CN108602943A - All aromatic liquid crystal polyester resin and its manufacturing method - Google Patents
All aromatic liquid crystal polyester resin and its manufacturing method Download PDFInfo
- Publication number
- CN108602943A CN108602943A CN201780006453.7A CN201780006453A CN108602943A CN 108602943 A CN108602943 A CN 108602943A CN 201780006453 A CN201780006453 A CN 201780006453A CN 108602943 A CN108602943 A CN 108602943A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal polyester
- polyester resin
- structural unit
- aromatic liquid
- 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.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 117
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 100
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 99
- 239000004645 polyester resin Substances 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 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 11
- 239000000945 filler Substances 0.000 claims description 7
- 239000012765 fibrous filler Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 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
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000021736 acetylation Effects 0.000 description 4
- 238000006640 acetylation reaction Methods 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000001125 extrusion 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
- 239000000463 material Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- -1 lead acetate Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 239000004425 Makrolon Substances 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003855 acyl compounds Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000000071 blow moulding Methods 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
- 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
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development 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
- 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 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
- 230000000379 polymerizing effect Effects 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
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 238000012545 processing 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 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
- 235000012222 talc Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Landscapes
- 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 present invention provides all aromatic liquid crystal polyester resin with high mechanical properties, excellent fillibility, resistance to foaming and low warpage properties.All aromatic liquid crystal polyester resin of the present invention is all aromatic liquid crystal polyester resin containing structural unit (I)~(V) indicated by formula (I)~(V), it is characterized in that, the ratio of components (mole %) of structural unit (I)~(V) in above-mentioned aromatic liquid-crystal polyester is：15 moles of %≤structural unit (I)≤35 mole %, 5 moles of %≤structural unit (II)≤15 mole %, 21 moles of %≤structural unit (III)≤29 mole %, 1 mole of %≤structural unit (IV)≤9 mole %, 25 moles of %≤structural unit (V)≤40 mole %, structural unit (I)~(V's) adds up to=100 moles of %, fusing point to be 320 DEG C or more.
Description
Technical field
The present invention relates to all aromatic liquid crystal polyester resin and its manufacturing methods.In turn, the present invention relates to include the full virtue
The all aromatic liquid crystal polyester resin composition of fragrant race's liquid-crystal polyester resin, molded product and electronic device comprising the composition.
Background technology
All aromatic liquid crystal polyester resin since mouldability, heat resistance and fillibility are excellent, using its manufacture at
Type product (such as injection-molded article) have been used for various electronic devices.
In recent years, due to the miniaturization of PC, smart phone etc., electronic device it is highly integrated, be thinning, be slim
Change development, the upswing in demand of the molded product with very thin wall thickness.Therefore, for all aromatic liquid crystal polyester resin requirement
With superior fillibility.
As fillibility, the i.e. method of mobility for improving the liquid crystal polymers such as all aromatic liquid crystal polyester resin, such as
Implement the molecular weight for reducing liquid crystal polymer, the method for making its lowering viscousity.
But other than reducing the reduction of the physical property such as mechanical strength of the molecular weight of liquid crystal polymer in addition to molded product can be caused,
There is also following problems：The reflow process carried out when molded product is applied to the electronic devices such as connector leads to molded product table
Bulging (blistering), warpage occur for face.Herein, all aromatic liquid for the generation that can inhibit blistering is proposed in patent document 1
Brilliant polyester resin.Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-126842 bulletins
Invention content
The present inventor this time obtains following opinion：By making structure contained in all aromatic liquid crystal polyester resin
Unit becomes specific structural unit, ratio of components, and the fusing point of all aromatic liquid crystal polyester resin is made to become 320 DEG C or more,
It can solve the above problems.The present invention is completed according to the opinion.
Therefore, the purpose of the present invention is to provide maintain the physical property such as mechanical strength and with excellent fillibility and resistance to
The all aromatic liquid crystal polyester resin of foaming characteristic and low warpage properties.
All aromatic liquid crystal polyester resin of the present invention is containing the structural unit indicated by following formula (I)s~(V)
(I) all aromatic liquid crystal polyester resin of~(V),
[changing 1]
[changing 2]
[changing 3]
[changing 4]
[changing 5]
It is characterized in that, the ratio of components (mole %) of structural unit (I)~(V) in aromatic liquid-crystal polyester meet it is following
Condition：
15 moles of %≤structural unit (I)≤35 mole %
5 moles of %≤structural unit (II)≤15 mole %
21 moles of %≤structural unit (III)≤29 mole %
1 mole of %≤structural unit (IV)≤9 mole %
25 moles of %≤structural unit (V)≤40 mole %
Structural unit (I)+structural unit (II)+structural unit (III)+structural unit (IV)+structural unit (V)=100
Mole %,
Fusing point is 320 DEG C or more.
In said program, the content of preferred structure unit (III) is the 2 times or more of the content of structural unit (IV).
The manufacturing method of above-mentioned all aromatic liquid crystal polyester resin of the present invention is characterized in that, including will be by following
The process for the monomer polymerization that formula (1)~(5) indicate.
[changing 6]
[changing 7]
[changing 8]
[changing 9]
[changing 10]
In said program, the polymerization process of preferred monomers includes：Relative to the monomer indicated by above-mentioned formula (1)~(4)
For the whole hydroxyls having for 1.05~1.15 molar equivalents acetic anhydride in the presence of, will be indicated by above-mentioned formula (1)~(5)
Molten monomer polymerization.
All aromatic liquid crystal polyester resin composition of the present invention is characterized in that, including above-mentioned Wholly aromatic liquid crystal
Polyester resin and inorganic filler.
In said program, preferably inorganic filler is fibrous filler and plate filler.
In said program, preferably：Relative to Wholly aromatic liquid crystal contained in all aromatic liquid crystal polyester resin composition
The content of 100 parts by weight of polyester resin, fibrous filler and plate filler is total 100 parts by weight or less.
Molded product of the present invention is characterized in that, contains above-mentioned all aromatic liquid crystal polyester resin composition.
Electronic device of the present invention is characterized in that, contains above-mentioned all aromatic liquid crystal polyester resin composition.
According to the present invention, have very due to that with high mechanical strength, fillibility and resistance to foaming, can manufacture
The molded product of thin wall thickness, can realize electronic device it is highly integrated, be thinning, be thinned.In addition, according to the present invention,
It can prevent the generation of warpage.
Description of the drawings
Fig. 1 is the vertical view and side view of the mold used during the fillibility of embodiment is tested.
The upward view for the box-shaped molded product that Fig. 2 (a) makes in the measurement for the case warpage of embodiment.
The front view for the box-shaped molded product that Fig. 2 (b) makes in the measurement for the case warpage of embodiment.
Specific implementation mode
(all aromatic liquid crystal polyester resin)
All aromatic liquid crystal polyester resin according to the present invention contains the structural unit (I) indicated by following formula (I)s~(V)
The ratio of components (mole %) of~(V), structural unit (I)~(V) in aromatic liquid-crystal polyester meet following conditions.Using this
The all aromatic liquid crystal polyester resin of sample, can be for using the molded product that the resin makes to assign high mechanical strength, filling
Property and resistance to foaming and low warpage properties.
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
15 moles of %≤structural unit (I)≤35 mole %
5 moles of %≤structural unit (II)≤15 mole %
21 moles of %≤structural unit (III)≤29 mole %
1 mole of %≤structural unit (IV)≤9 mole %
25 moles of %≤structural unit (V)≤40 mole %
Structural unit (I)+structural unit (II)+structural unit (III)+structural unit (IV)+structural unit (V)=100
Mole %.
With regard to the match ratio (mole %) of structural unit (III) and structural unit (IV) in all aromatic liquid crystal polyester resin
For, the content of preferred structure unit (III) is the 2 times or more of the content of structural unit (IV), more preferably 4 times or more.It is logical
Crossing makes structural unit (III) and the match ratio (mole %) of structural unit (IV) become above-mentioned numberical range, can improve full virtue
The fusing point of fragrant race's liquid-crystal polyester resin.
In addition, the fusing point of all aromatic liquid crystal polyester resin according to the present invention is 320 DEG C or more.
Since all aromatic liquid crystal polyester resin of the present invention has high-melting-point, disclosure satisfy that as electronics device
Heat resistance required by part.
Fusing point is based on ISO11357-3, ASTMD3418, such as the difference that can be manufactured by using Seiko electronics industry (strain)
Show scanning calorimeter (DSC) and measures.
It should be noted that keeping all aromatic liquid crystal polyester resin complete from room temperature to 380 DEG C with 20 DEG C/minute of heating rate
After melting entirely, cools to 50 DEG C for 10 DEG C/minute with speed, and then 420 DEG C are warming up to 20 DEG C/minute of speed, will obtain at this time
The vertex of endothermic peak be set as fusing point.
It is illustrated below for each structural unit contained in all aromatic liquid crystal polyester resin.
(structural unit (I))
All aromatic liquid crystal polyester resin contains above-mentioned structural unit (I), the structural unit in aromatic liquid-crystal polyester
(I) ratio of components (mole %) is 15 moles of %~35 mole %.More preferably 20 moles of %~35 mole %, further preferably
For 25 moles of %~35 mole %.
As the monomer for providing structural unit (I), can enumerate：P-hydroxybenzoic acid (HBA, following formula (1)), its acylation
Object, ester derivant, etheride etc..
[changing 16]
(structural unit (II))
All aromatic liquid crystal polyester resin contains above-mentioned structural unit (II), the structural unit in aromatic liquid-crystal polyester
(II) ratio of components (mole %) is 5 moles of %~15 mole %.More preferably 8 moles of %~15 mole %, further preferably
For 8 moles of %~10 mole %.
As the monomer for providing structural unit (II), can enumerate：6-Hydroxy-2-naphthoic acid (HNA, following formula (2)), its
Acylate, ester derivant, etheride etc..
[changing 17]
(structural unit (III))
All aromatic liquid crystal polyester resin contains above-mentioned structural unit (III), the structure list in aromatic liquid-crystal polyester
The ratio of components (mole %) of first (III) is 21 moles of %~29 mole %.More preferably 21 moles of %~28 mole %, further
Preferably 22 moles of %~26 mole %.
As the monomer for providing structural unit (III), can enumerate：Quinhydrones (HQ, following formula (3)), its acylate etc..
[changing 18]
(structural unit (IV))
All aromatic liquid crystal polyester resin contains above-mentioned structural unit (IV), the structural unit in aromatic liquid-crystal polyester
(IV) ratio of components (mole %) is 1 mole of %~9 mole %.More preferably 1.5 moles of %~9 mole %, further preferably
For 1.5 moles of %~7 mole %.
As the monomer for providing structural unit (IV), can enumerate：4,4- dihydroxybiphenyls (BP, following formula (4)), its acyl
Compound etc..
[changing 19]
(structural unit (V))
All aromatic liquid crystal polyester resin contains above-mentioned structural unit (V), the structural unit in aromatic liquid-crystal polyester
(V) ratio of components (mole %) is 25 moles of %~40 mole %.More preferably 25 moles of %~35 mole %, further preferably
For 27.5 moles of %~32.5 mole %.
As the monomer for providing structural unit (V), can enumerate：Terephthalic acid (TPA) (TPA, following formula (5)), its ester derive
Object, etheride etc..
[changing 20]
(manufacturing method of all aromatic liquid crystal polyester resin)
All aromatic liquid crystal polyester resin of the present invention can will be by above-mentioned formula by using known method
(1)~(5) indicate monomer polymerization and manufacture.
For example, all aromatic liquid crystal polyester resin of the present invention can be manufactured only with melt polymerization.In addition, also can
It is enough to make prepolymer by using melt polymerization, solid phase further is carried out to it and is manufactured.
It, preferably will be by above-mentioned formula from the viewpoint of efficiently obtaining Wholly aromatic polyester compound of the present invention
(1)~(5) indicate monomer with it is defined cooperation come a group merging become 100 moles of %, relative to by above-mentioned formula (1)~
(4) whole hydroxyls that the monomer indicated has, there are the acetic anhydride of 1.05~1.15 molar equivalents, are melted under acetic acid reflux
Melt polymerization.
By melt polymerization and subsequent solid phase this two benches progress polymerisation, melting will be used
It polymerize obtained prepolymer to crush after cooling and solidifying, after powdered or flake is made, preferably selects well known solid phase
Method, for example, under the inert atmospheres such as nitrogen or under vacuum 200~350 DEG C temperature range to prepolymer resin carry out 1~
The methods of heat treatment in 30 hours.Solid phase can carry out while stirring, in addition, also can not be stirred and in the state of standing
Lower progress.
Catalyst can be used in polymerisation, in addition, can also not use catalyst.As the catalyst used, can make
Be used as the known catalyst of catalyst for polymerization of polyester, can enumerate magnesium acetate, stannous acetate, butyl titanate,
It is nitrogen-containing heterocycle compounds such as the metal salt catalysts such as lead acetate, sodium acetate, potassium acetate, antimony trioxide, N- methylimidazoles etc., organic
Compound catalyst etc..The usage amount of catalyst is not particularly limited, relative to 100 parts by weight of total amount of monomer, preferably
0.0001~0.1 parts by weight.
Polymerizing reactor in melt polymerization is not particularly limited, it is preferable to use in the anti-of common high viscosity fluid
The reaction unit used in answering.As the example of these reaction units, such as can enumerate：With with anchor type, multistep, spiral shell
The stirring groove profile polymerization of the agitating device of variously-shaped stirring blade obtained by revolving banding pattern, spiral spindle-type etc. or deforming them
The mixing arrangement usually used in the mixing of resin such as reaction unit or kneader, roller mill, banbury mixers
Deng.
(all aromatic liquid crystal polyester resin composition)
All aromatic liquid crystal polyester resin composition according to the present invention contain above-mentioned all aromatic liquid crystal polyester resin and
Inorganic filler.
The content of all aromatic liquid crystal polyester resin in all aromatic liquid crystal polyester resin composition is preferably 50 weights
Measure % or more, more preferably 60~90 weight %.
In addition, as inorganic filler contained in all aromatic liquid crystal polyester resin composition, such as fibre can be used
Shape, plate, powdered inorganic filler are tieed up, they can be applied in combination.Wherein preferably fibrous filler and plate are filled out
Agent is filled to be applied in combination.
As inorganic filler, such as can enumerate：Glass fibre, milled glass fiber, silica alumina fiber,
Alumina fibre, carbon fiber, aramid fibre, potassium titanate crystal whisker, aluminium borate whisker, wollastonite, talcum, mica, graphite,
Calcium carbonate, dolomite, clay, glass flake, bead, barium sulfate and titanium oxide etc., all aromatic liquid crystal polyester resin combination
Object is containing one kind or two or more in these inorganic fillers.
Relative to 100 weight of all aromatic liquid crystal polyester resin contained in all aromatic liquid crystal polyester resin composition
Part, the content of the inorganic filler in all aromatic liquid crystal polyester resin composition is preferably 100 parts by weight hereinafter, more preferably
10~65 parts by weight.By making the content of inorganic filler be that can not influence fillibility when molding in above-mentioned numberical range
The generation of warpage when ground prevents molded product from manufacturing.
All aromatic liquid crystal polyester resin composition according to the present invention can be in the range for the effect for not damaging the present invention
The interior resin containing other than all aromatic liquid crystal polyester resin.Such as it can enumerate：Polyethylene terephthalate, poly- naphthalene two
Formic acid glycol ester, makrolon, polyarylate, polyamide, polyimides, polyether sulfone, polyether-ether-ketone, polyphenylene sulfide, polytetrafluoro
Ethylene etc., all aromatic liquid crystal polyester resin composition is containing one kind or two or more in these resins.
All aromatic liquid crystal polyester resin composition according to the present invention can be in the range for the effect for not damaging the present invention
It is interior to be inhaled comprising other additives, such as colorant, dispersant, plasticizer, antioxidant, fire retardant, heat stabilizer, ultraviolet light
Receive agent, antistatic agent, surfactant.
(manufacturing method of all aromatic liquid crystal polyester resin composition)
By coordinating filler etc. in all aromatic liquid crystal polyester resin, obtained complex is mixed using Banbury
Machine, kneader, single screw rod or double screw extruder etc. carry out melting mixing, can obtain all aromatic liquid crystal polyester resin combination
Object.
(molded product)
Molded product according to the present invention contains all aromatic liquid crystal polyester resin composition, can by the composition into
Row injection molding, extrusion molding and obtain.In addition, using same method, can obtain by all aromatic liquid crystal polyester resin
Film, sheet material and non-woven fabrics made of composition.
As specific film build method, can enumerate：Blow molding, melting extrusion molding, solution moulding by casting etc..In this way
Obtained film can be the monofilm made of Wholly aromatic polyester resin combination, can also be the multilayer with dissimilar material
Film.
It should be noted that in order to improve dimensional stability, mechanical property, it can be to through melting extrusion molding, solution moulding by casting
Obtained by film carry out uniaxial or biaxial stretching processing.In addition, in order to remove the anisotropy of these films, it is thermally processable.
(electronic device)
Electronic device according to the present invention contains above-mentioned all aromatic liquid crystal polyester resin composition.As electronic device,
Such as it can enumerate：High Speed Transfer connector, circuit board, flexible circuit board, stacking circuit board, is prevented CPU sockets
The collision insulating materials of secondary cells such as radar, RFID tag, capacitor, inverter device, insulating film, lithium ion battery,
Loudspeaker oscillating plate etc..Specifically, these electronic devices have and are molded made of all aromatic liquid crystal polyester resin composition
Product (such as injection-molded article), film etc..
Embodiment
The present invention is further illustrated with embodiment below, but the present invention is not limited to embodiments.
The manufacture ＞ of ＜ all aromatic liquid crystal polyester resins
(embodiment 1：All aromatic liquid crystal polyester resin A)
In the aggregation container with stirring blade, P-hydroxybenzoic acid (HBA) 24.9g (30 moles of %), 6- hydroxyls is added
Base -2- naphthoic acids (HNA) 11.3g (10 moles of %), quinhydrones (HQ) 15.9g (24 moles of %), 4,4- dihydroxybiphenyls (BP)
6.7g (6 moles of %), terephthalic acid (TPA) (TPA) 29.9g (30 moles of %), are loaded as the potassium acetate and magnesium acetate of catalyst,
Decompression-nitrogen the injection for carrying out 3 aggregation containers, after having carried out nitrogen displacement, further add acetic anhydride 66.2g (relative to hydroxyl,
For 1.08 molar equivalents), 150 DEG C are warming up to, has carried out 2 hours acetylization reactions at reflux.
After acetylation, it will be heated up in the aggregation container for the state for having distillated acetic acid with 0.5 DEG C/minute, in slot
Melt temperature extracts polymer out when becoming 310 DEG C, cooling and solidifying.Obtained polymer is crushed, is crushed to pass through net
The size of the sieve of eye size 1.0mm, has obtained prepolymer.
Next, prepolymer obtained above is filled in Chai Tian sections length of schooling glass tube baking oven, lasted when making it rotate
Make within 12 hours heter temperature from room temperature to after 290 DEG C, temperature is kept for 1 hour at 290 DEG C, has carried out solid polycondensation
It closes.Then the natural heat release at room temperature when making slot rotate, has obtained all aromatic liquid crystal polyester resin A.Using with
The petrographic microscope BH-2 that the microscope of METTLER is manufactured with the Olympus (strain) of thermal station FP82HT, makes polyester sample exist
Melting is heated on microscope warm table, confirms liquid crystal liquid crystal property according to whether there is or not optical anisotropies.
(embodiment 2：All aromatic liquid crystal polyester resin B)
Monomer feed is become into 30 moles of HBA 15 moles of %, HNA 26 moles of %, HQ 1.5 moles of %, BP %, TPA
27.5 moles of % obtain liquid-crystal polyester resin B, confirmed liquid crystal as described above similarly to Example 1 in addition to this
Property.
(embodiment 3：All aromatic liquid crystal polyester resin C)
Monomer feed is become into 30 moles of HBA 10 moles of %, HNA 21 moles of %, HQ 9 moles of %, BP %, TPA 30
Mole % obtains liquid-crystal polyester resin C, confirmed liquid crystal liquid crystal property as described above similarly to Example 1 in addition to this.
(embodiment 4：All aromatic liquid crystal polyester resin D)
Monomer feed is become into 30 moles of HBA 10 moles of %, HNA 25 moles of %, HQ 5 moles of %, BP %, TPA 30
Mole % obtains liquid-crystal polyester resin D, confirmed liquid crystal liquid crystal property as described above similarly to Example 1 in addition to this.
(comparative example 1：All aromatic liquid crystal polyester resin E)
Monomer feed is become into 20 moles of HBA 20 moles of %, HNA 10 moles of %, HQ 20 moles of %, BP %, TPA
30 moles of % similarly to Example 1, after acetylation, are obtained in the pre- of the state for having distillated acetic acid in addition to this
Polymers.
Next, prepolymer obtained above is filled in Chai Tian sections length of schooling glass tube baking oven, it is desirable to use solid phase
It is set to be aggregated to desired molecular weight, as a result prepolymer melts, and fails further to implement solid phase.Then, while slot is made to revolve
Turn side natural heat release at room temperature, obtains liquid-crystal polyester resin E.
(comparative example 2：All aromatic liquid crystal polyester resin F)
Monomer feed is become into 30 moles of HBA 10 moles of %, HNA 16 moles of %, HQ 14 moles of %, BP %, TPA
30 moles of % similarly to Example 1, after acetylation, are obtained in the pre- of the state for having distillated acetic acid in addition to this
Polymers.
Next, prepolymer obtained above is filled in Chai Tian sections length of schooling glass tube baking oven, it is desirable to use solid phase
It is set to be aggregated to desired molecular weight, as a result prepolymer melts, and fails further to implement solid phase.Then, while slot is made to revolve
Turn side natural heat release at room temperature, obtains liquid-crystal polyester resin F.
(comparative example 3：All aromatic liquid crystal polyester resin G)
Monomer feed is become into 6 moles of HBA 10 moles of %, HNA 42 moles of %, BP 42 moles of %, TPA %, removes this
In addition, acetylization reaction has been carried out similarly to Example 1.After acetylation, it will be in 0.5 DEG C/minute and distillate vinegar
The aggregation container of the state of acid is warming up to 310 DEG C, and as a result polymer is easy solidification, fails to extract out from aggregation container.
(comparative example 4：All aromatic liquid crystal polyester resin H)
Monomer feed is become into 15 moles of % of 60 moles of HBA 20 moles of %, BP %, TPA, M-phthalic acid 5 rubs
Your % obtains liquid-crystal polyester resin H, confirmed liquid crystal liquid crystal property as described above similarly to Example 1 in addition to this.
＜ ＜ extractable ＞ ＞
After the temperature of aggregation container has reached defined temperature, row when observation extracts polymer out from aggregation container
To be evaluated extractable according to evaluation criteria below.
(evaluation criteria)
○：It can be easily extracted out.
×：Extraction is difficult, and resin is remaining in container.
The measurement ＞ ＞ of ＜ ＜ fusing points
The differential scanning calorimetry (DSC) (DSC) manufactured using Seiko electronics industry (strain) is determined in embodiment and comparative example and is obtained
The fusing point of the liquid-crystal polyester resin arrived.At this point, with 20 DEG C/minute of heating rate from room temperature to 380 DEG C, keep polymer completely molten
After melting, 50 DEG C are cooled to for 10 DEG C/minute with speed, and then 420 DEG C are warming up to 20 DEG C/minute of speed, the heat absorption that will be obtained at this time
The vertex at peak is as fusing point.Measurement result is summarized in table 1.
[table 1]
The manufacture ＞ of ＜ all aromatic liquid crystal polyester resin compositions
By P-hydroxybenzoic acid 663.0g (30 moles of %), 6- in a manner of as monomer composition same as Example 1
Hydroxy-2-naphthoic acid 301.1g (10 moles of %), quinhydrones 422.8g (24 moles of %), (6 rub 4,4- dihydroxybiphenyls 178.8g
Your %), terephthalic acid (TPA) 797.4g (30 moles of %), the potassium acetate 0.30g as catalyst and magnesium acetate 0.30g be packed into
SUS316 is obtained under the condition that is similarly to Example 1 for material, in the polymerization tank of the internal volume 6L with double helix stirring blade
Prepolymer is arrived.
Next, prepolymer obtained above is filled in solid phase device, when making nitrogen circulate with rotary speed
5rpm lasts 1 hour by heter temperature from room temperature to after 150 DEG C, lasts 10 hours and is warming up to 250 DEG C, at 250 DEG C
It maintains 2 hours.
In turn, it lasts 6 hours and is warming up to 270 DEG C, and then last 6 hours and be warming up to 290 DEG C, it is small to maintain 2 at 290 DEG C
When.In turn, it lasts 6 hours and is warming up to 310 DEG C, kept for 1 hour at 310 DEG C, carried out solid phase.This results in full virtues
Fragrant race's liquid-crystal polyester resin A.
Relative to above-mentioned 100 parts by weight of all aromatic liquid crystal polyester resin A obtained in this way, coordinate fibrous filler
(manufacture of central Glass fiber Co., Ltd., trade name：EFH150-01) 7 parts by weight, plate filler (mica, mountain pass mica strain
The manufacture of formula commercial firm, trade name：AB-25S) 36 parts by weight, carbon black (Cabot Co., Ltd's manufacture, trade name：REGAL99I) 1 weight
Part, with double screw extruder melting mixing, obtained melting mixing object is granulated, all aromatic liquid crystal polyester resin group has been obtained
Close object A.
In addition, in addition to the Wholly aromatic liquid crystal polyester for becoming obtaining using comparative example 4 by all aromatic liquid crystal polyester resin A
Other than resin H, all aromatic liquid crystal polyester resin composition H has been got similarly.
＜ ＜ fillibilities test (measurement of length of flow) ＞ ＞
For the pellet of obtained all aromatic liquid crystal polyester resin composition A, injection moulding machine (Sodick systems are used
It makes, trade name：LD10EH2), the value that barrel temperatures set is melt viscosity when apparent melt viscosity measures (heating) is started surely
Fixed temperature (360 DEG C) is made mold temperature become 80 DEG C, is injected into mold within 133mm/ seconds with injection speed.
The mold used in fillibility experiment is mold as shown in Figure 1, using with wide 2.0mm, long 40mm, thickness
The mold of the thinner wall section of 0.1mm flows into the length of thinner wall section and the thinner wall section of formation to tree according to the resin combination injected
The fillibility of oil/fat composition is evaluated.
The experiment is repeated 20 times, the average value of the length of the thinner wall section of formation is recorded in table 2.
All aromatic liquid crystal polyester resin composition H is also subjected to the same test, is recorded its result in table 2.
＜ ＜ mechanical robustness testings (measurement of bending strength) ＞ ＞
For the pellet of the above-mentioned resin combination A obtained in this way, injection moulding machine (Sumitomo hoisting machinery industry (strain) is used
Manufacture, trade name：SG-25), under above-mentioned barrel temperature, mold temperature is made to become 80 DEG C, is carried out within 100mm/ seconds with injection speed
Injection molding makes the bend test piece (wide 13mm, long 130mm, thickness 3mm) on the basis of ASTM D790, and it is strong to determine bending
Degree.
In addition, using resin combination H, test film is similarly made, determines bending strength.Measurement result is summarized in
In table 2.
<<Resistance to foaming tests (measurement of resistant blister temperature)>>
(molding of test film)
For the pellet of the above-mentioned resin combination A obtained in this way, injection moulding machine (Sodick manufactures, trade name are used：
LD10EH2), under above-mentioned barrel temperature, mold temperature is made to become 80 DEG C, injection molding is carried out in 150mm/ seconds with injection speed,
Make the test film (wide 10mm, long 60mm, thickness 0.4mm) on the basis of JIS K71602 shapes.
In addition, using resin combination H, test film is similarly made.The above-mentioned test film obtained in this way is being held in
Placed 30 minutes in the air -oven of set point of temperature, using test film surface do not occur blister and deform maximum temperature as
Resistant blister temperature.Measurement result is summarized in table 2.
<<The measurement of case amount of warpage>>
For the pellet of the above-mentioned resin combination A obtained in this way, injection moulding machine (Sodick manufactures, trade name are used：
LD10EH2), so that barrel temperature is become+10 DEG C of fusing point, so that mold temperature is become 100 DEG C, noted within 133mm/ seconds with injection speed
It is moulded into type, has obtained box molded product shown in Fig. 2 (a) and (b).
The above-mentioned molded product obtained in this way is placed 10 minutes in the air -oven for being held in 260 DEG C, uses One-
Shot 3D Macroscope (KEYENCE CORPORATION manufactures, trade name：VR-3100 the molded product after heating) is measured
Bottom surface warpage (amount of warpage).Measurement result is summarized in table 2.It should be noted that shape stability is better, amount of warpage is got over
It is small.
[table 2]
| Table 2 | Length of flow (mm) | Bending strength (MPa) | Resistant blister temperature (DEG C) | Case amount of warpage (μm) |
| Embodiment 1 | 32.0 | 162 | 310 | 34 |
| Comparative example 4 | 24.4 | 161 | 290 | 45 |
Claims (9)
1. a kind of all aromatic liquid crystal polyester resin is containing structural unit (I)~(V) indicated by following formula (I)s~(V)
All aromatic liquid crystal polyester resin,
[changing 1]
[changing 2]
[changing 3]
[changing 4]
[changing 5]
It is characterized in that, the ratio of components of structural unit (I)~(V) in the aromatic liquid-crystal polyester meets following conditions,
The unit of the ratio of components is mole %,
15 moles of %≤structural unit (I)≤35 mole %
5 moles of %≤structural unit (II)≤15 mole %
21 moles of %≤structural unit (III)≤29 mole %
1 mole of %≤structural unit (IV)≤9 mole %
25 moles of %≤structural unit (V)≤40 mole %
Structural unit (I)+structural unit (II)+structural unit (III)+structural unit (IV)+structural unit (V)=100 rubs
You are %；
Fusing point is 320 DEG C or more.
2. all aromatic liquid crystal polyester resin according to claim 1, wherein the content of structural unit (III) is structure
The 2 times or more of the content of unit (IV).
3. a kind of method is the manufacturing method of all aromatic liquid crystal polyester resin as claimed in claim 1 or 2, it includes will be by
The process for the monomer polymerization that following formula (1)~(5) indicate,
[changing 6]
[changing 7]
[changing 8]
[changing 9]
[changing 10]
4. according to the method described in claim 3, wherein, the polymerization process of the monomer includes：Relative to by the formula (1)
For whole hydroxyls for having of monomer that~(4) indicate for the acetic anhydride of 1.05~1.15 molar equivalents in the presence of, will be by institute
State the molten monomer polymerization of formula (1)~(5) expression.
5. a kind of all aromatic liquid crystal polyester resin composition, including Wholly aromatic liquid crystal polyester tree as claimed in claim 1 or 2
Fat and inorganic filler.
6. all aromatic liquid crystal polyester resin composition according to claim 5, wherein the inorganic filler is fiber
Shape filler and plate filler.
7. all aromatic liquid crystal polyester resin composition according to claim 5 or 6, wherein relative to the full fragrance
100 parts by weight of all aromatic liquid crystal polyester resin contained in race's liquid crystal polyester resin compositions, the fibrous filler and
The content of the plate filler adds up to 100 parts by weight or less.
8. a kind of molded product contains all aromatic liquid crystal polyester resin composition described in claim 5~7.
9. a kind of electronic device contains all aromatic liquid crystal polyester resin composition described in claim 5~7.
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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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| US11505647B2 (en) * | 2018-06-26 | 2022-11-22 | Eneos Corporation | Resin molded article comprising wholly aromatic liquid crystalline polyester resin capable of reducing dielectric loss tangent by heat treatment and electrical and electronic component |
| KR20200060585A (en) | 2018-11-21 | 2020-06-01 | 삼성전자주식회사 | Liquid crystal polymer, composite composition, article, battery case, and battery |
| 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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| JP6626358B2 (en) | 2019-12-25 |
| JP2017137438A (en) | 2017-08-10 |
| TWI732820B (en) | 2021-07-11 |
| TW201739786A (en) | 2017-11-16 |
| WO2017135365A1 (en) | 2017-08-10 |
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