WO2011040138A1 - 液晶ポリエステル樹脂組成物、その成形体、及び光学装置 - Google Patents
液晶ポリエステル樹脂組成物、その成形体、及び光学装置 Download PDFInfo
- Publication number
- WO2011040138A1 WO2011040138A1 PCT/JP2010/063896 JP2010063896W WO2011040138A1 WO 2011040138 A1 WO2011040138 A1 WO 2011040138A1 JP 2010063896 W JP2010063896 W JP 2010063896W WO 2011040138 A1 WO2011040138 A1 WO 2011040138A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- crystal polyester
- resin composition
- liquid crystal
- polyester resin
- titanium oxide
- Prior art date
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 65
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 48
- 239000004645 polyester resin Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 230000003287 optical effect Effects 0.000 title claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229920000728 polyester Polymers 0.000 claims abstract description 58
- 238000011282 treatment Methods 0.000 claims abstract description 42
- 239000012765 fibrous filler Substances 0.000 claims abstract description 21
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 16
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 15
- 238000004381 surface treatment Methods 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 238000001746 injection moulding Methods 0.000 claims description 15
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 8
- 238000002310 reflectometry Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 description 30
- 239000011342 resin composition Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 238000006068 polycondensation reaction Methods 0.000 description 25
- 239000000155 melt Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- -1 aromatic diol Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001579 optical reflectometry Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 230000021736 acetylation Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 210000003746 feather Anatomy 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 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 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 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 2
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- XSTITJMSUGCZDH-UHFFFAOYSA-N 4-(4-hydroxy-2,6-dimethylphenyl)-3,5-dimethylphenol Chemical group CC1=CC(O)=CC(C)=C1C1=C(C)C=C(O)C=C1C XSTITJMSUGCZDH-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002356 laser light scattering Methods 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
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- 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
-
- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V7/00—Reflectors for light sources
- F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0079—Liquid crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
- B29L2011/0083—Reflectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- 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
- H01L33/483—Containers
- H01L33/486—Containers adapted for surface mounting
Definitions
- the present invention relates to a liquid crystal polyester resin composition, an injection molded product thereof, and an optical device using the molded product.
- the present invention relates to an optical device using a light emitting diode (hereinafter referred to as “LED”).
- LED light emitting diode
- Optical devices such as lighting devices and display devices using LEDs as light sources are used in a wide range of fields. These are usually equipped with an LED device in which LED elements are mounted on a circuit pattern on a substrate with a conductive adhesive, solder, or the like and necessary connections are made by wire bonding.
- a reflector for increasing the light utilization rate of the LED is provided around the LED element, and the LED element located in the reflector is sealed with a translucent resin. .
- white LEDs are obtained by combining a plurality of LEDs such as green (G: 525 nm), blue (B: 470 nm), red (R: 630 nm), etc., or in a sealing resin. Those using a wavelength conversion effect by blending a fluorescent material are known. In the latter case, an ultraviolet light emitting LED may be used as the light source.
- molded articles of a resin composition containing white pigment particles such as metal oxides may be used.
- heating process such as solder when mounting the LED element on the substrate, heat generation during thermosetting of the sealing resin, heating when bonding the LED device to other members, use the LED device It is required to have sufficient heat resistance against heating or the like in the environment where
- LED reflectors are required to maintain a high light reflectance over a long period of time. Particularly, in the case of a white LED reflector, it is required that the reflectance with respect to light in a wavelength region of 500 nm or less is sufficiently high.
- the LED reflector formed from the liquid crystal polyester resin composition of Patent Documents 1 and 2 has a reflectance with respect to light of 480 nm, which is a reflectance index of white light, from a polyamide-based resin composition that has been used in the past. It has the problem of being low compared to
- liquid crystal polyester resin composition injection molded articles of Patent Documents 3 and 4 above have improved light reflectance at 480 nm, it is necessary to add a large amount of white pigment to increase the reflectance.
- Mechanical strength may be reduced.
- electrical and electronic devices have been made lighter, thinner, and smaller, and electronic components such as LED reflectors have been made smaller and thinner. Accordingly, the required level for the strength of members has increased. Therefore, even the liquid crystal polyester resin compositions described in Patent Documents 3 and 4 still have room for improvement in terms of mechanical strength.
- titanium oxide As the white pigment to be added to the liquid crystal polyester, a metal oxide having heat resistance against its high processing temperature and high concealing power is used, and among these, titanium oxide is frequently used. Titanium oxide is known to have been subjected to a surface treatment such as an aluminum oxide treatment in order to improve affinity with the resin, dispersibility, and the like. In order to increase the reflectance of the liquid crystal polyester resin composition with respect to white light, it is conceivable to increase the amount of titanium oxide. However, according to the study by the present inventors, it has been found that even if titanium oxide is subjected to the above-described surface treatment, the resin composition becomes brittle and mechanical strength, particularly Izod impact strength, is greatly reduced when the amount is high. It was. Possible causes include secondary aggregation and poor dispersion of titanium oxide particles, and a relatively small amount of liquid crystal polyester in the resin composition.
- the addition of titanium oxide to the liquid crystal polyester is generally carried out by melt kneading. Since titanium oxide, which is a metal oxide, is an acidic compound, in the melt-kneading step, the liquid crystal polyester in a molten state and the acidic compound coexist and a large shearing force is continuously applied. As a result, the molecular chain of the liquid crystal polyester is broken, and the molecular weight is decreased and the low molecular weight component is easily generated. As a result, the melt viscosity of the resin composition is lowered, and the mechanical strength of the molded product, particularly Izod It is also conceivable that the impact strength decreases.
- both the light reflectivity and mechanical strength, particularly the Izod impact strength, of the LED reflector, which is remarkably reduced in size and thickness, are compatible at a high level. No such injection molded product was obtained.
- the present invention has been made in view of the above circumstances, and a liquid crystal polyester resin composition capable of obtaining a molded article having both high light reflectivity at 480 nm and mechanical strength such as Izod impact strength at a high level, It aims at providing a molded object and an optical apparatus provided with the said molded object.
- the reflectance to light having a wavelength of 480 nm has been conventionally increased by blending liquid crystal polyester with a specific ratio of titanium oxide subjected to a specific surface treatment.
- the present inventors have found that an injection-molded article having a higher Izod impact strength can be obtained, and based on this finding, the present invention has been completed.
- the liquid crystal polyester resin composition of the present invention comprises 100 parts by mass of liquid crystal polyester (A), 50 to 150 parts by mass of titanium oxide (B) subjected to aluminum oxide treatment, silicon oxide treatment and organosiloxane treatment as a surface treatment, It contains 0 to 50 parts by mass of an inorganic fibrous filler (C).
- liquid crystal polyester resin composition of the present invention by having the above-described configuration, a molded product having both high light reflectivity at 480 nm and mechanical strength such as Izod impact strength can be obtained. Moreover, the liquid crystalline polyester resin composition of the present invention can be prepared by a normal melt-kneading process or molded by injection molding. Even in this case, the effects of the present invention can be obtained. Furthermore, the liquid crystalline polyester resin composition of the present invention can obtain a molded article having excellent mechanical strength, although the melt viscosity at 370 ° C. is lower than that when using conventional titanium oxide. This is an unexpected effect in view of the problem of molecular chain breakage of liquid crystal polyester due to melt shear.
- the liquid crystalline polyester (A) is preferably a wholly aromatic thermotropic liquid crystalline polyester having a melting point of 320 ° C. or higher.
- the titanium oxide (B) preferably has a primary particle diameter in the range of 0.2 to 0.3 ⁇ m.
- the liquid crystal polyester resin composition of the present invention has a reflectance of 85% or more with respect to light having a wavelength of 480 nm on a molding surface of a molded product obtained by injection molding, and an Izod impact strength of the molded product is 40 kJ / m 2 or more. It is preferable that
- the present invention also provides a molded article obtained by injection molding any one of the liquid crystalline polyester resin compositions of the present invention.
- the present invention also provides an optical device comprising a light source and a light source reflector made of the molded article of the present invention.
- the light source is preferably a white LED.
- a liquid crystal polyester resin composition capable of obtaining a molded body having both high light reflectivity at 480 nm and mechanical strength such as Izod impact strength at a high level, the molded body, and an optical equipped with the molded body.
- An apparatus can be provided.
- the liquid crystal polyester resin composition of the present invention retains the excellent heat resistance and moldability of the liquid crystal polyester even though it is prepared through a normal melt-kneading process, and has excellent white light reflectance and Izod impact strength.
- the body can be formed by injection molding.
- the injection-molded product of the liquid crystal polyester resin composition of the present invention can be used as a reflector having the surface as a reflection surface, and can be used as a reflector particularly suitable for white LEDs. According to the present invention, since it is possible to realize a reflector that has a higher reflectance than the conventional one and is excellent in mechanical strength, it is possible to provide an optical device that includes this and has excellent light extraction efficiency.
- the liquid crystal polyester according to the present invention (hereinafter sometimes simply referred to as “LCP”) is a polyester called a thermotropic liquid crystal polymer, and forms an anisotropic melt at a temperature of 450 ° C. or lower.
- LCP include those composed of a structural unit selected from an aromatic hydroxycarbonyl unit, an aromatic and / or aliphatic dihydroxy unit, an aromatic and / or aliphatic dicarbonyl unit, and the like.
- aromatic hydroxycarbonyl unit examples include a structural unit formed from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like
- aromatic and / or aliphatic dihydroxy unit examples include 4,4′- Dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, Structural units formed from 2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, aromatic and / or aliphatic di
- carbonyl unit examples include Phosphoric acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′
- the liquid crystalline polyester used in the present invention is preferably a wholly aromatic thermotropic liquid crystalline polyester because of its excellent balance of moldability, mechanical strength and heat resistance.
- the wholly aromatic thermotropic liquid crystal polyester include, for example, a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, a combination of different aromatic hydroxycarboxylic acids, an aromatic dicarboxylic acid and an aromatic And those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate.
- a polyester such as polyethylene terephthalate.
- p-hydroxybenzoic acid is preferably used in an amount of 40 mol% or more as a raw material monomer.
- other known aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and aromatic dihydroxy compounds can be used in appropriate combination.
- polyesters obtained from aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid alone, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
- Preferred examples include acids and / or liquid crystalline polyesters obtained from aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene.
- mol% including (I) of p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4′-dihydroxybiphenyl (III) (including derivatives thereof) (II) is added to 60 mol% or more), and other aromatic compounds capable of polycondensation reaction with any of (I), (II) and (III) are polycondensed with 0 to 20 mol%. It is a wholly aromatic thermotropic liquid crystal polyester obtained.
- acetylation is preferably performed by supplying acetic anhydride 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 an acetylation reaction with a raw material monomer and acetic anhydride in a reaction vessel, and then proceed to a polycondensation reaction by raising the temperature after completion of the reaction.
- the reaction is preferably performed using a reaction tank equipped with a monomer supply means, an acetic acid discharge means, a molten polyester take-out means, and a stirring means. .
- a reaction vessel polycondensation apparatus
- the polymerization temperature is preferably 150 ° C to 350 ° C.
- the temperature is raised to the polymerization start temperature to start polycondensation, the temperature is raised in the range of 0.1 ° C./min to 2 ° C./min, and the final temperature is raised to 280 to 350 ° C. Is preferred.
- Compounds such as Ge, Sn, Ti, Sb, Co, Mn, and Mg can be used as the catalyst for the polycondensation reaction.
- the polycondensation temperature rises as the melting temperature of the produced polymer rises as the polycondensation proceeds.
- the fully aromatic thermotropic liquid crystalline polyester having a low polymerization degree is withdrawn from the polymerization tank in a molten state, and a steel belt or a drum cooler. Etc., cool and solidify.
- the solidified wholly aromatic thermotropic liquid crystal polyester having a low polymerization degree is pulverized to a size suitable for the subsequent solid phase polycondensation.
- the crushing method is not particularly limited.
- impact mills such as Hosokawa Micron feather mill, Victor mill, Coroplex, Pulverizer, Contraplex, scroll mill, ACM Pulverizer, etc., and Matsubo's crushing crusher. Examples thereof include a roll granulator. Particularly preferred is a feather mill manufactured by Hosokawa Micron.
- the particle size of the pulverized product is not particularly limited, but it is preferably in the range of 4 mesh to 2000 mesh not passing through an industrial sieve (Tyler mesh), preferably 5 mesh to 2000 mesh (0.01 to 4 mm). More preferably, it is most preferably 9 mesh to 1450 mesh (0.02 to 2 mm).
- 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.
- a well-known apparatus and method 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 content of the liquid crystal polyester (A) in the resin composition is preferably 40 to 60% by mass, and more preferably 40 to 50% by mass based on the total amount of the resin composition.
- Tianium oxide (B)> The titanium oxide used in the present invention has been subjected to aluminum oxide treatment, silicon oxide treatment, and organosiloxane treatment as surface treatments.
- Titanium oxide includes rutile type and anatase type, and rutile type titanium oxide having a large hiding power is preferable.
- As the production method of titanium oxide those obtained by any conventionally known production method such as sulfuric acid method and chlorine method can be used. Of these, those produced by the chlorine method are preferred because of their excellent whiteness.
- the primary particle diameter of titanium oxide (the number average particle diameter of the smallest unit particles that can be clearly separated from the others) is preferably 0.05 to 0.5 ⁇ m, more preferably 0.2 to 0.3 ⁇ m.
- the primary particle diameter is below the lower limit, the light shielding property and light reflectance may be insufficient, and in the melt kneading by the extruder, the powder material may not bite into the screw and the extrusion may occur. The amount is remarkably lowered and productivity is lowered, which is not preferable.
- the primary particle diameter exceeds the upper limit value, the impact strength may decrease.
- the number average particle diameter is measured by a general method such as a dynamic light scattering method or a laser light scattering method.
- the titanium oxide used in the present invention is surface-treated by aluminum oxide treatment, silicon oxide treatment, and organosiloxane treatment.
- these surface treatment methods known methods can be used.
- a method for treating the surface of titanium oxide with aluminum oxide for example, a method described in JP-A-5-286721 or a method described as a conventional method in the patent literature can be used.
- Examples of the method for treating the surface of titanium oxide with silicon oxide include the method described in paragraph “0032” of JP-A-9-124968.
- Examples of the method for treating the surface of titanium oxide with an organosiloxane include the methods described in paragraphs “0054” and “0055” of JP-A-2005-306927.
- These treatments may be performed in any order on silicon oxide, aluminum oxide treatment and organosiloxane treatment on titanium oxide.
- the treatment amount is preferably 0.1 to 10% by mass of aluminum oxide, 0.1 to 5% by mass of silicon oxide, and 0.1 to 5% by mass of organosiloxane with respect to the titanium oxide particles. If the treatment amount is below the lower limit, the affinity between the liquid crystal polyester and titanium oxide and the dispersibility of the titanium oxide in the liquid crystal polyester resin composition may be insufficient. If the treatment amount exceeds the upper limit, the liquid crystal polyester resin When the composition is produced, the treatment agent is thermally decomposed, which may lead to deterioration of the liquid crystal polyester resin.
- the titanium oxide used in the present invention must be subjected to three types of surface treatments: aluminum oxide treatment, silicon oxide treatment and organosiloxane treatment.
- the processing temperature at the time of manufacturing a liquid crystalline polyester resin composition using an extruder exceeds 300 degreeC.
- organic compounds such as organosiloxanes have a high risk of thermal decomposition at this temperature level.
- the combination of the aluminum oxide treatment and the silicon oxide treatment and the organosiloxane treatment makes the liquid crystal polyester resin remarkably decomposed by the decomposition of the treatment agent even at a high processing temperature exceeding 300 ° C. It is possible to obtain a liquid crystal polyester resin composition in which titanium oxide is highly blended without deterioration.
- Titanium oxide that has been subjected to aluminum oxide treatment, silicon oxide treatment, and organosiloxane treatment can also be obtained from the market.
- DCF-T-17008S (trade name) manufactured by Resino Color Industry Co., Ltd. may be mentioned.
- the amount of titanium oxide according to the present invention is in the range of 50 to 150 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester.
- the blending amount is less than 50 parts by mass, sufficient whiteness cannot be obtained, and when it exceeds 150 parts by mass, the moldability is significantly lowered.
- By making the blending amount of titanium oxide within the above range it is possible to more reliably obtain a molded product having a reflectance of 85% or more with respect to light having a wavelength of 480 nm on the molding surface and an Izod impact strength of 40 kJ / m 2 or more. Can do.
- Inorganic fibrous filler (C)> A known inorganic fibrous filler can be added to the resin composition of the present invention as long as the effects of the present invention are not impaired.
- Examples of the inorganic fibrous filler include glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, wollastonite and the like. These may be used alone or in combination of two or more.
- the fiber length of the inorganic fibrous filler is preferably 10 ⁇ m to 3 mm, more preferably 100 ⁇ m to 3 mm in terms of number average length.
- the thickness of the inorganic fibrous filler is preferably a number average diameter of 6 to 15 ⁇ m, and more preferably a number average diameter of 6 to 10 ⁇ m.
- the compounding amount of the inorganic fibrous filler is 0 to 50 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester.
- the amount of titanium oxide (B) is 100 parts by mass of the liquid crystal polyester from the viewpoint of obtaining high whiteness.
- it is preferably 60 to 150 parts by mass, more preferably 100 to 150 parts by mass.
- the blending amount of titanium oxide (B) and inorganic fibrous filler (C) from the viewpoint of increasing the bending strength are 50 to 150 parts by mass and 10 to 50 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester, and the total amount of titanium oxide (B) and inorganic fibrous filler (C) is 100 parts by mass of the liquid crystalline polyester.
- the amount is preferably 50 to 150 parts by mass with respect to parts.
- the liquid crystal polyester resin composition of the present invention has a reflectance of 85% or more with respect to light having a wavelength of 480 nm on a molding surface of a molded product obtained by injection molding, and an Izod impact strength of the molded product is 40 kJ / m 2 or more.
- the reflectance is 87% or more, and the Izod impact strength is 40 kJ / m 2 or more.
- liquid crystal polyester resin composition of the present invention liquid crystal polyester, titanium oxide that has been subjected to surface treatment of aluminum oxide treatment, silicon oxide treatment, and organosiloxane treatment, and if necessary, an inorganic fibrous filler, By containing in the ratio mentioned above, the molded object which has said reflectance and Izod impact strength can be obtained.
- the present inventor believes that this effect is due to the improved affinity between titanium oxide and liquid crystal polyester resin and the dispersibility of titanium oxide in the resin composition by the combination of the above three specific surface treatments. ing.
- liquid crystal polyester resin composition of the present invention containing conventional titanium oxide
- the liquid crystalline polyester resin composition of the present invention containing the prepared titanium oxide has a lower melt viscosity than a conventional product having an equivalent titanium oxide filling amount.
- the lowering of the melt viscosity is caused by deterioration (molecular cutting) of the liquid crystal polyester resin accompanying melt kneading, in which case the impact strength is greatly reduced.
- the Izod impact strength of the liquid crystal polyester resin composition of the present invention increases even when the melt viscosity decreases. The present inventor believes that this reason may also be due to the affinity of titanium oxide and liquid crystal polyester resin.
- the liquid crystal polyester resin composition of the present invention can be obtained by melt-kneading the above-described components (liquid crystal polyester, titanium oxide, and if necessary, an inorganic fibrous filler).
- 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 titanium oxide particles. preferable.
- it is a continuous extrusion type twin-screw kneader having a pair of two-screws, and among them, a co-rotating type that enables uniform dispersion of the filler by having a turning-back mechanism is preferable.
- the cylinder has a diameter of 40mm ⁇ or more.
- the screw has a large meshing ratio of 1.45 or more.
- the filler is supplied from the middle of the cylinder. If possible, the resin composition of the present invention can be obtained efficiently.
- Liquid crystalline polyester, titanium oxide, and inorganic fibrous filler are mixed using a known solid mixing equipment such as a ribbon blender, tumbler blender, Henschel mixer, etc., and if necessary, using a hot air dryer, a vacuum dryer, etc. It is preferable to dry and supply from the hopper of a twin-screw kneader.
- the inorganic fibrous filler In the production of a resin composition containing an inorganic fibrous filler, it is preferable to supply at least a part of the inorganic fibrous filler to be blended from the middle of a cylinder of a biaxial kneader (so-called side feed).
- side feed a biaxial kneader
- the mechanical strength of the weld part of the molded body formed by injection molding of the obtained resin composition Tend to improve more.
- the ratio of the side feed is preferably 50% or more, and most preferably 100%. When the ratio of the side feed is less than the above lower limit, compounding (mixing / mixing) becomes difficult, and it tends to be impossible to obtain a homogeneous resin composition.
- the molded product of the present invention is formed by molding the above-described liquid crystal polyester resin composition of the present invention.
- the molding method includes injection molding, extrusion molding, press molding, and the like, and injection molding using an injection molding machine is preferable in terms of ease of molding, mass productivity, cost, and the like.
- the liquid crystal polyester resin composition of the present invention that has been pelletized is injection-molded, and the surface of the injection-molded product is used as a reflective surface, so that it has excellent light reflectance and mechanical properties (particularly, Izod impact strength).
- An LED reflector suitable for an LED reflector in particular, a white LED having a good light reflectance with respect to light having a wavelength of 480 nm can be obtained.
- the cylinder temperature in the case of injection molding can be set in a range of ⁇ 20 ° C. based on the melting point of liquid crystal polyester.
- the optical device of the present invention includes a light source and a light source reflector made of the molded body of the present invention.
- the light source is preferably a white LED.
- reaction vessel system was sealed, and the inside of the reaction system was pressurized to 14.7 N / cm 2 (1.5 kgf / cm 2 ) with nitrogen, and the low degree of polymerization total fragrance as a melt polycondensation reaction product in the reaction vessel.
- About 480 kg of thermotropic liquid crystalline polyester was extracted from the outlet at the bottom of the reaction vessel and supplied to the cooling and solidifying device described below. The temperature of the melt polycondensation reaction product at this time was 310 ° C.
- the flow rate of cooling water in the pair of cooling rolls is adjusted to adjust the roll surface temperature, and the melt polycondensation reaction product is passed between the rolls.
- the melt polycondensation reaction product is passed between the rolls.
- a sheet-like solidified product having a thickness of 2 mm was obtained.
- the surface temperature of the low-polymerization degree fully aromatic thermotropic liquid crystal polyester which was cooled and solidified immediately after passing between the rolls was 220 ° C.
- the obtained sheet-like solidified product was crushed to approximately 50 mm square using a pulverizer (manufactured by Nippon Air Industry Co., Ltd.).
- crushed material obtained above was pulverized using a feather mill manufactured by Hosokawa Micron Corporation to obtain a solid phase polycondensation raw material.
- the pulverized material passed through a mesh having an opening of 1 mm.
- the pulverized product is stored in a rotary kiln, heated in a nitrogen atmosphere from room temperature to 170 ° C. over 3 hours under nitrogen flow, then heated to 250 ° C. over 5 hours, and further up to 280 ° C. for 3 hours. Over about 480 kg of wholly aromatic thermotropic liquid crystal polyester.
- the melting point of the liquid crystal polyester was measured with a differential scanning calorimeter (DSC) manufactured by Seiko Denshi Kogyo Co., Ltd. using ⁇ -alumina as a reference. At this time, the temperature was raised from room temperature to 400 ° C. at a temperature rising rate of 20 ° C./min to completely melt the polymer, then the temperature was lowered to 150 ° C. at a rate of 10 ° C./min, and further 420 ° C. at a rate of 20 ° C./min. The peak of the endothermic peak obtained when the temperature was raised to ° C. was taken as the melting point. The melting point measured by DSC was 350 ° C.
- Titanium oxide and other fillers Titanium oxide A; Product name: “DCF-T-17008S” (resin-treated by aluminum oxide treatment, silicon oxide treatment, organosiloxane treatment. Primary particle size: 0.25 ⁇ m) Titanium oxide B; Made by Sakai Chemical Industry Co., Ltd .: Trade name “SR-1” (Rutile titanium oxide obtained by sulfuric acid method including roasting step, surface-treated with aluminum oxide.
- Titanium oxide C Made by Sakai Chemical Industry Co., Ltd .: Trade name “R-21” (Rutile titanium oxide obtained by sulfuric acid method including roasting step, surface-treated with aluminum oxide and silicon oxide, primary particle size 0.20 ⁇ m) Glass fiber; “PX-1” manufactured by Owens Corning Co., Ltd. (average fiber length 3 mm, average diameter 10 ⁇ m)
- melt viscosity Regarding the melt viscosity of the liquid crystalline polyester resin composition, a capillary rheometer (2010 manufactured by Intesco Corporation) was used, and a capillary having a diameter of 1.00 mm, a length of 40 mm, and an inflow angle of 90 ° was used, and a shear rate of 100 sec. The apparent viscosity was measured while heating at a constant heating rate from 300 ° C. to + 4 ° C./min at ⁇ 1 to determine the apparent viscosity at 370 ° C., and this was taken as the melt viscosity. The results are shown in Table 1. In the measurement, the resin composition was previously dried at 150 ° C. for 4 hours in a vacuum dryer.
- titanium oxide A (treated with aluminum oxide treatment, silicon oxide treatment and organosiloxane treatment) was added to 100 parts by mass of liquid crystal polyester.
- it is highly filled in excess of 100 parts by mass, has a very high reflectivity of 90%, 89% and 87%, respectively, and has a high mechanical strength with an Izod impact strength of 40 kJ / m 2 or more.
- the injection-molded article produced using the resin composition of Example 2 is filled with titanium oxide A at a ratio of 67 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester, has a reflectance of 88%, and has an Izod impact.
- the injection-molded article produced using the resin composition of Example 3 was filled with titanium oxide A at a ratio of 60 parts by mass with respect to 100 parts by mass of liquid crystal polyester, and the composition of Comparative Example 1 using titanium oxide B was used. Although the amount of titanium oxide was smaller than that of the product, the reflectance was as high as 85%, and the Izod impact strength was also confirmed as high as 65 kJ / m 2 .
- all of the injection-molded articles produced using the resin compositions of Examples 1 to 5 have a high bending strength of 130 MPa or more, while the melt viscosity is low at less than 100 Pa ⁇ s even when titanium oxide is highly filled. It can be seen that the moldability is also good.
- the injection molded product produced using the resin composition of Comparative Example 1 is filled with the conventional titanium oxide B at a ratio of 75 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester, and the reflectance is 84.
- the Izod impact strength was as low as 30 kJ / m 2 and the mechanical strength was insufficient.
- An injection-molded article produced using the resin composition of Comparative Example 2 was filled with titanium oxide C surface-treated with two types of aluminum oxide and silicon oxide at a ratio of 75 parts by mass with respect to 100 parts by mass of liquid crystalline polyester.
- the reflectance was 82%, and the Izod impact strength was as low as 30 kJ / m 2 .
- the injection-molded product produced using the resin composition of Comparative Example 3 is filled with titanium oxide A at a ratio of 75 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. It is filled beyond the upper limit of the invention. As a result, the bending strength was as high as 190 MPa, but the reflectance was as low as 78%. In the resin composition of Comparative Example 4, since the content of titanium oxide A exceeded the upper limit according to the present invention, the Izod impact strength of the produced injection molded product was greatly reduced. In the resin composition of Comparative Example 5, since the content of titanium oxide A was too much, the production of the resin composition was difficult and pellets were not obtained.
- the liquid crystal polyester resin composition according to the present invention shown in the examples has high Izod impact strength even when the melt viscosity is low, and the reflectance is at a high level that surpasses that of conventional products. It was found that both high reflectivity and high mechanical strength can be realized.
- a liquid crystal polyester resin composition capable of obtaining a molded body having both high light reflectivity at 480 nm and mechanical strength such as Izod impact strength at a high level, the molded body, and an optical equipped with the molded body.
- An apparatus can be provided.
- the liquid crystal polyester resin composition of the present invention retains the excellent heat resistance and moldability of the liquid crystal polyester even if it is prepared through a normal melt-kneading process, and is excellent in white light reflectance and Izod impact strength.
- the molded body can be formed by injection molding.
- the injection-molded product of the liquid crystal polyester resin composition of the present invention can be used as a reflector having the surface as a reflection surface, and can be used as a reflector particularly suitable for white LEDs. According to the present invention, since it is possible to realize a reflector that has a higher reflectance than the conventional one and is excellent in mechanical strength, it is possible to provide an optical device that includes this and has excellent light extraction efficiency.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Mathematical Physics (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Led Device Packages (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本発明に係る液晶ポリエステル(以下、単に「LCP」と略称する場合もある)は、サーモトロピック液晶ポリマーと呼ばれるポリエステルで、450℃以下の温度で異方性溶融体を形成するものである。LCPとしては、例えば、芳香族ヒドロキシカルボニル単位、芳香族および/または脂肪族ジヒドロキシ単位、並びに、芳香族および/または脂肪族ジカルボニル単位などから選ばれる構造単位からなるものが挙げられる。芳香族ヒドロキシカルボニル単位としては、例えば、p-ヒドロキシ安息香酸、6-ヒドロキシ-2-ナフトエ酸などから生成した構造単位、芳香族および/ または脂肪族ジヒドロキシ単位としては、例えば、4,4’-ジヒドロキシビフェニル、ヒドロキノン、3,3’,5,5’-テトラメチル-4,4’-ジヒドロキシビフェニル、t-ブチルヒドロキノン、フェニルヒドロキノン、2,6-ジヒドロキシナフタレン、2,7-ジヒドロキシナフタレン、2,2-ビス(4-ヒドロキシフェニル)プロパンおよび4,4’-ジヒドロキシジフェニルエーテル、エチレングリコール、1,3-プロピレングリコール、1,4-ブタンジオールなどから生成した構造単位、芳香族および/または脂肪族ジカルボニル単位としては、例えば、テレフタル酸、イソフタル酸、2,6-ナフタレンジカルボン酸、4,4’-ジフェニルジカルボン酸、1,2-ビス(フェノキシ)エタン-4,4’-ジカルボン酸、1,2-ビス(2-クロロフェノキシ)エタン-4,4’-ジカルボン酸および4,4’-ジフェニルエーテルジカルボン酸、アジピン酸、セバシン酸などから生成した構造単位が挙げられる。
本発明で用いる酸化チタンは、表面処理として酸化アルミニウム処理、酸化ケイ素処理、及びオルガノシロキサン処理が施されたものである。
本発明の樹脂組成物には、公知の無機繊維状充填材を本発明の効果を損なわない範囲で添加することができる。無機繊維状充填材の例としては、ガラス繊維、炭素繊維、炭化ケイ素繊維、アルミナ繊維、ウォラストナイト等が挙げられる。これらは、単独で使用しても2種類以上使用してもよい。
本発明の液晶ポリエステル樹脂組成物は、上述した各成分(液晶ポリエステル、酸化チタン、および必要に応じて無機繊維状充填材)を溶融混練することにより得ることができる。溶融混練するための装置としては、単軸混練機、二軸混練機、バンバリーミキサー、加圧式ニーダー等が使用可能であるが、酸化チタン粒子の分散を好適にする点から二軸混練機が特に好ましい。より好ましくは、1対の2条スクリュを有する連続押出式の二軸混練機であって、その中でも切り返し機構を有することで充填材の均一分散を可能とする同方向回転式が好ましい。充填材の食い込みが容易となるバレルースクリュ間の空隙が大きい40mmφ以上のシリンダー径を有するものであり、スクリュ間の大きい、かみ合い率1.45以上のものであり、シリンダー途中から充填剤を供給可能なものを使用すると、本発明の樹脂組成物を効率よく得ることができる。また、無機繊維状充填材の少なくとも一部をシリンダーの途中へ供給するための設備を有するものを用いることが好ましい。
本発明の成形体は、上述した本発明の液晶ポリエステル樹脂組成物を成形してなるものである。成形方法としては、射出成形、押出成形、プレス成形などがあるが、成形の容易さ、量産性、コストなどの面で射出成形機を用いた射出成形が好ましい。例えば、ペレット化した本発明の液晶ポリエステル樹脂組成物を射出成形し、該射出成形品の表面を反射面とすることにより、光反射率及び機械的特性(特には、アイゾット衝撃強度)に優れたLEDリフレクター、特には波長480nmの光に対する光反射率の良好な白色LEDに適するLEDリフレクターを得ることができる。
ダブルヘリカル型攪拌翼を有し、内容積が1.7m3のSUS316L(ステンレス鋼)製の反応槽に、p-ヒドロキシ安息香酸(上野製薬株式会社製)298.3kg(2.16キロモル)、4,4’-ジヒドロキシジフェニル(本州化学工業株式会社製)134.1kg(0.72キロモル)、テレフタル酸(三井化学株式会社製)89.7kg(0.54キロモル)、イソフタル酸(エイ・ジ・インターナショナルケミカル株式会社製)29.9kg(0.18キロモル)、触媒として酢酸マグネシウム(キシダ化学株式会社製)0.11kg、及び酢酸カリウム(キシダ化学株式会社製)0.04kgを仕込んだ。そして、重合槽の減圧-窒素注入を2回行って窒素置換した後、無水酢酸377.7kg(3.7キロモル)を添加し、攪拌翼の回転数45rpmで150℃まで1.5時間で昇温して、還流状態で2時間アセチル化反応を行った。アセチル化終了後、酢酸留出状態にして0.5℃/分で昇温して310℃まで昇温し、発生する酢酸を除去しながら重合反応を5時間20分行った。
冷却固化装置として、特開2002-179779号公報に従い、直径630mmの一対の冷却ロール、ロール間距離2mm、距離1800mmの一対の堰を有する装置を用意した。この装置の一対の冷却ロールを18rpmの回転数で対向回転させ、一対の冷却ロールと一対の堰とで形成された凹部に、重縮合反応槽から抜出された流動状態の溶融重縮合反応生成物を徐々に供給し、凹部内に保持させつつ、一対の冷却ロール内の冷却水の流量を調整してロール表面温度を調整し、このロール間に溶融重縮合反応生成物を通過させることにより冷却固化して厚み2mmのシート状の固化物を得た。なお、ロール間を通過直後の冷却固化した低重合度全芳香族サーモトロピック液晶ポリエステルの表面温度は220℃であった。得られたシート状の固化物を解砕機(日空工業株式会社製)により、おおよそ50mm角に解砕した。
上記で得られた解砕物を、ホソカワミクロン株式会社製のフェザーミルを用いて粉砕して固相重縮合用原料を得た。粉砕物は、目開き1mmのメッシュを通過するものであった。この粉砕物をロータリーキルンに収納し、窒素雰囲気中で、窒素流通下、室温から170℃まで3時間かけて昇温した後、250℃まで5時間かけて昇温し、さらに、280℃まで3時間かけて昇温して固相重縮合を行い、全芳香族サーモトロピック液晶ポリエステル約480kgを得た。
液晶ポリエステルの融点は、セイコー電子工業(株)製の示差走査熱量計(DSC)により、リファレンスとしてα-アルミナを用いて測定した。このとき、昇温速度20℃/分で室温から400℃まで昇温してポリマーを完全に融解させた後、速度10℃/分で150℃まで降温し、更に20℃/分の速度で420℃まで昇温するときに得られる吸熱ピークの頂点を融点とした。DSCにより測定した融点は、350℃であった。
酸化チタンA;
レジノカラー工業(株)製:商品名「DCF-T-17008S」(酸化アルミニウム処理、酸化ケイ素処理、オルガノシロキサン処理により表面処理されたもの。一次粒子径0.25μm。)
酸化チタンB;
堺化学(株)製:商品名「SR-1」(焙焼工程を含む硫酸法により得られたルチル型酸化チタンを酸化アルミニウムで表面処理したもの。一次粒子径0.25μm。)
酸化チタンC;
堺化学(株)製:商品名「R-21」(焙焼工程を含む硫酸法により得られたルチル型酸化チタンを酸化アルミニウム、酸化ケイ素で表面処理したもの。一次粒子径0.20μm。)
ガラス繊維;
オーウェンスコーニング(株)製「PX-1」(平均繊維長3mm、平均径10μm)
(実施例1~5、及び、比較例1~5)
上記で得られた全芳香族サーモトロピック液晶ポリエステル100質量部に、酸化チタン粒子A、B、C、ガラス繊維の各成分を表1に示す組成(表中の組成は質量部を示す)となるようにそれぞれ別個に混合し、二軸押出機(池貝鉄鋼(株)製、PCM-30)を用いて、シリンダーの最高温度370℃で溶融混練することにより、樹脂組成物のペレットをそれぞれ得た。
得られたペレットを、射出成形機(住友重機械工業(株)製SG-25)を用いて、シリンダー温度350℃、射出速度100mm/sec、金型温度80℃で射出成形し、30mm(幅)×60mm(長さ)×3.0mm(厚さ)の射出成形品を得た。これを、白色光反射率の試験片とした。更に、上記と同様の条件で射出成形を行って、ASTM D790に準じた曲げ試験片を作成し、曲げ試験、衝撃試験の試験片とした。
各試験片の表面について、自記分光光度計(U-3500:(株)日立製作所製)を用いて480nmの光に対する拡散反射率の測定を行った。なお、反射率は硫酸バリウムの標準白板の拡散反射率を100%とした時の相対値である。結果を表1に示す。
上記で作製した曲げ試験の試験片を用い、ASTM D790に従い、曲げ強度の測定を行った。結果を表1に示す。
上記で作製した衝撃試験の試験片を用い、ASTM D256に従い、ノッチ無しでアイゾット衝撃強度の測定を行った。10回の測定の平均値を算出した。結果を表1に示す。
上記の樹脂組成物の製造条件で、樹脂組成物のペレットが得られたものを「A」、溶融混練押し出しが困難でペレットが得られなかったものを「C」とした。結果を表1に示す。なお、ペレットが得られなかったものは他の評価試験ができなかった。
液晶ポリエステル樹脂組成物の溶融粘度については、キャピラリーレオメーター(インテスコ(株)社製2010)を用い、キャピラリーとして径1.00mm、長さ40mm、流入角90°のものを用いて、せん断速度100sec-1で300℃から+4℃/分の昇温速度で等速加熱をしながら見掛け粘度を測定し、370℃における見掛け粘度を求め、これを溶融粘度とした。結果を表1に示す。なお、測定に際し、樹脂組成物は予め真空乾燥機にて、150℃で4時間乾燥した。
Claims (7)
- 液晶ポリエステル(A)100質量部と、表面処理として酸化アルミニウム処理、酸化ケイ素処理およびオルガノシロキサン処理が施された酸化チタン(B)50~150質量部と、無機繊維状充填材(C)0~50質量部と、を含有する、液晶ポリエステル樹脂組成物。
- 前記液晶ポリエステル(A)は、融点が320℃以上の全芳香族サーモトロピック液晶ポリエステルである、請求項1に記載の液晶ポリエステル樹脂組成物。
- 前記酸化チタン(B)は、一次粒子径が0.2~0.3μmの範囲にある、請求項1又は2に記載の液晶ポリエステル樹脂組成物。
- 射出成形して得られる成形体の成形表面における波長480nmの光に対する反射率が85%以上であり、かつ、前記成形体のアイゾット衝撃強度が40kJ/m2以上である、請求項1~3のいずれか一項に記載の液晶ポリエステル樹脂組成物。
- 請求項1~4のいずれか一項に記載の液晶ポリエステル樹脂組成物を射出成形して得られる成形体。
- 光源と、請求項5に記載の成形体からなる、前記光源のリフレクターと、を備える、光学装置。
- 前記光源が白色LEDである、請求項6に記載の光学装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/497,186 US9234092B2 (en) | 2009-09-29 | 2010-08-18 | Liquid-crystal polyester resin composition, molded object thereof, and optical device |
KR1020127008741A KR101715021B1 (ko) | 2009-09-29 | 2010-08-18 | 액정 폴리에스테르 수지 조성물, 이의 성형체, 및 광학 장치 |
CN201080043346.XA CN102549071B (zh) | 2009-09-29 | 2010-08-18 | 液晶聚酯树脂组合物、其成型体、及光学装置 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009224825A JP5939729B2 (ja) | 2009-09-29 | 2009-09-29 | 液晶ポリエステル樹脂組成物、その成形体、及び光学装置 |
JP2009-224825 | 2009-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011040138A1 true WO2011040138A1 (ja) | 2011-04-07 |
Family
ID=43825972
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/063896 WO2011040138A1 (ja) | 2009-09-29 | 2010-08-18 | 液晶ポリエステル樹脂組成物、その成形体、及び光学装置 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9234092B2 (ja) |
JP (1) | JP5939729B2 (ja) |
KR (1) | KR101715021B1 (ja) |
CN (1) | CN102549071B (ja) |
TW (1) | TWI530527B (ja) |
WO (1) | WO2011040138A1 (ja) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012141967A1 (en) * | 2011-04-14 | 2012-10-18 | Ticona Llc | Polymer composition for producing articles with light reflective properties |
JP2013181123A (ja) * | 2012-03-02 | 2013-09-12 | Dainippon Printing Co Ltd | リフレクター用樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形方法 |
US9062198B2 (en) | 2011-04-14 | 2015-06-23 | Ticona Llc | Reflectors for light-emitting diode assemblies containing a white pigment |
US9187621B2 (en) | 2011-12-30 | 2015-11-17 | Ticona Llc | Reflector for light-emitting devices |
US9284448B2 (en) | 2011-04-14 | 2016-03-15 | Ticona Llc | Molded reflectors for light-emitting diode assemblies |
US9453119B2 (en) | 2011-04-14 | 2016-09-27 | Ticona Llc | Polymer composition for producing articles with light reflective properties |
US9567460B2 (en) | 2012-12-18 | 2017-02-14 | Ticona Llc | Molded reflectors for light-emitting diode assemblies |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101792987B1 (ko) * | 2010-03-16 | 2017-11-02 | 제이엑스티지 에네루기 가부시키가이샤 | 전방향족 서모트로픽 액정 폴리에스테르 수지 조성물, 성형체 및 led 리플렉터 |
US8425798B2 (en) * | 2010-07-30 | 2013-04-23 | Sumitomo Chemical Company, Limited | Liquid crystal polyester composition, reflective plate and light-emitting device |
JP2013153144A (ja) * | 2011-12-27 | 2013-08-08 | Panasonic Corp | Ledリフレクター用不飽和ポリエステル樹脂組成物とそれを用いた粒状物、タブレット、ledリフレクター、表面実装型led発光装置、led照明器具 |
JP5914934B2 (ja) * | 2012-02-28 | 2016-05-11 | 住友化学株式会社 | 液晶ポリエステル組成物、成形体及び発光装置 |
EP2738203B1 (en) * | 2012-11-29 | 2018-04-18 | Solvay Specialty Polymers USA, LLC. | Polyester compositions with improved heat and light aging |
JP6689606B2 (ja) * | 2013-11-01 | 2020-04-28 | 住友化学株式会社 | 樹脂組成物 |
JP7175834B2 (ja) * | 2019-04-16 | 2022-11-21 | 上野製薬株式会社 | 液晶ポリエステル樹脂 |
US11637365B2 (en) | 2019-08-21 | 2023-04-25 | Ticona Llc | Polymer composition for use in an antenna system |
US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
US11646760B2 (en) | 2019-09-23 | 2023-05-09 | Ticona Llc | RF filter for use at 5G frequencies |
US11721888B2 (en) | 2019-11-11 | 2023-08-08 | Ticona Llc | Antenna cover including a polymer composition having a low dielectric constant and dissipation factor |
WO2021149723A1 (ja) * | 2020-01-22 | 2021-07-29 | Eneos株式会社 | 樹脂組成物および該樹脂組成物からなる樹脂成形品 |
US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
US11728559B2 (en) | 2021-02-18 | 2023-08-15 | Ticona Llc | Polymer composition for use in an antenna system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0638520B2 (ja) * | 1986-02-03 | 1994-05-18 | ポリプラスチックス株式会社 | 発光素子装置 |
JPH093211A (ja) * | 1995-04-18 | 1997-01-07 | Sakai Chem Ind Co Ltd | 樹脂組成物 |
JP2006037090A (ja) * | 2004-06-24 | 2006-02-09 | Ishihara Sangyo Kaisha Ltd | 二酸化チタン顔料及びその製造方法並びにそれを含む樹脂組成物 |
JP2007254669A (ja) * | 2006-03-24 | 2007-10-04 | Nippon Oil Corp | 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 |
JP2008088207A (ja) * | 2006-09-29 | 2008-04-17 | Asahi Kasei Chemicals Corp | ポリトリメチレンテレフタレート樹脂組成物発泡シート及びその製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4518544A (en) * | 1983-01-20 | 1985-05-21 | Baltimore Aircoil Company, Inc. | Serpentine film fill packing for evaporative heat and mass exchange |
JP3546064B2 (ja) | 1992-04-06 | 2004-07-21 | 昭和電工株式会社 | 二酸化チタンの表面処理方法 |
JPH0638520A (ja) | 1992-07-09 | 1994-02-10 | Murata Mfg Co Ltd | Dc−dcコンバータの過電流保護回路 |
JP4606573B2 (ja) | 2000-12-13 | 2011-01-05 | Jx日鉱日石エネルギー株式会社 | 溶融サーモトロピック液晶ポリマーの冷却固化方法、およびサーモトロピック液晶ポリマーの固相重合方法 |
JP2004256673A (ja) | 2003-02-26 | 2004-09-16 | Sumitomo Chem Co Ltd | 反射板用液晶性ポリエステル樹脂 |
JP2004277539A (ja) | 2003-03-14 | 2004-10-07 | Sumitomo Chem Co Ltd | 液晶性ポリエステル樹脂組成物 |
JP4550474B2 (ja) | 2004-04-19 | 2010-09-22 | 旭化成イーマテリアルズ株式会社 | 芳香族ポリカーボネート樹脂組成物および成形体 |
US8169129B2 (en) | 2007-11-29 | 2012-05-01 | Mitsubishi Plastics, Inc. | Metal laminated body, LED-mounted substrate, and white film |
KR100905089B1 (ko) | 2008-05-15 | 2009-06-30 | 제일모직주식회사 | 내광성 및 치수 안정성이 우수한 폴리카보네이트 수지조성물 |
JP5355184B2 (ja) | 2009-03-31 | 2013-11-27 | Jx日鉱日石エネルギー株式会社 | 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、成形体及びledリフレクター |
-
2009
- 2009-09-29 JP JP2009224825A patent/JP5939729B2/ja active Active
-
2010
- 2010-08-18 CN CN201080043346.XA patent/CN102549071B/zh active Active
- 2010-08-18 US US13/497,186 patent/US9234092B2/en active Active
- 2010-08-18 WO PCT/JP2010/063896 patent/WO2011040138A1/ja active Application Filing
- 2010-08-18 KR KR1020127008741A patent/KR101715021B1/ko active IP Right Grant
- 2010-08-27 TW TW099128972A patent/TWI530527B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0638520B2 (ja) * | 1986-02-03 | 1994-05-18 | ポリプラスチックス株式会社 | 発光素子装置 |
JPH093211A (ja) * | 1995-04-18 | 1997-01-07 | Sakai Chem Ind Co Ltd | 樹脂組成物 |
JP2006037090A (ja) * | 2004-06-24 | 2006-02-09 | Ishihara Sangyo Kaisha Ltd | 二酸化チタン顔料及びその製造方法並びにそれを含む樹脂組成物 |
JP2007254669A (ja) * | 2006-03-24 | 2007-10-04 | Nippon Oil Corp | 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 |
JP2008088207A (ja) * | 2006-09-29 | 2008-04-17 | Asahi Kasei Chemicals Corp | ポリトリメチレンテレフタレート樹脂組成物発泡シート及びその製造方法 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012141967A1 (en) * | 2011-04-14 | 2012-10-18 | Ticona Llc | Polymer composition for producing articles with light reflective properties |
US9062198B2 (en) | 2011-04-14 | 2015-06-23 | Ticona Llc | Reflectors for light-emitting diode assemblies containing a white pigment |
US9284448B2 (en) | 2011-04-14 | 2016-03-15 | Ticona Llc | Molded reflectors for light-emitting diode assemblies |
US9346933B2 (en) | 2011-04-14 | 2016-05-24 | Ticona Llc | Reflectors for light-emitting diode assemblies containing a white pigment |
US9453119B2 (en) | 2011-04-14 | 2016-09-27 | Ticona Llc | Polymer composition for producing articles with light reflective properties |
US9562666B2 (en) | 2011-04-14 | 2017-02-07 | Ticona Llc | Molded reflectors for light-emitting diode assemblies |
US9187621B2 (en) | 2011-12-30 | 2015-11-17 | Ticona Llc | Reflector for light-emitting devices |
JP2013181123A (ja) * | 2012-03-02 | 2013-09-12 | Dainippon Printing Co Ltd | リフレクター用樹脂組成物、リフレクター用樹脂フレーム、リフレクター、半導体発光装置、及び成形方法 |
US9567460B2 (en) | 2012-12-18 | 2017-02-14 | Ticona Llc | Molded reflectors for light-emitting diode assemblies |
Also Published As
Publication number | Publication date |
---|---|
JP2011074137A (ja) | 2011-04-14 |
US9234092B2 (en) | 2016-01-12 |
CN102549071A (zh) | 2012-07-04 |
CN102549071B (zh) | 2014-04-16 |
KR101715021B1 (ko) | 2017-03-10 |
JP5939729B2 (ja) | 2016-06-22 |
TWI530527B (zh) | 2016-04-21 |
KR20120088695A (ko) | 2012-08-08 |
TW201120131A (en) | 2011-06-16 |
US20120235559A1 (en) | 2012-09-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5939729B2 (ja) | 液晶ポリエステル樹脂組成物、その成形体、及び光学装置 | |
JP5201799B2 (ja) | 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 | |
JP5355184B2 (ja) | 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、成形体及びledリフレクター | |
JP5681700B2 (ja) | 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、成形体及びledリフレクター | |
JP2008231368A (ja) | 光線反射率および強度に優れた液晶ポリエステル樹脂組成物 | |
JP5751907B2 (ja) | Ledリフレクター | |
JP5866423B2 (ja) | 液晶ポリエステル樹脂組成物、成形体及びledリフレクター | |
WO2011033892A1 (ja) | 液晶ポリエステル樹脂組成物の成形方法および成形体 | |
JP2016041828A (ja) | 液晶ポリエステル樹脂組成物、成形体及びledリフレクター | |
WO2012050082A1 (ja) | 液晶ポリエステル樹脂組成物及びカメラモジュール部品 | |
JP2012224689A (ja) | 液晶ポリエステルの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080043346.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10820258 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127008741 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13497186 Country of ref document: US |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 10820258 Country of ref document: EP Kind code of ref document: A1 |