CN108602943B - Wholly aromatic liquid crystal polyester resin and method for producing same - Google Patents
Wholly aromatic liquid crystal polyester resin and method for producing same Download PDFInfo
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- CN108602943B CN108602943B CN201780006453.7A CN201780006453A CN108602943B CN 108602943 B CN108602943 B CN 108602943B CN 201780006453 A CN201780006453 A CN 201780006453A CN 108602943 B CN108602943 B CN 108602943B
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- aromatic liquid
- wholly aromatic
- crystalline polyester
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 103
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 100
- 239000004645 polyester resin Substances 0.000 title claims abstract description 100
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000004973 liquid crystal related substance Substances 0.000 title description 19
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 13
- 230000008018 melting Effects 0.000 claims abstract description 13
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000012765 fibrous filler Substances 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000011049 filling Methods 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 description 30
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 12
- 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 11
- 239000007790 solid phase Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- 238000006640 acetylation reaction Methods 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- -1 lead acetate Chemical compound 0.000 description 6
- 238000002156 mixing 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 230000021736 acetylation Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical class CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 3
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 3
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 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
- 239000011654 magnesium acetate Substances 0.000 description 3
- 229940069446 magnesium acetate Drugs 0.000 description 3
- 235000011285 magnesium acetate Nutrition 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-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
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000010354 integration Effects 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
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/79—Interfacial processes, i.e. processes involving a reaction at the interface of two non-miscible liquids
-
- 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
-
- 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
- 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
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a wholly aromatic liquid crystalline polyester resin having high mechanical strength, excellent filling property, blister resistance and low warpage. The wholly aromatic liquid crystalline polyester resin according to the present invention is a wholly aromatic liquid crystalline polyester resin containing structural units (I) to (V) represented by formulae (I) to (V), wherein the structural units (I) to (V) in the aromatic liquid crystalline polyester have a composition ratio (mol%): 15 mol% or more and 35 mol% or less of a structural unit (I), 5 mol% or more and 15 mol% or less of a structural unit (II), 21 mol% or more and 29 mol% or less of a structural unit (III), 1 mol% or more and 9 mol% or less of a structural unit (IV), 25 mol% or more and 40 mol% or less of a structural unit (V), the total of the structural units (I) to (V) being 100 mol%, and the melting point being 320 ℃ or higher.
Description
Technical Field
The present invention relates to a wholly aromatic liquid crystalline polyester resin and a method for producing the same. Further, the present invention relates to a wholly aromatic liquid crystalline polyester resin composition containing the wholly aromatic liquid crystalline polyester resin, a molded article containing the composition, and an electronic device.
Background
Since wholly aromatic liquid crystalline polyester resins are excellent in moldability, heat resistance and filling property, molded articles (e.g., injection molded articles) produced using the same have been used for various electronic devices.
In recent years, as personal computers, smart phones, and the like have been miniaturized, high integration, thin thickness, and thinning of electronic devices have been advanced, and there has been an increasing demand for molded products having a very thin thickness portion. Therefore, the wholly aromatic liquid crystalline polyester resin is required to have more excellent filling property.
As a method for improving the filling property, i.e., the fluidity, of a liquid crystal polymer such as a wholly aromatic liquid crystal polyester resin, for example, a method of reducing the molecular weight of the liquid crystal polymer and lowering the viscosity thereof has been carried out.
However, the decrease in the molecular weight of the liquid crystal polymer causes the decrease in physical properties such as mechanical strength of the molded article, and in addition, has the following problems: reflow treatment performed when a molded article is applied to an electronic device such as a connector causes bulging (blistering) and warping of the surface of the molded article. Here, patent document 1 proposes a wholly aromatic liquid crystalline polyester resin which can suppress the occurrence of foaming. Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012 and 126842
Disclosure of Invention
The inventors of the present invention obtained the following findings this time: the above problem can be solved by setting the structural unit contained in the wholly aromatic liquid crystal polyester resin to a specific structural unit and composition ratio and setting the melting point of the wholly aromatic liquid crystal polyester resin to 320 ℃ or higher. The present invention has been completed based on this finding.
Accordingly, an object of the present invention is to provide a wholly aromatic liquid crystalline polyester resin which maintains physical properties such as mechanical strength and has excellent filling properties, blister resistance and low warpage properties.
The wholly aromatic liquid crystalline polyester resin according to the present invention is a wholly aromatic liquid crystalline polyester resin containing structural units (I) to (V) represented by the following formulae (I) to (V),
[ solution 1]
[ solution 2]
[ solution 3]
[ solution 4]
[ solution 5]
Characterized in that the composition ratio (% by mole) of the structural units (I) to (V) in the aromatic liquid-crystalline polyester satisfies the following condition:
15 mol% or more and 35 mol% or less of the structural unit (I)
5 mol% or more and 15 mol% or less of the structural unit (II)
The structural unit (III) accounts for 21 mol% or more and 29 mol% or less
1 mol% or more and 9 mol% or less of the structural unit (IV)
25 mol% or more and 40 mol% or less of structural unit (V)
(III) 100 mol% of structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V),
the melting point is 320 ℃ or higher.
In the above embodiment, the content of the structural unit (III) is preferably 2 times or more the content of the structural unit (IV).
The method for producing the wholly aromatic liquid crystalline polyester resin according to the present invention is characterized by comprising a step of polymerizing monomers represented by the following formulae (1) to (5).
[ solution 6]
[ solution 7]
[ solution 8]
[ solution 9]
[ solution 10]
In the above aspect, the step of polymerizing the monomer preferably includes: the monomers represented by the formulae (1) to (5) are melt-polymerized in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride with respect to all hydroxyl groups of the monomers represented by the formulae (1) to (4).
The wholly aromatic liquid crystalline polyester resin composition according to the present invention is characterized by containing the wholly aromatic liquid crystalline polyester resin and an inorganic filler.
In the above aspect, the inorganic filler is preferably a fibrous filler or a plate-like filler.
In the above aspect, it is preferable that: the total content of the fibrous filler and the plate-like filler is 100 parts by weight or less based on 100 parts by weight of the wholly aromatic liquid crystalline polyester resin contained in the wholly aromatic liquid crystalline polyester resin composition.
The molded article according to the present invention is characterized by containing the wholly aromatic liquid crystalline polyester resin composition.
The electronic device according to the present invention is characterized by containing the wholly aromatic liquid crystalline polyester resin composition.
According to the present invention, since the molded article has high mechanical strength, filling property, and blister resistance, a molded article having a very thin thickness portion can be manufactured, and high integration, thin thickness, and thinning of an electronic device can be achieved. In addition, according to the present invention, the occurrence of warpage can be prevented.
Drawings
Fig. 1 is a top view and a side view of a mold used in the fillability test of the example.
Fig. 2(a) is a bottom view of the box-shaped molded article produced in the measurement of the warpage of the box in the example.
Fig. 2(b) is a front view of the box-shaped molded article produced in the measurement of the warpage of the box in the example.
Detailed Description
(wholly aromatic liquid crystal polyester resin)
The wholly aromatic liquid crystalline polyester resin according to the present invention contains structural units (I) to (V) represented by the following formulas (I) to (V), and the composition ratio (mol%) of the structural units (I) to (V) in the aromatic liquid crystalline polyester satisfies the following conditions. The wholly aromatic liquid crystalline polyester resin can impart high mechanical strength, filling property, blister resistance and low warpage to a molded article produced using the resin.
[ solution 11]
[ solution 12]
[ solution 13]
[ solution 14]
[ solution 15]
15 mol% or more and 35 mol% or less of the structural unit (I)
5 mol% or more and 15 mol% or less of the structural unit (II)
The structural unit (III) accounts for 21 mol% or more and 29 mol% or less
1 mol% or more and 9 mol% or less of the structural unit (IV)
25 mol% or more and 40 mol% or less of structural unit (V)
The sum of structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V) is 100 mol%.
The blending ratio (mol%) of the structural unit (III) and the structural unit (IV) in the wholly aromatic liquid crystal polyester resin is preferably 2 times or more, more preferably 4 times or more, the content of the structural unit (III) than the content of the structural unit (IV). When the blending ratio (mol%) of the structural unit (III) to the structural unit (IV) is in the above numerical range, the melting point of the wholly aromatic liquid crystal polyester resin can be increased.
In addition, the wholly aromatic liquid crystalline polyester resin according to the present invention has a melting point of 320 ℃ or more.
The wholly aromatic liquid crystalline polyester resin according to the present invention has a high melting point, and therefore can satisfy heat resistance required for electronic devices.
The melting point is determined by using a Differential Scanning Calorimeter (DSC) manufactured by Seiko electronics industries, Ltd., for example, based on ISO11357-3, ASTM D3418.
The temperature was raised from room temperature to 380 ℃ at a temperature raising rate of 20 ℃/min, the wholly aromatic liquid crystalline polyester resin was completely melted, and then the temperature was lowered to 50 ℃ at a rate of 10 ℃/min, and further raised to 420 ℃ at a rate of 20 ℃/min, and the peak of the endothermic peak obtained at this time was defined as the melting point.
The structural units contained in the wholly aromatic liquid crystal polyester resin will be described below.
(structural Unit (I))
The wholly aromatic liquid crystalline polyester resin contains the structural unit (I), and the composition ratio (% by mole) of the structural unit (I) in the aromatic liquid crystalline polyester is 15 to 35% by mole. More preferably 20 to 35 mol%, and still more preferably 25 to 35 mol%.
Examples of the monomer providing the structural unit (I) include: p-hydroxybenzoic acid (HBA, formula (1) below), its acylate, ester derivative, acid halide, and the like.
[ solution 16]
(structural Unit (II))
The wholly aromatic liquid crystalline polyester resin contains the structural unit (II), and the composition ratio (mol%) of the structural unit (II) in the aromatic liquid crystalline polyester is 5 to 15 mol%. More preferably 8 to 15 mol%, and still more preferably 8 to 10 mol%.
Examples of the monomer providing the structural unit (II) include: 6-hydroxy-2-naphthoic acid (HNA, formula (2)) and its acylate, ester derivative, acid halide, etc.
[ solution 17]
(structural Unit (III))
The wholly aromatic liquid crystalline polyester resin contains the structural unit (III), and the composition ratio (mol%) of the structural unit (III) in the aromatic liquid crystalline polyester is 21 to 29 mol%. More preferably from 21 to 28 mol%, still more preferably from 22 to 26 mol%.
Examples of the monomer providing the structural unit (III) include: hydroquinone (HQ, formula (3) below), and acylates thereof.
[ solution 18]
(structural Unit (IV))
The wholly aromatic liquid crystalline polyester resin contains the structural unit (IV), and the composition ratio (mol%) of the structural unit (IV) in the aromatic liquid crystalline polyester is 1 mol% to 9 mol%. More preferably 1.5 to 9 mol%, and still more preferably 1.5 to 7 mol%.
Examples of the monomer providing the structural unit (IV) include: 4, 4-dihydroxybiphenyl (BP, the following formula (4)), an acylate thereof, and the like.
[ solution 19]
(structural Unit (V))
The wholly aromatic liquid crystalline polyester resin contains the structural unit (V), and the composition ratio (% by mole) of the structural unit (V) in the aromatic liquid crystalline polyester is 25 to 40% by mole. More preferably, it is from 25 to 35 mol%, and still more preferably from 27.5 to 32.5 mol%.
Examples of the monomer providing the structural unit (V) include: terephthalic acid (TPA, formula (5)) ester derivatives, acid halides thereof, and the like.
[ solution 20]
(method for producing wholly aromatic liquid crystalline polyester resin)
The wholly aromatic liquid crystalline polyester resin according to the present invention can be produced by polymerizing the monomers represented by the above formulae (1) to (5) by a conventionally known method.
For example, the wholly aromatic liquid crystalline polyester resin according to the present invention can be produced by melt polymerization alone. Alternatively, the polymer can be produced by preparing a prepolymer by melt polymerization and further subjecting the prepolymer to solid-phase polymerization.
From the viewpoint of efficiently obtaining the wholly aromatic polyester compound according to the present invention, it is preferable that the monomers represented by the formulae (1) to (5) are combined in a predetermined blending ratio so as to be 100 mol%, and acetic anhydride is present in an amount of 1.05 to 1.15 mol equivalent to all hydroxyl groups of the monomers represented by the formulae (1) to (4), and the melt polymerization is performed under an acetic acid reflux.
In the case of carrying out the polymerization reaction in two stages of melt polymerization and subsequent solid-phase polymerization, it is preferable to select a known solid-phase polymerization method, for example, a method of heat-treating a prepolymer resin at a temperature ranging from 200 to 350 ℃ for 1 to 30 hours in an inert atmosphere such as nitrogen or in a vacuum, after cooling and solidifying the prepolymer obtained by melt polymerization and pulverizing the same into a powder or a flake. The solid-phase polymerization may be carried out with stirring, or may be carried out in a state of standing without stirring.
The polymerization reaction may be carried out using a catalyst, or may be carried out without using a catalyst. As the catalyst to be used, conventionally known catalysts for polymerization of polyesters can be used, and examples thereof include metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide, nitrogen-containing heterocyclic compounds such as N-methylimidazole, and organic compound catalysts. The amount of the catalyst used is not particularly limited, and is preferably 0.0001 to 0.1 part by weight based on 100 parts by weight of the total amount of the monomers.
The polymerization reaction apparatus in the melt polymerization is not particularly limited, and a reaction apparatus used for a reaction of a general high-viscosity fluid is preferably used. Examples of these reaction apparatuses include: a stirring tank type polymerization reaction apparatus having a stirring device with stirring blades of various shapes such as an anchor type, a multi-stage type, a spiral belt type, a spiral shaft type, and the like, or a stirring blade of various shapes obtained by deforming them, a mixing device generally used for kneading a resin such as a kneader, a roll mill, a banbury mixer, and the like.
(wholly aromatic liquid crystal polyester resin composition)
The wholly aromatic liquid crystalline polyester resin composition according to the present invention contains the wholly aromatic liquid crystalline polyester resin and an inorganic filler.
The content of the wholly aromatic liquid crystalline polyester resin in the wholly aromatic liquid crystalline polyester resin composition is preferably 50% by weight or more, and more preferably 60 to 90% by weight.
As the inorganic filler contained in the wholly aromatic liquid crystalline polyester resin composition, for example, fibrous, plate-like, or powdery inorganic fillers can be used, and these can be used in combination. Among them, a fibrous filler and a plate-like filler are preferably used in combination.
Examples of the inorganic filler include: glass fibers, milled glass fibers, silica alumina fibers, carbon fibers, aramid fibers, potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide, and the like, and the wholly aromatic liquid crystalline polyester resin composition may contain 1 or 2 or more of these inorganic fillers.
The content of the inorganic filler in the wholly aromatic liquid crystalline polyester resin composition is preferably 100 parts by weight or less, and more preferably 10 to 65 parts by weight, based on 100 parts by weight of the wholly aromatic liquid crystalline polyester resin contained in the wholly aromatic liquid crystalline polyester resin composition. When the content of the inorganic filler is within the above numerical range, the occurrence of warpage in the production of a molded article can be prevented without affecting the filling property during molding.
The wholly aromatic liquid crystalline polyester resin composition according to the present invention may contain a resin other than the wholly aromatic liquid crystalline polyester resin within a range not to impair the effects of the present invention. Examples thereof include: the wholly aromatic liquid crystal polyester resin composition may contain 1 or 2 or more of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyarylate, polyamide, polyimide, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polytetrafluoroethylene, and the like.
The wholly aromatic liquid crystalline polyester resin composition according to the present invention may contain other additives such as a colorant, a dispersant, a plasticizer, an antioxidant, a flame retardant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, and a surfactant, within a range not to impair the effects of the present invention.
(method for producing wholly aromatic liquid crystalline polyester resin composition)
The wholly aromatic liquid crystalline polyester resin composition can be obtained by blending a filler or the like with the wholly aromatic liquid crystalline polyester resin and melt-kneading the obtained blend using a banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder or the like.
(molded article)
The molded article according to the present invention contains the wholly aromatic liquid crystalline polyester resin composition, and can be obtained by injection molding or extrusion molding of the composition. In addition, a film, a sheet and a nonwoven fabric made of the wholly aromatic liquid crystal polyester resin composition can be obtained by the same method.
Specific examples of the film forming method include: blow molding, melt extrusion molding, solution casting molding, and the like. The film obtained in this way may be a single-layer film made of the wholly aromatic polyester resin composition or a multilayer film with a different material.
In order to improve dimensional stability and mechanical properties, a film obtained by melt extrusion molding or solution casting molding may be subjected to uniaxial or biaxial stretching treatment. In addition, heat treatment may be performed in order to remove the anisotropy of these films.
(electronic devices)
The electronic device according to the present invention contains the above wholly aromatic liquid crystalline polyester resin composition. Examples of the electronic device include: high-speed transmission connectors, CPU sockets, circuit boards, flexible circuit boards, laminated circuit boards, radar for collision prevention, RFID tags, capacitors, inverter devices, insulating films, insulating materials for secondary batteries such as lithium ion batteries, and microphone diaphragms. Specifically, these electronic devices include molded articles (for example, injection molded articles), films, and the like made of the wholly aromatic liquid crystal polyester resin composition.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
< production of wholly aromatic liquid crystalline polyester resin >
Example 1 wholly aromatic liquid crystalline polyester resin A)
24.9g (30 mol%) of p-hydroxybenzoic acid (HBA), 11.3g (10 mol%) of 6-hydroxy-2-naphthoic acid (HNA), 15.9g (24 mol%) of Hydroquinone (HQ), 6.7g (6 mol%) of 4, 4-dihydroxybiphenyl (BP), and 29.9g (30 mol%) of terephthalic acid (TPA) were charged into a polymerization vessel equipped with a stirring blade, and potassium acetate and magnesium acetate were charged as catalysts, and after 3 times of vacuum-nitrogen injection in the polymerization vessel, nitrogen substitution was performed, 66.2g (1.08 molar equivalent to hydroxyl group) of acetic anhydride was further added, and the temperature was raised to 150 ℃ and acetylation reaction was performed under reflux for 2 hours.
After the completion of acetylation, the polymerization vessel in a state where acetic acid was distilled out was heated at 0.5 ℃ per minute, and when the temperature of the melt in the tank became 310 ℃, the polymer was taken out, cooled and solidified. The obtained polymer was pulverized and pulverized into a size that passed through a sieve having a mesh size of 1.0mm, to obtain a prepolymer.
Then, the prepolymer obtained above was charged in a glass tube oven made by faggot science, the heater temperature was raised from room temperature to 290 ℃ for 12 hours while rotating the same, and then the temperature was maintained at 290 ℃ for 1 hour to perform solid phase polymerization. Then, the tank was rotated and spontaneously released heat at room temperature to obtain wholly aromatic liquid crystalline polyester resin A. The polyester sample was melted by heating on a microscope heating stage using a polarizing microscope BH-2 manufactured by Olympus having a microscope stage FP82HT manufactured by METTLER, and the presence or absence of optical anisotropy was confirmed to confirm the liquid crystallinity.
Example 2 wholly aromatic liquid crystalline polyester resin B)
A liquid crystal polyester resin B was obtained in the same manner as in example 1 except that the monomer feed was changed to 30 mol% of HBA, 15 mol% of HNA, 26 mol% of HQ, 1.5 mol% of BP, and 27.5 mol% of TPA, and liquid crystallinity was confirmed in the same manner as described above.
Example 3 wholly aromatic liquid crystalline polyester resin C
Liquid crystal polyester resin C was obtained in the same manner as in example 1 except that the monomer feed was changed to 30 mol% of HBA, 10 mol% of HNA, 21 mol% of HQ, 9 mol% of BP, and 30 mol% of TPA, and liquid crystallinity was confirmed in the same manner as described above.
Example 4 wholly aromatic liquid crystalline polyester resin D)
Liquid crystal polyester resin D was obtained in the same manner as in example 1 except that the monomer feed was changed to 30 mol% of HBA, 10 mol% of HNA, 25 mol% of HQ, 5 mol% of BP, and 30 mol% of TPA, and liquid crystallinity was confirmed in the same manner as described above.
Comparative example 1 wholly aromatic liquid crystalline polyester resin E)
A prepolymer in a state of acetic acid distilled after completion of acetylation was obtained in the same manner as in example 1 except that the monomer feed was changed to 20 mol% of HBA, 20 mol% of HNA, 10 mol% of HQ, 20 mol% of BP, and 78 mol% of TPA 30.
Next, the prepolymer obtained as described above was charged into a glass tube oven made by the field science, and was polymerized to a desired molecular weight by solid-phase polymerization, and as a result, the prepolymer was melted, and no further solid-phase polymerization was carried out. Then, the tank was rotated while naturally releasing heat at room temperature, and a liquid crystal polyester resin E was obtained.
Comparative example 2 wholly aromatic liquid crystalline polyester resin F
A prepolymer in a state of acetic acid distilled after completion of acetylation was obtained in the same manner as in example 1 except that the monomer feed was changed to 30 mol% of HBA, 10 mol% of HNA, 16 mol% of HQ, 14 mol% of BP, and 78 mol% of TPA 30.
Next, the prepolymer obtained as described above was charged into a glass tube oven made by the field science, and was polymerized to a desired molecular weight by solid-phase polymerization, and as a result, the prepolymer was melted, and no further solid-phase polymerization was carried out. Then, the tank was rotated while naturally releasing heat at room temperature, and a liquid crystal polyester resin F was obtained.
Comparative example 3 wholly aromatic liquid crystalline polyester resin G
Acetylation reaction was performed in the same manner as in example 1, except that the monomer feed was changed to 6 mol% of HBA, 10 mol% of HNA, 42 mol% of BP, and 42 mol% of TPA. After the completion of acetylation, the temperature of the polymerization vessel in a state where acetic acid was distilled out was increased to 310 ℃ at 0.5 ℃/min, and as a result, the polymer was easily solidified and could not be taken out from the polymerization vessel.
Comparative example 4 wholly aromatic liquid crystalline polyester resin H
Liquid crystal polyester resin H was obtained in the same manner as in example 1 except that the monomer feed was changed to 60 mol% of HBA, 20 mol% of BP, 15 mol% of TPA, and 5 mol% of isophthalic acid, and liquid crystallinity was confirmed in the same manner as described above.
(extractability)
After the temperature of the polymerization vessel reached a predetermined temperature, the behavior when the polymer was taken out from the polymerization vessel was observed, and the drawing-out property was evaluated according to the following evaluation criteria.
(evaluation criteria)
O: can be easily withdrawn.
X: the resin is difficult to extract and remains in the container.
< determination of melting Point >
The melting points of the liquid-crystalline polyester resins obtained in examples and comparative examples were measured by a Differential Scanning Calorimeter (DSC) manufactured by Seiko electronics industries, Ltd. At this time, the temperature was raised from room temperature to 380 ℃ at a temperature raising rate of 20 ℃ per minute to completely melt the polymer, and then the temperature was lowered to 50 ℃ at a rate of 10 ℃ per minute, and further raised to 420 ℃ at a rate of 20 ℃ per minute, and the peak of the endothermic peak obtained at this time was defined as the melting point. The results are summarized in Table 1.
[ Table 1]
< production of wholly aromatic liquid crystalline polyester resin composition >
663.0g (30 mol%) of p-hydroxybenzoic acid, 301.1g (10 mol%) of 6-hydroxy-2-naphthoic acid, 422.8g (24 mol%) of hydroquinone, 178.8g (6 mol%) of 4, 4-dihydroxybiphenyl, 797.4g (30 mol%) of terephthalic acid, 0.30g of potassium acetate as a catalyst, and 0.30g of magnesium acetate were charged into a polymerization vessel having an internal volume of 6L and made of SUS316 and having a double-helical stirring blade, to obtain a prepolymer under the same conditions as in example 1.
Then, the prepolymer obtained above was charged into a solid phase polymerization apparatus, and the heater temperature was raised from room temperature to 150 ℃ at a rotation speed of 5rpm for 1 hour while passing nitrogen gas, and then, the temperature was raised to 250 ℃ for 10 hours, and the temperature was maintained at 250 ℃ for 2 hours.
Further, the temperature was raised to 270 ℃ over 6 hours, further to 290 ℃ over 6 hours, and held at 290 ℃ for 2 hours. Further, the temperature was raised to 310 ℃ over 6 hours, and the mixture was held at 310 ℃ for 1 hour to carry out solid-phase polymerization. Thus, a wholly aromatic liquid crystalline polyester resin a was obtained.
The wholly aromatic liquid crystalline polyester resin composition A was prepared by mixing 7 parts by weight of a fibrous filler (EFH 150-01, trade name, manufactured by Central glass fiber Co., Ltd.), 36 parts by weight of a plate-like filler (AB-25S, manufactured by mica, manufactured by Kamot corporation) and 1 part by weight of carbon black (REGAL 99I, trade name, manufactured by Kabot corporation) with 100 parts by weight of the wholly aromatic liquid crystalline polyester resin A obtained as described above, and then melt-kneading the mixture by a twin-screw extruder and granulating the resulting melt-kneaded product.
A wholly aromatic liquid crystalline polyester resin composition H was obtained in the same manner as in comparative example 4, except that the wholly aromatic liquid crystalline polyester resin a was changed to the wholly aromatic liquid crystalline polyester resin H.
Filling test (determination of flow Length) >
The pellets of the wholly aromatic liquid crystalline polyester resin composition A thus obtained were subjected to injection molding using an injection molding machine (trade name: LD10EH2, manufactured by Sodick) at a temperature (360 ℃) at which the value of the melt viscosity becomes stable in the measurement (temperature rise) of the apparent melt viscosity, and the mold temperature was set to 80 ℃ and the injection speed was 133 mm/sec.
The mold used in the filling property test was the mold shown in fig. 1, and the filling property of the resin composition was evaluated based on the length of the thin portion formed by flowing the injected resin composition into the thin portion, using a mold having a thin portion 2.0mm in width, 40mm in length, and 0.1mm in thickness.
This test was repeated 20 times, and the average value of the lengths of the thin portions formed was shown in table 2.
The same test was carried out for the wholly aromatic liquid crystalline polyester resin composition H, and the results are shown in table 2.
< mechanical Strength test (measurement of bending Strength) >)
The pellets of the resin composition A thus obtained were subjected to injection molding at a cylinder temperature of 80 ℃ and an injection speed of 100 mm/sec using an injection molding machine (trade name: SG-25, manufactured by Sumitomo heavy machinery industries, Ltd.) to prepare bending test pieces (width: 13mm, length: 130mm, thickness: 3mm) based on ASTM D790, and the bending strength was measured.
Further, using the resin composition H, a test piece was similarly produced, and the bending strength was measured. The results of the measurements are summarized in Table 2.
< foaming resistance test (measurement of foaming temperature) >
(Molding of test piece)
The pellets of resin composition A thus obtained were subjected to injection molding at a cylinder temperature of 80 ℃ and an injection speed of 150 mm/sec using an injection molding machine (trade name: LD10EH2, manufactured by Sodick) to prepare test pieces (width: 10mm, length: 60mm, thickness: 0.4mm) based on JIS K71602.
Further, a test piece was similarly produced using the resin composition H. The test piece thus obtained was left in an air oven maintained at a predetermined temperature for 30 minutes, and the highest temperature at which no foaming or deformation occurred on the surface of the test piece was defined as the foaming resistance temperature. The results of the measurements are summarized in Table 2.
< measurement of Box warpage >
The pellets of the resin composition A thus obtained were subjected to injection molding using an injection molding machine (trade name: LD10EH2, manufactured by Sodick) at an injection speed of 133 mm/sec so that the cylinder temperature became a melting point +10 ℃ and the mold temperature became 100 ℃ to obtain a box-shaped molded article shown in FIGS. 2(a) and (b).
The molded article thus obtained was left in an air oven maintained at 260 ℃ for 10 minutes, and the warpage (warpage amount) of the bottom surface of the heated molded article was measured using One-shot 3D macro (product name: VR-3100, manufactured by KEYENCE CORPORATION). The results of the measurements are summarized in Table 2. The better the shape stability, the smaller the amount of warpage.
[ Table 2]
| TABLE 2 | Flow length (mm) | Flexural Strength (MPa) | Foaming temperature (. degree.C.) | Amount of case warping (mum) |
| Example 1 | 32.0 | 162 | 310 | 34 |
| Comparative example 4 | 24.4 | 161 | 290 | 45 |
Claims (9)
1. A wholly aromatic liquid crystalline polyester resin comprising structural units (I) to (V) represented by the following formulae (I) to (V),
[ solution 1]
[ solution 2]
[ solution 3]
[ solution 4]
[ solution 5]
Characterized in that the composition ratio of the structural units (I) to (V) in the aromatic liquid-crystalline polyester satisfies the following condition, and the unit of the composition ratio is mol%,
15 mol% or more and 35 mol% or less of the structural unit (I)
5 mol% or more and 15 mol% or less of the structural unit (II)
The structural unit (III) accounts for 21 mol% or more and 29 mol% or less
1 mol% or more and 9 mol% or less of the structural unit (IV)
25 mol% or more and 40 mol% or less of structural unit (V)
The total of structural unit (I) + structural unit (II) + structural unit (III) + structural unit (IV) + structural unit (V) is 100 mol%;
the melting point is 320 ℃ or higher.
2. The wholly aromatic liquid crystalline polyester resin according to claim 1, wherein the content of the structural unit (III) is 2 times or more the content of the structural unit (IV).
3. A method for producing the wholly aromatic liquid crystalline polyester resin according to claim 1 or 2, which comprises a step of polymerizing monomers represented by the following formulae (1) to (5),
[ solution 6]
[ solution 7]
[ solution 8]
[ solution 9]
[ solution 10]
4. The method of claim 3, wherein the step of polymerizing the monomer comprises: the monomers represented by the formulae (1) to (5) are melt-polymerized in the presence of 1.05 to 1.15 molar equivalents of acetic anhydride with respect to all hydroxyl groups of the monomers represented by the formulae (1) to (4).
5. A wholly aromatic liquid crystalline polyester resin composition comprising the wholly aromatic liquid crystalline polyester resin according to claim 1 or 2 and an inorganic filler.
6. The wholly aromatic liquid crystalline polyester resin composition according to claim 5, wherein the inorganic filler is a fibrous filler or a plate-like filler.
7. The wholly aromatic liquid crystalline polyester resin composition according to claim 6, wherein the total content of the fibrous filler and the plate-like filler is 100 parts by weight or less based on 100 parts by weight of the wholly aromatic liquid crystalline polyester resin contained in the wholly aromatic liquid crystalline polyester resin composition.
8. A molded article comprising the wholly aromatic liquid crystalline polyester resin composition according to any one of claims 5 to 7.
9. An electronic device comprising the wholly aromatic liquid crystalline polyester resin composition according to any one of claims 5 to 7.
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| PCT/JP2017/003746 WO2017135365A1 (en) | 2016-02-04 | 2017-02-02 | Wholly aromatic liquid crystal polyester resin and production method therefor |
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| KR20200060585A (en) | 2018-11-21 | 2020-06-01 | 삼성전자주식회사 | Liquid crystal polymer, composite composition, article, battery case, and battery |
| JP7194586B2 (en) * | 2018-12-27 | 2022-12-22 | Ｅｎｅｏｓ株式会社 | A resin molded article made of a liquid crystal polymer and a resin composition containing the liquid crystal polymer |
| JP6675028B1 (en) | 2019-05-17 | 2020-04-01 | 住友化学株式会社 | Pellet of liquid crystal polyester resin composition and method for producing pellet of liquid crystal polyester resin composition |
| JP6745008B1 (en) | 2019-05-17 | 2020-08-19 | 住友化学株式会社 | Liquid crystal polyester resin composition pellets |
| JP7284033B2 (en) | 2019-08-07 | 2023-05-30 | 上野製薬株式会社 | liquid crystal polyester resin |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| WO2022210967A1 (en) * | 2021-03-30 | 2022-10-06 | ポリプラスチックス株式会社 | Wholly aromatic polyester and polyester resin composition |
| JP7533792B2 (en) | 2022-04-11 | 2024-08-14 | 東レ株式会社 | Liquid crystal polyester resin, liquid crystal polyester resin composition and molded article made of the same |
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| JPS63210125A (en) * | 1987-02-26 | 1988-08-31 | Nippon Ester Co Ltd | Production of aromatic polyester |
| US5025082A (en) * | 1988-08-24 | 1991-06-18 | Mitsubishi Kasei Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
| JP3487656B2 (en) * | 1994-11-21 | 2004-01-19 | ポリプラスチックス株式会社 | Electronic components for surface mounting |
| US5688895A (en) * | 1996-06-24 | 1997-11-18 | E. I. Du Pont De Nemours And Company | Liquid crystalline poly(ester-amides) |
| US6129878A (en) * | 1998-09-10 | 2000-10-10 | Celanese Acetate Llc | Process for direct on-bobbin heat treating of high denier filaments of thermotropic liquid crystalline polymers |
| US6207790B1 (en) * | 2000-01-14 | 2001-03-27 | Ticona Llc | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability and polymers produced by same |
| JP4243963B2 (en) * | 2003-03-04 | 2009-03-25 | 新日本石油株式会社 | Method for producing thermotropic liquid crystal polymer |
| JP4702501B2 (en) * | 2008-07-30 | 2011-06-15 | Ｄｉｃ株式会社 | Liquid crystal polymer and method for producing the same |
| JP2010242246A (en) * | 2009-04-03 | 2010-10-28 | Toray Ind Inc | Method for producing liquid crystal polyester fiber |
| JP5616212B2 (en) * | 2010-12-16 | 2014-10-29 | 上野製薬株式会社 | Totally aromatic liquid crystal polyester resin and composition containing the same |
| JP5730704B2 (en) * | 2011-07-27 | 2015-06-10 | 上野製薬株式会社 | Liquid crystal polymer composition |
| JP6177191B2 (en) * | 2014-05-30 | 2017-08-09 | 上野製薬株式会社 | Liquid crystal polyester blend |
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