WO2017002852A1 - Pastille de polyester cristallin, son application et son procédé de production - Google Patents

Pastille de polyester cristallin, son application et son procédé de production Download PDF

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Publication number
WO2017002852A1
WO2017002852A1 PCT/JP2016/069262 JP2016069262W WO2017002852A1 WO 2017002852 A1 WO2017002852 A1 WO 2017002852A1 JP 2016069262 W JP2016069262 W JP 2016069262W WO 2017002852 A1 WO2017002852 A1 WO 2017002852A1
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pellet
polyester
pellets
mass
polymerization
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PCT/JP2016/069262
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English (en)
Japanese (ja)
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豪 坂野
雅紀 田中
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株式会社クラレ
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Priority to JP2017526395A priority Critical patent/JP6689846B2/ja
Publication of WO2017002852A1 publication Critical patent/WO2017002852A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion

Definitions

  • the present invention relates to a crystalline polyester pellet comprising a resin composition containing a polyester containing terephthalic acid units and ethylene glycol units as main components and composite particles. Moreover, it is related with the use and its manufacturing method.
  • Polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) are excellent in properties such as transparency, mechanical properties, gas barrier properties, and flavor barrier properties. Furthermore, polyester has less concern about residual monomers and harmful additives when formed into molded articles, and is excellent in hygiene and safety. Therefore, taking advantage of these characteristics, polyester is a hollow container for filling juice, soft drinks, seasonings, oils, cosmetics, detergents, beverage cans, etc. Widely used as a coating film for laminated steel plates. In recent years, it has been widely used as an optical film such as a protective film for a liquid crystal display.
  • the film Since the contamination of foreign substances in optical films is severely restricted, the film is often formed by removing foreign substances from the molten resin using a fine filter. Therefore, in the polyester resin used as the raw material for the optical film, if the content of unmelted foreign matter is large, it will cause clogging of the extrusion filter during melt molding. Therefore, a polyester resin pellet having a small size and a small amount of foreign matter is desired.
  • PET resin is industrially produced by the esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, and then using bis (2-hydroxyethyl) terephthalate as a catalyst at high temperature under vacuum. Obtained by polycondensation.
  • a method for removing minute foreign matters during polymerization of such polyester a method of filtering a high temperature oligomer with a heat resistant filter and a method of filtering a PET resin after polycondensation with a heat resistant filter are generally used.
  • One of the main factors of foreign particles contained in the polyester resin is a polymerization catalyst.
  • catalysts have their own problems.
  • antimony oxide (Sb 2 O 3 ) is used, since the transparency of the resulting polyester resin is lowered, it is not suitable for applications requiring high transparency.
  • an organic titanium catalyst such as titanium (IV) tetraisoproxide, the resulting polyester resin is colored yellow, and the inherent viscosity is lowered due to thermal decomposition during melt molding, and further the coloration proceeds. ing.
  • germanium dioxide GeO 2
  • the carboxyl group content of the resulting polyester is increased, and a decrease in intrinsic viscosity when the resin is recovered and melt-formed again cannot be avoided, and the catalyst cost is greatly increased. To rise.
  • a copolymerized PET resin containing a comonomer component is used.
  • comonomer components can be used depending on the application.
  • a PET resin in which is copolymerized is used (see, for example, Patent Documents 1 and 2).
  • a polyester resin having a high intrinsic viscosity is used in order to improve the strength of the molded product. Therefore, after polycondensation is performed in the liquid phase to obtain pellets, the pellets are solid-phase polymerized to produce crystalline polyester pellets with high intrinsic viscosity.
  • a preliminary crystallization step is performed in which crystallization is performed by heating at a relatively low temperature before solid phase polymerization.
  • it is unmodified PET, it can be sufficiently pre-crystallized in a short time, but in the case of copolymerized PET containing a certain amount of comonomer component or more, the crystallization speed is greatly reduced, and pre-crystallization The process took a long time. This not only reduced productivity, but also increased energy consumption.
  • Patent Document 3 reports a composite particle catalyst in which the surface of solid base particles is covered with titanium oxide as a polyester polymerization catalyst, and a high molecular weight polyester having excellent color and transparency by using it. Is supposed to be obtained. However, in that example, only liquid phase polymerization of unmodified PET is carried out.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide copolymerized PET crystal pellets having a low environmental load and uses thereof. Moreover, it aims at manufacturing such a pellet by the method excellent in productivity.
  • the above problem is a crystalline polyester pellet comprising a resin composition containing polyester and composite particles
  • the polyester comprises 25 to 50 mol% terephthalic acid units, 25 to 49.5 mol% ethylene glycol units, 0.5 to 2.5 mol% diethylene glycol units, and other comonomer units having 5 or more carbon atoms. Containing 1.5 to 25 mol%, The polyester has an intrinsic viscosity of 0.75 to 1.5 dL / g, The crystal melting enthalpy of the pellet is 20 J / g or more, This is solved by providing pellets characterized in that the composite particles are composite particles of hydrotalcite and titanium dioxide, and the content of the composite particles is 10 to 300 ppm.
  • the total volume of particles having a diameter of 1 to 5 ⁇ m contained in 1 g of the pellet was 5.0 ⁇ 10. It is preferably ⁇ 14 m 3 / g or more.
  • the total volume of particles having a diameter of 5 to 20 ⁇ m contained in 1 g of the pellet was 1.2 ⁇ 10 ⁇ 12 m. It is also preferable that it is 3 / g or less.
  • the polyester has a carboxyl group content of 18 ⁇ mol / g or less.
  • a preferred embodiment of the present invention is a film formed by molding the pellet.
  • Another preferred embodiment of the present invention is a laminated metal plate in which a film formed by forming the pellet is laminated on a metal plate.
  • Another preferred embodiment of the present invention is an extrusion blow molded container formed by molding the pellet.
  • terephthalic acid or its ester-forming derivative, ethylene glycol, and another comonomer having 5 or more carbon atoms are melt-polymerized in the presence of a catalyst composed of composite particles of hydrotalcite and titanium dioxide and then cut.
  • a catalyst composed of composite particles of hydrotalcite and titanium dioxide and then cut.
  • the crystalline polyester pellets of the present invention include copolymerized PET, but have a high crystallization speed during preliminary crystallization, excellent productivity, and a low environmental load. Since the pellet contains copolymerized PET having a high degree of polymerization and the content of foreign matter having a large particle size is small, it is excellent in strength, transparency, moldability, adhesiveness, etc., and suitable for various applications. Can be used. Moreover, since the density
  • the present invention relates to a crystalline polyester pellet made of a resin composition containing polyester and composite particles.
  • the composite particles are composite particles of hydrotalcite and titanium dioxide, the crystallization rate can be increased even if the polyester is a copolymer polyester having a lowered crystallinity.
  • precrystallization can be performed in a short time prior to solid phase polymerization, a polyester having a high degree of polymerization can be obtained with high productivity.
  • the polyester contained in the crystal pellet of the present invention comprises 25 to 50 mol% of terephthalic acid units, 25 to 49.5 mol% of ethylene glycol units, 0.5 to 2.5 mol% of diethylene glycol units, and 5 carbon atoms. It contains 1.5 to 25 mol% of the above other comonomer units.
  • polyethylene terephthalate units are the main constituents.
  • the regularity of the polyethylene terephthalate crystal is lowered, so that the melting point is lowered and the crystallinity is also lowered.
  • the content of the terephthalic acid unit is 25 to 50 mol%, and if it is less than this, the melting point and the crystallinity are significantly lowered.
  • the content of the terephthalic acid unit is preferably 30 mol% or more, and more preferably 35 mol% or more.
  • the content of ethylene glycol units is 25 to 49.5 mol%, and if it is less than this, the melting point and crystallinity are remarkably lowered.
  • the content of ethylene glycol units is preferably 30 mol% or more, and more preferably 35 mol% or more.
  • the content of the diethylene glycol unit is 0.5 to 2.5 mol%, and usually, a unit by-produced by dimerization of ethylene glycol during the polycondensation reaction is contained in the polyester.
  • the content of diethylene glycol units is preferably 2 mol% or less.
  • the polyester contained in the crystal pellet of the present invention contains 1.5 to 25 mol% of another comonomer unit having 5 or more carbon atoms.
  • the crystallinity of polyethylene terephthalate can be reduced, and transparency, moldability, adhesiveness, and the like can be improved.
  • the content of other comonomer units is more preferably 2 mol% or more, and even more preferably 2.5 mol% or more.
  • the content of other comonomer units is more preferably 20 mol% or less, further preferably 15 mol% or less, and particularly preferably 10 mol% or less.
  • the polyester contained in the crystal pellet of the present invention contains a comonomer unit other than a terephthalic acid unit, an ethylene glycol unit, and a diethylene glycol unit.
  • the comonomer unit has 5 or more carbon atoms. When the number of carbon atoms is less than 5, the boiling point is lowered and volatilizes during the condensation polymerization reaction, which may make it difficult to recover ethylene glycol. Moreover, crystallinity can be reduced effectively by having 5 or more carbon atoms.
  • the carbon number of the dicarboxylic acid unit or diol unit is more preferably 8 or more. The upper limit of the carbon number is not particularly limited, but is usually 50 or less.
  • the method for producing the crystal pellet of the present invention is not particularly limited, but a catalyst comprising terephthalic acid or an ester-forming derivative thereof, ethylene glycol, and another comonomer having 5 or more carbon atoms, composed of composite particles of hydrotalcite and titanium dioxide. It is preferable to melt-polymerize in the presence of and then cut to produce amorphous polyester pellets, and then to pre-crystallize the amorphous polyester pellets before solid-phase polymerization.
  • bifunctional compounds such as dicarboxylic acid and ester-forming derivatives thereof, diol, hydroxycarboxylic acid and ester-forming derivatives thereof are mainly used.
  • a polyfunctional compound having three or more carboxyl groups, hydroxyl groups, or ester-forming groups thereof, or a monofunctional compound that is a monocarboxylic acid, a monoalcohol, or an ester-forming derivative thereof may be used in combination.
  • Dicarboxylic acids and ester-forming derivatives thereof include aliphatic dicarboxylic acids and ester-forming derivatives thereof such as glutaric acid, adipic acid, azelaic acid, sebacic acid and dimer acid (and hydrogenated products thereof); cyclohexanedicarboxylic acid and norbornene Alicyclic dicarboxylic acids such as dicarboxylic acid and tricyclodecane dicarboxylic acid and ester-forming derivatives thereof; isophthalic acid, phthalic acid, biphenyldicarboxylic acid, diphenylether dicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenylketonedicarboxylic acid, sulfoisophthalic acid Aromatic dicarboxylic acids such as sodium, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and ester
  • diol examples include aliphatic diols such as 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and methylpentanediol; alicyclic diols such as cyclohexanedimethanol, norbornene dimethanol, and tricyclodecane dimethanol.
  • Etc. A diol in which one or more molecules of ethylene oxide are added to two hydroxyl groups of an aromatic diol can also be used.
  • a diol (bisphenol A ethylene oxide adduct) in which 1 to 8 molecules of ethylene oxide are added to two phenolic hydroxyl groups of bisphenol A can be exemplified.
  • Hydroxycarboxylic acid and its ester-forming derivatives include aliphatic hydroxycarboxylic acids such as 10-hydroxyoctadecanoic acid or ester-forming derivatives thereof; hydroxymethylcyclohexanecarboxylic acid, hydroxymethylnorbornenecarboxylic acid, hydroxymethyltricyclodecanecarboxylic acid Alicyclic hydroxycarboxylic acids such as acids or ester-forming derivatives thereof; hydroxybenzoic acid, hydroxytoluic acid, hydroxynaphthoic acid, 3- (hydroxyphenyl) propionic acid, hydroxyphenylacetic acid, 3-hydroxy-3-phenylpropion Aromatic hydroxycarboxylic acids such as acids and their ester-forming derivatives.
  • polyfunctional compounds having three or more carboxyl groups, hydroxyl groups or ester-forming groups thereof include trimellitic acid, pyromellitic acid, trimesic acid, cyclohexane-1,2,4-tricarboxylic acid, trimethylolpropane, pentaerythritol And triol components contained in bisphenol A ethylene oxide adducts, and ester-forming derivatives thereof. These can be added in a small amount to increase the melt tension and can be used to adjust the melt extrusion moldability.
  • the content of the unit derived from the polyfunctional compound is preferably 1 mol% or less, and more preferably 0.5 mol% or less. If the ratio of the polyfunctional compound unit exceeds 1 mol%, gelation tends to occur, which is not preferable.
  • Examples of monofunctional compounds having only one carboxyl group, hydroxyl group or ester-forming group thereof include benzoic acid, 2,4,6-trimethoxybenzoic acid, 2-naphthoic acid, stearic acid and stearyl alcohol. . These function as sealing monomer units, seal molecular chain end groups in the polyester, and may be blended to prevent excessive crosslinking and gel formation in the polyester.
  • the content of the unit derived from the monofunctional compound is preferably 1 mol% or less, and more preferably 0.5 mol% or less. When the ratio of the monofunctional compound unit exceeds 1 mol%, the polymerization rate in producing the polyester is slowed, and the productivity tends to be lowered.
  • terephthalic acid or an ester-forming derivative thereof and ethylene glycol are heated to advance an esterification reaction or a transesterification reaction to obtain an oligomer.
  • another comonomer having 5 or more carbon atoms may be added in advance and an esterification reaction or transesterification reaction may be allowed to proceed simultaneously to obtain an oligomer, or another comonomer having 5 or more carbon atoms may be obtained after obtaining the oligomer. May be added to the melt polymerization reaction.
  • the esterification reaction or transesterification reaction is preferably carried out at a temperature of 180 to 300 ° C.
  • the ratio of raw materials in the esterification reaction or transesterification reaction is preferably such that the molar ratio (diol component / dicarboxylic acid component) is in the range of 1.1 to 2.5.
  • a cocatalyst for improving the speed of the polycondensation reaction may be added, or the reaction can be carried out without a catalyst.
  • the cocatalyst include zinc compounds, nickel compounds, and cobalt compounds.
  • the zinc compound include fatty acid zinc salts such as zinc acetate, zinc carbonate, zinc chloride, zinc acetylacetonate salt, zinc phosphate, zinc phosphite and the like, and zinc acetate and zinc carbonate are particularly preferable.
  • cobalt compound examples include fatty acid cobalt salts such as cobalt acetate, cobalt carbonate, cobalt chloride, cobalt acetylacetonate salt, and the like, and cobalt acetate and cobalt carbonate are particularly preferable.
  • nickel compound examples include fatty acid nickel salts such as nickel acetate, nickel carbonate, nickel chloride, nickel acetylacetonate salt, and nickel acetate and nickel carbonate are particularly preferable.
  • the amount of the cocatalyst used is preferably 0.001 to 0.02 parts by mass with respect to 100 parts by mass of the dicarboxylic acid component. When the amount of the cocatalyst is too small, the reaction rate is not sufficiently improved. On the other hand, when the amount of the cocatalyst is too large, the pressure increase speed of the filter used at the time of extrusion molding may be increased.
  • the amount of the cocatalyst is more preferably 0.015 parts by mass or less.
  • the transesterification reaction when the transesterification reaction is performed using dimethyl terephthalate, one or more metal compounds such as calcium, manganese, magnesium, zinc, titanium, sodium and lithium are preferably used as the transesterification catalyst.
  • metal compounds such as calcium, manganese, magnesium, zinc, titanium, sodium and lithium are preferably used as the transesterification catalyst.
  • composite particles of hydrotalcite and titanium dioxide can be added in advance as a polymerization catalyst, but after the esterification reaction is completed, the polymerization catalyst is added and the subsequent melt polymerization reaction It is preferable to use it for increasing the precrystallization rate.
  • the melt polycondensation reaction following the esterification reaction or transesterification reaction is performed in the presence of a catalyst composed of composite particles of hydrotalcite and titanium dioxide.
  • a catalyst composed of composite particles of hydrotalcite and titanium dioxide it is important to use a catalyst composed of composite particles of hydrotalcite and titanium dioxide, and amorphous pellets having a high crystallization rate can be obtained by polymerization using the catalyst.
  • the composite particles may have a structure in which titanium dioxide is introduced between the layers of hydrotalcite, or may have a structure in which the surface of the hydrotalcite particles is covered with titanium dioxide. It preferably comprises 50 to 95% by weight of hydrotalcite and 5 to 50% by weight of titanium dioxide.
  • the particle size is not particularly limited, but is preferably fine particles having an average particle size of 1 ⁇ m or less, and more preferably fine particles having an average particle size of 0.4 ⁇ m or less.
  • Hydrotalcite is a compound comprising magnesium and aluminum carbonate and hydroxide, typically having a chemical composition that Mg 6 Al 2 (CO 3) (OH) 16 ⁇ 4 (H 2 O).
  • the amount of the catalyst used is preferably 0.001 to 0.03 parts by mass with respect to 100 parts by mass of the dicarboxylic acid component. When the amount of the catalyst used is too small, the polymerization reaction rate decreases. The amount of the catalyst used is more preferably 0.002 parts by mass or more, and further preferably 0.003 parts by mass or more. On the other hand, when the amount of the catalyst used is too large, the pressure increase rate of the filter used during extrusion molding increases. The amount of the catalyst used is more preferably 0.02 parts by mass or less, and further preferably 0.015 parts by mass or less.
  • melt polycondensation reaction if necessary, an additive such as a coloring inhibitor or an antioxidant is added to obtain a polyester having a desired viscosity at a temperature of 200 to 300 ° C. under a reduced pressure of 1 kPa or less. It is preferable to carry out until it is done.
  • the melt polycondensation reaction can be performed using, for example, a tank-type batch polycondensation apparatus or a continuous polycondensation apparatus including a biaxial rotating horizontal reactor.
  • an anti-coloring agent for example, phosphorous acid, phosphoric acid, trimethyl phosphite, triphenyl phosphite, tridecyl phosphite, trimethyl phosphate, tridecyl phosphate, triphenyl Phosphorus compounds such as phosphate can be used. These phosphorus compounds may be used alone or in combination of two or more. When using an anti-coloring agent comprising the above-described phosphorus compound, it is preferably in the range of 0.001 to 0.5 mass% based on the mass of the dicarboxylic acid component.
  • the phosphorus compound When adding a promoter such as a zinc compound, a nickel compound, or a cobalt compound, it is preferable to use the phosphorus compound in combination from the viewpoint of preventing coloring. At this time, the phosphorus compound is preferably added at the time of the esterification reaction. By doing so, it is possible to suppress a decrease in the polymerization rate due to the addition of the phosphorus compound and obtain pellets with good color tone.
  • a promoter such as a zinc compound, a nickel compound, or a cobalt compound
  • antioxidants such as antioxidants, UV absorbers, light stabilizers, antistatic agents, antiblocking agents, lubricants (fatty acid amides, etc.), flame retardants, inorganic or organic fillers, crosslinking agents, dyes, Colorants such as pigments and additives such as modifying resins may be blended.
  • Such an additive may be mixed with the raw material slurry, may be added during the esterification reaction, or may be added during the polycondensation.
  • the intrinsic viscosity of the polyester obtained by melt polycondensation is preferably in the range of 0.4 to 0.85 dL / g from the viewpoint of handleability.
  • the intrinsic viscosity of the polyester obtained by melt polycondensation is less than 0.4 dL / g, when the polyester is taken out from the reactor, the melt viscosity is too low and it becomes difficult to extrude in the form of a strand or a sheet, Moreover, it becomes difficult to cut into pellets uniformly. Furthermore, when solid-phase polymerization is performed, it takes a long time to increase the molecular weight, resulting in a decrease in productivity.
  • the intrinsic viscosity is more preferably 0.5 dL / g or more, and still more preferably 0.6 dL / g or more.
  • the melt viscosity is too high, so that it is difficult to take out the polyester from the reactor, and coloration due to thermal deterioration tends to occur.
  • the intrinsic viscosity is more preferably 0.8 dL / g or less, and still more preferably 0.75 dL / g or less.
  • the polyester obtained by melt polymerization as described above is extruded into a strand shape, a sheet shape, and the like, cooled, and then cut with a strand cutter or a sheet cutter to obtain a cylindrical shape, an elliptical column shape, a disk shape, a die shape. Amorphous pellets of the shape such as are manufactured.
  • the above-described cooling after extrusion can be performed by, for example, a water cooling method using a water tank, a method using a cooling drum, an air cooling method, or the like.
  • the amorphous pellets thus obtained are preferably heated in a temperature range of 100 to 160 ° C. and preliminarily crystallized before being subjected to solid phase polymerization. If it is not pre-crystallized, the pellets will easily stick together during solid phase polymerization. In the case of precrystallization, unmodified PET can be sufficiently crystallized in a short time, but in the case of copolymerized PET containing a certain amount of comonomer components, the crystallization speed is greatly reduced and precrystallization is performed. The problem was that the process took a long time. The present inventors have found that the crystallization rate can be greatly improved by producing amorphous pellets using a catalyst comprising composite particles of hydrotalcite and titanium dioxide.
  • crystallization may be performed in a vacuum tumbler, or crystallization may be performed by heating in an air circulation type heating apparatus.
  • the time required for the precrystallization is not particularly limited, but is usually about 30 minutes to 24 hours.
  • the pellets Prior to precrystallization, the pellets may be dried at a temperature below 100 ° C.
  • the amorphous pellets used for the precrystallization may be a blend of two or more kinds of polyesters.
  • amorphous pellets obtained by melt-kneading two or more kinds of polyester pellets obtained by melt polymerization can be subjected to preliminary crystallization. In this case, what is necessary is just to satisfy the ratio of the monomer unit contained, a polymerization degree, etc. as the whole amorphous pellet obtained by blending.
  • the pellets obtained by pre-crystallizing the amorphous pellets and solid-phase polymerization may satisfy the conditions defined by the present invention as a whole.
  • the solid-state polymerization of the pre-crystallized pellet is preferably performed under reduced pressure or in an inert gas such as nitrogen gas. Further, it is preferable to carry out solid phase polymerization while moving the pellets by an appropriate method such as a rolling method or a gas fluidized bed method so that no sticking occurs between the pellets of the polyester resin composition. Among these, it is preferable to perform solid-state polymerization under reduced pressure.
  • the pressure when solid-state polymerization is performed under reduced pressure is preferably 10 kPa or less, and more preferably 1 kPa or less.
  • the solid phase polymerization temperature is preferably 170 to 230 ° C. When the solid-phase polymerization temperature is less than 170 ° C., the solid-phase polymerization time becomes long and the productivity may be lowered.
  • the solid state polymerization temperature is more preferably 180 ° C. or higher. On the other hand, when the solid phase polymerization temperature exceeds 230 ° C., the pellets may be stuck.
  • the solid state polymerization temperature is more preferably 220 ° C. or lower, and further preferably 210 ° C. or lower.
  • the solid phase polymerization time is usually about 5 to 70 hours.
  • the intrinsic viscosity of the polyester after solid phase polymerization is 0.75 to 1.5 dL / g.
  • the intrinsic viscosity is more preferably 0.8 dL / g or more, and even more preferably 0.85 dL / g or more.
  • the intrinsic viscosity exceeds 1.5 dL / g, the melt viscosity becomes too high, the melt moldability is lowered, and the productivity is also lowered.
  • the intrinsic viscosity is more preferably 1.4 dL / g or less, and even more preferably 1.3 dL / g or less.
  • the intrinsic viscosity of the polyester after the solid phase polymerization is preferably 1.15 times or more, more preferably 1.2 times or more, more preferably 1.25 times or more of the intrinsic viscosity of the polyester before melt kneading. More preferably.
  • the carboxyl group content of the polyester after the solid phase polymerization is preferably 18 ⁇ mol / g or less.
  • it is widely practiced to produce molded products by blending scrap crushed material collected in the factory, such as pinch-off parts generated during extrusion blow molding and ear parts generated during film extrusion, into crystal pellets. It has been broken.
  • the degree of polymerization decreases when the molded product is remelted and recycled. Therefore, when using a polyester having a low carboxyl group content, it is possible to suppress a decrease in the degree of polymerization during remelting and facilitate recycling. Thus, it is possible to realize a manufacturing process with little waste and a low environmental load.
  • the carboxyl group content is more preferably 15 ⁇ mol / g or less.
  • the crystal melting enthalpy of the polyester contained in the crystal pellet of the present invention is 20 J / g or more. Since the crystal pellets obtained by solid-phase polymerization contain polyester that has been crystallized at high temperature for a long time, it has a larger crystal melting enthalpy than the polyester contained in the pellet after precrystallization. ing. The polyester contained in the pellets of the present invention has a large crystal melting enthalpy despite the fact that it contains a certain amount or more of another comonomer unit having 5 or more carbon atoms and thus the crystallinity is lowered.
  • the crystal melting enthalpy is preferably 25 J / g or more, and more preferably 30 J / g or more.
  • the crystal melting enthalpy is usually 50 J / g or less.
  • the melting point of the polyester contained in the crystal pellet of the present invention is preferably 190 to 250 ° C. Decreasing the melting point can improve transparency, moldability, adhesion and the like.
  • the melting point is more preferably 245 ° C. or less, and further preferably 240 ° C. or less. On the other hand, when the melting point is less than 190 ° C., the crystallinity and the melting point become too low, and it becomes easy to stick at the time of solid phase polymerization, and the heat resistance of the obtained molded product is lowered.
  • the melting point is more preferably 200 ° C. or higher, and even more preferably 205 ° C. or higher.
  • the content of the composite particles of hydrotalcite and titanium dioxide contained in the pellet of the present invention is 10 to 300 ppm.
  • the content of the composite particles is more preferably 20 ppm or more, and further preferably 30 ppm or more.
  • the content of the composite particles is more preferably 200 ppm or less, and even more preferably 140 ppm or less.
  • the crystal pellet of the present invention may contain a resin component other than polyester as long as the effects of the present invention are not impaired.
  • the content is usually 5% by mass or less, preferably 1% by mass, and more preferably substantially not contained.
  • the crystal pellet of the present invention may contain inorganic particles other than the composite particles of hydrotalcite and titanium dioxide as long as the effects of the present invention are not impaired.
  • the content is usually 1000 ppm or less, preferably 100 ppm or less, and more preferably substantially free.
  • the crystal pellet of the present invention When the crystal pellet of the present invention was dissolved in an equal mass mixed solvent of phenol and tetrachloroethane and measured with a particle counter, the total volume of particles having a diameter of 1 to 5 ⁇ m contained in 1 g of the pellet was 5.0 ⁇ 10. It is preferably ⁇ 14 m 3 / g or more. It has now been clarified that the crystallization rate of amorphous pellets increases as the total volume of particles having a diameter of 1 to 5 ⁇ m increases. As shown in FIG. 1 and FIG. 2, it seems that a large number of particles having a diameter of less than 1 ⁇ m does not affect the crystallization rate, and particles in a specific particle size range affect the crystallization rate. It seems.
  • the total volume of particles having a diameter of 1 to 5 ⁇ m is more preferably 1.0 ⁇ 10 ⁇ 13 m 3 / g or more, and further preferably 2.5 ⁇ 10 ⁇ 13 m 3 / g or more.
  • the total volume of particles having a diameter of 1 to 5 ⁇ m is usually 1 ⁇ 10 ⁇ 10 m 3 / g or less, and in many cases 1 ⁇ 10 ⁇ 11 m 3 / g or less.
  • the crystal pellet of the present invention when the crystal pellet of the present invention is dissolved in an equal mass mixed solvent of phenol and tetrachloroethane and measured with a particle counter, the total volume of particles having a diameter of 5 to 20 ⁇ m contained in 1 g of the pellet is 1.2. X10 ⁇ 12 m 3 / g or less is preferable. Since the total volume of particles having a diameter of 5 to 20 ⁇ m is small, the pressure increase rate of the filter during extrusion molding can be reduced, and a highly transparent molded product can be continuously melt-formed over a long period of time.
  • the total volume of particles having a diameter of 5 to 20 ⁇ m is more preferably 1.0 ⁇ 10 ⁇ 12 m 3 / g or less, and further preferably 0.9 ⁇ 10 ⁇ 12 m 3 / g or less.
  • the total volume of particles having a diameter of 5 to 20 ⁇ m is usually 1 ⁇ 10 ⁇ 14 m 3 / g or more, and in many cases 1 ⁇ 10 ⁇ 13 m 3 / g or more.
  • the use of the crystalline polyester pellets thus obtained is not particularly limited. Since it contains copolymerized PET containing a comonomer component, it is suitably used for applications that require transparency, adhesion, or moldability. Further, since the degree of polymerization is increased by solid phase polymerization, it is suitably used for applications requiring further strength and impact resistance. Optical films that require a high degree of transparency, film-laminated metal plates that require adhesion and formability, and extrusion blow molded containers that require transparency and impact resistance are particularly suitable applications.
  • the optical film is suitably used as a surface protective film for flat display devices such as liquid crystal displays and organic EL displays, and a polarizing plate support film for liquid crystal displays. Since the crystalline polyester pellets of the present invention have a low pressure increase rate even when a fine filter is used during extrusion molding, by using the pellets, a film having excellent transparency with few coarse particles can be obtained with high productivity. Can be molded.
  • a film laminated metal plate for can making is suitable.
  • the pellet of the present invention having good adhesion and formability.
  • the polyester of the present invention having a high degree of polymerization is preferable because the film is hardly damaged when the molded can is deformed.
  • the metal plate on which the polyester film is laminated include a steel plate and an aluminum plate.
  • the extrusion blow molded container it is suitably used as a blow molded bottle for storing cosmetics, beverages, pharmaceuticals, seasonings and the like.
  • the crystalline polyester pellet of the present invention has high transparency and is less likely to be whitened due to crystallization during molding.
  • the degree of polymerization is high and the impact resistance is also excellent.
  • a polyfunctional monomer as a comonomer, it is possible to obtain pellets having good draw-down resistance and good moldability.
  • the volume of particles having a diameter of 1 to 5 ⁇ m was integrated, and the total volume was determined as a value per 1 g of pellets. Further, the volume of particles having a diameter of 5 to 20 ⁇ m was integrated, and the total volume was determined as a value per 1 g of pellets.
  • the resin color (b value) of the crystal pellets after solid-phase polymerization is determined according to ASTM-D2244 (color scale system 2), a colorimetric color difference meter “ZE-2000” manufactured by Nippon Denshoku Industries Co., Ltd. It measured using.
  • Example 1 Melt polycondensation A slurry consisting of 85.0 parts by mass of terephthalic acid (TA), 15.0 parts by mass of isophthalic acid (IPA) and 44.8 parts by mass of ethylene glycol (EG) was prepared and subjected to pressure (gauge pressure 0 The oligomer was produced by heating to 250 ° C. at a temperature of 250 MPa for esterification reaction. The obtained oligomer was transferred to a polycondensation tank, and 0.033 parts by mass of SATICA SPC-124-20 (manufactured by Sakai Chemical Industry Co., Ltd.), which is an ethylene glycol dispersion of composite particles of hydrotalcite and titanium dioxide.
  • SATICA SPC-124-20 manufactured by Sakai Chemical Industry Co., Ltd.
  • polyester having an intrinsic viscosity of 0.69 dL / g was produced by melt polycondensation at 0.1 kPa and 280 ° C. for 90 minutes. The obtained polyester was extruded into a strand form from a nozzle and cooled with water, and then cut into a cylindrical shape (diameter: about 2.5 mm, length: about 2.5 mm) to obtain an amorphous pellet of polyester.
  • the melting point (Tm), glass transition temperature (Tg) and melting enthalpy ( ⁇ Hm) were 212 ° C., 76 ° C. and 38 J / g, respectively.
  • the b value was 8.
  • the volume of particles having a diameter of 1 to 5 ⁇ m is 7.2 ⁇ 10 ⁇ 13 m 3 / g
  • the volume of particles having a diameter of 5 to 20 ⁇ m is 7.6 ⁇ 10 ⁇ 13 m 3 / g. there were.
  • the melt viscosity at 260 ° C. and 15 sec ⁇ 1 was 2000 Pa ⁇ sec.
  • Example 2 Example 1 except that the amount of the polymerization catalyst was 0.0023 parts by mass, the amount of phosphorous acid was 0.0023 parts by mass, the melt polymerization time was 120 minutes, and the solid-phase polymerization time was 40 hours. In the same manner, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Example 3 Example 1 except that the amount of the polymerization catalyst was 0.010 parts by mass, the amount of phosphorous acid was 0.010 parts by mass, the melt polymerization time was 80 minutes, and the solid phase polymerization time was 17 hours. In the same manner, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Example 4 Example 1 except that the amount of the polymerization catalyst was 0.017 parts by mass, the amount of phosphorous acid was 0.017 parts by mass, the melt polymerization time was 75 minutes, and the solid phase polymerization time was 12 hours. In the same manner, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Comparative Example 1 Melt polymerization was carried out in the same manner as in Example 1 except that the amount of the polymerization catalyst was 0.0006 parts by mass and the amount of phosphorous acid was 0.0006 parts by mass, but the degree of polymerization was sufficiently increased. As a result, pellets could not be obtained and subsequent evaluation was not performed. The results are summarized in Tables 1 and 2.
  • Comparative Example 2 Example except that 0.041 parts by mass of titanium (IV) tetraisopropoxide was added as a polymerization catalyst, the amount of phosphorous acid was 0.007 parts by mass, and the solid phase polymerization time was 35 hours. In the same manner as in Example 1, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Comparative Example 3 As a polymerization catalyst, it is the same as Example 1 except that 0.012 parts by mass of germanium dioxide (GeO 2 ) is added, the amount of phosphorous acid is 0.012 parts by mass, and the solid phase polymerization time is 20 hours. Crystal pellets were manufactured and evaluated. The results are summarized in Tables 1 and 2.
  • Comparative Example 4 Example except that 0.042 parts by mass of antimony trioxide (Sb 2 O 3 ) was compounded as a polymerization catalyst, the amount of phosphorous acid was 0.012 parts by mass, and the solid phase polymerization time was 25 hours.
  • Sb 2 O 3 antimony trioxide
  • Example 5 A slurry composed of 85.0 parts by mass of terephthalic acid, 15.0 parts by mass of isophthalic acid, and 44.8 parts by mass of ethylene glycol was prepared, and “SATA SPC-124-20” (manufactured by Sakai Chemical Industry Co., Ltd.) 033 parts by mass (of which 0.007 parts by mass of composite particles as a polymerization catalyst and 0.026 parts by mass of ethylene glycol) and 0.007 parts by mass of phosphorous acid were added.
  • This slurry was heated to a temperature of 250 ° C. under pressure (gauge pressure of 0.25 MPa) to carry out an esterification reaction to produce a low polymer.
  • crystal pellets were produced and evaluated in the same manner as in Example 1 except that the solid phase polymerization time was set to 70 hours. The results are summarized in Tables 1 and 2.
  • Example 5 except that 0.041 parts by mass of titanium (IV) tetraisopropoxide was added as a polymerization catalyst, the amount of phosphorous acid was 0.007 parts by mass, and the solid-state polymerization time was 40 hours. In the same manner, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Comparative Example 6 As Example 5, except that 0.012 parts by mass of germanium dioxide (GeO 2 ), 0.012 parts by mass of phosphorous acid, and 20 hours of solid phase polymerization were used. Crystal pellets were manufactured and evaluated. The results are summarized in Tables 1 and 2.
  • Comparative Example 7 Example except that 0.042 parts by mass of antimony trioxide (Sb 2 O 3 ) was compounded as a polymerization catalyst, the amount of phosphorous acid was 0.012 parts by mass, and the solid phase polymerization time was 25 hours. In the same manner as in Example 5, crystal pellets were produced and evaluated. The results are summarized in Tables 1 and 2.
  • Sb 2 O 3 antimony trioxide
  • Example 6 That 0.007 parts by mass of zinc acetate was added before the esterification reaction, that the addition time of 0.007 parts by mass of phosphorous acid was changed before the esterification reaction, that the melt polymerization time was 80 minutes, Crystal pellets were produced and evaluated in the same manner as in Example 1 except that the polymerization time was 25 hours. The results are summarized in Tables 1 and 2.
  • Example 7 A slurry composed of 73.1 parts by mass of terephthalic acid, 10.7 parts by mass of isophthalic acid, 16.2 parts by mass of hydrogenated dimer acid (HDA) and 39.0 parts by mass of ethylene glycol was prepared, and the solid-state polymerization time was 30 hours. Except that, crystal pellets were produced and evaluated in the same manner as in Example 1. The results are summarized in Tables 1 and 2.
  • Example 8 (1) Production of crystal pellets A slurry consisting of 100 parts by mass of terephthalic acid, 42.6 parts by mass of ethylene glycol and 9.5 parts by mass of bisphenol A ethylene oxide adduct (BPE) was prepared. Crystal pellets were produced and evaluated in the same manner as in Example 1 except that the phase polymerization time was 40 hours. The filter pressurization test during extrusion was not performed. The results are summarized in Tables 1 and 2.
  • Bottle drop test After putting water (water temperature 20-25 ° C) so that the total weight becomes 263 g ⁇ 0.5 g in the bottle immediately after molding, it is passed through a 10 cm diameter cylinder installed vertically, From a height of 100 cm, it was dropped alternately on a horizontal concrete surface and a concrete surface inclined 45 degrees. The number of cycles until the bottle was cracked or cracked (the bottle was dropped twice in total, once on the horizontal surface and once on the 45 ° slope) was measured. Up to 10 cycles were repeated. As a result of a drop test of a total of 10 bottles, no bottles were broken.
  • Example 9 That 0.007 parts by mass of cobalt acetate was added before the esterification reaction, that the addition time of 0.007 parts by mass of phosphorous acid was changed before the esterification reaction, that the melt polymerization time was 80 minutes, Crystal pellets and extrusion blow molded bottles were produced and evaluated in the same manner as in Example 8 except that the polymerization time was 35 hours. The results are summarized in Tables 1 and 2.
  • Example 10 A slurry consisting of 100 parts by weight of terephthalic acid, 38.1 parts by weight of ethylene glycol and 13.0 parts by weight of cyclohexanedimethanol (CHDM) is prepared and heated to a temperature of 250 ° C. under pressure (gauge pressure of 0.25 MPa) to form an ester. A low polymer was produced by carrying out a polymerization reaction. The obtained low polymer was transferred to a polycondensation tank, and 0.033 parts by mass of SATICA SPC-124-20 (manufactured by Sakai Chemical Industry Co., Ltd.) (of which, composite particles as a polymerization catalyst were 0.007 parts by mass).
  • CHDM cyclohexanedimethanol
  • ethylene glycol is 0.026 parts by mass
  • hindered phenol-based antioxidant (“Irganox 1010” manufactured by BASF) 0.012 parts by mass
  • phosphite-based antioxidant (“ADEKA STAB PEP-36 manufactured by ADEKA Corporation) ]
  • Polyester having an intrinsic viscosity of 0.69 dL / g was produced by melt polycondensation at 280 ° C. for 90 minutes under 0.1 kPa. The obtained polyester was extruded into a strand form from a nozzle and cooled with water, and then cut into a cylindrical shape (diameter: about 2.5 mm, length: about 2.5 mm) to obtain an amorphous pellet of polyester.
  • Comparative Example 8 Except that a slurry consisting of 98.0 parts by mass of terephthalic acid, 2.0 parts by mass of isophthalic acid and 44.8 parts by mass of ethylene glycol was prepared, the solid phase polymerization temperature was 225 ° C., and the solid phase polymerization time was 20 hours. As in Example 8, crystal pellets and extrusion blow molded bottles were produced and evaluated. Since the mouth of the bottle was whitened during molding and a bottle with good transparency could not be obtained, the bottle drop test was not performed. The results are summarized in Tables 1 and 2.
  • FIG. 1 and FIG. 2 show the particle size distribution measurement charts of Example 1 using composite particles of hydrotalcite and titanium dioxide as a catalyst and Comparative Example 3 using germanium dioxide (GeO 2 ) as a catalyst. Contrast. In Comparative Example 3, the peak of the particle size distribution was 0.60 ⁇ m, whereas in Example 1, it was 1.04 ⁇ m, and the peak value of Comparative Example 3 was smaller. However, the number of particles having a diameter of 1 to 5 ⁇ m was larger in Example 1, and the number of particles having a diameter of 5 to 20 ⁇ m was larger in Comparative Example 3. From this, it is presumed that particles having a diameter of 1 to 5 ⁇ m have an influence on the crystallization speed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une pastille de polyester cristallin comprenant une composition de résine contenant du polyester et une particule complexe. Le polyester contient 25 à 50 % en mole de motifs acide téréphtalique, 25 à 49,5 % en mole de motifs éthylène glycol, 0,5 à 2,5 % en mole de motifs diéthylène glycol, et 1,5 à 25 % en moles d'autres motifs co-monomères ayant 5 atomes de carbone ou plus. La viscosité intrinsèque du polyester est de 0,75 à 1,5 dl/g. L'enthalpie de fusion cristalline de la pastille est de 20 J/g ou plus. La particule complexe est une particule complexe d'hydrotalcite et de dioxyde de titane. La teneur en particule complexe de la pastille est de 10 à 300 ppm. De cette manière, une pastille de cristal de copolymère de PET provoquant peu de stress pour l'environnement peut être produite par un procédé présentant une excellente productivité.
PCT/JP2016/069262 2015-06-30 2016-06-29 Pastille de polyester cristallin, son application et son procédé de production WO2017002852A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018150468A (ja) * 2017-03-14 2018-09-27 三菱ケミカル株式会社 ポリエステルの製造方法
WO2022209940A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Pastille

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006188567A (ja) * 2004-12-30 2006-07-20 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
WO2008001473A1 (fr) * 2006-06-28 2008-01-03 Sakai Chemical Industry Co., Ltd. catalyseur de polycondensation pour la production de polyester et production de polyester
JP2008007588A (ja) * 2006-06-28 2008-01-17 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2009046593A (ja) * 2007-08-20 2009-03-05 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とその製造方法とこれを用いるポリエステルの製造方法
JP2010209358A (ja) * 2010-06-28 2010-09-24 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2011063640A (ja) * 2009-09-15 2011-03-31 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2012077112A (ja) * 2010-09-30 2012-04-19 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
WO2014021206A1 (fr) * 2012-07-31 2014-02-06 堺化学工業株式会社 Catalyseur de polycondensation pour la fabrication de polyester et fabrication de polyester à l'aide du catalyseur de polycondensation pour la fabrication de polyester
WO2015041271A1 (fr) * 2013-09-20 2015-03-26 堺化学工業株式会社 Procédé de production de polyester

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1244549B (it) * 1991-02-06 1994-07-15 Montedipe Srl Composizioni da stampaggio a base di poliestere
US9777111B2 (en) * 2005-10-20 2017-10-03 Grupo Petrotemex, S.A. De C.V. PET polymer with improved properties

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006188567A (ja) * 2004-12-30 2006-07-20 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
WO2008001473A1 (fr) * 2006-06-28 2008-01-03 Sakai Chemical Industry Co., Ltd. catalyseur de polycondensation pour la production de polyester et production de polyester
JP2008007588A (ja) * 2006-06-28 2008-01-17 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2009046593A (ja) * 2007-08-20 2009-03-05 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とその製造方法とこれを用いるポリエステルの製造方法
JP2011063640A (ja) * 2009-09-15 2011-03-31 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2010209358A (ja) * 2010-06-28 2010-09-24 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
JP2012077112A (ja) * 2010-09-30 2012-04-19 Sakai Chem Ind Co Ltd ポリエステル製造用重縮合触媒とこれを用いるポリエステルの製造方法
WO2014021206A1 (fr) * 2012-07-31 2014-02-06 堺化学工業株式会社 Catalyseur de polycondensation pour la fabrication de polyester et fabrication de polyester à l'aide du catalyseur de polycondensation pour la fabrication de polyester
WO2015041271A1 (fr) * 2013-09-20 2015-03-26 堺化学工業株式会社 Procédé de production de polyester

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018150468A (ja) * 2017-03-14 2018-09-27 三菱ケミカル株式会社 ポリエステルの製造方法
WO2022209940A1 (fr) * 2021-04-02 2022-10-06 住友化学株式会社 Pastille

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