Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—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

Definitions

• the present invention relates to a polyester resin that provides molded articles with excellent moldability, transparency, mechanical properties, heat resistance, and thermal oxidation stability. Specifically, the present invention provides improved moldability in extrusion molding, profile extrusion molding, direct blow molding, inflation molding, injection blow molding, and calendering molding that require high melt tension, as well as transparency and mechanical properties. , relates to a polyester resin that achieves improved heat and oxidation stability.
• polyester resins for example, crystalline polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are used for heat-resistant parts by injection molding, films, sheets, and the like by extrusion molding. Blow-molded beverage bottles, melt-spun fibers, etc. are also used in various melt-molded products.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene naphthalate
• the present invention was made against the background of such problems of the prior art, and an object of the present invention is to improve gelation suppression, moldability, surface smoothness, transparency, mechanical properties, heat resistance, and heat-oxidation stability.
• An object of the present invention is to provide a polyester resin that gives excellent molded articles.
• the present invention is excellent in gelation suppression, surface smoothness, transparency, mechanical properties, heat resistance, and thermal oxidation stability, and can be used in extrusion molding, profile extrusion molding, and direct molding, which require high melt tension.
• a polyester resin which gives a molded product excellent in moldability in blow molding, inflation molding, injection blow molding and calendering molding.
• the present invention has the following configurations.
• the molded article of the polyester resin excellent in gelatinization suppression, moldability, surface smoothness, transparency, mechanical property, heat resistance, and heat-oxidation stability is obtained.
• the moldability is excellent in extrusion molding, profile extrusion molding, direct blow molding, inflation molding, injection blow molding, and calendering molding, which require higher melt tension than conventional molding.
• polyester resin of the present invention comprises terephthalic acid as a dicarboxylic acid component, ethylene glycol as an alcohol component, a bisphenol A-ethylene oxide adduct, and a compound represented by the following formula (I), and terephthalic acid is a dicarboxylic acid.
• the acid component it is 85 to 100 mol%, and the ratio is 2 to 15 mol% of the bisphenol A-ethylene oxide adduct with respect to 85 to 98 mol% of ethylene glycol, and the compound represented by the following formula (I) is an alcohol component. It is 0.001 to 5% by mass in 100% by mass.
• R 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms
• R 2 , R 3 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms
• R 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• the polyester resin of the present invention contains a polymer of a predetermined dicarboxylic acid component and an alcohol component, and is characterized by containing a predetermined amount of the compound represented by the formula (I) as the alcohol component.
• the compound represented by formula (I) is a branching agent for polyester resins, and is used together with a commonly used diol component.
• the compound represented by the formula (I) has two or more functional groups (hydroxyl groups) per molecule that can react with the carboxyl groups of the dicarboxylic acid component, and the polyester resin has a partially branched structure as a whole. can be introduced into
• the polyester resin of the present invention uses the compound represented by formula (I), it is possible to suppress gelation, and during melt extrusion, the melt tension decreases as the temperature increases.
• melt viscosity decreases under high shear, melt fracture does not occur during molding, and it is excellent in moldability, surface smoothness, transparency, mechanical properties, heat resistance, and thermal oxidation stability. Become.
• R 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms
• R 2 , R 3 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms
• R 4 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• R 1 represents an aromatic hydrocarbon group having 6 to 20 carbon atoms.
• Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R 1 include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5- dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 3,5-di(tert-butyl)phenyl group, 3,5-d
• the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-15, still more preferably 6-12.
• the aromatic hydrocarbon group is particularly preferably a phenyl group, an o-tolyl group, an m-tolyl group, or a p-tolyl group, most preferably a phenyl group.
• R 2 , R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
• alkyl groups having 1 to 10 carbon atoms represented by R 2 , R 3 and R 4 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, a linear alkyl group such as a decyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group, 1,1,3,3-tetramethylbutyl group, 1-methylbutyl group, 1-ethyl propyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 2-methylpentyl group, 3-ethylpentyl group, 1,3-dimethylbutyl group, 2-propylpentyl group, 1-ethyl-1 , 2-
• the number of carbon atoms in the alkyl group is preferably 1-8, more preferably 1-6, and still more preferably 1-4.
• the alkyl group is particularly preferably a methyl group, an ethyl group, a propyl group, or a butyl group, most preferably a methyl group.
• R 2 and R 3 are preferably C 1-10 alkyl groups, and R 4 is preferably a hydrogen atom.
• l, m, and n are the ratios of the following copolymer components (L), (M), and (N) contained in one molecule, and the average number of each component contained in one molecule is Below is a value (ratio) expressed as an integer by rounding off to the nearest digit. The ratio and average number of each component contained in one molecule were obtained from 1 H-NMR analysis and 13 C-NMR analysis.
• Each of m and n which may be the same or different, represents an integer of 1-1000, preferably an integer of 2-800, more preferably an integer of 5-600, still more preferably an integer of 10-400.
• l is an integer of 0-1000, preferably an integer of 1-700, more preferably an integer of 2-400, and still more preferably an integer of 5-100.
• the compound represented by formula (I) is a random copolymer obtained by randomly copolymerizing the copolymer components (L), (M), and (N), the copolymer components (L), ( A block copolymer in which at least one component of M) and (N) is a block may be used, but a random copolymer is preferred.
• the polyester resin of the present invention may be one or more polyester resins as long as the above m, n, and l are satisfied.
• Compounds of formula (I) can be prepared in two gallons of free-radical continuous water, see, for example, US Pat. It is possible to prepare in a conventional polymerization reactor system.
• the content of the compound represented by formula (I) is 0.001 to 5% by mass, preferably 0.005 to 5% by mass, more preferably 0.005 to 5% by mass, in 100% by mass of the alcohol component, which is a constituent component of the polyester resin. is 0.01 to 4.5% by mass, more preferably 4% by mass or less, particularly preferably 3.5% by mass or less. If the content of the compound represented by formula (I) is less than 0.001% by mass, drawdown will occur during molding, and the molding will not be stable, or even if it can be molded, the molded product will tend to have uneven thickness. be.
• the compound represented by formula (I) may have a predetermined weight average molecular weight, and the weight average molecular weight of the compound represented by formula (I) is preferably 200 or more and 500,000 or less, more preferably It is 500 or more, more preferably 700 or more, still more preferably 1000 or more, more preferably 300,000 or less, still more preferably 100,000 or less, and even more preferably 50,000 or less. If the weight average molecular weight of the compound represented by formula (I) is less than 200, the unreacted compound may bleed out onto the surface of the molded product, contaminating the surface of the molded product.
• the weight average molecular weight can be determined, for example, by GPC in terms of standard polystyrene. Specifically, the weight average molecular weight is 0.2 ⁇ m after weighing 4 mg of a sample of the compound represented by formula (I) and dissolving it in 4 ml of a mixed solvent of chloroform and isofluoroisopropanol (60/40% by volume). It can be obtained by filtering with a membrane filter, subjecting the obtained sample solution to GPC, and converting to standard polystyrene.
• the dicarboxylic acid component and alcohol component used in the present invention are as follows.
• Dicarboxylic acid components include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc.
• Saturated aliphatic dicarboxylic acids exemplified in or ester-forming derivatives thereof e.g., alkyl esters having 1 to 20 carbon atoms
• fumaric acid e.g., maleic acid
• unsaturated aliphatics exemplified by itaconic acid etc.
• Dicarboxylic acids or ester-forming derivatives thereof for example, alkyl esters having 1 to 20 carbon atoms
• orthophthalic acid isophthalic acid, terephthalic acid, 5-(alkali metal)sulfoisophthalic acid, diphenic acid, 1, 3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4 Aromatic dicarboxylic acids exemplified by '-biphenylsulfonedicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, pamoic acid, anthracenedicarboxylic acid, etc. and ester-forming derivative
• isophthalic acid isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid are preferred, and terephthalic acid is particularly preferred in terms of the physical properties of the resulting polyester resin.
• carboxylic acids may be used in small amounts.
• carboxylic acid include ethanoic acid, tricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3′,4′-biphenyltetracarboxylic acid, and esters thereof. forming derivatives (for example, alkyl esters having 1 to 20 carbon atoms) and the like.
• the alcohol component other than the compound represented by formula (I) is preferably a diol component.
• the diol component is preferably 99.999 to 95% by mass, more preferably 99.995 to 95% by mass, still more preferably 99.99 to 95.5% by mass, and still more It is preferably 96% by mass or more, particularly preferably 96.5% by mass or more.
• the diol component contains ethylene glycol and bisphenol A-ethylene oxide adduct (hereinafter referred to as bisphenol A-EO adduct).
• Diols that may be used other than ethylene glycol and bisphenol A-EO adducts include 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3 -butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12- Dodecanediol, isosorbide, polyethylene glycol, polytrimethylene glycol, polyt
• diol components tri- or tetrahydric alcohols, hydroxycarboxylic acids, cyclic esters, etc. may be used as diol components.
• Examples of the alcohol include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, and hexanetriol.
• the hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or Ester-forming derivatives thereof (for example, alkyl esters having 1 to 20 carbon atoms) and the like can be mentioned.
• Cyclic esters include ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -methyl- ⁇ -propiolactone, ⁇ -valerolactone, glycolide, lactide and the like.
• the polyester resin of the present invention contains 85 to 100 mol% of terephthalic acid in 100 mol% of the dicarboxylic acid component, and 87 to 100 mol% of the total of ethylene glycol and bisphenol A-EO adduct in 100 mol% of the diol component.
• Terephthalic acid is contained in 100 mol% of the dicarboxylic acid component, more preferably 90 to 100 mol%, more preferably 95 to 100 mol%
• the total of ethylene glycol and bisphenol A-EO adduct is in 100 mol% of the diol component. , more preferably 90 to 100 mol %, more preferably 95 to 100 mol %.
• the ratio of ethylene glycol to bisphenol A-EO adduct is 85-98 mol % of ethylene glycol and 2-15 mol % of bisphenol A-EO adduct. It may be considered that 85 to 98 mol % of ethylene glycol and 2 to 15 mol % of bisphenol A-EO adduct are contained in 100 mol % of the diol component. It is preferable that the bisphenol A-EO adduct is 3 to 13 mol% with respect to 87 to 97 mol% of ethylene glycol, and the bisphenol A-EO adduct is 4 to 11 mol% with respect to 89 to 96 mol% of ethylene glycol. is more preferable.
• the polyester resin of the present invention is preferably a copolymerized polyethylene terephthalate resin.
• the polyester resin of the present invention is a crystalline polyester resin and has a branched structure, and can improve processability such as moldability due to the "melt strength enhancement effect" of increasing molecular weight, and can adjust melt viscosity and melt tension. , the whitening resistance on bending of the molded product and the bleeding out of unreacted substances to the surface layer of the molded product can be suppressed. If the content of terephthalic acid and ethylene glycol is out of the above range, the polyester resin becomes amorphous and the viscosity cannot be increased by solid-phase polymerization, and there is a possibility that a molded article having high mechanical properties cannot be obtained.
• the polyester resin of the present invention may have a given intrinsic viscosity IV.
• the intrinsic viscosity IV is preferably 0.40 to 2.10 dl/g, more preferably 0.50 to 1.90 dl/g, still more preferably 0.60 to 1.70 dl/g.
• the intrinsic viscosity can be measured at 30° C. using an Ostwald viscometer after dissolving the polyester resin in a mixed solvent of parachlorophenol/tetrachloroethane (3/1: weight ratio).
• the acid value (AV) of the polyester resin used in the present invention is preferably 100 eq/10 6 g (ton) or less, more preferably 60 eq/10 6 g or less, still more preferably 50 eq/10 6 g or less.
• the lower the lower limit the more preferable, and the closer to 0 eq/10 6 g the more preferable.
• the acid value can be obtained by dissolving a polyester resin sample in an alcohol and/or ether solution and titrating with an alcoholic sodium hydroxide solution or an alcoholic potassium hydroxide solution using a phenolphthalein reagent as an indicator. can.
• a specific method for measuring the acid value is as shown in Examples.
• the polyester resin of the present invention may have a predetermined melting point, and the melting point of the polyester resin is preferably 190 to 300°C, more preferably 195 to 280°C, still more preferably 210 to 260°C, still more preferably. is above 220°C.
• the melting point can be measured with a differential scanning calorimeter (DSC) at a heating rate of 20° C./min up to 310° C., and the maximum peak temperature of the heat of fusion can be determined as the crystalline melting point.
• DSC differential scanning calorimeter
• the polyester resin of the present invention is preferably produced via a polymerization catalyst containing at least an aluminum compound and a phosphorus compound, and may have an aluminum content of 3 to 1000 ppm and a phosphorus content of 5 to 10000 ppm derived from the polymerization catalyst. preferable.
• a polymerization catalyst containing at least an aluminum compound and a phosphorus compound, and may have an aluminum content of 3 to 1000 ppm and a phosphorus content of 5 to 10000 ppm derived from the polymerization catalyst.
• another polymerization catalyst one or more selected from titanium compounds and germanium compounds may be used.
• the aluminum compound is preferably at least one selected from aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, and aluminum hydroxychloride, and at least one selected from aluminum acetate and basic aluminum acetate. is more preferred, and aluminum acetate is even more preferred.
• the amount of aluminum is preferably 3 to 1000 ppm, more preferably 5 to 800 ppm, and even more preferably 8 to 500 ppm as aluminum atoms relative to the total mass of the polyester resin. If the amount of aluminum is too small, the polymerization activity may decrease, and if the amount of aluminum is too large, a large amount of aluminum-derived foreign matter may be generated.
• the phosphorus compound is preferably at least one selected from phosphonic acid compounds and phosphinic acid compounds, more preferably phosphonic acid compounds.
• Phosphorus compound preferably has a phenol structure in the same molecule, more preferably at least one selected from phosphonic acid compounds and phosphinic acid compounds having a phenol structure in the same molecule, in the same molecule A phosphonic acid compound having a phenol structure is more preferred.
• Phosphorus compounds having a phenol structure in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis(p-hydroxyphenyl ) phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphenylphosphinic acid phenyl, p-hydroxyphenylphosphinate, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and the like.
• the phosphorus compound is particularly preferably diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.
• a phosphorus compound for example, Irgamod (registered trademark) 295 (manufactured by BASF) can be used.
• the amount of phosphorus is preferably 5 to 10000 ppm, more preferably 8 to 8000 ppm, and even more preferably 10 to 6000 ppm as phosphorus atoms relative to the total mass of the polyester resin. If the amount of phosphorus is small, the polymerization activity may be lowered, and a large amount of foreign matter derived from aluminum may be generated. If the amount of phosphorus is large, the catalyst cost may increase.
• Titanium compounds include tetrabutyltitanium, tetrabenzyltitanium, tetra-n-propyltitanate, tetraisopropyltitanate, tetra-n-butyltitanate, tetraisobutyltitanate, tetra-tert-butyltitanate, tetracyclohexyltitanate, tetraphenyltitanate, tetra Benzyl titanate, lithium oxalate titanate, potassium oxalate titanate, ammonium oxalate titanate, titanium oxide, composite oxides of titanium and silicon, zirconium, alkali metals, alkaline earth metals, etc., titanium orthoesters or condensed orthoesters, a reaction product of titanium orthoester or condensed orthoester and hydroxycarboxylic acid, a reaction product of titanium orthoester or condensed orthoester
• the amount of titanium is preferably 1 to 300 ppm, more preferably 2 to 200 ppm, and still more preferably 3 to 100 ppm as titanium atoms relative to the total mass of the polyester resin.
• Germanium compounds include germanium dioxide, germanium acetate and the like.
• the amount of germanium is preferably 1 to 500 ppm, more preferably 2 to 400 ppm, and still more preferably 3 to 300 ppm as titanium atoms relative to the total mass of the polyester resin.
• the amount of atoms may be calculated, for example, by fluorescent X-ray analysis.
• the polyester resin of the present invention preferably has a predetermined melt tension and melt viscosity when melted.
• the polyester resin of the present invention has the property that the higher the temperature is above 250°C, the lower the melt tension.
• the melt tension is preferably 15 mN or more at a temperature of 270° C., a take-up speed of 100 m/min, and a shear rate of 243 s ⁇ 1 , more preferably 15 mN or more, from the viewpoint of exhibiting performance equal to or higher than that of high-density polyethylene or the like. It is 17 mN or more, more preferably 19 mN or more, and the upper limit of the melt tension is, for example, 170 mN or less or 120 mN or less.
• the melt tension can be measured, for example, using a capillary rheometer under predetermined conditions (capillary length 10 mm, capillary diameter 1 mm, temperature 270° C., shear rate 243 s ⁇ 1 , maximum take-up speed 200 m/min, take-up start speed 10 m/min, or take-up speed 100 m /min (constant), take-up time 90 seconds).
• a capillary rheometer under predetermined conditions (capillary length 10 mm, capillary diameter 1 mm, temperature 270° C., shear rate 243 s ⁇ 1 , maximum take-up speed 200 m/min, take-up start speed 10 m/min, or take-up speed 100 m /min (constant), take-up time 90 seconds).
• the polyester resin of the present invention has a property that at a shear rate of 2000 s -1 during melting, the melt viscosity decreases as the temperature rises above 250°C.
• the melt viscosity is 26000 dPa s or more at a temperature of 270 ° C. and a shear rate of 30 s -1 at a temperature of 270 ° C. and a shear rate of 2000 s -1 . , 6500 dPa ⁇ s or less.
• the polyester resin of the present invention exhibits thixotropy at high temperatures during melting, can suppress the occurrence of melt fracture, and provides good moldability.
• the melt viscosity at a temperature of 270° C. and a shear rate of 30 s ⁇ 1 is preferably 26000 dPa ⁇ s or more, more preferably 28000 dPa ⁇ s or more, and still more preferably 30000 dPa ⁇ s or more. s or less or 45000 dPa ⁇ s or less.
• melt viscosity can be measured, for example, based on JIS K7199.
• the melt viscosity at a temperature of 270° C. and a shear rate of 2000 s ⁇ 1 is preferably 6500 dPa s or less, more preferably 6300 dPa s or less, and still more preferably 6200 dPa s or less. It is 5500 dPa ⁇ s or more.
• the melt viscosity can be determined, for example, using a capillary rheometer under predetermined conditions (capillary length 10 mm, capillary diameter 1 mm, temperature 270° C., shear rate 30 s ⁇ 1 or 2000 s ⁇ 1 ).
• the polyester resin of the present invention may have a predetermined thermal oxidation decomposition parameter (TOD) and a predetermined thermal decomposition parameter (TD).
• the thermal oxidative decomposition parameter (TOD) of the polyester resin is preferably 0.390 or less.
• the TOD can be calculated by the method described in the Examples section below.
• the TOD is more preferably 0.385 or less, still more preferably 0.380 or less, particularly preferably 0.375 or less, and most preferably 0.370 or less.
• the lower limit of the TOD is, for example, 0.010 or more or 0.020 or more. When the TOD is more than 0.390, the moldability during drawdown tends to be deteriorated.
• the thermal decomposition parameter (TD) of the polyester resin is preferably 0.55 or less.
• TD can be calculated by the method described in the Examples section below.
• TD is more preferably 0.54 or less, more preferably 0.53 or less, particularly preferably 0.52 or less, and most preferably 0.50 or less.
• the lower limit of the TD is, for example, 0.18 or more or 0.20 or more. When the TD is more than 0.50, the moldability during drawdown tends to be deteriorated.
• the polyester resin of the present invention may contain additives such as organic, inorganic, and organometallic toners and fluorescent brighteners. By containing one or more of these additives, coloring such as yellowing of the polyester resin can be suppressed to a more excellent level. It also contains other optional polymers, antistatic agents, antifoaming agents, dyeability improvers, dyes, pigments, matting agents, optical brighteners, stabilizers, antioxidants, and other additives. good too. As antioxidants, antioxidants such as aromatic amines and phenols can be used. is available.
• the polyester resin is directly introduced into the molding process in a molten state after the melt polycondensation process is completed as described above, or in a chip state after the treatment such as solid phase polymerization is completed. Molded bodies can also be used.
• a predetermined amount of additives such as crystallization property improvers, aldehyde reducers, color improvers, stabilizers, etc. are added to any reactor or transport pipe in the production process of the melt polycondensation polymer, and the desired results are obtained.
• the product can be directly introduced into the molding process to obtain a molded product, either as it is, or after finishing treatment such as solid phase polymerization.
• a polyester resin molded article made from the polyester resin of the present invention may have a predetermined three-dimensional roughness center plane average (SRa).
• the SRa of the polyester resin molded product is preferably less than 0.15 ⁇ m, more preferably 0.14 ⁇ m or less, still more preferably 0.13 ⁇ m or less, even more preferably 0.12 ⁇ m or less, and preferably 0.01 ⁇ m or more. Or it is 0.02 ⁇ m or more.
• the center plane average (SRa) of the three-dimensional roughness can be obtained, for example, using a surface roughness measuring instrument (fine shape measuring instrument, Surfcoder ET4000A manufactured by Kosaka Laboratory Ltd.).
• the polyester resin of the present invention can be produced by a conventionally known method. For example, when producing PET, terephthalic acid, ethylene glycol and, if necessary, other copolymerization components are directly reacted to effect esterification by distilling off water, followed by polycondensation under reduced pressure by a direct esterification method. Alternatively, dimethyl terephthalate, ethylene glycol and, if necessary, other copolymer components are reacted to distill off the methyl alcohol and transesterify, followed by polycondensation under reduced pressure. be. Further, solid state polymerization may be carried out to increase the intrinsic viscosity, if necessary.
• the melt-polymerized polyester may be made to absorb moisture and then heated to crystallize, or water vapor may be blown directly onto the polyester chips to crystallize by heating.
• the method of adding the compound represented by formula (I) it is preferably added during polymerization.
• the compound represented by the formula (I) may be dispersed and added at the time of addition.
• the polycondensation reaction may be carried out in a batch reactor or a continuous reactor.
• the esterification reaction or transesterification reaction may be carried out in one step, or may be carried out in multiple steps.
• the polycondensation reaction may be carried out in one step, or may be carried out in multiple steps.
• the solid-phase polymerization reaction can be carried out in a batch system or a continuous system, like the polycondensation reaction. Polycondensation and solid phase polymerization may be carried out continuously or separately. An example of a preferred continuous production method will be described below, taking PET as an example of the polyester resin.
• the esterification reaction is carried out using a multi-stage apparatus in which 1 to 3 esterification reactors are connected in series, and under the condition that ethylene glycol is refluxed, the water or alcohol produced by the reaction is removed in a rectification column. It is carried out while removing it from the system.
• the temperature of the first-stage esterification reaction is preferably 240 to 270°C, more preferably 245 to 265°C, and the pressure is preferably 0.2 to 3 kg/cm 2 G, more preferably 0.5 to 2 kg/cm. 2G .
• the temperature of the final esterification reaction is usually 250 to 290°C, preferably 255 to 275°C, and the pressure is usually 0 to 1.5 kg/cm 2 G, preferably 0 to 1.3 kg/cm 2 G. be.
• the reaction conditions for the esterification reaction in the intermediate stage are the conditions between the reaction conditions in the first stage and the reaction conditions in the final stage. These esterification reaction rate increases are preferably distributed smoothly in each stage. It is desired that the final esterification reaction rate reaches preferably 90% or more, more preferably 93% or more. A low order condensate having a molecular weight of about 500 to 5,000 is obtained by these esterification reactions.
• the above esterification reaction can be carried out without a catalyst due to the catalytic action of terephthalic acid as an acid, but it may be carried out in the presence of a polycondensation catalyst.
• tertiary amines such as triethylamine, tri-n-butylamine and benzyldimethylamine
• quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide and trimethylbenzylammonium hydroxide
• lithium carbonate sodium carbonate, potassium carbonate, sodium acetate, etc.
• the ratio of dioxyethylene terephthalate component units in the main chain of polyethylene terephthalate is reduced to a relatively low level ( 5 mol % or less relative to the total diol component), which is preferable.
• the transesterification reaction is carried out using an apparatus in which 1 to 2 transesterification reactors are connected in series, and under conditions where ethylene glycol is refluxed, the methanol produced by the reaction is removed from the system in a rectification column. Carry out while removing.
• the temperature of the first-stage transesterification reaction is preferably 180 to 250°C, more preferably 200 to 240°C.
• the temperature of the transesterification reaction in the final stage is usually 230 to 270°C, preferably 240 to 265°C.
• Pb, Zn, Sb, Ge oxide, or the like may be used.
• a low order condensate having a molecular weight of about 200 to 500 is obtained by these transesterification reactions.
• the obtained low-order condensate is then supplied to a multistage liquid-phase polycondensation process.
• the reaction temperature of the first stage polycondensation is preferably 250 to 290° C., more preferably 260 to 280° C.
• the pressure is preferably 500 to 20 Torr, more preferably 200 to 30 Torr
• the temperature of the polycondensation reaction in the final stage is preferably 265-300° C., more preferably 275-295° C.
• the pressure is preferably 10-0.1 Torr, more preferably 5-0.5 Torr.
• the reaction conditions for the polycondensation reaction in the intermediate stage are the conditions between the reaction conditions in the first stage and the reaction conditions in the final stage.
• the degree of increase in intrinsic viscosity achieved in each of these polycondensation reaction steps is smooth.
• the polycondensed polyester resin thus obtained is then solid phase polymerized.
• the above polyester resin is solid-phase polymerized by a conventionally known method.
• the polyester resin to be subjected to solid phase polymerization is preliminarily heated at a temperature of 100 to 190° C. for 1 to 5 hours under an inert gas or under reduced pressure, or in an atmosphere of steam or steam-containing inert gas. Crystallized. Solid phase polymerization is then carried out at a temperature of 190 to 230° C. for 1 to 50 hours in an inert gas atmosphere or under reduced pressure.
• the catalyst used in the present invention has catalytic activity not only in polycondensation reactions but also in esterification reactions and transesterification reactions.
• a catalyst can be used in the transesterification reaction between a dicarboxylic acid alkyl ester such as dimethyl terephthalate and a glycol such as ethylene glycol.
• the catalyst used in the present invention has catalytic activity not only in melt polymerization but also in solid phase polymerization and solution polymerization, and polyester resin can be produced by any method.
• the polymerization catalyst used in the present invention can be added to the reaction system at any stage of the polymerization reaction.
• it can be added to the reaction system before the start of the esterification reaction or transesterification reaction, at any stage during the reaction, immediately before the start of the polycondensation reaction, or at any stage during the polycondensation reaction.
• it is preferable to add aluminum or an aluminum compound immediately before starting the polycondensation reaction.
• the addition method of the polymerization catalyst other than the phosphorus compound used in the present invention may be addition in the form of powder or neat, or addition in the form of slurry or solution of a solvent such as ethylene glycol.
• a solvent such as ethylene glycol.
• aluminum or an aluminum compound or a phosphorus compound and other components may be premixed and added as a mixture, or they may be added separately.
• aluminum, an aluminum compound or a phosphorus compound and other components may be added to the polymerization system at the same time of addition, or each component may be added at different times of addition.
• the total amount of the catalyst may be added at once or may be added in multiple portions.
• the polyester resin of the present invention is preferably subjected to blow molding (preferably direct blow molding) after polycondensation and solid phase polymerization.
• blow molding preferably direct blow molding
• a precursor having a bottom generally called a preform
• this preform may be blow-stretched in a mold and heat-set.
• Methods such as compression molding and injection molding are used to manufacture the preform.
• a preform can be obtained by heating and melting to 260 to 350° C. and injecting it into a preform mold.
• the preform has a thick-walled test-tube shape with a gate at the bottom and a screw for capping at the mouth.
• the spout of the obtained preform may be crystallized. Crystallization can prevent deformation of the spout even when high-temperature contents are filled. Crystallization of the spout is preferably carried out by heating to 130 to 200°C, more preferably 140 to 190°C. As a heating method, an infrared heater, hot air, induction heating, immersion in an oil bath, or the like can be used, and the use of an infrared heater is preferable from the viewpoint of productivity. The heat crystallization of the spout may be performed after the blow molding.
• a preform is heated, stretched in the bottle length direction (longitudinal direction) and blow-molded in the circumferential direction to obtain a bottle. It is stretched in the longitudinal direction with a rod-shaped stretching rod, and in the circumferential direction, a pressurized gas such as air or nitrogen is used.
• the pressurized gas is preferably 1-10 MPa.
• a method of simultaneously stretching in the longitudinal direction and the circumferential direction by blowing pressurized gas while inserting a stretching rod is preferred, but stretching in the longitudinal direction may be followed by stretching in the circumferential direction.
• An infrared heater, hot air, induction heating, or the like is used for heating. The heating temperature is usually 80-130°C, preferably 90-120°C.
• the lower limit of the draw ratio in the bottle length direction is preferably 1.5 times, more preferably 2 times. If it is less than the above, stretching may be uneven.
• the upper limit of the draw ratio in the bottle length direction is preferably 6 times, more preferably 5 times, and still more preferably 4 times. If the above is exceeded, tearing or the like is likely to occur.
• the lower limit of the draw ratio in the bottle circumferential direction is preferably 2 times, more preferably 2.5 times. If it is less than the above, stretching may be uneven.
• the upper limit of the stretch ratio in the bottle circumferential direction is preferably 6 times, more preferably 5 times, and still more preferably 4 times. If the above is exceeded, tearing or the like is likely to occur.
• the lower limit of the mold temperature for blow molding is preferably 80° C., more preferably 120° C., still more preferably 130° C., most preferably 140°C. If it is less than the above range, the subsequent heat setting may not promote sufficient crystallization, resulting in insufficient heat resistance, or the need to take a long heat setting time, which may lead to a decrease in productivity.
• the upper limit of the mold temperature is preferably 350°C, more preferably 340°C, still more preferably 330°C, particularly preferably 320°C, and the lower limit of the mold temperature is preferably 280°C, It is more preferably 290°C, still more preferably 300°C. Since the polyester resin of the present invention has the property that the melt tension decreases as the temperature increases during melting, when the mold temperature is increased, the melt tension decreases when the mold and the polyester resin contact each other. While the occurrence of fractures is reduced, after ejection from the mold, the melt tension will be higher and the occurrence of drawdown will be reduced.
• the blow-molded bottle continues to be heat-set in the mold.
• the lower limit of the heat setting time is preferably 0.5 seconds, more preferably 1 second, still more preferably 1.5 seconds. If it is less than the above, sufficient crystallization may not be promoted, resulting in insufficient heat resistance.
• the upper limit of the heat setting time is preferably 15 seconds, more preferably 10 seconds, and even more preferably 5 seconds. A long heat setting time not only results in poor productivity, but also requires a large number of molds in the case of a rotary blow molding machine, which may result in poor economic efficiency if the apparatus is large. After heat setting in the mold, additional heat setting may be performed by further heating with infrared rays, hot air, induction heating, or the like.
• the blow molding apparatus may be equipped with one mold, but in the case of mass production, it is equipped with a plurality of molds. It is preferable to use a system that sequentially moves between a place for heat setting, a place for heat setting, and a place for ejecting bottles.
• the content of the bottle to be molded is preferably 200 mL to 6 L, more preferably 300 mL to 2 L.
• the shape of the bottle body can be any shape such as circular, square (including shapes with cut corners), hexagons, and the like.
• the polyester resin of the present invention is subjected to blow molding (preferably direct blow molding) and is suitably used for containers (for example, bottles) for cosmetics, detergents, beverages, and the like.
• composition of the polyester resin was determined by 1 H-NMR analysis in heavy chloroform solvent using RUKER's AVANCE 500 Fourier transform nuclear magnetic resonance spectrometer and from the integral ratio thereof.
• Polyester resin was heated to a melting point +20 ° C in a stainless steel circular ring with a thickness of 5 mm and an inner diameter of 50 mm to prepare a sample piece. Elemental amounts were determined by fluorescent X-ray analysis and displayed in ppm. In determining the amount, a calibration curve obtained in advance from samples with known amounts of each element was used.
• a sizing mold is installed, and the product is molded by a profile extrusion molding facility equipped with a take-up machine via a water tank, and the drawdown during molding and the mechanical properties, surface smoothness, and transparency of the molded product are evaluated according to the following criteria. was evaluated according to Table 2 shows the results.
• SRa center plane average
• a molded plate having a thickness of 7 mm was molded under the following conditions.
• the polyester resin was preliminarily dried under reduced pressure using a vacuum dryer Model DP61 manufactured by Yamato Scientific, and the inside of the molding material hopper was purged with a dry inert gas (nitrogen gas) in order to prevent moisture absorption during molding.
• the injection speed and pressure holding speed were adjusted to 20%, and the injection pressure and holding pressure were adjusted so that the weight of the molded product was 146 ⁇ 0.2 g. It was adjusted.
• the upper limits of the injection time and pressure holding time are set to 10 seconds and 7 seconds, respectively, and the cooling time is set to 50 seconds. Cooling water having a temperature of 10°C is constantly introduced into the mold for temperature control, but the mold surface temperature is around 22°C when the molding is stable.
• the molded plate for evaluation was arbitrarily selected from stable molded plates at 11th to 18th shots from the start of molding after the introduction of the molding material and replacement with the resin.
• the HAZE of the molded plate was measured with a haze meter, model NDH2000, manufactured by Nippon Denshoku Co., Ltd., and the transparency was evaluated according to the following criteria. ⁇ : HAZE is less than 5% ⁇ : HAZE is 5% or more and less than 8% ⁇ ⁇ ⁇ : HAZE is 8% or more and less than 10% ⁇ : HAZE is 10% or more
• Synthesis Examples 1 to 6 (Preparation of Compound (Branching Agent) Represented by Formula (I)) Compounds of formula (I) are prepared in a two gallon free radical continuous polymerization reaction as described in US Pat. prepared in situ. The compositions and weight-average molecular weights of the compounds represented by Formula (I) obtained in Synthesis Examples 1 to 6 are shown in Table 1 below. The weight average molecular weight of the compound represented by formula (I) was calculated by GPC in terms of standard polystyrene.
• l, m and n of the compound represented by formula (I) were determined by 1H-NMR and 13C-NMR analyses. That is, l, m, and n were expressed as integers by rounding off one decimal place as the average number. Specifically, a sample of the compound represented by formula (I) was prepared in a mixed solvent of deuterated chloroform/trifluoroacetic acid (85/15 by volume) for 1H-NMR, and deuterated chloroform or a heavy solvent for 13C-NMR.
• the compound represented by formula (I) used in the synthesis examples has the following methacrylic monomer structural unit (hereinafter abbreviated as DEMA-E structural unit) (* indicates other monomer structural unit (for example, styrene structural unit unit, represents a bond with the methyl methacrylate structural unit)).
• DEMA-E structural unit methacrylic monomer structural unit
• a compound containing this DEMA-E structural unit can be obtained by a method of synthesizing glycidyl methacrylate by ring-opening reaction with water and adding a diol, a method of synthesizing by adding a diol to methacrylic acid, or the like.
• copolymers of styrene and glycidyl methacrylate and/or methyl methacrylate are synthesized according to US Patent Application Nos. 09/354,350 and 09/614,402, followed by ring-opening with water. It may be subjected to a method of synthesizing by adding a diol.
• STY styrene
• MMA methyl methacrylate
• DEMA-E methacrylic monomer structural unit of the above chemical formula.
• Example 1 2432 g of terephthalic acid (Mitsui Chemicals Co., Ltd.), 1772 g of ethylene glycol (Nippon Shokubai Co., Ltd.), bisphenol A-EO adduct (Sanyo Kasei BPE-20F ) and 4 g of triethylamine (manufactured by Nacalai Tesque) were charged, and esterification was carried out at 240° C. for 3.0 hours under a pressure of 0.35 MPa.
• the compound represented by the formula (I) obtained in Synthesis Example 1 was continuously added to 0.2% by mass with respect to 100% by mass of the alcohol component of the resulting polyester resin while controlling the flow rate. , allowing the reaction to proceed stepwise.
• the polyester resin With respect to the mass of the polyester resin, add 30 ppm of aluminum acetate as an aluminum atom and 72 ppm of Irgamod 295 (manufactured by BASF) as a phosphorus atom as a polycondensation catalyst, and then add 1 ppm of Solvent Blue 45 (manufactured by Clariant) to the polyester resin.
• the mixture was stirred at 260° C. for 5 minutes under normal pressure in a nitrogen atmosphere. After that, the pressure of the reaction system was gradually lowered to 13.3 Pa (0.1 Torr) while the temperature was raised to 280° C. over 60 minutes, and polycondensation reaction was further carried out at 280° C. and 13.3 Pa.
• the resin under slight pressure was extruded into cold water in the form of a strand, rapidly cooled, held in cold water for 20 seconds, and cut to obtain cylindrical pellets with a length of about 3 mm and a diameter of about 2 mm. rice field.
• the polyester pellets obtained by melt polymerization were dried under reduced pressure (13.3 Pa or less, 80°C, 12 hours), and then subjected to crystallization treatment (13.3 Pa or less, 130°C, 3 hours, further 13.3 Pa or less, 160° C., 3 hours) was performed.
• the polyester pellets after standing to cool are solid-phase polymerized in a solid-phase polymerization reactor while maintaining the system at 13.3 Pa or less and 200° C. to 220° C. to obtain polyester pellets having an IV of 1.11 dl / g. rice field.
• the ratio of the diol component of the polyester resin was 95 mol % of ethylene glycol and 5 mol % of the bisphenol A-EO adduct. Table 2 shows the results of each evaluation.
• Example 2 In Example 1, the addition amount of the compound represented by formula (I) obtained in Synthesis Example 1 was changed to 0.001% by mass, and polymerization was performed under the same conditions as in Example 1 to obtain polyester pellets. .
• Example 3 In Example 1, the addition amount of the compound represented by formula (I) obtained in Synthesis Example 1 was changed to 4% by mass, and polymerization was performed under the same conditions as in Example 1 to obtain polyester pellets.
• Example 4 In Example 1, the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to the compound represented by Formula (I) obtained in Synthesis Example 2, and polymerized under the same conditions as in Example 1. was performed to obtain polyester pellets.
• Example 5 In Example 1, the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to the compound represented by Formula (I) obtained in Synthesis Example 3, and polymerized under the same conditions as in Example 1. was performed to obtain polyester pellets.
• Example 6 In Example 1, the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to the compound represented by Formula (I) obtained in Synthesis Example 4, and polymerized under the same conditions as in Example 1. was performed to obtain polyester pellets.
• Example 7 In Example 1, the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to the compound represented by Formula (I) obtained in Synthesis Example 5, and polymerized under the same conditions as in Example 1. was performed to obtain polyester pellets.
• Example 8 In Example 1, the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to the compound represented by Formula (I) obtained in Synthesis Example 6, and polymerized under the same conditions as in Example 1. was performed to obtain polyester pellets.
• Example 9 Polymerization was carried out under the same conditions as in Example 1 except that the esterification time was changed to 1.5 hours to obtain polyester pellets.
• Example 10 Polymerization was carried out under the same conditions as in Example 1 except that the amount of ethylene glycol charged was changed to 1002 g and the esterification time was changed to 1.0 hour to obtain polyester pellets.
• Example 11 In Example 1, germanium dioxide as a polycondensation catalyst was changed to 100 ppm of germanium atoms relative to the mass of the polyester resin, and triethyl phosphate was changed to 30 ppm of phosphorus atoms relative to the mass of the polyester resin. Polymerization was carried out under the same conditions as in Example 1 to obtain polyester pellets.
• Example 12 In Example 1, tetrabutyl titanium as a polycondensation catalyst is changed so that the titanium atom atom is 10 ppm relative to the mass of the polyester resin, and triethyl phosphate is changed so that the phosphorus atom atom is 100 ppm relative to the mass of the polyester resin. , Polymerization was carried out under the same conditions as in Example 1 to obtain polyester pellets.
• Example 13 In Example 1, the conditions were the same as in Example 1, except that the charging amount was changed so that the diol component of the polyester resin had a ratio of 2 mol% of the bisphenol A-EO adduct with respect to 98 mol% of ethylene glycol. Polymerization was carried out to obtain polyester pellets.
• Example 14 In Example 1, the conditions were the same as in Example 1, except that the charging amount was changed so that the ratio of the diol component of the polyester resin was 15 mol% of the bisphenol A-EO adduct with respect to 85 mol% of ethylene glycol. Polymerization was carried out to obtain polyester pellets.
• Comparative example 1 In Example 1, without adding the compound represented by formula (I), as a polycondensation catalyst, germanium dioxide was added to the polyester resin so that the germanium atom was 100 ppm with respect to the mass of the polyester resin, and triethyl phosphate was added to the polyester resin. Polymerization was carried out under the same conditions as in Example 1, except that the amount of phosphorus atoms was changed to 30 ppm with respect to the mass, to obtain polyester pellets.
• the compound represented by formula (I) as a polycondensation catalyst
• Comparative example 2 In Example 1, the amount of the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to 0.0001% by mass, and germanium dioxide was added as a polycondensation catalyst to the mass of the polyester resin. Polymerization was carried out under the same conditions as in Example 1, except that the amount of triethyl phosphate was changed to 30 ppm of phosphorus atoms with respect to the mass of the polyester resin so as to obtain 100 ppm atoms, to obtain polyester pellets.
• Comparative example 3 In Example 1, the addition amount of the compound represented by Formula (I) obtained in Synthesis Example 1 was changed to 6% by mass, and germanium dioxide was used as a polycondensation catalyst in an amount of germanium atom 100 ppm with respect to the mass of the polyester resin. Polymerization was carried out under the same conditions as in Example 1, except that triethyl phosphate was changed to 30 ppm of phosphorus atoms with respect to the mass of the polyester resin, to obtain polyester pellets.
• Comparative example 4 In Example 1, as the polycondensation catalyst, germanium dioxide was changed so that the germanium atom was 100 ppm relative to the mass of the polyester resin, and triethyl phosphate was changed so that the phosphorus atom was 30 ppm relative to the mass of the polyester resin. Polymerization was carried out under the same conditions as in Example 1, except that the charging amount was changed so that the diol component of the polyester resin had a ratio of 1 mol% of the bisphenol A-EO adduct to 99 mol% of ethylene glycol. A pellet was obtained.
• Example 1 As the polycondensation catalyst, germanium dioxide was changed so that the germanium atom was 100 ppm relative to the mass of the polyester resin, and triethyl phosphate was changed so that the phosphorus atom was 30 ppm relative to the mass of the polyester resin. Polymerization was carried out under the same conditions as in Example 1, except that the charging amount was changed so that the diol component of the polyester resin had a ratio of 16 mol% of the bisphenol A-EO adduct to 84 mol% of ethylene glycol. A pellet was obtained.
• melt viscosity was 26000 dPa ⁇ s or more at a temperature of 270° C. and a shear rate of 30 s ⁇ 1 and was 6500 dPa ⁇ s or less at a temperature of 270° C. and a shear rate of 2000 s ⁇ 1 .
• the polyester resin of the present invention has improved moldability in extrusion molding, profile extrusion molding, direct blow molding, inflation molding, injection blow molding, calendering molding, which requires high melt tension, and mechanical properties while maintaining transparency. It is expected that the improvement of characteristics can be realized and that it will greatly contribute to the industrial world.

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• 2022
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