-
2016
- 2016-04-13 CN CN201610226651.1A patent/CN105907058B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5397502A (en) * | 1993-06-10 | 1995-03-14 | E. I. Du Pont De Nemours And Company | Heat resistant liquid crsytalline polymers |
| CN1680486A (en) * | 2004-04-02 | 2005-10-12 | 住友化学株式会社 | Organic resin composition, solution of the same and shaped article of the same |
| CN101932654A (en) * | 2007-12-03 | 2010-12-29 | 住友化学株式会社 | Liquid crystalline polyester and molded article thereof |
| JP2013203993A (en) * | 2012-03-29 | 2013-10-07 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition and molded article |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
| US12032272B2 (en) | 2019-03-20 | 2024-07-09 | Ticona Llc | Polymer composition for use in a camera module |
| CN112126243A (en) * | 2020-09-09 | 2020-12-25 | 金发科技股份有限公司 | Liquid crystal polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105907058B (en) | 2018-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5332081B2 (en) | Resin composition and molded article comprising the same | |
| KR101413835B1 (en) | Thermoplastic resin composition and molded article using same | |
| WO2012090407A1 (en) | Wholly aromatic liquid crystal polyester and method for manufacturing same | |
| WO2013099111A1 (en) | Thermoplastic resin composition and molded article thereof | |
| CN109790361A (en) | The manufacturing method of liquid crystalline polyester resin composition, molded product and molded product | |
| KR20140043846A (en) | Polyphenylene sulfide resin composition, method for producing same, and molded product of same | |
| WO2019198665A1 (en) | Liquid crystal polyester resin, method for manufacturing same, and molded article comprising same | |
| CN105907058B (en) | A kind of liquid-crystalline polyester composition | |
| CN105860445A (en) | Liquid crystal polyester composition | |
| JP2017043772A (en) | Modified polyphenylene sulfide resin and resin composition | |
| JP5742377B2 (en) | Polyphenylene sulfide resin composition and molded article | |
| CN105801823A (en) | Liquid crystal polyester composition | |
| CN105801824A (en) | Liquid crystal polyester composition | |
| CN105733219A (en) | Liquid crystal polyester composition | |
| WO2017069109A1 (en) | Polyarylene sulfide resin composition, molded product, and methods for producing said composition and product | |
| CN105885370A (en) | Liquid crystal polyester composition | |
| WO2019093237A1 (en) | Polyphenylene sulfide resin composition, method for producing same, and molded article | |
| JP6206174B2 (en) | Liquid crystalline polyester resin composition and molded product thereof | |
| CN105885369A (en) | Liquid crystal polyester composition | |
| JPH10298430A (en) | Polyphenylene sulfide resin composition | |
| CN105860465A (en) | Liquid crystal polyester composition | |
| CN105801822A (en) | Liquid crystal polyester composition | |
| CN105838386A (en) | Liquid crystalline polyester composition | |
| JP2007238693A (en) | Process for producing polyphenylene sulfide resin composition | |
| JP2002201344A (en) | Liquid crystalline resin composition, method for producing the same and molded product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |