WO2020070904A1 - Résine de polyester à cristaux liquides - Google Patents

Résine de polyester à cristaux liquides

Info

Publication number
WO2020070904A1
WO2020070904A1 PCT/JP2018/048153 JP2018048153W WO2020070904A1 WO 2020070904 A1 WO2020070904 A1 WO 2020070904A1 JP 2018048153 W JP2018048153 W JP 2018048153W WO 2020070904 A1 WO2020070904 A1 WO 2020070904A1
Authority
WO
WIPO (PCT)
Prior art keywords
liquid crystal
polyester resin
crystal polyester
formula
mol
Prior art date
Application number
PCT/JP2018/048153
Other languages
English (en)
Japanese (ja)
Inventor
大輔 齋尾
山下　哲也
久成 藤原
Original Assignee
上野製薬株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 上野製薬株式会社 filed Critical 上野製薬株式会社
Priority to JP2018568460A priority Critical patent/JP6533881B1/ja
Publication of WO2020070904A1 publication Critical patent/WO2020070904A1/fr

Links

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
    • 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

Definitions

  • Thermotropic liquid crystal polyester resin (hereinafter also referred to as liquid crystal polyester resin or LCP) is excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., so that it is not only used for molded articles but also for fibers and films. Its use is expanding for various uses.
  • blisters are caused by air present in the mold or hopper, decomposed gas contained in the resin, air or moisture.
  • the filler such as talc contains a trace amount of water
  • the occurrence of warpage of the molded product is suppressed, but the generation of blisters is suppressed. Has a problem that it tends to increase more.
  • Patent Documents 3 to 10 a method of blending a silicone rubber, a phosphorus compound, a boron compound, or the like as an additive
  • Patent Document 11 a method of adjusting a screw compression ratio during injection molding
  • Patent Document 12 a method of adjusting the screw engagement ratio when melt-kneading a material and an inorganic filler
  • JP 2017-179127 A Japanese Patent No. 6411706 Japanese Patent Application Laid-Open No. 02-075653 JP 06-032880 A JP-A-10-036641 JP-A-10-158482 JP-A-11-140283 JP-A-11-197761 JP-A-2003-096279 JP 2004-196886 A JP-A-11-048278 JP-A-2003-212443
  • the method of adjusting the screw setting at the time of injection molding or at the time of melt-kneading the liquid crystal polyester resin and the inorganic filler has a problem that a large work load is required as compared with the method of compounding the additive.
  • An object of the present invention is to provide a liquid crystal polyester resin which is excellent in mechanical properties and in which blister generation during reflow is suppressed.
  • the present inventors have conducted intensive studies and, as a result, by condensation polymerization of a monomer that gives a specific repeating unit, while maintaining excellent mechanical properties, generation of blisters during reflow is suppressed. It was found that a liquid crystal polyester resin was obtained, and the present invention was completed.
  • the present invention relates to a liquid crystal polyester resin composed of repeating units represented by the following formulas (I) to (VII).
  • the liquid crystal polyester resin of the present invention is excellent in mechanical properties such as tensile strength / tensile elastic modulus and bending strength / flexural elasticity, and remarkably suppresses blistering during reflow. Therefore, the liquid crystal polyester resin of the present invention can be suitably used as a material for electrical and electronic parts such as thinned and highly integrated connectors, camera modules, antennas, and substrates.
  • liquid crystal polyester resin is a polyester resin that forms an anisotropic molten phase, and is referred to in the art as a thermotropic liquid crystal polyester resin.
  • the property of the anisotropic molten phase of the liquid crystal polyester resin can be confirmed by a normal polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere.
  • the liquid crystal polyester resin of the present invention exhibits optical anisotropy, that is, it transmits light when inspected between orthogonal polarizers. If the sample is optically anisotropic, polarized light will be transmitted, even in the stationary state.
  • the liquid crystal polyester resin of the present invention is composed of the repeating units represented by the formulas (I) to (VII).
  • the composition ratio p of the repeating unit represented by the formula (I) to all the repeating units is 15 to 30 mol%, preferably 16 to 25 mol%, more preferably 17 to 24 mol%, More preferably, it is 18 to 24 mol%.
  • the composition ratio q of the repeating unit represented by the formula (II) to all the repeating units is 70 to 85 mol%, preferably 75 to 84 mol%, more preferably 76 to 83 mol%, More preferably, it is 76 to 82 mol%.
  • composition ratio p according to the formula (I) is more than 30 mol% or the composition ratio q according to the formula (II) is less than 70 mol%, the crystal melting temperature of the obtained liquid crystal polyester resin decreases. If the composition ratio p according to the formula (I) is less than 15 mol% or the composition ratio q according to the formula (II) is more than 85 mol%, polymerization becomes difficult.
  • Examples of the monomer giving the repeating unit represented by the formula (I) include 4-hydroxybenzoic acid and its ester-forming derivatives such as acylated products, ester derivatives and acid halides.
  • Examples of the monomer giving the repeating unit represented by the formula (II) include 6-hydroxy-2-naphthoic acid and its ester-forming derivatives such as acylated products, ester derivatives and acid halides.
  • the composition ratio r of the repeating unit represented by the formula (III) to all the repeating units the composition ratio s of the repeating unit represented by the formula (IV) to all the repeating units, and the formula (V)
  • the composition ratio t of the repeating unit represented by the formula (VI) with respect to all the repeating units and the composition ratio u of the repeating unit represented by the formula (VI) and the composition of the repeating unit represented by the formula (VII) with respect to all the repeating units.
  • the total amount (r + s + t + u + v) of the ratio v is 0.01 mol% or more and less than 2 mol%, preferably 0.03 to 1.9 mol%, more preferably 0.05 to 1.8 mol%, and still more preferably 0 to 1.8 mol%. 0.1 to 1.7 mol%, particularly preferably 0.2 to 1.6 mol%.
  • r, s, t, u, and v are each 0 or more and less than 2. However, any two or more of these are not zero. That is, the liquid crystal polyester resin of the present invention contains at least two or more arbitrary repeating units selected from the repeating units represented by the formulas (III) to (VII).
  • the total amount (r + s + t + u + v) of the composition ratios r to v in each of the formulas (III) to (VII) is less than 0.01 mol%, the effect of suppressing the generation of blisters becomes insufficient, and is 2 mol% or more. As a result, mechanical properties such as tensile strength and tensile elastic modulus and bending strength and flexural modulus are reduced, and it is difficult to obtain the effect of suppressing blister generation.
  • Examples of the monomer giving the repeating unit represented by the formula (III) include isophthalic acid and its alkyl, alkoxy or halogen-substituted product, and ester derivatives and ester-forming derivatives thereof such as acid halides. .
  • Examples of the monomer giving the repeating unit represented by the formula (IV) include, for example, 2,6-naphthalenedicarboxylic acid and its alkyl, alkoxy or halogen-substituted product, and ester derivatives of these, and ester formation such as acid halides Sex derivatives.
  • Examples of the monomer that gives the repeating unit represented by the formula (V) include terephthalic acid and its alkyl, alkoxy or halogen-substituted product, and ester derivatives and ester-forming derivatives thereof such as acid halides. .
  • Examples of the monomer giving the repeating unit represented by the formula (VI) include hydroquinone and alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives such as acylated products thereof.
  • Examples of the monomer giving the repeating unit represented by the formula (VII) include 4,4′-dihydroxybiphenyl and its alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives such as acylated products thereof.
  • the liquid crystal polyester resin of the present invention contains at least two arbitrary units among the repeating units represented by the formulas (III) to (VII), and combinations thereof are not limited.
  • Preferred combinations of the repeating units represented by the formulas (III) to (VII) included in the liquid crystal polyester resin of the present invention are as follows. (1) Combination of repeating units represented by Formula (III) and Formula (IV) (2) Combination of repeating units represented by Formula (III) and Formula (V) (3) Formula (IV) and Formula ( (4) Combination of repeating units represented by Formula (III), Formula (IV) and Formula (V) (5) Combination of repeating units represented by Formula (IV) and Formula (VI) (6) Combination of repeating units represented by formulas (IV) and (VII) (7) Combination of repeating units represented by formulas (V) and (VI) (8) Formula ( (IV) Combination of repeating units represented by formula (VII) (9) Combination of repeating units represented by formula (III) and formula (VI)
  • the combination of (1) to (4) is particularly preferred.
  • the ratio (r / t) of the composition ratio t according to V) and the ratio (s / t) of the composition ratio t according to the formula (IV) and the composition ratio t according to the formula (V) are 0.1 to 10 respectively. Is preferably, more preferably 0.2 to 5, and further preferably 0.4 to 2.5.
  • the ratio (r / s / t) of the composition ratio r according to the formula (III), the composition ratio s according to the formula (IV), and the composition ratio t according to the formula (V) is 0. It is preferably from 1 to 10 / 0.1 to 10 / 0.1 to 10, more preferably from 0.2 to 5 / 0.2 to 5 / 0.2 to 5, and from 0.4 to 5 / 0.2 to 5 / 0.2 to 5. More preferably, it is 2.5 / 0.4 to 2.5 / 0.4 to 2.5.
  • the combination of (2) or the combination of (3) is preferably adopted.
  • the ratio (r / t) of the composition ratio r according to the formula (III) and the composition ratio t according to the formula (V) is 1 or more (that is, 1 or 1 Is more preferable, the value is more preferably 1.2 or more, and further preferably 1.5 or more.
  • the above ratio (r / t) is usually 5 or less, preferably 4 or less, more preferably 3 or less.
  • the ratio (s / t) between the composition ratio s according to the formula (IV) and the composition ratio t according to the formula (V) is 1 or more (that is, 1 or 1). 1 or more), more preferably 1.2 or more, and even more preferably 1.5 or more.
  • the above ratio (s / t) is usually 5 or less, preferably 4 or less, more preferably 3 or less.
  • the ratio (r / t) of the composition ratio r according to the formula (III) to the composition ratio t according to the formula (V) is preferably less than 1; It is more preferably from 1 to 0.9, further preferably from 0.2 to 0.8, and particularly preferably from 0.3 to 0.7.
  • the ratio (s / t) of the composition ratio s according to the formula (IV) and the composition ratio t according to the formula (V) is preferably less than 1; It is more preferably from 0.1 to 0.9, further preferably from 0.2 to 0.8, and particularly preferably from 0.3 to 0.7.
  • the total [p + q + r + s + t + u + v] of the composition ratios of the respective repeating units is preferably 100 mol%, but other repeating units may be further contained as long as the object of the present invention is not impaired.
  • the composition ratio ⁇ of the other repeating unit is 10 mol% or less based on 100 mol% of the total of the repeating units constituting the liquid crystal polyester resin. Is more preferably 5 mol% or less, further preferably 3 mol% or less, and particularly preferably 1 mol% or less.
  • Examples of the monomer giving another repeating unit include aromatic hydroxycarboxylic acid, aromatic diol, aromatic dicarboxylic acid, aromatic hydroxydicarboxylic acid, aromatic hydroxyamine, aromatic diamine, aromatic aminocarboxylic acid, and alicyclic ring.
  • Examples thereof include aromatic dicarboxylic acids, aliphatic diols, alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols, and aromatic mercaptophenols.
  • the method for producing the liquid crystal polyester resin of the present invention is not particularly limited, and a known polyester resin polycondensation method for forming an ester bond between the above monomer components, for example, a melt acidilysis method, a slurry polymerization method, or the like may be used. it can.
  • Molten acid lysis is a method in which a monomer is first heated to form a molten solution of a reactant, and then the reaction is continued to obtain a molten polymer.
  • vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, and the like) by-produced in the final stage of the condensation. This method is particularly preferably used in the present invention.
  • Slurry polymerization is a method in which a reaction is performed in the presence of a heat exchange fluid, and a solid product is obtained in a state of being suspended in a heat exchange medium.
  • the polymerizable monomer component used in producing the liquid crystal polyester resin should be subjected to the reaction as a modified form in which a hydroxyl group is esterified, that is, a lower acyl ester.
  • the lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method in which an acetic acid ester of the monomer component is used for the reaction.
  • the lower acyl ester of the monomer may be separately acylated and used in advance, or may be produced in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystal polyester resin. it can.
  • ⁇ A catalyst may be used as required in either the melt acidilysis method or the slurry polymerization method.
  • the catalyst include organic tin compounds such as dialkyltin oxide (eg, dibutyltin oxide) and diaryltin oxide; organic titanium compounds such as titanium dioxide, antimony trioxide, alkoxytitanium silicate, and titanium alkoxide; alkali and alkali carboxylic acids.
  • Earth metal salts eg, potassium acetate
  • alkali and alkaline earth metal salts of inorganic acids eg, potassium sulfate
  • gaseous acid catalysts such as Lewis acids (eg, BF 3 ), hydrogen halides (eg, HCl), and the like.
  • the use ratio of the catalyst is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the total amount of the monomers.
  • the thus obtained liquid crystal polyester resin of the present invention has a crystal melting temperature measured by a differential scanning calorimeter (DSC) described later, preferably from 290 to 340 ° C, more preferably from 295 to 335 ° C, and still more preferably.
  • the temperature is 300 to 330 ° C, particularly preferably 305 to 325 ° C.
  • the liquid crystal polyester resin of the present invention preferably has a melt viscosity measured at 350 ° C. of 1 to 1000 Pa ⁇ s, more preferably 5 to 300 Pa ⁇ s, still more preferably 8 to 200 Pa ⁇ s, and particularly preferably. Is 12 to 150 Pa ⁇ s.
  • the liquid crystal polyester resin of the present invention has a tensile strength of preferably 180 MPa or more measured using a dumbbell-shaped test piece having a length of 63.5 mm ⁇ a width of 3.5 mm ⁇ a thickness of 2.0 mm in accordance with ASTM D638.
  • the tensile modulus is preferably 7.7 GPa or more.
  • the tensile strength is more preferably 190 MPa or more, still more preferably 200 MPa or more, and usually 280 MPa or less.
  • the tensile modulus is more preferably 8.0 GPa or more, still more preferably 8.2 GPa or more, and usually 15.0 GPa or less.
  • the liquid crystal polyester resin of the present invention has a bending strength of 165 MPa or more measured using a rectangular test piece having a length of 65 mm ⁇ a width of 12.7 mm ⁇ a thickness of 2.0 mm in accordance with ASTM D790.
  • the elastic modulus is 9.0 GPa or more.
  • the bending strength is more preferably 170 MPa or more, still more preferably 175 MPa or more, and usually 250 MPa or less.
  • the flexural modulus is more preferably 9.5 GPa or more, further preferably 10.0 GPa or more, and usually 15.0 GPa or less.
  • the present invention further provides a liquid crystal polyester resin composition obtained by mixing one or more of a fibrous, plate-like, or powdery filler with the liquid crystal polyester resin of the present invention.
  • the filler may be appropriately selected from substances conventionally known to be used in resin compositions according to the intended use and application of the liquid crystal polyester resin composition.
  • the fibrous filler examples include glass fiber, silica-alumina fiber, alumina fiber, carbon fiber, and aramid fiber.
  • glass fibers are preferred because they have an excellent balance between physical properties and cost.
  • Plate-like or powdery fillers include, for example, talc, mica, graphite, wollastonite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide and the like. Of these, talc is preferred because of its excellent balance between physical properties and cost.
  • the total amount of the filler is preferably from 0.1 to 200 parts by weight, particularly preferably from 10 to 100 parts by weight, based on 100 parts by weight of the liquid crystal polyester resin.
  • the compounding amount of the filler exceeds 200 parts by mass, the molding processability of the liquid crystal polyester resin composition is reduced, and the cylinder and the mold of the molding machine tend to be abraded.
  • the liquid crystal polyester resin or liquid crystal polyester resin composition of the present invention includes a mold release of a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid metal salt, a polysiloxane, a fluororesin, etc., as long as the effects of the present invention are not impaired.
  • Colorants such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; antistatic agents; surfactants and other known additives, depending on the purpose and application. Or one or more of them may be combined.
  • Those having an external lubricant effect such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants, may be used by adhering them to pellets before molding.
  • the liquid crystal polyester resin composition of the present invention is obtained by adding all components such as fillers and additives to the polyester resin, and melting the crystal of the liquid crystal polyester resin using a Banbury mixer, a kneader, a single screw or twin screw extruder, or the like. It can be prepared by melting and kneading at a temperature close to the crystal melting temperature + 100 ° C.
  • liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention thus obtained can be obtained by injection molding, compression molding, extrusion molding, blow molding, and other known molding methods, such as injection molded articles, films, sheets, and nonwoven fabrics. Can be processed.
  • the liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention are excellent in blister resistance, heat resistance, mechanical strength such as tensile strength / tensile elastic modulus, flexural strength / flexural modulus, and so on. It is suitably used as a material for electric and electronic parts such as antennas and substrates.
  • melt viscosity The melt viscosity under a condition of a shear rate of 1000 sec -1 and 350 ° C. was measured with a melt viscosity measuring device (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.) using a capillary of 0.7 mm ⁇ ⁇ 10 mm.
  • Example 1 In a reaction vessel equipped with a stirrer equipped with a torque meter and a distilling tube, POB: 204.7 g (22.8 mol%), BON 6: 935.7 g (76.5 mol%), IPA 5.5 g (0.5 mol) %) And 2.2 g (0.2 mol%) of TPA, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (mol) of all the monomers. was done.
  • the temperature was raised from room temperature to 150 ° C. over 1 hour in a nitrogen gas atmosphere, and the temperature was maintained for 30 minutes. Next, the temperature was quickly raised to 210 ° C. while distilling off by-produced acetic acid, and kept at the same temperature for 30 minutes. Thereafter, the temperature was raised to 350 ° C. over 4 hours, and then reduced to 10 mmHg over 80 minutes.
  • the polymerization reaction was terminated when a predetermined torque was obtained, the contents of the reaction vessel were taken out, and pellets of liquid crystal polyester resin were obtained with a pulverizer. The amount of acetic acid distilled at the time of polymerization was almost the same as the theoretical value.
  • Examples 2 to 6, 8 to 10 and Comparative Examples 1 to 5, 7 to 9 Pellets of a liquid crystal polyester resin were obtained in the same manner as in Example 1, except that POB, BON6, IPA, NDA, TPA, HQ, and BP were changed so as to have the ratios (mol%) shown in Table 1. Using the obtained pellets, the crystal melting temperature, tensile strength, tensile modulus, tensile strain, bending strength, flexural modulus, Izod impact strength, DTUL and blister generation were measured and evaluated by the above-described methods. The results are shown in Tables 1 and 2.
  • Example 7 Using the resin of Example 1 as a liquid crystal polyester resin, 10 parts by mass of glass fiber (chopped glass having a fiber diameter of 10.5 ⁇ m and a fiber length of 3 mm) and talc (average particles) were used as fillers with respect to 100 parts by mass of the liquid crystal polyester resin. 20 parts by mass (diameter: 19 ⁇ m) were blended and melt-kneaded with a twin-screw extruder (TEX-30, manufactured by Nippon Steel Corporation) into pellets to obtain pellets of a liquid crystal resin composition. Using the obtained pellets, blister generation was evaluated by the above method. The results are shown in Tables 1 and 2.
  • liquid crystal polyester resin and the liquid crystal polyester resin composition according to each of the examples of the present invention were all excellent in mechanical properties and excellent in blister resistance during reflow.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le but de la présente invention est de produire une résine de polyester à cristaux liquides qui présente d'excellentes propriétés mécaniques et supprime la formtion de cloques au moment de la refusion. La présente invention concerne une résine de polyester à cristaux liquides configurée à partir d'unités structurales représentées par les formules (I)- (VII) [dans la formule, p, q, r, s, t, u et v représentent le rapport de composition (% en moles)) de chaque unité structurale dans la résine de polyester à cristaux liquides, et satisfont les expressions suivantes: 15≤p≤30, 70≤q≤85, et 0,01≤r+s+t+u+v<2. Dans la présente invention, les r, s, t, u et v représentent chacun au moins 0 et moins de 2, et un nombre arbitraire de deux ou plus de ceux-ci ne représentent pas 0].
PCT/JP2018/048153 2018-10-02 2018-12-27 Résine de polyester à cristaux liquides WO2020070904A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2018568460A JP6533881B1 (ja) 2018-10-02 2018-12-27 液晶ポリエステル樹脂

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2018-187393 2018-10-02
JP2018187393 2018-10-02

Publications (1)

Publication Number Publication Date
WO2020070904A1 true WO2020070904A1 (fr) 2020-04-09

Family

ID=70055371

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/048153 WO2020070904A1 (fr) 2018-10-02 2018-12-27 Résine de polyester à cristaux liquides

Country Status (1)

Country Link
WO (1) WO2020070904A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023228573A1 (fr) * 2022-05-26 2023-11-30 Ｅｎｅｏｓ株式会社 Résine de polyester à cristaux liquides, article moulé et composant électrique / électronique
JP7520734B2 (ja) 2021-01-27 2024-07-23 上野製薬株式会社 液晶ポリマー

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05186578A (ja) * 1992-01-09 1993-07-27 Kuraray Co Ltd 熱液晶ポリエステルの製造方法
JP2002179776A (ja) * 2000-09-22 2002-06-26 Polyplastics Co 全芳香族ポリエステル及びポリエステル樹脂組成物
JP2006001990A (ja) * 2004-06-16 2006-01-05 Sumitomo Chemical Co Ltd 芳香族液晶ポリエステルフィルムおよび積層体
JP2006206824A (ja) * 2005-01-31 2006-08-10 Ueno Seiyaku Oyo Kenkyusho:Kk 液晶ポリエステル樹脂およびその製造方法
JP2009108191A (ja) * 2007-10-30 2009-05-21 Ueno Fine Chem Ind Ltd 液晶ポリエステルブレンド
WO2011018837A1 (fr) * 2009-08-11 2011-02-17 東レ株式会社 Polyester cristallin liquide et son procédé de production
JP2017179127A (ja) * 2016-03-30 2017-10-05 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品
WO2018008612A1 (fr) * 2016-07-04 2018-01-11 Ｊｘｔｇエネルギー株式会社 Résine de polyester à cristaux liquides entièrement aromatique, article moulé et composante électrique/électronique

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05186578A (ja) * 1992-01-09 1993-07-27 Kuraray Co Ltd 熱液晶ポリエステルの製造方法
JP2002179776A (ja) * 2000-09-22 2002-06-26 Polyplastics Co 全芳香族ポリエステル及びポリエステル樹脂組成物
JP2006001990A (ja) * 2004-06-16 2006-01-05 Sumitomo Chemical Co Ltd 芳香族液晶ポリエステルフィルムおよび積層体
JP2006206824A (ja) * 2005-01-31 2006-08-10 Ueno Seiyaku Oyo Kenkyusho:Kk 液晶ポリエステル樹脂およびその製造方法
JP2009108191A (ja) * 2007-10-30 2009-05-21 Ueno Fine Chem Ind Ltd 液晶ポリエステルブレンド
WO2011018837A1 (fr) * 2009-08-11 2011-02-17 東レ株式会社 Polyester cristallin liquide et son procédé de production
JP2017179127A (ja) * 2016-03-30 2017-10-05 Ｊｘｔｇエネルギー株式会社 全芳香族液晶ポリエステル樹脂、成形品、および電気電子部品
WO2018008612A1 (fr) * 2016-07-04 2018-01-11 Ｊｘｔｇエネルギー株式会社 Résine de polyester à cristaux liquides entièrement aromatique, article moulé et composante électrique/électronique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7520734B2 (ja) 2021-01-27 2024-07-23 上野製薬株式会社 液晶ポリマー
WO2023228573A1 (fr) * 2022-05-26 2023-11-30 Ｅｎｅｏｓ株式会社 Résine de polyester à cristaux liquides, article moulé et composant électrique / électronique

Similar Documents

Publication Publication Date Title
JP5616212B2 (ja) 全芳香族液晶ポリエステル樹脂およびそれを含む組成物
JP6920924B2 (ja) 液晶ポリエステル樹脂
JP4625340B2 (ja) 液晶ポリエステル樹脂およびその製造方法
JP5730704B2 (ja) 液晶ポリマー組成物
JP6533880B1 (ja) 液晶ポリエステル樹脂
JP6533881B1 (ja) 液晶ポリエステル樹脂
KR102269982B1 (ko) 액정 중합체 조성물
WO2005033177A1 (fr) Resine de polyester a cristaux liquides
US10711134B2 (en) Liquid crystal polyester resin composition
WO2020070904A1 (fr) Résine de polyester à cristaux liquides
WO2020070903A1 (fr) Résine de polyester à cristaux liquides
JP2018080242A (ja) 液晶ポリマー組成物
JP4368079B2 (ja) 液晶ポリエステル樹脂組成物
JP7284033B2 (ja) 液晶ポリエステル樹脂
JP2017043705A (ja) 液晶ポリマー
JP7266633B2 (ja) 液晶ポリマー組成物
JP6751009B2 (ja) 液晶ポリエステル樹脂組成物
JP2020176174A (ja) 液晶ポリエステル樹脂
JP7578507B2 (ja) 液晶ポリエステルアミド樹脂
JP2024108735A (ja) 液晶ポリエステル樹脂
JP2024108563A (ja) 液晶ポリエステル樹脂
JP2022129986A (ja) 液晶ポリエステルアミド樹脂
JP2023065057A (ja) 液晶ポリエステル樹脂組成物

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018568460

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18936040

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18936040

Country of ref document: EP

Kind code of ref document: A1