CN105764988A - Wholly aromatic liquid crystal polyester resin composition and camera module component including injection-molded article of same as constituent member - Google Patents
Wholly aromatic liquid crystal polyester resin composition and camera module component including injection-molded article of same as constituent member Download PDFInfo
- Publication number
- CN105764988A CN105764988A CN201480066356.3A CN201480066356A CN105764988A CN 105764988 A CN105764988 A CN 105764988A CN 201480066356 A CN201480066356 A CN 201480066356A CN 105764988 A CN105764988 A CN 105764988A
- Authority
- CN
- China
- Prior art keywords
- mass
- polyester resin
- wholly aromatic
- aromatic liquid
- liquid crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 38
- 239000004645 polyester resin Substances 0.000 title claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- 239000004973 liquid crystal related substance Substances 0.000 title abstract description 43
- 239000000470 constituent Substances 0.000 title description 2
- 229920000728 polyester Polymers 0.000 claims abstract description 32
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 235000012241 calcium silicate Nutrition 0.000 claims description 4
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 3
- 229910052623 talc Inorganic materials 0.000 abstract description 2
- 238000004898 kneading Methods 0.000 abstract 1
- 239000000454 talc Substances 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- -1 aromatic diol Chemical class 0.000 description 11
- 238000010276 construction Methods 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 230000004927 fusion Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 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 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 235000010216 calcium carbonate Nutrition 0.000 description 5
- 239000012765 fibrous filler Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 241001597008 Nomeidae Species 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 239000011654 magnesium acetate Substances 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000208202 Linaceae Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000027950 fever generation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- 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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B17/00—Details of cameras or camera bodies; Accessories therefor
- G03B17/02—Bodies
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
- G03B30/00—Camera modules comprising integrated lens units and imaging units, specially adapted for being embedded in other devices, e.g. mobile phones or vehicles
Abstract
The present invention makes it possible to obtain a wholly aromatic liquid crystal polyester resin composition with which it is possible to mold a camera module component in which the number of particles that occur when a mobile terminal device such as a smartphone equipped with a camera suffers an impact or falls is low. The invention is implemented by means of a wholly aromatic liquid crystal polyester resin composition that can be obtained by melt-kneading 50-80 mass% of a wholly aromatic liquid crystal polyester, 10-30 mass% of whiskers, 0.5-5 mass% of carbon black, 0-20 parts by mass of talc, and 3-20 parts by mass of precipitated barium sulfate (together, the above constitute 100 mass%), and is characterized in that the heat deflection temperature is at least 220 DEG C, and the melt viscosity at a shear rate of 100/s and a melting point of +10 DEG C is 20-100 Pa*s.
Description
Technical field
The built-in Miniature digital camera of smart mobile phone, flat terminal etc. is in terms of the performance raising such as pixel count, image quality
Progress, is become the status as one of major function portion by additional function portion.
Background technology
With above-mentioned condition, the problem preventing the granule departed from from camera module components surface to be attached to camera lens highlights,
And carried out the reply research of this problem.The present invention relates to be suitable for the liquid-crystal polyester resin group of such camera module components
Compound, further to camera module components, this camera module components contains and is injected into by described liquid crystal polyester resin compositions
The molded body that type obtains is as member of formation.
The major part of these researchs is to produce when playing automatic focusing function, due to camera module components and camera lens
Slip and carry out studying (patent documentation 1-4) centered by the granule etc. that component surface departs from.
But in recent years, along with the lightweight of change, smart mobile phone and the portable terminal device of life style, taking of they
Band frequency increases, and equipment and the design of component, miniaturization, slimming are developed, then when sliding except suppression is described
Granule outside, suppression equipment when impact, the time of falling the granule that produces (following, about the granule produced in the situation of the latter
Suppression, can be described as " the resistance to detachment of granule ") highlight as new problem.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-242453 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-242454 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-242455 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2009-242456 publication.
Summary of the invention
Invent problem to be solved
The problem of the present inventor is: for above-mentioned condition, it is thus achieved that a kind of wholly aromatic liquid-crystalline polyester resin compositions, it may be molded to
When the portable terminal device class such as the smart mobile phone impact carrying camera or the few camera model portion of the granule number that produces of the time of falling
Part.
Therefore, it is an object of the invention to provide a kind of wholly aromatic liquid-crystalline polyester resin compositions, it can obtain in recent years
The excellent injection-molded article of the resistance to detachment of the granule required by camera module components.
Solve the scheme of problem
The present inventor conducts in-depth research for achieving the above object, found that: by will be containing specific liquid crystal polyester
Resin and whisker, the wholly aromatic liquid-crystalline polyester resin compositions injection moulding of white carbon black, can obtain and have " the resistance to detachment of granule "
Injection-molded article, thus complete the present invention.
That is, the Section 1 of the present invention relates to wholly aromatic liquid-crystalline polyester resin compositions, it is characterised in that: this Wholly aromatic liquid-crystalline
Polyester and resin composition is by 50-80 mass % Wholly aromatic liquid-crystalline polyester, 10-30 mass % whisker, 0.5-5 mass % white carbon black, 0-20
Mass parts Pulvis Talci, 3-20 mass parts blanc fixe (adding up to 100 mass % above) melting mixing obtain；Load deflection
Temperature is more than 220 DEG C, and in shear rate 100s-1, melt viscosity at fusing point+10 DEG C be 20-100Pa S.
The Section 2 of the present invention relates to wholly aromatic liquid-crystalline polyester resin compositions, it is characterised in that: described whisker be very than
Weigh the calcium silicates of less than 3.0, at least any of in calcium carbonate.
The Section 3 of the present invention relates to camera module components, it is characterised in that: it contains the Section 1 or second of the present invention
The injection-molded article product of the wholly aromatic liquid-crystalline polyester resin compositions described in Xiang are as member of formation.
Invention effect
Wholly aromatic liquid-crystalline polyester resin compositions involved in the present invention has the good rigidity of its products formed, thermostability, machine
Tool intensity, the thin-walled processability of resin combination, mold shape transferability, products formed surface install (SMT) patience and
" the resistance to detachment of granule ", can provide the camera model component with extremely excellent characteristic by injection moulding.
Accompanying drawing explanation
Fig. 1 is top view and the side view of fusion point (weld) strength detection test film.
Fig. 2 is top view and the side view of the mensuration test film of the resistance to detachment of granule.
Detailed description of the invention
The wholly aromatic liquid-crystalline polyester resin used in the present invention presents melted anisotropy.The Wholly aromatic liquid-crystalline of the present invention gathers
In ester resin composition, in order to make its products formed have thermostability and the rigidity of excellence, it is necessary to utilize based on molecular structure firm
Straightforward anisotropy so that it is there is (during melt molding) strong liquid crystal aligning when injection moulding.Therefore, at liquid crystal polyester
In the Wholly aromatic liquid-crystalline polyester that only obtained by the polycondensation reaction of aromatic compounds main by assuring that so-called " mesomorphic
(mesogen) " (show the upright and outspoken position of liquid crystal liquid crystal property) and there is the flat of the outspoken nature of fusing point, processing and forming temperature, strand
The liquid crystal liquid crystal property that weighing apparatus is excellent, preferably.
The construction unit of the liquid-crystal polyester resin constituting the liquid crystal polyester resin compositions of the present invention such as can be enumerated: comprises
The construction unit of the combination of aromatic dicarboxylic acid and aromatic diol and aromatic hydroxycarboxylic acids, comprise aromatic hydroxycarboxylic acids the most of the same race
Construction unit, the construction unit of the combination comprising aromatic hydroxycarboxylic acids and aromatic dicarboxylic acid and aromatic diol, make aromatic hydroxy carboxylic
The construction unit etc. of the pet reaction gained of acid and polyethylene terephthalate etc., concrete construction unit such as can be enumerated
Following construction unit.
Construction unit from aromatic hydroxycarboxylic acids:
[changing 1]
(X1: halogen atom or alkyl)
Construction unit from aromatic dicarboxylic acid:
[changing 2]
(X2: halogen atom, alkyl or aryl)
Constitutional repeating unit from aromatic diol:
[changing 3]
(X2: halogen atom, alkyl or aryl)
(X3: H, halogen atom or alkyl)
From thermostability, mechanical properties, molding processibility balance from the point of view of, preferred liquid-crystal polyester resin is to have 30 to rub
The resin of the said structure unit (A1) of you more than %, further preferably has (A1) and (B1) adding up to 60 moles of more than %.
Particularly preferred liquid crystal polyester is following Wholly aromatic liquid-crystalline polyester: by the P-hydroxybenzoic acid of 80-100 mole of %
(I), p-phthalic acid (II), 4,4 '-dihydroxybiphenyl (III) (comprising their derivant) (wherein, (I) and conjunction of (II)
Be calculated as 60 moles of more than %) and 0-20 mole of % can with (I), (II), (III) any one carry out dehydration condensation
Other aromatic compounds of (de-conjunction is anti-) carries out the Wholly aromatic liquid-crystalline polyester that fusing point is more than 320 DEG C of polycondensation；Or
Person is that (P-hydroxybenzoic acid (I) of 90-99 mole of %, p-phthalic acid (II), 4,4 '-dihydroxybiphenyl (III) are comprised it
Derivant) (wherein, (I) and (II) add up to 60 moles of more than %) and 1-10 mole of % can with (I), (II),
(III) other aromatic compounds (above composition adds up to 100 moles of %) of dehydration condensation is occurred to carry out the molten of polycondensation
Point is the Wholly aromatic liquid-crystalline polyester of more than 320 DEG C.
As the combination of said structure unit, preferably
(A1)
(A1)、(B1)、(C1)
(A1)、(B1)、(B2)、(C1)
(A1)、(B1)、(B2)、(C2)
(A1)、(B1)、(B3)、(C1)
(A1)、(B1)、(B3)、(C2)
(A1)、(B1)、(B2)、(C1)、(C2)
(A1), (A2), (B1), (C1),
As particularly preferred monomer ratio of components, have by the P-hydroxybenzoic acid of 80-100 mole of %, p-phthalic acid, 4,4 '-two
Xenol (comprising their derivant) and the aromatic diol beyond them of 0-20 mole of %, aromatic hydroxy dicarboxyl
The Wholly aromatic liquid-crystalline polyester tree of aromatic compounds (above composition the adds up to 100 moles of %) polycondensation of acid and aromatic dicarboxylic acid
Fat.If P-hydroxybenzoic acid, p-phthalic acid, 4,4 '-dihydroxybiphenyl is 80 moles of below %, then thermostability has inclining of reduction
To, the most preferably.In the resin combination of the present invention, make the scope consisting of 50-80 mass % of above-mentioned liquid-crystal polyester resin.If
Depart from this scope, be then difficult to obtain sufficient injection moulding characteristic (melt fluidity, short cycle time etc.).
The preparation method of the liquid-crystal polyester resin used in the present invention can use known method, can use only by molten
Melt the preparation method that polymerization is carried out, or be polymerized, by the two-stage nitration of melt polymerization and solid phase, the preparation method carried out.As tool
Style, can be by the monomer selected from aromatic dihydroxy compound, aromatic hydroxy carboxylic acid compound and aromatic dicarboxylic compound
Join in reactor, add acetic anhydride, make the acetylating hydroxyl groups of monomer, then prepared by desacetoxy polycondensation reaction.Such as
Following method can be enumerated: P-hydroxybenzoic acid, p-phthalic acid, M-phthalic acid and 4,4 '-dihydroxybiphenyl are joined
In reactor under blanket of nitrogen, add acetic anhydride, under acetic anhydride refluxes, carry out acetoxylation, heat up afterwards,
Distillate acetic acid within the temperature range of 150-350 DEG C, carry out desacetoxy melt polycondensation, thus prepare polyester resin.During polymerization
Between can select in the range of 1 hour to tens of hours.In the preparation of the liquid-crystal polyester resin used in the present invention, before preparation
The dehydrate of moisture in monomer can be carried out, it is also possible to do not carry out.
When the polymer obtained by melt polymerization is carried out solid phase further, by obtained by melt polymerization
Pulverize after polymer solidification, make powder or fragment shape, then preferably select known method for solid phase polymerization, such as at nitrogen etc.
The method carrying out the heat treatment etc. of 1-30 hour under inert gas atmosphere, within the temperature range of 200-350 DEG C.Solid phase can
To carry out while stirring, it is also possible to without stirring, carry out when standing.
In polyreaction, catalyst can use and can not also use.As the catalyst used, it is possible to use as
The polycondensation catalyst of polyester and known catalyst, can enumerate: magnesium acetate, stannous acetate, butyl titanate, acetic acid
The metal salt catalyst of lead, sodium acetate, potassium acetate, antimony trioxide etc., the organic compound catalyst etc. of N-Methylimidazole. etc..
Polymerizing reactor in melt polymerization is not particularly limited, and is preferably used in the reaction of common high viscosity fluid
The reaction unit used.The example of these reaction units such as can be enumerated: has the stirring slot type polyreaction dress of agitating device
Put, this agitating device with anchor formula, multisection type, ribbon flight, screw shaft type etc. or they are carried out deform variously-shaped
Agitator；Or the usual mixing arrangement etc. in the mixing middle use of resin of kneader, roller mill, Banbury mixer etc..
The shape of the liquid-crystal polyester resin used in the present invention can be the arbitrary shape of powder, graininess, partical,
Consider dispersibility when mixing, preferred powder powder or graininess with packing material.
<about whisker (whiskers)>
Known liquid crystal polyester resin compositions can contain diversified fibrous filler, due to the main cause of its shape
And present the thermostability of excellence, rigidity etc..In the present invention, it is desirable to so-called " whisker " containing promising whiskers is as threadiness
Packing material, and then contain, with the most specific proportioning, the filler being different from.
" the resistance to detachment of granule " of camera model liquid crystal polyester resin compositions by containing whisker as described by spy
Surely fibrous filler in the resin combination cooperatively formed and significantly improve.
The present inventor not yet understands for its reason, but can be at the glass with the representation example as fibrous filler
The comparison of fiber speculates.
Have been recognized that: the granule in drop impact of the liquid crystal polyester resin compositions containing various packing materials is mainly
The flinders of various fibrous filler materials and derive from liquid crystal polyester substrate destroy the fibril produced.
The fibrous filler material that generation about granule, it is believed that into the filler material, length-width ratio and size (length) are big
Big with the factor that the failure mode of the interface peel of liquid crystal polyester causes.
By the glass fibre that melt spinning, the surface configuration of melt-blown manufacture and plane of disruption shape thereof are coarse, with by crystalline substance
In the whiskers that the surface configuration of bulk-growth manufacture and plane of disruption shape matching thereof smooth, with the liquid crystal polyester as substrate
Interfacial structure has fine difference, it is envisioned that the failure mode at interface is different.
Such as, the whiskers interface of surface relative smooth is easily peeled off with liquid-crystal polyester resin, is formed more small
Space, the apparatus with shock absorbing due to the formation in these spaces, it is believed that inhibit and the fibril from liquid crystal polyester substrate
The destruction in the substrate portion that the generation of (one of " granule " main component) is associated.
The whisker that can use in the present invention does not limit.Preferably in whisker, there is below average diameter 5 μm of toughness
Whisker the most applicable.Specifically can enumerate: (i) potassium titanate (chemical formula: (n is 6 or 8 to K2O nTiO2, and true specific gravity is 3.4-
3.6, fiber diameter 0.3-0.6 μm.Such as can with trade name " TISMO (テ ィ ス モ) " (big chemistry (strain) manufacture) from
The material that market obtains)；(ii) calcium silicates (chemical formula: CASiO3, true specific gravity 2.5-2.6, fibre diameter 1-5 μm.Such as can make
The material obtained from market for " wollastonite (ワ ラ ス ト Na イ ト) ")；(iii) calcium carbonate (chemical formula: CaCO3, true specific gravity 2.8,
Fiber diameter 0.5-1 μm.Such as can with trade name " U ~ isukaru (ウ ィ ス カ Le) " (Maruo Calcium Co.,
Ltd. prepared by (ball tail カ Le シ ウ system (strain))) material that obtains from market)；(iv) zinc oxide (chemical formula: ZnO, true specific gravity
5.78, fiber diameter 0.2-3 μm.Such as can be with trade name " Pana-Tetra (パ Na テ ト ラ) " (PANASONIC (パ Na
ソ ニ ッ Network) prepared by (strain)) material that obtains from market)；Wherein, the ease for operation from compounding procedure, constitute substrate liquid
From the point of view of easily dispersion in brilliant polyester, preferably fibre diameter holds compared with big and little with the difference in specific gravity of liquid crystal polyester, good dispersion
Easy (ii) and (iii).They can be used alone, it is also possible to two or more is used in mixed way with arbitrary cooperation.In the present invention
In resin combination, preferably make the scope that containing ratio is 10-30 mass % of whisker.Do not fill less than 10 mass % then additive effect
Point, then can be difficult to more than 30 mass % obtain good mobility.
<blanc fixe>
The liquid crystal polyester resin compositions of the present invention contains blanc fixe.Barium sulfate is substantially to have spherical packing material,
It is believed that the probability obtaining the interface delaminating damage mode being associated with particles generation is low, it is additionally, since its specific high ratio
Weight (about 4.5), is considered to improve the impact energy absorption efficiency of liquid-crystalline polyester composition, it is provided that the effect of suppression particles generation
Really.Additionally from as amorphous, the most soft, it is difficult to destroying, this suppression being recognized as with particles generation is associated.The present invention
Resin combination in, add blanc fixe time, the scope preferably making its containing ratio be 3-20 mass %.If less than 3 matter
Amount % then additive effect is insufficient, if more than 20 mass %, can be difficult to obtain good mobility.
<Pulvis Talci>
In the present invention, preferably liquid crystal polyester resin compositions contains Pulvis Talci.Pulvis Talci is substantially to have oval spherical, surface ratio
Smoother packing material, gives dimensional stability due to anisotropic reduction to products formed, therefore, even if at camera mould
The reliability of the resistance to detachment of granule etc. can also be improved under the life-time service of block part.In the resin combination of the present invention, adding
When adding Pulvis Talci, preferably its containing ratio is the scope of 5-20 mass %.If less than 5 mass %, additive effect is insufficient, if exceeding
20 mass % then can be difficult to obtain good mobility.
<about white carbon black>
The white carbon black used in the present invention is present to ensure that the purpose of the light-proofness of camera module components uses, as long as therefore
The typically available white carbon black used in coloring resin, is not particularly limited.
In the resin combination of the present invention, preferably make the scope that containing ratio is 0.5-5 mass % of white carbon black.Further preferably
For 2-4 mass %.If the use level of white carbon black is less than 0.5 mass %, then the pitch-dark property of gained resin combination reduces, it is impossible to the most true
Protecting light-proofness, if more than 5 mass %, physical property reduces, and additionally produces pimple (the tiny knob-like projection that white carbon black is assembled
Thing) probability improve.
Do not damaging in the range of the purpose of the present invention, can add the most further antioxidant and
Heat stabilizer (such as hindered phenol, hydroquinone, phosphite ester (salt) class and their substitution product etc.), UV absorbent (example
Such as resorcinol, salicylate (salt), benzotriazole, benzophenone etc.), lubricant and releasing agent (montanic acid and salt thereof, its
Ester, its partial ester, higher fatty acids and salt, its ester such as stearic acid, higher alcohol, stearyl amido-propyl and the Tissuemat E such as stearyl alcohol
Deng polyolefin-wax etc.), plasticizer, antistatic additive, the common additive such as fire retardant, other packing material other than the above or its
Its thermoplastic resin, to give the characteristic of regulation.It should be noted that, it is many that the granule of glass fibre produces number, is not suitable for this
The purpose (with reference to comparative example) of invention.
The liquid crystal polyester resin compositions of the present invention can be melted by melted and mixing with other composition for liquid crystal polyester and obtain
As long as the equipment of mixing middle use and method of operation are generally used for the melting mixing of liquid crystal polyester, limit the most especially
Fixed.
Preferably use the mixing roll with a pair screw rod, add liquid crystal polyester, whisker, white carbon black, blanc fixe from hopper, enter
One step adds Pulvis Talci, melting mixing the method making pellet as required.
They are referred to as biaxial extruder, the most preferably by have switching mechanism, can make packing material dispersed with
And the heterodromy of suppression local pyrexia.
<about melt viscosity scope>
In the present invention, the liquid crystal polyester resin compositions so obtained is in shear rate 100s-1, measure at fusing point+10 DEG C molten
Melt-viscosity is 20-100Pa S, the scope of preferably 30-80Pa S.If resin viscosity departs from this scope, then injection-molded article
Surface texture is deteriorated, and is likely to be due to this reason and produces granule.Melt viscosity uses INTESCO (イ Application テ ス U) Co., Ltd.
The capillary rheometer (model 2010) manufactured, uses diameter 1.00mm, long 40mm, the capillary tube of fluid inlet angle 90 °, is shearing speed
Degree 100s-1Lower while heating while carrying out apparent viscosity mensuration by-40 DEG C of constant speed of fusing point with the programming rate of+4 DEG C/min, will
Individual position rounds up, and obtains the apparent viscosity at fusing point+10 DEG C.
<about temperature of deflection under load>
In the present invention, the temperature of deflection under load of the injection-molded article of the liquid crystal polyester resin compositions so obtained is necessary for 220
More than DEG C.Here, temperature of deflection under load refers to the temperature of deflection under load (DTUL) measured according to ASTM D648.If load deflection
Temperature is less than 220 DEG C, then during surface is installed, thermostability during Reflow Soldering may come into question, and is therefore not suitable for.
In the resin combination of the present invention, respective characteristic and the good mobility of these constituent materials are being injected into
Type operation synthetically plays, particularly the one-tenth of the injection-molded article in the thin-wall construction portion with 0.3-0.9mm ranges of thicknesses
In type, it is possible to provide there is the camera module components of " the resistance to detachment of granule " of excellence.It should be noted that, for injection molding note
As long as penetrate forming machine normally used known equipment in the molding of liquid crystal polyester, it is not particularly limited.
Embodiment
It is further elaborated with the present invention below by way of embodiments and comparative examples, but the present invention is not limited to following enforcement
Example.
The preparation example of liquid crystal polyester described below (LCP).
(preparation of preparation example thermotropic liquor polyester A)
With SUS316 as material, there is internal volume 1700L polymerization tank (Co., Ltd. of Kobe Steel system of Double helix agitator
Make) in add 298kg (2.16 kilomol) P-hydroxybenzoic acid (prepared by Ueno Seiyaku K.K.), (0.72 thousand rub 134kg
You) 4,4 '-dihydroxybiphenyl (prepared by Honshu Chemical Ind), 90kg (0.54 kilomol) p-phthalic acid (three wells
Prepared by KCC), 30kg (0.18 kilomol) M-phthalic acid (A.G.. International Chemical
Co., prepared by Inc.), as catalyst 0.04kg potassium acetate (KISHIDA CHEMICAL Co., Ltd. (and キ シ ダ chemistry
Co., Ltd.) prepare), 0.10kg magnesium acetate (KISHIDA CHEMICAL Co., Ltd. (キ シ ダ KCC) system
Standby), the decompression-nitrogen injection carrying out 2 polymerization tanks carries out nitrogen displacement, then adds 386kg (3.78 kilomol) acetic anhydride,
It is warming up to 150 DEG C with 1.5 hours under the rotating speed 45rpm of agitator, carries out the acetylization reaction of 2 hours at reflux.Second
After acylated end, with 0.5 DEG C/min of intensification under acetic acid distillates state, when temperature of reactor reaches 305 DEG C, from reactor
The outlet of bottom takes out polymer, cools and solidifies with chiller.Resulting polymers is used Hosokawa Micron
It is big that the pulverizer that Corporation (ホ ソ カ ワ ミ Network ロ Application Co., Ltd.) manufactures is pulverized as by the sieve of aperture 2.0mm
Little, obtain prepolymer.
Gained prepolymer is carried out solid phase by the rotary kiln using Takasago Kogyo KK to manufacture.Prepolymer is filled
In this kiln, with 16Nm3/ hour flow rate nitrogen, under rotating speed 2rpm, with 1 hour by heter temperature by room temperature
To 350 DEG C, keep 10 hours at 350 DEG C.Confirm that the toner temperature in kiln reaches 295 DEG C, stop heating, make revolution
Kiln rotates while with cooling in 4 hours, obtaining the liquid crystal polyester of powder.Fusing point is 360 DEG C, and melt viscosity is 70Pa S.Need
Bright, fusing point measures (following identical) according to ISO11357-3, ASTM D3418.
(preparation of preparation example thermotropic liquor polyester B)
Prepolymer is obtained according to the method as thermotropic liquor polyester A.Use the rotary kiln that Takasago Kogyo KK manufactures
Gained prepolymer is carried out solid phase.Prepolymer is filled in this kiln, with 16Nm3/ hour flow rate nitrogen, at rotating speed
Under 2rpm, with 1 hour by heter temperature by room temperature to 350 DEG C, keep 9 hours at 350 DEG C.Confirm the resin-oatmeal in kiln
End temperature reaches 290 DEG C, stops heating, makes rotary kiln rotate and uses cooling in 4 hours, and the liquid crystal obtaining powder gathers
Ester.Fusing point is 350 DEG C, and melt viscosity is 20Pa S.
(preparation of preparation example thermotropic liquor polyester C)
Prepolymer is obtained according to the method as thermotropic liquor polyester A.Use the rotary kiln that Takasago Kogyo KK manufactures
Gained prepolymer is carried out solid phase.Prepolymer is filled in this kiln, with 16Nm3/ hour flow rate nitrogen, at rotating speed
Under 2rpm, with 1 hour by heter temperature by room temperature to 350 DEG C, keep 11 hours at 350 DEG C.Confirm the resin in kiln
Powder temperature reaches 300 DEG C, stops heating, makes rotary kiln rotate and uses cooling in 4 hours, and the liquid crystal obtaining powder gathers
Ester.Fusing point is 370 DEG C, and melt viscosity is 140Pa S.
(preparation of preparation example thermotropic liquor polyester D)
With SUS316 as material, there is internal volume 1700L polymerization tank (Co., Ltd. of Kobe Steel system of Double helix agitator
Make) middle addition 97.5kg (1.43 kilomol) P-hydroxybenzoic acid (prepared by Ueno Seiyaku K.K.), 71.7kg (0.385 thousand
Mole) 4,4 '-dihydroxybiphenyl (prepared by Honshu Chemical Ind), 64.0kg (0.385 kilomol) p-phthalic acid
(prepared by Mitsui Chemicals, Inc), 0.06kg potassium acetate (KISHIDA CHEMICAL Co., Ltd. (キ as catalyst
シ ダ KCC) prepare), 0.10kg magnesium acetate (KISHIDA CHEMICAL Co., Ltd. (キ シ ダ chemistry strain formula
Commercial firm) prepare), the decompression-nitrogen injection carrying out 2 polymerization tanks carries out nitrogen displacement, then adds 242.6kg (2.4 kilomol)
Acetic anhydride, was warming up to 150 DEG C with 1.5 hours under the rotating speed 45rpm of agitator, carries out the acetyl of 2 hours at reflux
Change reaction.After acetylation terminates, with 0.5 DEG C/min of intensification under acetic acid distillates state, when 305 DEG C from reactor lower part
Outlet takes out polymer, cools and solidifies with chiller.By resulting polymers Hosokawa Micron Corporation
The pulverizer that (ホ ソ カ ワ ミ Network ロ Application Co., Ltd.) manufactures is pulverized as the size by the sieve of aperture 2.0mm, obtains pre-polymerization
Thing.
Gained prepolymer is carried out solid phase polycondensation by the rotary kiln using Takasago Kogyo KK to manufacture.The shape of kiln inner core
Substantially regular hexagon, a length of 500mm, total length 3500mm.150kg prepolymer is filled in this kiln, with 15Nm
Circulation nitrogen 3 hours, under revolution 2rpm, is warming up to 400 DEG C with 5 hours by the temperature from ambient in heater, 400 DEG C of holdings
12 hours.Confirm that the temperature of ground product reaches 340 DEG C, stop heating, make rotary kiln rotate and carry out cooling in 7 hours,
Obtain Wholly aromatic liquid-crystalline polyester D.Fusing point is 380 DEG C, and melt viscosity is 70Pa S.
The characteristic of the various filleies used in examples and comparative examples of the present invention is as shown below.
(1) whisker:
I () potassium titanate: chemical formula: K2O nTiO2, n are 6 or 8, true specific gravity is 3.4-3.6, and fibre diameter is 0.3-0.6 μm
(trade name " TISMO (テ ィ ス モ) ", big chemistry (strain) manufactures)
(ii) calcium silicates: chemical formula: CaSiO3, true specific gravity is 2.5-2.6, and fiber diameter is that 1-5 μm (can be with " silicon ash
Stone " title obtained by market)
(iii) calcium carbonate: chemical formula: CaCO3, true specific gravity is 2.8, fiber diameter be 0.5-1 μm (trade name " U ~
Isukaru (ウ ィ ス カ Le) ", Maruo Calcium Co., Ltd. (ball tail カ Le シ ウ system (strain) manufacture)
(iv) zinc oxide: chemical formula: ZnO, true specific gravity is 5.78, and fiber diameter is 0.2-3 μm (trade name " Pana-
Tetra (パ Na テ ト ラ) ", Amtec Corporation ((strain) ア system テ ッ Network) manufactures)
(2) white carbon black (CB): Cabot Corporation (キ ャ ボ ッ ト (strain) society) manufactures, " REGAL 660 " (primary particle size
24nm)
(3) blanc fixe: chemical industry (strain) manufactures, " BMH-40 " (mean diameter 1 μm, proportion 4.5)
(4) Pulvis Talci: NIPPON TALC Co., Ltd. (タ Le Network (strain) society of Japan) manufactures, " MS-KY " (number average bead diameter 23 μ
m)
(5) glass fibre: day east twist flax fibers and weave (strain) company manufacture, PF100E-001SC (number average fiber length 100 μm, number equal fibers
Diameter 10 μm).
(test method)
(1) mensuration of melt viscosity
About the melt viscosity of thermotropic liquor polyester resin combination, use capillary rheometer (INTESCO (イ Application テ ス U
(strain)) company's manufacture 2010), use diameter 1.00mm, length 40mm, the capillary tube of fluid inlet angle 90 °, in shear rate 100s-1
Under with the programming rate of+4 DEG C/min by (fusing point-40) DEG C constant speed heating, carry out apparent viscosity mensuration simultaneously, individual position four given up
Five enter, and obtain the apparent viscosity at fusing point+10 DEG C, as test value.It should be noted that, test uses and does at hot-air in advance
Dry stove has been dried the resin combination of 4 hours with 150 DEG C.
(2) mensuration of fusion point intensity
(molding of test film)
The pellet of gained resin combination is used injection (mo(u)lding) machine (Nissei Plastic Industrial Co., Ltd manufactures, UH-1000),
Test film is obtained at barrel maximum temperature 370 DEG C, injection speed 300mm/ second, mold temperature 80 DEG C.The injection of resin is watered at 2
Mouth is carried out.Use such as lower mold: there is the die cavity of 48mm × 15mm × 0.3mm, at its approximate centre, by different cast gate notes
The melt front of the resin entered is collided, and generates the fusion point traversing products formed.The above-mentioned test film obtained with this mould
Top view and side view are shown in Fig. 1.
(evaluation of fusion point intensity)
For a kind, being arranged on resin-made frame by 5 test films, two ends are configured on framework, have in fusion point
Centre part is configured on frame window, and the two ends adhesive tape on frame is fixed on frame.Stickup is maintained the frame of this test film from 1.5 meters
Highly fall 5 times, then confirm that there is crack-free in fusion point portion by magnifier.Rupture is designated as "○", ruptures
Be designated as "×".(with reference to table 1)
(3) mensuration of temperature of deflection under load (DTUL)
The pellet of gained resin combination is used injection (mo(u)lding) machine, at barrel maximum temperature 370 DEG C, injection speed 100mm/
The injection-molded article of 13mm (wide) × 130mm (length) × 3mm (thick) is obtained, as load deflection temperature at second, mold temperature 80 DEG C
The test film that degree measures.For each test film, according to ASTM D648 measuring load deflection temperature.Pacify as if appropriate for surface
The benchmark of dress, by more than 220 DEG C be designated as "○", be designated as "×" less than 220 DEG C.
(4) as the mensuration of the resistance to detachment of granule of camera module components
(molding of test film)
The pellet of gained resin combination is used injection (mo(u)lding) machine (Nissei Plastic Industrial Co., Ltd manufactures, UH-1000),
Test film is obtained at barrel maximum temperature 370 DEG C, injection speed 300mm/ second, mold temperature 80 DEG C.The injection of resin is by 1
Cast gate is carried out, and mould uses the circular depressions in the central authorities of the square shape of a piece of 8mm with 6mm φ, and at its center
There is the mould of the window of 3mm φ.Minimum thickness is 0.9mm.It should be noted that, the window portion of products formed corresponds to actual phase
The camera lens of machine modular unit inserts fixed part, in such products formed, inevitably results from dotted line part fusion point.This mould
Top view and the side view of the above-mentioned test film obtained are shown in Fig. 2.
(evaluation of the resistance to detachment of granule)
50 above-mentioned test films are contained in SUS container, close the lid.This receiving container is highly fallen 50 times from 1.5m,
Then open lid, test film is separated with the granule fallen on test film, " FPIA-3000 " manufactured with Sysmex company
The number of particle count.
Carry out resistance to degranulated evaluation with 3 grades, generate number being designated as in the range of less than 100 of granule
" ◎ ", more than 100～less than being designated as "○" in the range of 200, will be designated as "×" more than 200.
(5) anisotropic evaluation
It is evaluated with the difference in TD direction and the molding shrinkage in MD direction.For a kind, by 5 above-mentioned (3) gained
The test film that " temperature of deflection under load " measures at room temperature is placed more than 24 hours, then measures as MD in units of mm
The length in (molding) direction, width as TD (laterally) direction, measure 2 figure places to arithmetic point.By this size each averagely
Value and the actual size (" length "=130.02mm, " width "=13.02mm) of mould compare, and obtain becoming of TD direction and MD direction
Type shrinkage factor.
The difference of TD direction and the molding shrinkage in MD direction is designated as "○" less than 8 times, is more than 8 times be designated as
“△”。
[table 1]
Industrial applicability
The injection-molded article of the wholly aromatic liquid-crystalline polyester resin compositions containing the present invention is as the camera model portion of member of formation
Part has reflux-resisting welded thermostability, is applicable to the injection moulding with the parts of thinner wall section, additionally in being assembled into product
After, " the resistance to detachment of granule " during product drop impact is excellent, therefore can be equipped on portable phone, portable computer, number
Camera, digital video recorder, smart mobile phone, flat terminal camera etc. in barrel portion, mounting bracket portion and " CMOS
(imageing sensor) frame ", the various uses such as " shutter and fast door frame " uses.
Claims (3)
1. wholly aromatic liquid-crystalline polyester resin compositions, it is characterised in that this wholly aromatic liquid-crystalline polyester resin compositions is to add up to
It is that the following component melting mixing of 100 mass % obtains: the Wholly aromatic liquid-crystalline polyester of 50-80 mass %, the crystalline substance of 10-30 mass %
Palpus, the white carbon black of 0.5-5 mass %, 0-20 mass parts Pulvis Talci, 3-20 mass parts blanc fixe；Temperature of deflection under load is 220 DEG C
Above, and in shear rate 100s-1, melt viscosity at (fusing point+10) DEG C be 20-100Pa S.
2. the wholly aromatic liquid-crystalline polyester resin compositions described in claim 1, it is characterised in that: described whisker is that true specific gravity is
At least any of in the calcium silicates of less than 3.0, calcium carbonate.
3. camera module components, it is characterised in that: containing the wholly aromatic liquid-crystalline polyester resin compositions described in claim 1 or 2
Injection-molded article as member of formation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013250275A JP6165608B2 (en) | 2013-12-03 | 2013-12-03 | Camera module parts comprising a wholly aromatic liquid crystal polyester resin composition and an injection molded product thereof as constituent members |
| JP2013-250275 | 2013-12-03 | ||
| PCT/JP2014/082054 WO2015083759A1 (en) | 2013-12-03 | 2014-11-27 | Wholly aromatic liquid crystal polyester resin composition and camera module component including injection-molded article of same as constituent member |
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| CN105764988A true CN105764988A (en) | 2016-07-13 |
| CN105764988B CN105764988B (en) | 2018-06-26 |
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| JP (1) | JP6165608B2 (en) |
| KR (1) | KR101831543B1 (en) |
| CN (1) | CN105764988B (en) |
| TW (1) | TW201522578A (en) |
| WO (1) | WO2015083759A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112533977A (en) * | 2018-10-22 | 2021-03-19 | 引能仕株式会社 | Crystalline wholly aromatic polyester and polyester resin composition |
| WO2022100030A1 (en) * | 2020-11-16 | 2022-05-19 | 金发科技股份有限公司 | Liquid crystal polymer composition and preparation method therefor |
| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6616322B2 (en) | 2014-04-09 | 2019-12-04 | ティコナ・エルエルシー | The camera module |
| JP2017014357A (en) * | 2015-06-30 | 2017-01-19 | 上野製薬株式会社 | Liquid crystal polymer for electronic component |
| WO2016043091A1 (en) | 2014-09-19 | 2016-03-24 | 上野製薬株式会社 | Liquid crystal polymer |
| KR102627886B1 (en) | 2017-12-05 | 2024-01-19 | 티코나 엘엘씨 | Aromatic polymer compositions for use in camera modules |
| WO2019164723A1 (en) | 2018-02-20 | 2019-08-29 | Ticona Llc | Thermally conductive polymer composition |
| WO2020190569A1 (en) | 2019-03-20 | 2020-09-24 | Ticona Llc | Polymer composition for use in a camera module |
| KR102545958B1 (en) * | 2020-06-30 | 2023-06-22 | 포리프라스틱 가부시키가이샤 | Liquid crystalline resin composition for ball bearing sliding wear resistance and ball bearing sliding wear resistance using the same |
| KR102461065B1 (en) | 2020-12-29 | 2022-11-01 | 세양폴리머주식회사 | Liquid crystal polyester resin composition and electronic component material containing the same |
| JPWO2023276699A1 (en) * | 2021-06-30 | 2023-01-05 | ||
| CN117396556A (en) * | 2021-06-30 | 2024-01-12 | 大塚化学株式会社 | Liquid crystal polymer composition and liquid crystal polymer molded body |
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| CN112533977A (en) * | 2018-10-22 | 2021-03-19 | 引能仕株式会社 | Crystalline wholly aromatic polyester and polyester resin composition |
| US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
| WO2022100030A1 (en) * | 2020-11-16 | 2022-05-19 | 金发科技股份有限公司 | Liquid crystal polymer composition and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105764988B (en) | 2018-06-26 |
| WO2015083759A1 (en) | 2015-06-11 |
| KR20160096086A (en) | 2016-08-12 |
| KR101831543B1 (en) | 2018-02-26 |
| TW201522578A (en) | 2015-06-16 |
| JP2015108036A (en) | 2015-06-11 |
| JP6165608B2 (en) | 2017-07-19 |
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