WO2001005865A1 - Composition de resine de polyester - Google Patents

Composition de resine de polyester Download PDF

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Publication number
WO2001005865A1
WO2001005865A1 PCT/JP2000/003676 JP0003676W WO0105865A1 WO 2001005865 A1 WO2001005865 A1 WO 2001005865A1 JP 0003676 W JP0003676 W JP 0003676W WO 0105865 A1 WO0105865 A1 WO 0105865A1
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WIPO (PCT)
Prior art keywords
polyester resin
resin composition
compounds
cobalt
compound
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PCT/JP2000/003676
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English (en)
Japanese (ja)
Inventor
Chihiro Okamoto
Original Assignee
Kuraray Co., Ltd.
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Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to AU51059/00A priority Critical patent/AU5105900A/en
Publication of WO2001005865A1 publication Critical patent/WO2001005865A1/fr

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    • 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

Definitions

  • the present invention relates to a polyester resin composition, and a molded article such as a bottle using the polyester resin composition. More specifically, the present invention is excellent in resistance to hydrogen peroxide, swells even when exposed to hydrogen peroxide, does not cause intrusion of hydrogen peroxide, and is excellent in transparency.
  • the present invention relates to a polyester resin composition having excellent mechanical properties, heat resistance, flavor barrier properties, gas barrier properties and the like, and molded articles such as bottles comprising the same.
  • Containers such as bottles obtained by blow molding or injection blow molding of polyethylene terephthalate have excellent transparency, mechanical strength, sanitary properties, flavor-barrier properties, gas barrier properties, and economic efficiency. Widely used as beverage containers for soft drinks, mineral water, tea, etc.
  • a method using hydrogen peroxide is generally used.However, if hydrogen peroxide treatment is performed, the swelling of the container and intrusion of hydrogen peroxide into the container wall will occur. This is likely to occur, and hydrogen peroxide migrates into beverages filled in containers, which may lead to a decrease in food quality and safety.
  • an object of the present invention is to maintain excellent properties such as mechanical strength, heat resistance, flavor barrier property, and gas barrier property of a polyester resin, and have excellent resistance to hydrogen peroxide. Peracid Even when sterilized with hydrogen fluoride, it does not cause problems such as swelling, intrusion of hydrogen peroxide into the container wall, transfer of hydrogen peroxide to beverages filled in containers, etc., and it has excellent transparency An object of the present invention is to provide a polyester resin composition.
  • an object of the present invention is to provide a molded article such as a bottle made of the polyester resin composition described above. Disclosure of the invention
  • the polyester resin has at least one selected from the group consisting of isophthalic acid units, cyclohexanedimethanol units and naphthalenedicarboxylic acid units.
  • a polyethylene terephthalate resin having one type of structural unit at a predetermined ratio is used, and a specific amount of a cobalt compound is contained in the polyester resin.
  • the polyester resin composition and the molded article obtained therefrom have high resistance to hydrogen peroxide, swell even when subjected to a sterilization treatment with hydrogen peroxide, and the container wall. No problems such as intrusion of hydrogen peroxide into water and migration of hydrogen peroxide into beverages filled in containers, etc., as well as excellent transparency, and the good machinery inherent in polyester resin It has been found that it has the properties such as mechanical strength, heat resistance, flavor barrier properties and gas barrier properties without loss.
  • the present inventor selected from the group consisting of a manganese compound, a zinc compound, a copper compound, an iron compound, a silver compound, a tin compound, a chromium compound, a Nigger compound, and a lead compound in the above polyester resin composition.
  • a polyester resin composition comprising at least one structural unit selected from the group consisting of 0.5 to 4.5 mol% based on the total number of moles of all structural units;
  • C c. Is the content of cobalt compound in terms of cobalt atom relative to the total number of dicarboxylic acid units in the polyester resin (millimol, CP is the content of phosphorous compound in terms of phosphorus atom in relation to the total number of dicarboxylic acid units in the polyester resin ( (Millimol%)].
  • the polyester resin comprises at least one structural unit selected from the group consisting of an isophthalic acid unit, a cyclohexanedimethanol unit and a naphthalenedicarboxylic acid unit, based on the total number of moles of all the structural units.
  • the polyester resin composition according to the above (1) which has a proportion of about 4.0 mol%;
  • the polyester resin has at least one structural unit selected from the group consisting of an isophthalic acid unit, a cyclohexanedimethanol unit and a naphthalenedicarboxylic acid unit, based on the total number of moles of all structural units in a range of 1.5 to 1.5.
  • the ratio (CPZCC) of the phosphorus compound content (c P ) (milli mol%) to the cobalt compound content (C c .) (Milli mol%) is expressed by the following formula: 0 ⁇ C P / The polyester resin composition of (1), which satisfies Cco ⁇ 0.05; and
  • CM is at least one selected from the group consisting of manganese compounds, zinc compounds, copper compounds, iron compounds, silver compounds, tin compounds, chromium compounds, nickel compounds, and lead compounds based on the total number of moles of dicarboxylic acid units in the polyester resin. Represents the content (millimol%) of the metal compound in terms of metal atom. ].
  • the content of at least one metal compound selected from the group consisting of manganese compounds, zinc compounds, copper compounds, iron compounds, silver compounds, tin compounds, chromium compounds, nickel compounds and lead compounds (CM ) (Millimol%) satisfy the formula: 15 ⁇ C M ⁇ 50, and the content of cobalt compound (Cc.) (Millimol%) and the content of metal compound (CM) ( total formula Rimoru%): 4 satisfies 5 ⁇ Cco + C M ⁇ 1 5 0, the polyester resin composition of the (1 0); and,
  • An alkali metal salt of an aliphatic carboxylic acid having 1 to 15 carbon atoms is The polyester resin composition according to any one of the above (1) to (12), which is contained at a rate of 100 to 10,000 ppm in terms of metal atoms based on the weight of the ester resin; and
  • Bottonore comprising the polyester resin composition according to any one of (1) to (14);
  • the polyester resin which is a main component of the polyester resin composition of the present invention is mainly composed of a diol unit mainly composed of an ethylene glycol unit and a dicarboxylic acid unit mainly composed of a terephthalic acid unit, and further includes an isophthalic acid unit and a cyclohexanedimethanol.
  • the polyester resin used in the polyester resin composition of the present invention has the structural unit composition described above.
  • the fat composition and molded articles such as bottles obtained therefrom are excellent in transparency and also excellent in mechanical properties, heat resistance, flavor barrier properties, gas barrier properties, and the like.
  • the polyester resin crystallizes. Blow moldability when producing a molded article such as a bottle from the composition containing the polyester resin is impaired, and the resulting molded article has reduced transparency.
  • the polyester resin becomes It becomes non-crystalline or close to it, causing agglutination during solid-phase polymerization, making solid-phase polymerization difficult to increase the degree of polymerization of polyester resin, resulting in low intrinsic viscosity of polyester resin and heat resistance Properties and mechanical properties are reduced.
  • a polyester resin that has not been highly polymerized contains a large amount of a low polymer (oligomer)
  • a mold such as a mold using the low polymer is used. The device is easily soiled.
  • the polyester resin used in the present invention comprises at least one structural unit selected from the group consisting of an isophthalic acid unit, a cyclohexane dimethanol unit and a naphthalenedicarboxylic acid unit, and a total mole number of all the structural units constituting the polyester resin. It is preferably contained in a proportion of 1.0 to 4.0 mol%, more preferably in a proportion of 1.5 to 4.0 mol%, based on
  • the excess of the polyester resin composition In order to improve properties such as resistance to hydrogen oxide, transparency, mechanical properties, gas barrier properties, and flavor barrier properties, terephthalic acid is used based on the total number of moles of all structural units constituting the polyester resin.
  • the proportion of the acid unit is preferably from 45.5 to 50 mol%, more preferably from 46 to 50 mol%, and the proportion of the ethylene glycol unit is from 45.5 to 50 mol%. And more preferably 46 to 50 mol%.
  • the polyester resin used in the present invention may be any of the above-mentioned terephthalic acid units and ethylene glycol within a range that does not impair the properties such as resistance to hydrogen peroxide, transparency, mechanical properties, heat resistance, flavor barrier properties, and gas barrier properties. It may have a structural unit other than at least one structural unit selected from the group consisting of a unit, an isophthalic acid unit, a cyclohexanedimethanol unit, and a naphthalenedicarboxylic acid unit.
  • Such other structural units include diol units derived from diols such as diethylene glycol, 1,4-butanediol, polyethylene glycol (preferably molecular weight 400-3000); Aromatic dicarboxylic acids such as para-perylenedicarboxylic acid and sulfoisophthalic acid; aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and sebacic acid or ester-forming derivatives thereof And the like.
  • the polyester resin may have one or more of the other structural units described above. In general, the proportion of the above-mentioned other structural units in the polyester resin is preferably 5 mol% or less, and more preferably 3 mol% or less, based on the total moles of all the structural units of the polyester resin. More preferred.
  • the polyester resin used in the present invention has an intrinsic viscosity (measured at 30 ° C in a mixed solvent of phenol Z tetrachloroethane in an equal weight) of 0.60 to less.
  • the content is within the range of 1.50 d1 Zg, the moldability when producing a molded article such as a bottle from the polyester resin composition and the mechanical properties of the obtained molded article are improved. preferable.
  • the polyester resin composition of the present invention contains a cobalt compound in the polyester resin having the above-mentioned specific structural unit composition in a ratio satisfying the following formula (1).
  • C c Is the content of cobalt compound in terms of cobalt atom (milli mol%) relative to the total number of moles of dicarboxylic acid units in the polyester resin, and CP is the content of phosphorus compound in terms of phosphorus atom (total mole number of dicarboxylic acid units in the polyester resin). (Millimol%).
  • the polyester resin composition and the bottles and the like obtained from the composition may be used.
  • the resistance of the molded article to hydrogen peroxide is reduced, and swelling and intrusion of hydrogen peroxide are liable to occur when the hydrogen peroxide treatment is performed, resulting in peroxides in beverages filled in such molded articles (containers). Hydrogen is easily eluted.
  • the polyester resin composition may be melt-molded. The resin decomposes and the strength of molded products such as bottles decreases.
  • the polyester resin composition of the present invention has a cobalt compound content (C co) is preferably in the range of from 30 to 100 millimol%.
  • C co cobalt compound content
  • cobalt compound used in the polyester resin composition of the present invention For example, cobalt salts of fatty acids such as cobalt formate, cobalt acetate, and cobalt propionate; cobalt halides such as cobalt chloride, cobalt bromide, cobalt iodide, and cobalt fluoride; cobalt sulfate; cobalt sulfide; and cobalt oxide.
  • cobalt hydroxide and one or more of these can be used.
  • cobalt compound one or more of cobalt acetate, cobalt sulfate and cobalt oxide are preferably used from the viewpoint of catalytic activity when a polyester resin is produced by a transesterification reaction. .
  • the content of the phosphorus compound [the ratio of the content of the phosphorus compound to the content of the cobalt compound (C PZ C co)] satisfies the following formula (1). is necessary.
  • C C The content of cobalt atoms in terms of a cobalt compound to the total moles of the dicarboxylic acid units in the polyester resin (Mi Rimoru%)
  • C P is the content of phosphorus atoms in terms of the phosphorus compound to the total moles of the dicarboxylic acid units in the polyester resin (Millimol%).
  • the cobalt compound contained in the polyester resin composition may contain the phosphorus compound. And thereby the resistance of the polyester resin composition and molded articles such as bottles to hydrogen peroxide is reduced, and the swelling resin composition due to the hydrogen peroxide and the hydrogen peroxide in the molded articles are reduced. Intrusion easily occurs, and elution of hydrogen peroxide into foods such as beverages filled in a container made of the polyester resin composition easily occurs.
  • the ratio of the content of the phosphorus compound to the content of the cobalt compound (C PZ CCO) is from 0 to 0.05. It is preferable from the viewpoint of resistance to hydrogen peroxide, and more preferably 0 to 0.01.
  • polyester resin composition of the present invention contains a phosphorus compound
  • examples of the phosphorus compound that can be used include phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, and the like. Trioctylphosphonate, triphenylphosphine and the like can be mentioned. As will be described later, these phosphorus compounds prevent coloring and molecular weight reduction due to thermal decomposition of the polyester resin during melt molding of the polyester resin composition during the melt polycondensation reaction for producing the polyester resin. Often used for
  • the polyester resin composition of the present invention comprises, together with a cobalt compound, at least one selected from the group consisting of a manganese compound, a zinc compound, a copper compound, an iron compound, a silver compound, a tin compound, a chromium compound, a Nigel compound, and a lead compound.
  • Metal compounds can be included. By containing these metal compounds, the resistance of the polyester resin composition to hydrogen peroxide is often further improved.
  • the polyester resin composition of the present invention contains these metal compounds, the content thereof (CM) [the content of these metal compounds in terms of metal atoms relative to the total number of moles of dicarboxylic acid units in the polyester resin (M )] Is less than or equal to 150 millimol%, and the sum (CC.
  • the polyester resin composition of the present invention together with a cobalt compound, at least one selected from the group consisting of a manganese compound, a zinc compound, a copper compound, an iron compound, a silver compound, a tin compound, a chromium compound, a Nigger compound, and a lead compound.
  • a cobalt compound at least one selected from the group consisting of a manganese compound, a zinc compound, a copper compound, an iron compound, a silver compound, a tin compound, a chromium compound, a Nigger compound, and a lead compound.
  • the content (content rate) of these metal compounds is particularly preferably an amount that satisfies the following formulas (3) and (4).
  • the resistance to hydrogen peroxide of the polyester resin composition can be further improved while preventing decomposition.
  • C c. And CM are the above-mentioned contents of cobalt compound in terms of cobalt atom (millimol%), and manganese compounds, zinc compounds, copper compounds, iron compounds, silver compounds, tin compounds, chromium compounds, nickel compounds And the content (milli-mol%) of at least one metal compound selected from the group consisting of lead compounds and lead compounds in terms of metal atoms. ]
  • CM is in the range of 15 to 50 millimol%, and the sum (CC. + CM) of the content (CM) of the metal compound and the content (Cc) of the cobalt compound is 45. More preferably, it is in the range of ⁇ 150 millimol%.
  • manganese compounds that can be used in the polyester resin composition of the present invention
  • Manganese salts of fatty acids such as manganese formate, manganese acetate, and manganese propionate
  • manganese halides such as manganese chloride, manganese bromide, manganese iodide, and manganese fluoride
  • manganese sulfate manganese sulfide, and manganese oxide And manganese hydroxide.
  • fatty acids such as manganese formate, manganese acetate, and manganese propionate
  • manganese halides such as manganese chloride, manganese bromide, manganese iodide, and manganese fluoride
  • manganese sulfate manganese sulfide
  • manganese oxide And manganese hydroxide One or more of these can be used.
  • Examples of zinc compounds that can be used in the polyester resin composition of the present invention include zinc salts of fatty acids such as zinc formate, zinc acetate, zinc propionate, zinc chloride, zinc bromide, zinc iodide, and zinc fluoride. Examples thereof include zinc halide, zinc sulfate, zinc sulfide, zinc oxide, and zinc hydroxide, and one or more of these can be used.
  • Examples of copper compounds that can be used in the polyester resin composition of the present invention include copper salts of fatty acids such as copper formate, copper acetate, and copper propionate; and copper such as copper chloride, copper bromide, iodide, and copper fluoride. Halide, copper sulfate, copper sulfide, copper oxide, copper hydroxide and the like, and one or more of these can be used.
  • One or more kinds can be used.
  • Examples of lead compounds that can be used in the polyester resin composition of the present invention include lead salts of fatty acids such as lead formate, lead acetate and lead propionate, and lead such as lead chloride, lead bromide, lead iodide and lead fluoride. Halide, lead sulfate, lead sulfide, lead oxide, lead hydroxide and the like, and one or more of these can be used.
  • the polyester resin composition of the present invention contains 100 ppm or less of an alkali metal salt of an aliphatic carboxylic acid having 1 to 15 carbon atoms in terms of an alkali metal atom based on the weight of the polyester resin. May be further contained.
  • the alkali metal salt of the aliphatic carboxylic acid When the alkali metal salt of the aliphatic carboxylic acid is contained, its content in terms of alkali metal atom should be within the range of 100 to 100 ppm based on the weight of the polyester resin. Is more preferably in the range of 200 to 800 ppm, whereby the resistance to hydrogen peroxide of the polyester resin composition and molded articles such as bottles obtained therefrom is further improved. .
  • the content of alkali metal salts of aliphatic carboxylic acids in terms of alkali metal atoms exceeds 1000 ppm, the transparency of molded articles such as bottles obtained therefrom decreases, which is desirable. Absent.
  • Examples of the alkali metal salt of an aliphatic carboxylic acid having 1 to 15 carbon atoms that can be used in the polyester resin composition of the present invention include: sodium formate, sodium acetate, sodium acetate acetate, sodium propionate, potassium propionate, Sodium butyrate, potassium butyrate, sodium valerate, sodium valerate, sodium cabrate, potassium cabrate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, etc. One or more of these can be used.
  • the polyester resin used in the polyester resin composition of the present invention can be produced according to a method generally employed for producing a general-purpose polyester resin such as polyethylene terephthalate, and is not particularly limited.
  • a polyester resin comprising a dicarboxylic acid component mainly composed of dicarboxylic acid or a lower alkyl ester of terephthalic acid and a diol component mainly composed of ethylene glycol, and is a raw material for isophthalic acid, naphthalenedicarboxylic acid, Raw materials for polyester resins containing at least one of hexane dimethanol and their ester-forming derivatives at a predetermined ratio (ie, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane dimethanol and their ester-forming properties) At least one selected from derivatives is used in an amount such that the proportion of the structural units derived therefrom is 0.5 to 4.5 mol% based on the total moles of all
  • the oligomer by melt polycondensation Po Producing a polyester resin which can be effectively used in the polyester resin composition of the present invention by producing a polyester, then forming the polyester into a chip pellet having an arbitrary shape, and subjecting it to solid phase polymerization, if desired. Can be.
  • the above-mentioned low polymer is produced by an esterification reaction
  • the above-mentioned raw material for the polyester resin is The esterification reaction may be performed at a temperature of about 230 to 280 ° C. under a normal pressure or an absolute pressure of 3 kg / cm 2 or less.
  • the molar ratio of the dicarboxylic acid component to the diol component is preferably in a molar ratio of 1: 1 to 1: 1.5.
  • the above-mentioned polyester resin raw material is preferably subjected to a transesterification reaction at about 170 to 230 ° C. under normal pressure or near normal pressure.
  • the molar ratio of the dicarboxylic acid component to the diol component is preferably 1: 1 to 1: 3.
  • the catalyst used for the transesterification reaction include the above-mentioned metal compounds (for example, cobalt compounds and manganese compounds) contained in the polyester resin composition of the present invention, or tetraisopropyl titanate and tetrabutyl titanate which have been conventionally used widely. And titanates such as tetrastearyl titanate.
  • the above-mentioned melt polycondensation for obtaining a polyester from a low polymer is usually performed at a temperature of about 260 to 290 ° C in the presence of a polycondensation catalyst such as germanium dioxide or antimony trioxide.
  • a polycondensation catalyst such as germanium dioxide or antimony trioxide.
  • germanium dioxide in an amount in the range of 50 to 300 ppm with respect to the obtained polyester resin, it has excellent resistance to hydrogen peroxide and When treated with hydrogen, a polyester resin free from swelling and intrusion of hydrogen peroxide can be obtained, which is preferable.
  • a polyester having an intrinsic viscosity of 0.5 to 1.5 d1 / g is obtained.
  • the above melt polycondensation reaction is carried out by converting a phosphorus compound such as phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like.
  • a phosphorus compound such as phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like.
  • the addition is preferable because it is possible to prevent coloring of the resulting polyester resin by thermal decomposition and a decrease in the molecular weight during melt molding, as described above.
  • the phosphorus compound may be changed to the cobalt compound contained in the polyester resin composition, the manganese compound, the zinc compound, the copper compound, and the iron compound described above.
  • esterification, transesterification, and polycondensation reactions described above are carried out by adding a diethylene glycol by-product inhibitor such as tetraethylammonium hydroxide, triethanolamine, or triethylamine as necessary. You may.
  • a diethylene glycol by-product inhibitor such as tetraethylammonium hydroxide, triethanolamine, or triethylamine as necessary. You may.
  • the polyester obtained by the above melt polycondensation reaction is generally formed into chips or pellets and, if desired, is preliminarily crystallized at a temperature of 190 ° C. or lower, and then subjected to solid-state polymerization.
  • solid-state polymerization heat is applied to about 190 to 240 ° C under reduced pressure or under the flow of an inert gas such as nitrogen gas while flowing chips (pellets) so that they do not fuse together. It is preferable to do it.
  • the intrinsic viscosity (measured at 30 ° C in a mixed solvent of phenol, tetrachloro-mouth and ethane with an equal weight) of the resulting polyester resin is about 0.6 to 1.5 dl / It is preferable to perform solid-phase polymerization so as to be in the range of g.
  • polyester resin preferably used in the polyester resin composition of the present invention can be obtained.
  • the polyester resin composition of the present invention may contain conventionally known various additives depending on the use and the like as long as the object of the invention is not impaired.
  • a hydrolysis inhibitor, a colorant, a flame retardant examples include antioxidants, ultraviolet absorbers, antistatic agents, lubricants and the like.
  • antioxidants ultraviolet absorbers, antistatic agents, lubricants and the like.
  • the polyester resin composition of the present invention is used for the production of a molded article used in direct contact with food such as a bottle, it is necessary to select the type of additive in consideration of safety. There is.
  • Alcohol force of cobalt compound, phosphorus compound, manganese compound, zinc compound, copper compound, iron compound, silver compound, tin compound, chromium compound, nickel compound, lead compound, and aliphatic carboxylic acid in the polyester resin composition of the present invention is not particularly limited, and these compounds can be added during or after the production of the polyester resin.
  • the form of the polyester resin composition of the present invention is not particularly limited, but if it is in the form of pellets or chips, it can be conveniently used for various moldings.
  • the polyester resin composition of the present invention is subjected to heat-melt molding to obtain various molded articles such as a film, a sheet, a plate-like body, a tubular body, a hollow molded article, a molded article, and a laminate. Therefore, the present invention includes the above various molded articles within the scope of the present invention.
  • any molding method used for molding a thermoplastic resin can be used, for example, an extrusion molding method, an extrusion blow molding method, an injection molding method, an injection blow molding method, a casting molding method. , Calender molding method, press molding method, casting method, various lamination molding methods and the like can be adopted.
  • the polyester resin composition of the present invention utilizes the properties such as good hydrogen peroxide resistance, transparency, mechanical properties, heat resistance, flavor barrier properties, gas barrier properties, etc. It can be used particularly effectively in the manufacture of containers.
  • Examples of the method for manufacturing the hollow container include a conventional extrusion blow molding method, an injection blow molding method, and a method in which a preformed body (parison) is blow-molded after reheating (cold parison method). Can be.
  • various drinks such as carbonated drinks, fruit drinks, lactic acid drinks, coffee drinks, mineral water, barley tea, oolong tea, green tea, black tea, etc., soy sauce, sauces, marin, dressing, ⁇
  • various hollow containers suitable for filling with various seasonings such as soup, edible oil and the like can be manufactured.
  • the present invention will be described specifically with reference to Examples and the like, but the present invention is not limited thereto.
  • the intrinsic viscosity of the polyester resin (polyester resin composition), the melting point and the heat of crystal fusion ( ⁇ ) of the polyester resin composition, and the resistance of the bottle to hydrogen peroxide (swelling due to hydrogen peroxide) Properties; the amount of hydrogen peroxide eluted) and the transparency (haze value) were measured or evaluated as follows.
  • germanium dioxide 2 O Op pm was added as a catalyst to the low polymer composition containing cobalt acetate tetrahydrate obtained in the above (1), and the resulting mixture was heated at a reduced pressure of 1 Torr absolute pressure. Melt polycondensation at a temperature of ° C to prepare a polyester composition with an ultimate viscosity of 0.53 d1 Zg, extrude this polyester composition from a nozzle into strands, and cut to produce cylindrical chips did. The chips were dried at 150 ° C. for 5 hours and then subjected to solid-state polymerization at 205 ° C. for 15 hours under a nitrogen stream to produce chips of a polyester resin composition having an intrinsic viscosity of 0.75 d 1.
  • the content of cobalt acetate in the chips of this polyester resin composition was 49 millimol% in terms of cobalt atoms with respect to the total number of moles of dicarboxylic acid units in the polyester resin. Further, the melting point and the heat of crystal fusion ( ⁇ ) of this polyester resin composition were measured by the above-mentioned methods, and the results were as shown in Table 1 below.
  • a slurry composed of 70.9 parts by weight of ethylene glycol, 100 parts by weight of dimethyl terephthalate and 2.2 parts by weight of cyclohexanedimethanol (molar ratio of diol component: dicarboxylic acid component 2.25: 1) Using 485 ppm of cobalt acetate tetrahydrate (115 ppm in terms of cobalt atom) and 357 ppm of manganese acetate tetrahydrate (manganese atom (Equivalent to 80 ppm) in a transesterification reaction by gradually increasing the temperature from 170 ° C to a temperature of 220 ° C over a period of 2 hours and 30 minutes to carry out the transesterification of cobalt acetate and manganese acetate.
  • a low polymer composition containing a water salt was produced.
  • the low polymer composition containing cobalt acetate tetrahydrate and manganese acetate tetrahydrate obtained in the above (1) was added as a catalyst with germanium dioxide 200 ppm and trimethyl phosphate 9.
  • a polyester composition with an intrinsic viscosity of 0.52 d1 Zg was prepared. The polyester composition was extruded from a nozzle into a strand and cut to produce a columnar chip.
  • the chips were subjected to solid-state polymerization at 205 ° C for 15 hours under a nitrogen stream to produce chips of a polyester resin composition having an intrinsic viscosity of 0.74 d1 Zg.
  • the content of cobalt acetate was 38 millimol% in terms of cobalt atoms
  • the content of manganese acetate was in terms of manganese atoms, based on the total moles of dicarboxylic acid units in the polyester resin.
  • the content of the phosphorus compound was 1.9 mmol% in terms of the phosphorus atom.
  • the melting point and heat of crystal fusion ( ⁇ ) of this polyester resin composition were measured by the above-mentioned methods, and were as shown in Table 1 below.
  • a slurry consisting of 70.5 parts by weight of ethylene glycol, 90.1 parts by weight of dimethyl terephthalate and 9.9 parts by weight of dimethyl naphthalenedicarboxylate (diol component: dicarboxylic acid component molar ratio 2.25: 1) in the presence of 570 ppm of cobalt acetate tetrahydrate (135 ppm in terms of cobalt atom) and 260 ppm of tin acetate tetrahydrate (100 ppm in terms of tin atom).
  • a low polymer composition containing cobalt acetate tetrahydrate and tin acetate tetrahydrate by gradually increasing the temperature from a temperature of ° C to a temperature of 220 ° C over a period of 2 hours and 30 minutes to carry out a transesterification reaction. was manufactured.
  • polyester resin composition having an intrinsic viscosity of 0.69 d 1 Zg.
  • the content of cobalt acetate was 45 mol% in terms of cobalt atoms
  • the content of tin acetate was 16 mol in terms of tin atoms, based on the total number of moles of dicarboxylic acid units in the polyester resin. It was remote%.
  • the melting point and the heat of crystal fusion ( ⁇ ) of this polyester resin composition were measured by the above-mentioned methods, and the results were as shown in Table 1 below.
  • the content of cobalt acetate was 49 mol% in terms of cobalt atoms, based on the total number of moles of dicarboxylic acid units in the polyester resin. Further, the content of sodium acetate is determined based on the weight of the polyester resin in the polyester resin composition. The conversion was 200 ppm. Further, the melting point and heat of crystal fusion ( ⁇ ) of the polyester resin composition were measured by the above-mentioned methods, and the results were as shown in Table 1 below.
  • polyester resin composition with respect to the total number of moles of dicarboxylic acid units in the polyester resin, The content of manganese acetate was 8 millimol% in terms of manganese atoms.
  • melting point and heat of crystal fusion ( ⁇ ) of the polyester resin composition were measured by the above-mentioned methods, and the results were as shown in Table 2 below.
  • Example 1 (1) In (1) of Example 1, except that the amount of cobalt acetate tetrahydrate used was changed to 169 ppm (40 ppm in terms of cobalt atom), A low polymer composition containing cobalt acetate tetrahydrate was produced.
  • melt polycondensation was carried out in the same manner as in (2) of Example 1 to obtain the intrinsic viscosity.
  • 0.53 d1 g of a polyester composition was prepared, and the polyester composition was extruded into a strand shape from a nozzle and cut to produce a columnar chip. After drying the chips at 150 ° C. for 5 hours, the chips were subjected to solid-state polymerization at 205 ° C. for 15 hours under a nitrogen stream to produce chips of a polyester resin composition having an intrinsic viscosity of 0.75 dl / g.
  • the content of cobalt acetate was 13 mol% in terms of cobalt atoms, based on the total number of moles of dicarboxylic acid units in the polyester resin. Further, the melting point and heat of crystal fusion ( ⁇ ) of this polyester resin composition were measured by the above-mentioned methods, and as shown in Table 2 below. (3) After drying the chips of the polyester resin composition obtained in (2) above at 150 ° C for 5 hours, the chips were used and described in the above-mentioned “Bottle swelling by hydrogen peroxide” test method.
  • the bottle was molded according to the method, and the test piece cut out from the body of the obtained bottle was used to evaluate the swellability with hydrogen peroxide (measurement of the amount of hydrogen peroxide eluted) and the transparency.
  • the results were as shown in Table 2 below.
  • germanium dioxide 2 OOP pm was added as a catalyst to the low polymer composition containing cobalt acetate tetrahydrate obtained in (1) above, and the mixture was heated at 280 ° C. under a reduced pressure of 1 Torr absolute. Melt polycondensation was performed at a temperature of C to prepare a polyester composition having an ultimate viscosity of 0.55 d1 Zg, and the polyester composition was extruded into a strand shape from a nozzle and cut to produce a columnar chip. After drying the chips at 150 ° C for 5 hours, the chips were subjected to solid-state polymerization at 205 ° C for 15 hours under a nitrogen stream to produce chips of a polyester resin composition having an intrinsic viscosity of 0.78 d1.
  • the content of cobalt acetate was 49 millimol% in terms of cobalt atom, based on the total number of moles of dicarboxylic acid units in the polyester resin. Further, the melting point and the heat of crystal fusion of the polyester resin composition
  • a slurry composed of 68.4 parts by weight of ethylene glycol, 76.1 parts by weight of dimethyl terephthalate and 23.9 parts by weight of dimethyl naphthalenedicarboxylate (molar ratio of diol component: dicarboxylic acid component 2.25: Using 1), gradually increase the temperature from 170 ° C to 220 ° C over 2 hours and 30 minutes in the presence of 634 ppm of cobalt acetate tetrahydrate (150 ppm in terms of cobalt atoms). The transesterification reaction was performed by heating to produce a low polymer composition containing cobalt acetate tetrahydrate.
  • germanium dioxide 2 OOP pm was added as a catalyst to the low polymer composition containing cobalt acetate tetrahydrate obtained in (1) above, and the mixture was heated at 280 ° C. under a reduced pressure of 1 Torr absolute. Melt polycondensation was performed at a temperature of C to prepare a polyester composition having an ultimate viscosity of 0.63 d1, and this polyester composition was extruded from a nozzle into a strand and cut to produce a columnar chip. In this polyester resin composition, the content of cobalt acetate was 51 mol% in terms of covanolate atoms based on the total number of moles of dicarboxylic acid units in the polyester resin.
  • this polyester resin composition since this polyester resin composition was non-crystalline, had no melting point, and could not be subjected to solid-state polymerization, it contained a large amount of a low polymer (oligomer) (based on the weight of the polyester resin composition). Low polymer content 1.5% by weight).
  • the chip After drying the chip at 150 ° C for 5 hours, the chip was subjected to solid-state polymerization at 205 ° C for 15 hours under a nitrogen stream to produce a chip of a polyester resin composition having an intrinsic viscosity of 0.75 d1 Zg. .
  • this polyester resin composition based on the total number of moles of dicarboxylic acid units in the polyester resin, thus, the content of cobalt acetate was 49 millimol% in terms of cobalt atoms, and the content of phosphorus compounds was 25 millimol% in terms of phosphorus atoms. Further, the melting point and heat of crystal fusion ( ⁇ ) of this polyester resin composition were measured by the above-mentioned methods, and were as shown in Table 2 below.
  • Copolymerization component "(mol%) IPAC 2.5) Garden (1.5) NDCAC 4.0 0) IPAC 2.5) Acetic acid; Total amount of carbon 1 ⁇ (Co atom conversion) (ppm) 150 115 135 150 Amount (Mn atom conversion) (ppm) 0 80 0 0 Tin acetate addition (Sn atom conversion) (ppm) 0 0 100 0 Trimethyl host addition (P atom conversion) (ppm) 0 200 Acetate W addition Amount (Na atom conversion) (ppm) 0 0 0 200
  • NDCA Naphthalene Range Ruponic Acid Unit
  • the polyester resin compositions of Examples 1 to 4 and the molded articles (bottles) made thereof have a low haze value and excellent transparency, and also have high intrinsic viscosity, melting point and heat of crystal fusion ( ⁇ ). It has a high degree of polymerization and excellent mechanical properties.
  • the polyester resin composition of Example 3 containing the cobalt compound and the soot compound in a ratio satisfying the above formulas (3) and (4), and the cobalt compound And the polyester resin of Example 4 containing an alkali metal salt of an aliphatic carboxylic acid in an amount of 100 to 100 ppm in terms of alkali metal atom based on the weight of the polyester resin. It can be seen that the molded article (bottle) obtained from the composition has a smaller amount of eluted hydrogen peroxide and is more excellent in terms of resistance to hydrogen peroxide.
  • the polyester resin composition of Comparative Example 1 was mainly composed of a diol unit mainly composed of ethylene glycol units and a dicarboxylic acid unit mainly composed of terephthalic acid units.
  • a polyester resin having 2.5 mol% of disophthalic acid units based on the total number of moles of all structural units contains only a manganese compound without containing a cobalt compound, thereby producing hydrogen peroxide.
  • the amount of hydrogen peroxide eluted from the test piece immersed in an aqueous solution of hydrogen peroxide was extremely high, indicating that there was no resistance to hydrogen peroxide.
  • the total number of moles of the diol unit mainly composed of the ethylene glycol unit and the dicarbonic acid unit mainly composed of the terephthalic acid unit, and the isophthalic acid unit being the total number of all structural units Comparative Example 1 is a polyester resin composition containing a cobalt compound in a polyester resin having a proportion of 2.5 mol% based on the above, but the content of the cobalt compound is less than the range specified by the above formula (1).
  • the molded article (bottle) made of the polyester resin composition of (2) swells with hydrogen peroxide, has a high amount of hydrogen peroxide dissolved from a test piece immersed in an aqueous solution of hydrogen peroxide, and has a high resistance to hydrogen peroxide. It turns out that resistance is inferior.
  • the compound did not have at least one structural unit selected from the group consisting of an isophthalic acid unit, a cyclohexanedimethanol unit, and a naphthalenedicarboxylic acid unit.
  • the content of the cobalt compound in the polyester resin composition was within the range of the above formula (1). Even so, the polyester resin composition and the molded article (bottle) have a high haze value and are inferior in transparency.
  • Comparative Example 4 in Table 2 above Comparative Example using a polyester resin having a naphthalenedicarboxylic acid unit content of 10 mol% based on the total number of moles of all structural units of the polyester resin and exceeding the range specified in the present invention.
  • the polyester resin composition of 4 the solid-state polymerization of the polyester resin is difficult, and the obtained polyester resin composition is non-crystalline, contains a large amount of low polymer, and is not suitable for the production of molded articles.
  • the polyester resin composition has a low intrinsic viscosity and poor mechanical properties.
  • the polyester resin composition of the present invention and the molded article comprising the same have excellent resistance to hydrogen peroxide, and do not invade swollen hydrogen peroxide even when exposed to hydrogen peroxide.
  • the polyester resin composition of the present invention and a molded article comprising the same have excellent transparency, and also have excellent mechanical properties, heat resistance, flavor barrier properties, gas barrier properties, etc. inherent to the polyester resin. I have.
  • the polyester resin composition of the present invention can be effectively used for the production of various molded articles by utilizing the above-mentioned excellent properties.
  • Various beverages such as carbonated drinks, fruit juice drinks, lactate drinks, coffee drinks, mineral water, barley tea, oolong tea, green tea, black tea, and other tea drinks, soy sauce, sauces, and malin It is suitable for manufacturing various types of hollow containers to be filled with various seasonings such as dressing, pork soup, and cooking oil.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne une composition de résine de polyester qui est une composition de résine de polyéthylène téréphtalate contenant des unités d'acide isophthalique, des unités de cyclohexanediméthanol et/ou des unités d'acide naphtalène dicarboxylique en dose de 0,5 à 4,5 mol % sur la base de la quantité totale de toutes les unités structurelles, et dans laquelle la teneur d'un composé de cobalt et d'un composé de phosphore satisfait aux relations suivantes (1) et (2): 25 ≤ CCo ≤ 150 (1); Cp/CCo ≤ 0,07 (2) [dans lesquelles CCo représente la teneur du composé de cobalt (mmol%) en termes de quantité d'atomes de cobalt sur la base de la quantité molaire des unités d'acide dicarboxylique contenue dans la résine de polyester; et Cp représente la teneur du composé de phosphore (mmol%) en termes de quantité d'atomes de phosphore sur la base de la quantité molaire des unités d'acide dicarboxylique contenue dans la résine de polyester]. La composition résine de polyester présente une résistance au péroxyde d'hydrogène et des caractéristiques de transparence excellentes, des propriétés mécaniques, une résistance à la chaleur, des propriétés de barrière au goût et d'étanchéité aux gaz, etc. Elle convient pour la fabrication de récipients creux, par exemple des bouteilles, et d'autres moulages.
PCT/JP2000/003676 1999-07-16 2000-06-07 Composition de resine de polyester WO2001005865A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU51059/00A AU5105900A (en) 1999-07-16 2000-06-07 Polyester resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/203879 1999-07-16
JP11203879A JP2001031845A (ja) 1999-07-16 1999-07-16 ポリエステル樹脂組成物

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WO2001005865A1 true WO2001005865A1 (fr) 2001-01-25

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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
FR2836476B1 (fr) * 2002-02-22 2005-03-18 Rhodianyl Materiau thermoplastique a proprietes barrieres elevees
FR2871807B1 (fr) * 2004-06-22 2006-08-11 Rhodia Chimie Sa Composition thermoplastique a base de polyester, et procede de fabrication et corps creux obtenus a partir de ces compositions
WO2015118966A1 (fr) * 2014-02-07 2015-08-13 東レ株式会社 Composition de résine de polyester et procédé de production de celle-ci
EP3434442A4 (fr) * 2016-03-22 2019-08-07 Kuraray Co., Ltd. Film d'étanchéité et procédé de fabrication s'y rapportant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5538838A (en) * 1978-09-12 1980-03-18 Nippon Ester Co Ltd Preparation of polyester
JPH11166046A (ja) * 1997-12-04 1999-06-22 Nippon Ester Co Ltd 共重合ポリエステルの製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5538838A (en) * 1978-09-12 1980-03-18 Nippon Ester Co Ltd Preparation of polyester
JPH11166046A (ja) * 1997-12-04 1999-06-22 Nippon Ester Co Ltd 共重合ポリエステルの製造法

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