CN104592718A - Liquid crystal polyester composite - Google Patents
Liquid crystal polyester composite Download PDFInfo
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- CN104592718A CN104592718A CN201410589023.0A CN201410589023A CN104592718A CN 104592718 A CN104592718 A CN 104592718A CN 201410589023 A CN201410589023 A CN 201410589023A CN 104592718 A CN104592718 A CN 104592718A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
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- 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
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- 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
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/12—Reflex reflectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/58—Optical field-shaping elements
- H01L33/60—Reflective elements
Abstract
Provided is a liquid crystal polyester composite including a liquid crystal polyester and white pigment. The liquid crystal polyester includes a repetitive unit (A) of a naphthalene skeleton which accounts for 0-10 Mol/% relative to the total quantity of all the repetitive units, a repetitive unit (B) of the naphthalene skeleton which accounts for 0-10 Mol/% relative to the total quantity of all the repetitive units, and the total quantity of the repetitive unit (A) and the repetitive unit (B) is 0-10 Mol/% relative to the total quantity of all the repetitive units.
Description
Technical field
The present invention relates to the liquid-crystalline polyester composition comprising liquid crystal polyester and white pigment.
Background technology
As the material of reflector, studying the liquid-crystalline polyester composition comprising liquid crystal polyester and white pigment.This liquid-crystalline polyester composition has the melt fluidity of the excellence that liquid crystal polyester brings, and has the reflecting properties that white pigment brings.
Such as, following example is disclosed: as described liquid crystal polyester in JP2004-256673A1, use and there are the repeating unit 60 % by mole deriving from P-hydroxybenzoic acid, the repeating unit 15 % by mole deriving from terephthalic acid or 18 % by mole, derive from the repeating unit 5 % by mole of m-phthalic acid or 2 % by mole and derive from the liquid crystal polyester of repeating unit 20 % by mole of 4,4-dihydroxybiphenyl; As described liquid crystal polyester, use the liquid crystal polyester with the repeating unit 73 % by mole deriving from P-hydroxybenzoic acid and the repeating unit 27 % by mole deriving from 6-Hydroxy-2-naphthoic acid.
Following example is disclosed: as described liquid crystal polyester in JP2007-320996A1, use have the repeating unit 54 % by mole deriving from P-hydroxybenzoic acid, the repeating unit 15 % by mole deriving from terephthalic acid, derive from m-phthalic acid repeating unit 8 % by mole, derive from the repeating unit 15 % by mole of 4,4-dihydroxybiphenyl and derive from the liquid crystal polyester of repeating unit 7% of Resorcinol; As described liquid crystal polyester, use and there is the repeating unit 67 % by mole deriving from P-hydroxybenzoic acid, the repeating unit 17 % by mole deriving from terephthalic acid, derive from the repeating unit 8 % by mole of 4,4-dihydroxybiphenyl and derive from the liquid crystal polyester of repeating unit 8% of ethylene glycol; As described liquid crystal polyester, use the liquid crystal polyester with the repeating unit 73 % by mole deriving from P-hydroxybenzoic acid and the repeating unit 27 % by mole deriving from 6-Hydroxy-2-naphthoic acid.
Following example is disclosed: as described liquid crystal polyester in JP2012-177103A1, use the liquid crystal polyester of the repeating unit 20 % by mole that there are the repeating unit 60 % by mole deriving from P-hydroxybenzoic acid, the repeating unit 12 % by mole deriving from terephthalic acid, 15 % by mole or 17 % by mole, the repeating unit 8 % by mole deriving from m-phthalic acid, 5 % by mole or 3 % by mole and derive from 4,4-dihydroxybiphenyl; As described liquid crystal polyester, use there are the repeating unit 50 % by mole that derives from P-hydroxybenzoic acid or 70 % by mole, the repeating unit 25 % by mole that derives from m-phthalic acid or 15 % by mole and derive from the repeating unit 25 % by mole of 4,4-dihydroxybiphenyl or the liquid crystal polyester of 15 % by mole.
Summary of the invention
The object of the present invention is to provide and comprise liquid crystal polyester and white pigment and the liquid-crystalline polyester composition of excellent in light-resistance.
The invention provides a kind of liquid-crystalline polyester composition, it comprises liquid crystal polyester and white pigment, in described liquid crystal polyester, the content comprising the repeating unit (A) of naphthalene skeleton is 0 ~ 10 % by mole relative to the total amount of whole repeating unit, the content comprising the repeating unit (B) of biphenyl backbone is 0 ~ 5 % by mole relative to the total amount of whole repeating unit, and the total content of repeating unit (A) and repeating unit (B) is 0 ~ 10 % by mole relative to the total amount of whole repeating unit.
The excellent in light-resistance of liquid-crystalline polyester composition of the present invention.
Embodiment
Liquid crystal polyester is the polyester demonstrating liquid crystal liquid crystal property in the molten state, the material of melting at the temperature preferably below 450 DEG C.
Liquid crystal polyester can be liquid crystal polyesteramide, can be liquid crystal polyester ether, can be liquid crystal polyester carbonic ether, also can be liquid crystal polyester imide.
From the view point of thermotolerance, liquid crystal polyester is preferably and only uses aromatics as the Wholly aromatic liquid crystal polyester of starting monomer.
As the typical case of liquid crystal polyester, can enumerate:
Make aromatic hydroxy-carboxylic, aromatic dicarboxylic acid and at least a kind of compound be selected from aromatic diol, aromatic hydroxyl amine and aromatic diamine carries out being polymerized the liquid crystal polyester of (polycondensation);
Make the liquid crystal polyester that multiple aromatic hydroxy-carboxylic is polymerized;
Make aromatic dicarboxylic acid and at least a kind of compound be selected from aromatic diol, aromatic hydroxyl amine and aromatic diamine carries out the liquid crystal polyester that is polymerized; And,
Make the liquid crystal polyester that the polyester such as polyethylene terephthalate and aromatic hydroxy-carboxylic are polymerized.
As the example of liquid crystal polyester, also can enumerate: the derivative (below these derivatives that can carry out being polymerized being called " derivative ") that can carry out being polymerized of aromatic hydroxy-carboxylic, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxyl amine, aromatic diamine.
As the example of derivative of compound (aromatic hydroxy-carboxylic, aromatic dicarboxylic acid etc.) with carboxyl, can enumerate:
Carboxyl is changed to the derivative (ester) of carbalkoxy or aryloxy carbonyl;
Carboxyl is changed to the derivative (etheride) of halogen formyl radical; With the derivative (acid anhydrides) carboxyl being changed to acyl-oxygen carbonyl.
As the example of derivative of compound (aromatic hydroxy-carboxylic, aromatic diol, aromatic hydroxyl amine etc.) with hydroxyl, can enumerate: the derivative (acylate) acylated hydroxy being changed to acyloxy.
As the example of derivative with amino compound (aromatic hydroxyl amine, aromatic diamine etc.), can enumerate: the derivative (acylate) aminoacylates being changed to amido.
Liquid crystal polyester preferably has the repeating unit shown in formula (1) (hereinafter sometimes referred to " repeating unit (1) ".), more preferably there is repeating unit (1), the repeating unit shown in formula (2) (hereinafter sometimes referred to " repeating unit (2) ".) and the repeating unit shown in formula (3) (hereinafter sometimes referred to " repeating unit (3) ".)。
(1)-O-Ar
1-CO-
(2)-CO-Ar
2-CO-
(3)-X-Ar
3-Y-
(Ar
1represent phenylene, naphthylidene or biphenylene.Ar
2and Ar
3separately represent phenylene, naphthylidene, biphenylene or the group shown in following formula (4).X and Y separately represents Sauerstoffatom or imino-(-NH-).Ar
1, Ar
2or Ar
3hydrogen atom in shown group can separately be replaced by halogen atom, alkyl or aryl.)
(4)-Ar
4-Z-Ar
5-
(Ar
4and Ar
5separately represent phenylene or naphthylidene.Z represents Sauerstoffatom, sulphur atom, carbonyl, alkylsulfonyl or alkylidene.)
As described halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atoms and atomic iodine.
As the example of described alkyl, can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-hexyl, 2-ethylhexyl, n-octyl and positive decyl, its carbonatoms is generally 1 ~ 10.
As the example of described aryl, can enumerate: phenyl, o-tolyl, a tolyl, p-methylphenyl, 1-naphthyl and 2-naphthyl, its carbonatoms is generally 6 ~ 20.
Ar
1, Ar
2or Ar
3in shown group, substituent number is generally less than 2, is preferably less than 1.
As the example of described alkylidene, can enumerate: methene base, ethidine, isopropylidene, positive fourth fork base and 2-ethyl hexyl fork base, its carbonatoms is generally 1 ~ 10.
Repeating unit (1) is for deriving from the repeating unit of the aromatic hydroxy-carboxylic of regulation.As repeating unit (1), preferred Ar
1for the repeating unit (deriving from the repeating unit of P-hydroxybenzoic acid) to phenylene and Ar
1it is the repeating unit (deriving from the repeating unit of 6-Hydroxy-2-naphthoic acid) of 2,6-naphthylidene.
Repeating unit (2) is for deriving from the repeating unit of the aromatic dicarboxylic acid of regulation.As repeating unit (2), preferred Ar
2for repeating unit (deriving from the repeating unit of terephthalic acid), Ar to phenylene
2for repeating unit (deriving from the repeating unit of m-phthalic acid), the Ar of metaphenylene
2be repeating unit (deriving from the repeating unit of 2,6-naphthalene dicarboxylic acids) and the Ar of 2,6-naphthylidene
2for UVINUL MS 40, the repeating unit (deriving from UVINUL MS 40, the repeating unit of 4 '-dicarboxylic acid) of 4 '-two base.
Repeating unit (3) is for deriving from the repeating unit of the aromatic diol of regulation, aromatic hydroxyl amine or aromatic diamine.As repeating unit (3), preferred Ar
3for the repeating unit (deriving from the repeating unit of Resorcinol, p-aminophenol or P-pHENYLENE dI AMINE) to phenylene and Ar
3be 4, the repeating unit (deriving from 4,4 '-dihydroxybiphenyl, 4-amino-4 '-xenol or 4, the repeating unit of 4 '-benzidine) of 4 '-biphenylene.
The content of repeating unit (1) is generally more than 30 % by mole relative to the total amount of whole repeating unit, is preferably 30 ~ 80 % by mole, is more preferably 40 ~ 70 % by mole, more preferably 45 ~ 65 % by mole.
The content of repeating unit (2) is generally less than 35 % by mole relative to the total amount of whole repeating unit, is preferably 10 ~ 35 % by mole, is more preferably 15 ~ 30 % by mole, more preferably 17.5 ~ 27.5 % by mole.
The content of repeating unit (3) is generally less than 35 % by mole relative to the total amount of whole repeating unit, is preferably 10 ~ 35 % by mole, is more preferably 15 ~ 30 % by mole, more preferably 17.5 ~ 27.5 % by mole.
In this specification sheets, the total amount of whole repeating unit refers to value amount equivalent (mole) total of each repeating unit of formation liquid crystal polyester obtained.This amount equivalent is by obtaining divided by the molecular weight of its repeating unit by the quality of each repeating unit.
The content of repeating unit (1) is more, and melt fluidity, thermotolerance, mechanical characteristics are more easy to improve.If this content is in above-mentioned scope, then melt temperature, melt viscosity are in the scope of appropriateness, and the required temperature that is therefore shaped also is easy to the scope being in appropriateness.
The ratio of the content of repeating unit (2) and the content of repeating unit (3) is represented by [content of repeating unit (2)]/[content of repeating unit (3)] (moles/mole), is generally 0.9/1 ~ 1/0.9, is preferably 0.95/1 ~ 1/0.95, is more preferably 0.98/1 ~ 1/0.98.
Liquid crystal polyester separately has two or more repeating unit (1) ~ (3).
Liquid crystal polyester can have the repeating unit beyond repeating unit (1) ~ (3), and its content is generally less than 10 % by mole relative to the total amount of whole repeating unit, is preferably less than 5 % by mole.
About liquid crystal polyester, because melt viscosity is easy to reduce, therefore as repeating unit (3), preferably there is X and Y to be respectively the repeating unit of Sauerstoffatom, namely there is the repeating unit of the aromatic diol deriving from regulation, more preferably only there is the repeating unit that X and Y is respectively Sauerstoffatom.
In the present invention, in liquid crystal polyester, the content of the repeating unit (A) comprising naphthalene skeleton is made to be 0 ~ 10 % by mole relative to the total amount of whole repeating unit, make the content of the repeating unit (B) comprising biphenyl backbone be 0 ~ 5 % by mole relative to the total amount of whole repeating unit, make the total content of repeating unit (A) and repeating unit (B) be 0 ~ 10 % by mole relative to the total amount of whole repeating unit.
By using the liquid crystal polyester of this regulation, the liquid-crystalline polyester composition of excellent in light-resistance can be obtained.
In liquid crystal polyester, from the sunproof viewpoint of liquid-crystalline polyester composition, the total content of repeating unit (A) and repeating unit (B) is preferably less than 7 % by mole relative to the total amount of whole repeating unit, is more preferably less than 5 % by mole, on the other hand, from the view point of the mechanical characteristics of liquid-crystalline polyester composition, the total content of repeating unit (A) and repeating unit (B) is preferably more than 3 % by mole relative to the total amount of whole repeating unit, is more preferably more than 5 % by mole.
When liquid crystal polyester comprises repeating unit (A), repeating unit (A) preferably comprises 2,6-naphthylidene skeleton.Repeating unit (A) is preferably repeating unit (1) or repeating unit (2).
When liquid crystal polyester comprises repeating unit (B), repeating unit (B) preferably comprises 4,4-biphenylene skeleton.Repeating unit (B) is preferably repeating unit (3).
Liquid crystal polyester preferably by the starting monomer melt polymerization made corresponding to its repeating unit of formation, by obtained polymkeric substance (hereinafter sometimes referred to " prepolymer ".) carry out the incompatible manufacture of solid polycondensation.Thereby, it is possible to operability produces the liquid crystal polyester of thermotolerance, intensity, high molecular that rigidity is high well.
Melt polymerization can carry out in the presence of a catalyst.As the example of this catalyzer, can enumerate: the metallic compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, ANTIMONY TRIOXIDE SB 203 99.8 PCT; The nitrogenous heterocyclic compounds such as 4-(dimethylamino) pyridine, 1-Methylimidazole, preferably use nitrogenous heterocyclic compound.
The flow starting temperature of liquid crystal polyester is generally more than 270 DEG C, is preferably 270 ~ 400 DEG C, is more preferably 280 ~ 350 DEG C, more preferably 290 ~ 340 DEG C.
Flow starting temperature is higher, is more easy to improve thermotolerance, intensity, rigidity.If this content is in above-mentioned scope, then melt temperature, melt viscosity are in the scope of appropriateness, and the required temperature that is therefore shaped also is easy to be in the scope of appropriateness.
Flow starting temperature, also referred to as flow temperature or yield temperature, is use capillary rheometer, at 9.8MPa (100kg/cm
2) load under, limit heats up with the speed of 4 DEG C/min, while make liquid crystal polyester melting, and when it is extruded from the nozzle of internal diameter 1mm and length 10mm, demonstrate the temperature of the viscosity of 4800Pas (48000 pool), for the molecular weight of liquid crystal polyester standard (littlely go out straight to write, " liquid crystal Port リ マ mono-(liquid crystalline polymers)-synthesis shaping ying with-", Co., Ltd. C MC, on June 5th, 1987, reference p.95).
By coordinating white pigment in liquid crystal polyester in the present invention, can obtain there is reflecting properties and the liquid-crystalline polyester composition of excellent in light-resistance.
As white pigment, preferably use the mineral compound such as zinc oxide, zinc sulphide, white lead, titanium oxide, also can use two or more in them as required.Wherein, preferential oxidation titanium.
Being easy to be dispersed in liquid crystal polyester from the view point of white pigment and being easy to obtain having the liquid-crystalline polyester composition of high-reflectivity, the particle diameter of white pigment represents with bulk averaged value and is preferably 0.05 ~ 2 μm, is more preferably 0.1 ~ 1 μm, more preferably 0.15 ~ 0.5 μm, is particularly preferably 0.2 ~ 0.4 μm.
Above-mentioned volume average particle size takes white pigment with scanning electron microscope (SEM:Scanning ElectronMicroscope), obtained SEM photo image analysis apparatus (" the Luzex IIIU " of (strain) Nireco) is analyzed, obtain the particle weight of primary particle in each particle size interval (%), in the distribution curve that this amount obtains with volume reference accumulation, particle diameter when accumulation degree is 50%.
In liquid-crystalline polyester composition, the content of white pigment is preferably 5 ~ 200 mass parts relative to liquid crystal polyester 100 mass parts, is more preferably 25 ~ 150 mass parts, more preferably 40 ~ 120 mass parts.
The content of white pigment is more, and the reflectivity of liquid-crystalline polyester composition more easily improves.If this content is in above-mentioned scope, be then easy to the melt fluidity, the mechanical characteristics that adjust liquid-crystalline polyester composition.
The crystal type of titanium oxide can be rutile-type, also can be Detitanium-ore-type, also can be that both mixing exist.From the view point of being easy to obtain that there is the also excellent liquid-crystalline polyester composition of high-reflectivity, weathering resistance, preferably comprise the crystal type of Titanium Dioxide (Rutile) Top grade, the crystal type be more preferably in fact only made up of Titanium Dioxide (Rutile) Top grade.
Titanium oxide can implement surface treatment.Such as by using inorganic, metal oxide to implement surface treatment, dispersiveness, weathering resistance can be improved.As inorganic, metal oxide, preferably use aluminum oxide (aluminium dioxide).From the view point of thermotolerance, intensity, surface-treated titanium oxide is not implemented in preferred use.
The manufacture method of titanium oxide can be chlorine method, also can be sulfuric acid process, but when manufacturing Titanium Dioxide (Rutile) Top grade, preferred chlorine method.Preferred when manufacturing titanium oxide by chlorine method: first, make to react near 1000 DEG C as the ore (the titania ore deposit obtained by rutile ore, ilmenite) in titanium source and chlorine and obtain crude titanic chloride, this crude titanic chloride, is oxidized with oxygen after purifying by rectifying.
As the example of the titanium oxide commercially available product manufactured by chlorine method, can enumerate: stone originates in " the TIPAQUE CR-60 " and " TIPAQUE CR-58 " of industry (strain).As the example of the titanium oxide commercially available product manufactured by sulfuric acid process, can enumerate: " SR-1 ", " SR-1R " and " D-2378 " of " the TITANIX JR-301 " of TAYCA (strain) and " WP0042 " and Sakai chemistry (strain).
Liquid-crystalline polyester composition of the present invention can contain other compositions such as the additive beyond more than a kind packing material, white pigment, the resin beyond liquid crystal polyester.
Packing material can be fibrous filler material, can be tabular packing material, also can be spherical and granulated filler material except threadiness and tabular.Packing material can be inorganic filling material, also can be organic filler material.
As the example of fibrous inorganic filling material, can enumerate: glass fibre; The carbon fiber such as carbonized polyacrylonitrile fibre, pitch-based carbon fiber; The ceramic fibers such as silica fiber, sapphire whisker, silica alumina fiber; With steel fibers such as Stainless Steel Fibres.Also can enumerate: the whiskers such as potassium titanate crystal whisker, barium titanate whisker, wollastonite whisker, aluminium borate whisker, silicon nitride crystal whisker, silicon carbide whisker.
As the example of fibrous organic filler material, can enumerate: trevira and Kevlar.
As the example of plate like inorganic packing material, can enumerate: talcum, mica, graphite, wollastonite, glass flake, barium sulfate and calcium carbonate.Mica can be white mica, also can be phlogopite, also can be fluorophlogopite, also can be four silicon micas.As the example of particulate inorganic packing material, can enumerate: silicon-dioxide, aluminum oxide, glass microballon, glass microsphere, boron nitride, silicon carbide and calcium carbonate.
In liquid-crystalline polyester composition, the content of packing material is generally 0 ~ 100 mass parts relative to liquid crystal polyester 100 mass parts.
As the example of the additive beyond white pigment, can enumerate: antioxidant, thermo-stabilizer, photostabilizer, antistatic agent, tensio-active agent, fire retardant.As the tinting material beyond white pigment, the pigment beyond white pigment, dyestuff can be used.The content of the additive beyond white pigment is generally 0 ~ 5 mass parts relative to liquid crystal polyester 100 mass parts.
As the example of the resin beyond liquid crystal polyester, can enumerate: the thermoplastic resin beyond the liquid crystal polyesters such as the polyester beyond polypropylene, polymeric amide, liquid crystal polyester, polysulfones, polyphenylene sulfide, polyetherketone, polycarbonate, polyphenylene oxide, polyetherimide; With thermosetting resins such as resol, epoxy resin, polyimide resin, cyanate ester resins.
The content of the resin beyond liquid crystal polyester is generally 0 ~ 20 mass parts relative to liquid crystal polyester 100 mass parts.
Liquid-crystalline polyester composition of the present invention carries out melting mixing preferably by by liquid crystal polyester, white pigment and other composition forcing machines of using as required, extrudes as wire and carries out granulating to prepare.
As forcing machine, preferably there is barrel, the screw rod of more than 1 of being configured in barrel, be arranged at barrel 1 place more than the forcing machine of supplying opening, more preferably also there is the forcing machine of the exhaust oral area at more than 1 place being arranged at barrel.
By being shaped by liquid-crystalline polyester composition of the present invention, the reflector of excellent in light-resistance can be obtained.The reflector that this liquid-crystalline polyester composition is shaped also is fallen into category of the present invention.
As the moulding method of liquid-crystalline polyester composition, preferred molten moulding method, as its example, can enumerate: extrusion molding method, compression forming method, blowing (blow) moulding method, vacuum forming process and the press formings such as injection molding method, T-shaped die head method, blowing (inflation) method.Wherein, preferred injection molding method.
Pass through injection molding method, easily can obtain that there is the reflector of thinner wall section, complex-shaped reflector, the small-sized reflector that the thickness especially obtaining thinner wall section is 0.01mm ~ 3.0mm, is preferably 0.02 ~ 2.0mm, is more preferably 0.05 ~ 1.0mm, is applicable to injection molding method.
About reflector of the present invention, the diffuse reflectance of the light of wavelength 460nm is preferably to more than 70%, is more preferably more than 80%.This reflectivity is obtained based on total light reflectance assay method A (standard white plate: barium sulfate) of JIS K7105-1981.
The reflector of luminous reflectance, particularly visible reflectance in the fields such as reflector of the present invention is suitable as electrically, electronics, automobile, machinery uses.Such as be suitable as the lamp reflector of the light supply apparatus such as halogen lamp, HID, employ the light-emitting device of the luminous element such as LED, organic EL, the reflector of display unit utilize.The reflector being particularly suitable as the light-emitting device employing LED utilizes.The light-emitting device with reflector of the present invention and luminous element also falls into category of the present invention.In light-emitting device of the present invention, luminous element is preferably LED.
Embodiment
Embodiment 1
(synthesis of liquid crystal polyester)
P-hydroxybenzoic acid 552.5g (4.0 moles), terephthalic acid 83.1g (0.5 mole), m-phthalic acid 415.3g (2.5 moles), Resorcinol 330.3g (3.0 moles), diacetyl oxide 1072.0g (10.5 moles) and 1-Methylimidazole 0.2g is added in the reactor possessing whipping appts, torquer, nitrogen ingress pipe, thermometer and reflux exchanger, after the gas in nitrogen replacement reactor, under stream of nitrogen gas, be warming up to 150 DEG C from room temperature with 30 minutes while stirring, reflux 1 hour at 150 DEG C.
Then, add 1-Methylimidazole 1.2g, the acetic acid and unreacted diacetyl oxide that remove as by product are distilled in limit, while be warming up to 310 DEG C from 150 DEG C with 2 hours 50 minutes, take out content, and be cooled to room temperature in the moment confirming moment of torsion rising from reactor.
Pulverized by obtained solid substance pulverizer, be warming up to 170 DEG C under nitrogen atmosphere from room temperature with 1 hour, and be warming up to 250 DEG C from 170 DEG C with 5 hours, keep 5 hours at 250 DEG C, after carrying out solid state polymerization thus, cooling, obtains Powdered liquid crystal polyester.
This liquid crystal polyester has Ar
1for repeating unit (1) 40 % by mole, Ar to phenylene
2for repeating unit (2) 5 % by mole, Ar to phenylene
2for repeating unit (2) 25 % by mole and the Ar of metaphenylene
3for the repeating unit (3) 30% to phenylene, its flow starting temperature is 333 DEG C.
(modulation of liquid-crystalline polyester composition)
By liquid crystal polyester 100 mass parts, titanium oxide, (stone originates in " the TIPAQUE CR-58 " of industry (strain): the alumina surface item for disposal of the titanium oxide manufactured by chlorine method.Volume average particle size 0.28 μm) 80 mass parts and glass fibre (" CS03JAPX-1 " of Owens Corning (strain)) 20 mass parts mixing after, use biaxial extruder (" PCM-30 " in pond shellfish ironworker (strain)), under the barrel temperature of 330 DEG C, carry out granulation, particulate state liquid-crystalline polyester composition.
(sunproof evaluation)
Use injection machine (" the PS40E5ASE type " of day essence Resin Industry (strain)), the barrel temperature of obtained liquid-crystalline polyester composition at 340 DEG C is betted in the mould after being mapped to mirror finish, is configured as the test film of the reflector of 64mm × 64mm × 1mm.For this test film, use ozone free metal halide lamp MAN250L, with 1200W/m
2exposure intensity, across UV glass-cutting (Shot company.Thickness 3mm) rayed 4 hours.For the test film before and after rayed, use from recording spectrophotometer (" U-3500 " of (strain) Hitachi) according to total light reflectance assay method A (standard white plate: barium sulfate) of JIS K7105-1981, the diffuse reflectance carried out for the light of wavelength 460nm measures.Result is as shown in table 1.This diffuse reflectance is the relative value when diffuse reflectance of the standard white plate of barium sulfate being set to 100%.
(mensuration of flexural strength)
Use injection machine (" the PS40E5ASE type " of day essence Resin Industry (strain)), obtained liquid-crystalline polyester composition is configured as under the barrel temperature of 350 DEG C the test film of length 127mm, width 12.7mm, thickness 6.4mm, measures flexural strength according to ASTM D790.Result is as shown in table 1.
Embodiment 2 ~ 12 and comparative example 1 and 2
When synthesizing liquid crystal polyester, the composition of starting monomer is as shown in table 1, carries out operation similarly to Example 1 in addition.Result is as shown in table 1.
Table 1
In table, each abbreviation, represents following compound.
HBA: P-hydroxybenzoic acid
HNA:6-hydroxy-2-naphthoic acid
TPA: terephthalic acid
IPA: m-phthalic acid
NDCA:2,6-naphthalene dicarboxylic acids
HQ: Resorcinol
DHBi:4,4 '-dihydroxybiphenyl
DHBe:4,4 '-dihydroxy benaophenonel
Claims (8)
1. a liquid-crystalline polyester composition, it comprises liquid crystal polyester and white pigment,
In liquid crystal polyester, the content comprising the repeating unit (A) of naphthalene skeleton is 0 ~ 10 % by mole relative to the total amount of whole repeating unit,
The content comprising the repeating unit (B) of biphenyl backbone is 0 ~ 5 % by mole relative to the total amount of whole repeating unit,
The total content of repeating unit (A) and repeating unit (B) is 0 ~ 10 % by mole relative to the total amount of whole repeating unit.
2. liquid-crystalline polyester composition as claimed in claim 1, wherein,
Liquid crystal polyester for having the liquid crystal polyester of the repeating unit shown in the repeating unit shown in the repeating unit shown in formula (1), formula (2) and formula (3),
(1)-O-Ar
1-CO-
(2)-CO-Ar
2-CO-
(3)-X-Ar
3-Y-
Ar
1represent phenylene, naphthylidene or biphenylene, Ar
2and Ar
3separately represent phenylene, naphthylidene, biphenylene or the group shown in following formula (4), X and Y separately represents Sauerstoffatom or imino-, Ar
1, Ar
2or Ar
3hydrogen atom in shown group can separately be replaced by halogen atom, alkyl or aryl,
(4)-Ar
4-Z-Ar
5-
Ar
4and Ar
5separately represent phenylene or naphthylidene, Z represents Sauerstoffatom, sulphur atom, carbonyl, alkylsulfonyl or alkylidene group.
3. liquid-crystalline polyester composition as claimed in claim 1 or 2, wherein,
In liquid crystal polyester, the total content of repeating unit (A) and repeating unit (B) is more than 3 % by mole relative to the total amount of whole repeating unit.
4. the liquid-crystalline polyester composition according to any one of claims 1 to 3, wherein,
White pigment is titanium oxide.
5. the liquid-crystalline polyester composition according to any one of Claims 1 to 4, wherein,
The content of white pigment is 5 ~ 200 mass parts relative to liquid crystal polyester 100 mass parts.
6. a reflector, it forms by being shaped by the liquid-crystalline polyester composition according to any one of Claims 1 to 5.
7. a light-emitting device, it has reflector according to claim 6 and luminous element.
8. light-emitting device as claimed in claim 7, wherein,
Luminous element is LED.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013226432A JP6324701B2 (en) | 2013-10-31 | 2013-10-31 | Liquid crystalline polyester composition |
| JP2013-226432 | 2013-10-31 |
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| CN104592718A true CN104592718A (en) | 2015-05-06 |
| CN104592718B CN104592718B (en) | 2018-04-27 |
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| CN201410589023.0A Active CN104592718B (en) | 2013-10-31 | 2014-10-28 | Liquid-crystalline polyester composition |
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| JP (1) | JP6324701B2 (en) |
| KR (1) | KR102215676B1 (en) |
| CN (1) | CN104592718B (en) |
| TW (1) | TWI628267B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651607A (en) * | 2018-12-03 | 2019-04-19 | 成都博斐特新材料有限公司 | A kind of resinous polymeric material and its preparation method and application |
| CN112979934A (en) * | 2021-02-07 | 2021-06-18 | 东华大学 | Thermotropic liquid crystal block polyarylate and preparation and application thereof |
| CN116199866A (en) * | 2022-03-16 | 2023-06-02 | 住友化学株式会社 | Liquid crystal polyester, method for producing liquid crystal polyester, liquid crystal polyester composition, film, method for producing film, and circuit board |
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| US5110896A (en) * | 1990-12-10 | 1992-05-05 | E. I. Du Pont De Nemours And Company | Thermotropic liquid crystalline polyester compositions |
| CN1451033A (en) * | 2000-07-05 | 2003-10-22 | 纳幕尔杜邦公司 | High tracking index liquid crystalline polymers and related applications |
| JP2005179627A (en) * | 2003-11-28 | 2005-07-07 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition |
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| JP2004059702A (en) * | 2002-07-26 | 2004-02-26 | Matsushita Electric Works Ltd | Thermoplastic resin composition for high frequency and molded article |
| WO2011115043A1 (en) * | 2010-03-16 | 2011-09-22 | Ｊｘ日鉱日石エネルギー株式会社 | Fully-aromatic thermotropic liquid crystal polyester resin composition, molded object, and led reflector |
| KR101711214B1 (en) * | 2010-11-12 | 2017-02-28 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | Reflector and light emitting device having the same |
-
2013
- 2013-10-31 JP JP2013226432A patent/JP6324701B2/en active Active
-
2014
- 2014-10-27 KR KR1020140146242A patent/KR102215676B1/en active IP Right Grant
- 2014-10-28 CN CN201410589023.0A patent/CN104592718B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5110896A (en) * | 1990-12-10 | 1992-05-05 | E. I. Du Pont De Nemours And Company | Thermotropic liquid crystalline polyester compositions |
| CN1451033A (en) * | 2000-07-05 | 2003-10-22 | 纳幕尔杜邦公司 | High tracking index liquid crystalline polymers and related applications |
| JP2005179627A (en) * | 2003-11-28 | 2005-07-07 | Sumitomo Chemical Co Ltd | Liquid crystal polyester resin composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651607A (en) * | 2018-12-03 | 2019-04-19 | 成都博斐特新材料有限公司 | A kind of resinous polymeric material and its preparation method and application |
| CN109651607B (en) * | 2018-12-03 | 2021-05-14 | 成都博斐特新材料有限公司 | Resin polymer material and preparation method and application thereof |
| CN112979934A (en) * | 2021-02-07 | 2021-06-18 | 东华大学 | Thermotropic liquid crystal block polyarylate and preparation and application thereof |
| CN112979934B (en) * | 2021-02-07 | 2022-10-11 | 东华大学 | Thermotropic liquid crystal block polyarylate and preparation and application thereof |
| CN116199866A (en) * | 2022-03-16 | 2023-06-02 | 住友化学株式会社 | Liquid crystal polyester, method for producing liquid crystal polyester, liquid crystal polyester composition, film, method for producing film, and circuit board |
| CN116199866B (en) * | 2022-03-16 | 2024-03-19 | 住友化学株式会社 | Liquid crystal polyester, method for producing liquid crystal polyester, liquid crystal polyester composition, film, method for producing film, and circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102215676B1 (en) | 2021-02-16 |
| JP2015086302A (en) | 2015-05-07 |
| KR20150050405A (en) | 2015-05-08 |
| TW201522585A (en) | 2015-06-16 |
| TWI628267B (en) | 2018-07-01 |
| JP6324701B2 (en) | 2018-05-16 |
| CN104592718B (en) | 2018-04-27 |
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