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
  • C08G63/605—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 the hydroxy and carboxylic groups being bound to aromatic rings
• • 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
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
  • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
  • H01B3/421—Polyesters

Definitions

• the present invention relates to a wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and to this polyester resin composition.
• Liquid crystalline polymers represented by liquid crystalline polyester resins have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and are therefore widely used as high-performance engineering plastics. Yes.
• Patent Document 1 discloses an improved method for producing a heat-stable thermotropic liquid crystalline polyester having a predetermined chain length.
• thermal stability is improved by adding a small amount of 1,4-phenylenedicarboxylic acid to liquid crystalline polyester.
• the thermal stability of this liquid crystalline polyester is not always sufficient.
• Patent Document 2 also discloses a method for producing a heat-stable thermotropic liquid crystalline polyester having a predetermined chain length.
• thermal stability is improved by incorporating a small amount of 2,6-dihydroxynaphthalene or 4,4'-dihydroxybiphenyl into a liquid crystalline polyester.
• the thermal stability of this liquid crystalline polyester is not always sufficient.
• Patent Document 3 discloses a liquid crystalline aromatic polyester for insulating material and a resin composition thereof.
• a low dielectric loss tangent is achieved by adding a large amount of 6-hydroxy-2-naphthoic acid to a liquid crystalline aromatic polyester.
• this liquid crystalline aromatic polyester has a problem that it has only a highly reactive hydroxycarboxylic acid composition, has poor thermal stability, and has a large amount of decomposition gas.
• liquid crystalline polyesters are not necessarily sufficient in terms of hydrolysis resistance, and when a polyester molded product obtained by molding a polyester resin composition is used in a humid heat environment such as high temperature and high humidity, hydrolysis is not possible. There is a problem that heat resistance and mechanical strength are remarkably lowered.
• the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a wholly aromatic polyester having high thermal stability and good hydrolysis resistance, and this polyester resin composition.
• 6-hydroxy-2-naphthoic acid is 60 to 85 mol%
• 4-hydroxybenzoic acid is 12 to 40 mol%
• 1,4-phenylenedicarboxylic acid or 4,4 The present inventors have found that the above-mentioned problems can be solved by using a wholly aromatic polyester comprising 0.1 to 3 mol% of '-dihydroxybiphenyl, and the present inventors have completed the present invention. More specifically, the present invention provides the following.
• the following constituent units (I), (II), and (III) or (IV) consist of:
• the content of the structural unit (I) is 60 to 85 mol% with respect to all the structural units,
• the content of the structural unit (II) is 12 to 40 mol% with respect to all the structural units,
• the content of the structural unit (III) or (IV) is 0.1 to 3 mol% with respect to all the structural units,
• the total content of the structural units (I), (II), and (III) or (IV) is 100 mol% with respect to all the structural units. Totally aromatic polyester.
• the wholly aromatic polyester according to the present invention comprises the following constituent units (I), (II), and (III) or (IV) as essential constituent components, and the constituent units (I)
• the content is 60 to 85 mol%
• the content of the structural unit (II) is 12 to 40 mol% with respect to all the structural units
• the structural unit (III) or (IV) is based on the total structural units.
• the content is 0.1 to 3 mol%
• the total content of the structural units (I), (II), and (III) or (IV) is 100 mol% with respect to all the structural units.
• the structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as “HNA”).
• the wholly aromatic polyester of the present invention contains 60 to 85 mol% of the structural unit (I) with respect to all the structural units.
• the content of the structural unit (I) is less than 60 mol%, the melting point is lowered and the heat resistance is insufficient. If the content of the structural unit (I) exceeds 85 mol%, solidification occurs during polymerization and a polymer cannot be obtained.
• the content of the structural unit (I) is preferably 63 to 85 mol%, more preferably 63 to 83 mol%, still more preferably 65 to 83 mol%, still more preferably 65 to 80 mol%, and most preferably 68. ⁇ 80 mol%.
• the structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as “HBA”).
• HBA 4-hydroxybenzoic acid
• the wholly aromatic polyester of the present invention contains 12 to 40 mol% of the structural unit (II) with respect to the total structural units.
• content of structural unit (II) is less than 12 mol%, the polymer is solidified in the polymerization vessel during production, and the polymer cannot be discharged.
• the content of the structural unit (II) is preferably 15 to 40 mol%, more preferably 15 to 35 mol%, still more preferably 18 to 35 mol%, still more preferably 18 to 30 mol%, most preferably 20-30 mol%.
• the structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”), and the structural unit (IV) is 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”). .)
• the wholly aromatic polyester of the present invention contains 0.1 to 3 mol% of the structural unit (III) or the structural unit (IV) with respect to all the structural units. Thermal stability falls that content of structural unit (III) or structural unit (IV) is less than 0.1 mol%. When the content of the structural unit (III) or the structural unit (IV) exceeds 3 mol%, the molecular weight (melt viscosity) does not increase.
• the content of the structural unit (III) or the structural unit (IV) is preferably 0.2 to 2.5 mol%, more preferably 0.2 to 2 mol%, still more preferably. Is 0.3 to 2 mol%, more preferably 0.3 to 1.5 mol%, most preferably 0.4 to 1.5 mol%.
• the wholly aromatic polyester of the present invention contains a specific amount of specific structural units (I) to (IV) with respect to the total structural units, and therefore generates less gas and has a high thermal stability. In addition to being high, hydrolysis resistance is good.
• the wholly aromatic polyester of the present invention contains 100 mol% of the structural units (I) to (IV) in total with respect to the total structural units.
• the wholly aromatic polyester of the present invention exhibits optical anisotropy when melted.
• An optical anisotropy when melted means that the wholly aromatic polyester of the present invention is a liquid crystalline polymer.
• the fact that the wholly aromatic polyester is a liquid crystalline polymer is an indispensable element when the wholly aromatic polyester has both thermal stability and easy processability.
• the wholly aromatic polyester composed of the structural units (I) to (IV) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer. Limited to wholly aromatic polyesters that exhibit optical anisotropy when melted.
• melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere.
• the liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.
• a nematic liquid crystalline polymer causes a significant decrease in viscosity at a melting point or higher, generally exhibiting liquid crystallinity at a melting point or higher is an index of workability.
• the melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferably 380 ° C. or lower in consideration of thermal deterioration during the melt processing of the polymer, the heating ability of the molding machine, and the like.
• the melting point is more preferably 250 to 370 ° C., further preferably 270 to 370 ° C., still more preferably 270 to 350 ° C., and most preferably 290 to 350 ° C.
• melt viscosity of the wholly aromatic polyester at a temperature 10 to 30 ° C. higher than the melting point of the wholly aromatic polyester of the present invention and a shear rate of 1000 / sec is preferably 1000 Pa ⁇ s or less, more preferably 3 to 500 Pa. ⁇ S, even more preferably 3 to 250 Pa ⁇ s.
• melt viscosity means the melt viscosity measured based on ISO11443.
• the total crystallization heat amount of the wholly aromatic polyester of the present invention is preferably 2.5 J / g or more, more preferably 2.5 to 4.4 J / g. If the crystallization heat amount, which indicates the crystallization state of the polymer determined by differential calorimetry, is less than 2.5 J / g, the crystallinity is lowered and the hydrolysis resistance is deteriorated. Moreover, when the amount of crystallization heat exceeds 4.4 J / g, toughness will become low and it is not preferable. It should be noted that the heat of crystallization is 2 at a temperature of (Tm1 + 40) ° C. after observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature from 20 ° C./min. It refers to the calorific value of the exothermic peak obtained from the peak of the exothermic peak temperature that is observed when the temperature is measured for 20 ° C./min.
• the value of [melting point ⁇ crystallization temperature] which is a value obtained by subtracting the crystallization temperature from the melting point, is preferably 20 ° C. or more, and preferably 30 to 90 ° C. More preferred.
• the value of [melting point ⁇ crystallization temperature] is within the above range, the wholly aromatic polyester itself or the composition containing the wholly aromatic polyester is easy to ensure fluidity at the time of molding, Filling pressure is unlikely to be excessive.
• the wholly aromatic polyester of the present invention is polymerized using a direct polymerization method or a transesterification method.
• a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these are used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. Is preferably used.
• an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used.
• the acylating agent include fatty acid anhydrides such as acetic anhydride.
• various catalysts can be used. Typical examples include potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2 , 4-pentanedionato) cobalt (III) and the like, and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine.
• the amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.
• the inorganic filler to be blended in the polyester resin composition of the present invention includes fibrous, granular and plate-like ones.
• the fibrous inorganic filler glass fiber, milled glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite
• inorganic fiber materials such as silicate fibers, magnesium sulfate fibers, aluminum borate fibers, and metal fibers such as stainless steel, aluminum, titanium, copper, and brass.
• a particularly typical fibrous filler is glass fiber.
• powdered inorganic fillers include carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, and wollastonite.
• Acid salts iron oxide, titanium oxide, zinc oxide, antimony trioxide, oxides of metals such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other ferrites , Silicon carbide, silicon nitride, boron nitride, various metal powders, and the like.
• examples of the plate-like inorganic filler include mica, glass flakes, talc, and various metal foils.
• organic fillers blended in the polyester resin composition of the present invention include heat-resistant high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamides, and polyimide fibers.
• the fibrous inorganic filler is glass fiber
• the platy filler is mica and talc.
• the blending amount thereof is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester. It is.
• the polyester resin composition is particularly prominent in improving the heat distortion temperature and mechanical properties.
• a sizing agent or a surface treatment agent can be used if necessary.
• the polyester resin composition of the present invention contains the wholly aromatic polyester of the present invention and, if necessary, an inorganic or organic filler as essential components, as long as the effects of the present invention are not impaired.
• Other components may be included.
• the other component may be any component, and examples thereof include other resins, antioxidants, stabilizers, pigments, crystal nucleating agents and the like.
• the method for producing the polyester resin composition of the present invention is not particularly limited, and the polyester resin composition can be prepared by a conventionally known method.
• the polyester molded article of the present invention is formed by molding the wholly aromatic polyester or polyester resin composition of the present invention.
• the molding method is not particularly limited, and a general molding method can be employed. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, inflation molding, and the like.
• the polyester molded product formed by molding the wholly aromatic polyester of the present invention is excellent in heat resistance. Moreover, since the polyester molded product formed by shape
• the wholly aromatic polyester and polyester resin composition of the present invention are excellent in moldability and can be processed into various three-dimensional molded products, fibers, films and the like.
• Preferred applications of the polyester molded product of the present invention having the above properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, electronic circuit boards, or heat fixing rolls for OA equipment. It is done.
• Example 1 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a decompression / outflow line was charged with the following raw material monomers, fatty acid metal salt catalyst, and acylating agent, and nitrogen substitution was started.
• melt viscosity ISO 11443 using a capilograph manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice having an inner diameter of 0.5 mm and a length of 30 mm at a temperature 10 to 30 ° C. higher than the melting point of the wholly aromatic polyester and a shear rate of 1000 / sec. The melt viscosity of the wholly aromatic polyester was measured.
• Example 2 A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer and the charging ratio (mol%) were as shown in Table 1. The obtained polymer was heated from room temperature to 290 ° C. over 20 minutes in a nitrogen atmosphere, held for 3 hours, and then allowed to cool to obtain a further polymer. Moreover, the same evaluation as Example 1 was performed. The evaluation results are shown in Table 1.
• Example 3 A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a decompression / outflow line was charged with the following raw material monomers, fatty acid metal salt catalyst, and acylating agent, and nitrogen substitution was started.
• Comparative Examples 1 to 8 A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer and the charging ratio (mol%) were as shown in Tables 1 and 2. Moreover, the same evaluation as Example 1 was performed. The evaluation results are shown in Tables 1 and 2. In Comparative Example 4, the polymer was solidified in the polymerization vessel during production, and the polymer could not be discharged.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Polyesters Or Polycarbonates (AREA)

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• 2018
  • 2018-01-22 KR KR1020197020777A patent/KR102120296B1/ko active IP Right Grant
  • 2018-01-22 WO PCT/JP2018/001718 patent/WO2018139393A1/ja active Application Filing
  • 2018-01-22 JP JP2018527815A patent/JP6412296B1/ja active Active
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