WO2007111361A1 - 全芳香族サーモトロピック液晶ポリエステル樹脂組成物、その射出成形体および該成形体を使用した光学装置 - Google Patents
全芳香族サーモトロピック液晶ポリエステル樹脂組成物、その射出成形体および該成形体を使用した光学装置 Download PDFInfo
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- WO2007111361A1 WO2007111361A1 PCT/JP2007/056749 JP2007056749W WO2007111361A1 WO 2007111361 A1 WO2007111361 A1 WO 2007111361A1 JP 2007056749 W JP2007056749 W JP 2007056749W WO 2007111361 A1 WO2007111361 A1 WO 2007111361A1
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- WIPO (PCT)
- Prior art keywords
- resin composition
- liquid crystal
- white pigment
- crystal polyester
- wholly aromatic
- Prior art date
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 38
- 230000003287 optical effect Effects 0.000 title claims description 9
- 239000004974 Thermotropic liquid crystal Substances 0.000 title abstract 4
- 239000000203 mixture Substances 0.000 title description 8
- 229920001225 polyester resin Polymers 0.000 title description 5
- 239000004645 polyester resin Substances 0.000 title description 5
- 239000012463 white pigment Substances 0.000 claims abstract description 42
- 229920000728 polyester Polymers 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000011342 resin composition Substances 0.000 claims abstract description 23
- 238000004898 kneading Methods 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004973 liquid crystal related substance Substances 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000006640 acetylation reaction Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002310 reflectometry Methods 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- 230000021736 acetylation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
-
- 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
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers 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 having potential barriers 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
Definitions
- the present invention relates to a wholly aromatic thermopick liquid crystal polyester resin composition excellent in reflectance of light of a specific wavelength, an injection molded body thereof, and an optical apparatus using the molded body.
- the present invention relates to an optical device using a white light emitting diode (hereinafter referred to as “LED”).
- LED white light emitting diode
- Optical devices such as lighting devices and display devices using LEDs are used in a wide range of fields. These devices have LED elements mounted on the circuit pattern on the substrate with conductive adhesive, solder, etc.
- a reflector (reflective frame) is provided around the LED element, and the LED element located in the reflector is sealed with a translucent resin. Things are being used.
- Various types of white LEDs are known! /, For example, in general, combine multiple LEDs such as green (G), blue (B), and red (R) to obtain white.
- RGB blue LEDs
- Blue LEDs are mainly used for wavelength conversion, but UV LEDs can also be used as light sources.
- a molded product of a resin composition filled with white pigment particles made of a metal oxide may be used.
- a reflector containing a resin composition is used for heating processes such as soldering when mounting LED elements on a substrate, heat generation during thermosetting of the sealing resin, heating when the LED device is bonded to other components, LED Heat resistance to heating, etc. in the environment where the equipment is used, and maintenance of high reflectivity during the period including subsequent use are required.
- white LEDs are required to maintain good reflectivity, particularly in the region below 500 nm.
- thermopick liquid crystal polyester with excellent heat resistance especially a resin composition comprising a wholly aromatic thermopick liquid crystal polyester with a melting point exceeding 320 ° C and a white pigment, is used for LED reflectors. It became so. (For example, see Patent Documents 1 to 3.)
- Patent Document 1 Japanese Patent Publication No. 6-38520
- Patent Document 2 JP 2004-256673 A
- Patent Literature: 3 Japanese Patent Laid-Open No. 2005-23210 Disclosure of Invention
- LED reflectors made of wholly aromatic thermopick-pick liquid crystal polyesters have a 480 nm wavelength as a reflectance index of white light compared to those made of polyamide resin compositions that have been used in the past.
- the reflectance (hereinafter referred to as “white light reflectance” in the present specification) is inadequate.
- the white pigment added to the wholly aromatic liquid crystal polyester it is known to use white pigment particles made of a metal oxide having heat resistance at a high processing temperature and high hiding power. These pigment additives are generally added by melt-kneading.
- the metal oxide constituting the white pigment particles is an acidic compound
- the total aromatic liquid crystal polyester is decomposed and the molecular weight is decreased by coexisting an acidic compound with the liquid aromatic polyester that is in a molten state and continuously applying a large shearing force. Generation of low molecular weight components occurs. This phenomenon also occurs in the plasticizing process when the obtained resin composition is injection molded. Since this phenomenon is expected to become more prominent at high temperatures, the higher the melting point of the wholly aromatic thermopick liquid crystal polyester, the greater the effect.
- the present invention relates to a resin composition obtained from a white pigment particle and a wholly aromatic thermopick liquid crystal polyester through a melt-kneading process, and has excellent heat resistance and moldability of the wholly aromatic thermopick liquid crystal polyester. It is an object to achieve a good white light reflectance while maintaining.
- a white pigment obtained by a production method including a firing step is surface-treated with 3 to 15% by mass of aluminum oxide (the total is 100% by mass).
- the second of the present invention in the first invention, than it also relates to a resin composition, wherein the white pigment is titanium oxide obtained by a sulfuric acid method (Ti_ ⁇ 2).
- the third aspect of the present invention is an injection composition from the first or second resin composition of the present invention.
- the present invention relates to a molded article having a molding surface with a reflectance of 80% or more obtained by shaping the 480 nm wave.
- a fourth aspect of the present invention relates to an optical device in which the third molded body of the present invention is used as a light emitting device member and / or a reflector. Furthermore, a fifth aspect of the present invention relates to an optical device characterized in that the fourth light emitting device of the present invention uses a white LED. The invention's effect
- a molded product having excellent white light reflectance can be obtained by a normal melt-kneading process without impairing the excellent heat resistance and moldability of the all aromatic thermopick liquid crystal polyester.
- a resin composition is obtained. Therefore, a reflector having the surface of the injection molded product of the resin composition as a reflecting surface, particularly a reflector suitable for a white LED, can be obtained, and a light emitting device having excellent performance can be provided.
- thermopick liquid crystal polyester in order to use it as an LED reflector, a soldering heat resistance is required, so that the melting point is preferably 320 ° C or higher. Better! /.
- p-hydroxybenzoic acid should be used in an amount of 40 mol% or more as a raw material monomer.
- other known aromatic hydroxycarboxylic acids, aromatic dicarbons, and aromatic dihydroxy compounds can be used in appropriate combination.
- polyesters obtained only from aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and aromatics such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid.
- Preferred examples include liquid crystalline polyesters obtained from dicarboxylic acids and aromatic dihydroxy compounds such as Z or hydroquinone, resorcin, 4,4, -dihydroxydiphenyl, 2,6-dihydroxynaphthalene.
- aromatic dihydroxy compounds such as Z or hydroquinone, resorcin, 4,4, -dihydroxydiphenyl, 2,6-dihydroxynaphthalene.
- p- hydroxybenzoic acid (I), terephthalic acid ( ⁇ ), 4, 4 ' 80 ⁇ one dihydroxy Biff We sulfonyl (III) (including the derivatives thereof.): L00 Monore 0/0 (where be the total of 60 mole 0/0 or more (I) and (II).), and, (I) (II) or a polycondensation reaction can be other aromatic compounds 0-20 moles of (III) % Is a wholly aromatic thermopick liquid crystal polyester obtained by polycondensation.
- melt polycondensation should be carried out after acetylating the above-mentioned monomeric hydroxyl groups in advance in order to shorten the melt polycondensation time and reduce the influence of thermal history during the process.
- acetylation is preferably performed by supplying anhydrous acetic acid to the monomer in the reaction vessel.
- This acetylation step is preferably performed using the same reaction vessel as the melt polycondensation step. That is, it is preferable to carry out a acetylation reaction with a raw material monomer and acetic anhydride in a reaction vessel, and after the completion of the reaction, the temperature is raised to shift to a polycondensation reaction.
- a melt polycondensation reaction is performed with a deacetic acid reaction of the acetylated monomer.
- the reaction is preferably carried out using a reaction vessel equipped with monomer supply means, acetic acid discharge means, molten polyester take-out means and stirring means.
- a reaction vessel polycondensation apparatus
- the polymerization temperature is preferably 150 ° C to 350 ° C.
- a catalyst for the polycondensation reaction compounds such as Ge, Sn, Ti, Sb, Co, Mn, and Mg can be used.
- the fully aromatic thermopick liquid crystal polyester having a low polymerization degree is withdrawn from the polymerization tank in a molten state, Supply to a cooler such as a steel belt or drum cooler and cool to solidify.
- the solidified low-polymerization wholly aromatic thermopick liquid crystal polyester is pulverized to a size suitable for the subsequent solid-phase polycondensation.
- the crushing method is not particularly limited.
- Roll durnator which is a crushed powdered stone.
- a feather mill manufactured by Hosokawa Micron Corporation is particularly preferable.
- there is no particular limitation on the particle size of the pulverized product but it is preferred that the range of 4 mesh to 2000 mesh not pass through industrial mesh (Tyler mesh) is 5 mesh to 2000 mesh (0.01 to 4 mm). ) Is more preferable, and 9 mesh to 1450 mesh (0.02 to 2 mm) is most preferable.
- the pulverized product obtained in the pulverization step is subjected to a solid phase polycondensation step to perform solid phase polycondensation.
- a solid phase polycondensation step to perform solid phase polycondensation.
- the equipment and operating conditions used in the solid phase polycondensation process there are no particular restrictions on the equipment and operating conditions used in the solid phase polycondensation process, and known equipment and methods can be used. In order to use it as an LED reflector, it is preferable to carry out a solid phase polycondensation reaction until a melting point of 320 ° C or higher is obtained.
- the white pigment particles 97-85% by mass of white pigment and 3-15% by mass of aluminum oxide (both are combined to make 100% by mass) are used.
- the white pigment means one excluding acid aluminum.
- the white pigment is not particularly limited as long as it has heat resistance to heating in the melt-kneading process, the injection molding temperature, the solder mounting process, etc. with the wholly aromatic thermoto
- the white pigment obtained in production method comprising the roasting step, (2 Ti0) titanium oxide, zinc oxide (ZnO), white lead (2PbC0 3 'Pb (OH) 2) or the like can be used.
- Metal oxide white pigments with excellent heat resistance are preferred. Among them, the hiding power is great! It is most preferable to use those having an average particle diameter of 0 /;!-0.5 / m. Depending on the hue preference, zinc oxide can also be used.
- titanium oxide produced by a sulfuric acid method including a roasting step is particularly preferable.
- the present inventors have removed components that adversely affect the white light reflectance of a molded article of a composition obtained by blending with a wholly aromatic thermopick liquid crystal polyester resin and melt-kneading in a roasting step. I think.
- a known method for surface-treating the white pigment with aluminum oxide a known method can be used. For example, either the method described in JP-A-5-286721 or the method described as a conventional method in the patent document may be used.
- This patent document can also be subjected to the same surface treatment even if it is applied to other white pigments mainly related to the surface treatment of titanium oxide.
- White pigments surface-treated with acid aluminum can also be obtained from Kashiwa. For example, Sakaii ⁇ Ltd. "SR- 1" (rutile acid Ihichitan average mean particle size 0. 25 mu m, a surface treatment agent [alpha] 1 2 ⁇ 3, Treatment amount 5%).
- the function of adsorbing impurities in the polymer and the surface of the metal oxyhydride white pigment are coated, and the metal oxide as an acidic compound promotes the hydrolysis of the wholly aromatic thermopick liquid crystal polyester, etc. This is a function to mitigate the effects of
- the content of aluminum oxide is less than mass%, the effect of coating the surface of the white pigment and the effect of adsorbing impurities in the polymer cannot be fully achieved. May occur. Therefore, 97 to 85% by weight of white pigment and 3 to 15% by weight of aluminum oxide (both are 100% by weight) are used as white pigment particles. A particularly preferable range of aluminum oxide is 5 to 10% by mass.
- the method and apparatus for melt-kneading the wholly aromatic thermopick liquid crystal polyester and the white pigment particles composed of the white pigment surface-treated with aluminum oxide those used for known melt-kneading can be suitably used. .
- a single-screw kneader, a twin-screw kneader, a Banbury mixer, a pressure kneader, or the like can be used, but a twin-screw kneader is particularly preferable from the viewpoint of suitable dispersion of white pigment particles.
- the amount of white pigment particles added is in the range of 35 to 100 parts by mass with respect to 100 parts by mass of the wholly aromatic thermopick liquid crystal polyester. If the amount is less than 35 parts by mass, sufficient whiteness cannot be obtained, and if it exceeds 100 parts by weight, the moldability is remarkably lowered, and it becomes difficult to obtain a molded surface having a white light reflectance of 80% or more.
- a known inorganic filler and organic filler can be added to the resin composition of the present invention within a range not impairing the effects of the present invention. These may be used alone or in combination of two or more.
- thermopick liquid crystal polyester melt polycondensation
- P-Hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.) 298.3 kg (2.16 kgol) ), 4, 4-dihydroxydiphenyl (Honshu Chemical Co., Ltd.) 134. lkg (0.72 kgmol), terephthalic acid (Mitsui Chemicals) 89.7 kg (0.54 kgmol), isophthalic acid ( 2) 99.9 kg (0.18 kgmol), 0.11 kg of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.), and 0.04 kg of potassium acetate (manufactured by Kishida Chemical Co., Ltd.) were used as catalysts.
- the cooling P solidification apparatus an apparatus having a pair of cooling rolls having a diameter of 630 mm, a distance between rolls of 2 mm, and a distance of 1800 mm according to Japanese Patent Laid-Open No. 2002-179979 was used.
- the pair of cooling rolls are rotated opposite to each other at a rotation speed of 18 rpm, and a melt polycondensation reaction in a fluid state extracted from a polycondensation reaction tank is formed in a recess formed by the pair of cooling rolls and the pair of weirs.
- the low polymerization degree is achieved by gradually supplying the product and holding it in the recess, adjusting the flow rate of the cooling water in the pair of cooling rolls to adjust the roll surface temperature, and cooling and solidifying immediately after passing between the rolls.
- the surface temperature of the aromatic thermopick liquid crystal polyester was 220 ° C.
- the obtained sheet-like solidified product having a thickness of 2 mm was crushed to approximately 50 mm square by a crusher (manufactured by Nisso Kogyo Co., Ltd.).
- This pulverized product was pulverized using a feather mill manufactured by Hosokawa Micron Corporation to obtain a raw material for solid phase polycondensation.
- the pulverized material passed through a mesh with an opening of 1 mm.
- the pulverized product is stored in a rotary kiln, heated to a room temperature force of 170 ° C over 3 hours under nitrogen flow, then heated to 280 ° C over 5 hours, Furthermore, the temperature was raised to 300 ° C over 3 hours, and solid-phase polycondensation was performed to obtain about 480 kg of fully aromatic thermopick liquid crystal polyester.
- R-310 Rutile titanium oxide obtained by sulfuric acid method including roasting process. No surface treatment. Average particle size 0.20 m.
- the total aromatic thermopick liquid crystal polyester of the amount shown in Table 1 is mixed with white pigment particles 1 to 3 and glass fiber separately, and the maximum temperature of the cylinder is 430 ° by a twin screw extruder (Ikegai Steel Co., Ltd.). Pellet was obtained by melt-kneading with C.
- the diffuse reflectance with respect to light of 480 nm was measured using a self-recording spectrophotometer (U-3500: manufactured by Hitachi, Ltd.).
- the reflectance is a relative value when the diffuse reflectance of a standard white plate of barium sulfate is 100%. The results are shown in Table 1.
- the titanium oxide contained in the former is white pigment particles 1 (which satisfies the requirements of the present invention), and in the latter, white pigment particles 2 or white pigment particles 3 (The force reflectivity value that is different from that of the requirements of the present invention! / ⁇ .) Is higher in both the specimen thickness of 3. Omm and 0.5 mm than the latter. It can be seen that the value is shown.
- Example 4 shows white pigment particles 2 contained in Comparative Example 1 (meeting the requirements of the present invention). Not enough. ) Of the 75 parts by mass, 50 parts by mass were replaced with white pigment particles 1 (meeting the requirements according to the present invention). It is remarkable that the value is higher than that of Comparative Example 1 under any condition of 5 mm.
- Example 1 to 4 it is a composition that satisfies the requirements of the present invention, and the reflectance is high at any of the specimen thicknesses of 3. Omm and 0.5 mm. Recognize. Industrial applicability
- the present invention is provided with an excellent reflectivity, and has a high reflectivity such as a light emitting device member and / or a reflector.
- a high reflectivity such as a light emitting device member and / or a reflector.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Led Device Packages (AREA)
- Optical Elements Other Than Lenses (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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CN2007800088472A CN101400733B (zh) | 2006-03-24 | 2007-03-22 | 全芳族热致液晶聚酯树脂组合物、其注射成型制品及使用该成型制品的光学器件 |
KR1020087023435A KR101313410B1 (ko) | 2006-03-24 | 2007-03-22 | 전방향족 서모트로픽 액정 폴리에스테르 수지 조성물, 그 사출 성형체 및 그 성형체를 사용한 광학 장치 |
US12/225,567 US7713439B2 (en) | 2006-03-24 | 2007-03-22 | Wholly aromatic thermotropic liquid crystal polyester resin composition, injection molded article thereof, and optical device using the molded article |
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JP2006-083306 | 2006-03-24 | ||
JP2006083306A JP5201799B2 (ja) | 2006-03-24 | 2006-03-24 | 全芳香族サーモトロピック液晶ポリエステル樹脂組成物、その射出成形体および該成形体を使用した光学装置 |
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US (1) | US7713439B2 (ja) |
JP (1) | JP5201799B2 (ja) |
KR (1) | KR101313410B1 (ja) |
CN (1) | CN101400733B (ja) |
TW (1) | TWI394792B (ja) |
WO (1) | WO2007111361A1 (ja) |
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JP5201799B2 (ja) | 2013-06-05 |
JP2007254669A (ja) | 2007-10-04 |
TWI394792B (zh) | 2013-05-01 |
US7713439B2 (en) | 2010-05-11 |
CN101400733A (zh) | 2009-04-01 |
CN101400733B (zh) | 2012-11-28 |
KR101313410B1 (ko) | 2013-10-01 |
US20090250662A1 (en) | 2009-10-08 |
TW200736333A (en) | 2007-10-01 |
KR20080108483A (ko) | 2008-12-15 |
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