TW200938563A - Polyester with improved heat resistance produced from biomass ethylene glycol - Google Patents

Abstract

A polyester having improved heat resistance for which use was made, as a diol ingredient, of ethylene glycol (EG) which is derived from a biomass and has a 14C concentration of 80% or higher based on that 14C concentration in cyclic carbon at the year 1950 contained in all carbon atoms which is taken as 100%. The polyester is a poly(ethylene/aromatic dicarboxylate ester) having a 14C concentration of 11% or higher based on that 14C concentration in cyclic carbon at the year 1950 contained in all carbon atoms which is taken as 100%. Also provided is a process for producing a poly(ethylene/aromatic dicarboxylate ester) in which the dimethyl ester of an aromatic dicarboxylic acid is used as an acid-ingredient raw material and EG having a 14C concentration of 80% or higher based on that14C concentration in cyclic carbon at the year 1950 contained in all carbon atoms which is taken as 100% is used as a diol-ingredient raw material.

Description

[Technical Field] The present invention relates to a polyester which uses ethylene glycol having a biochemical ratio of 80% or more as a glycol component, and is a polyester having excellent heat resistance. [Prior Art] Polyester, in particular, polyethylene terephthalate is widely used in various applications such as fibers and films because it has excellent properties. Further, fibers and films are generally produced by melt molding. However, the melting temperature at the time of melt molding is a temperature equal to or higher than the melting point of the polyester, and the quality of the molded article deteriorates due to thermal deterioration accompanying the retention of the polyester during melting. In order to improve the heat resistance, it is important to suppress the decrease in the inherent viscosity of the polyester in the gas in a high temperature atmosphere, but the thermal deterioration of the polyester is considered to be related to the ethylene glycol content in the polyester. That is, the lower the content of the diethylene glycol in the polyester, the more the thermal deterioration can be suppressed, and as a result, the reduction in the inherent viscosity of the polyester is suppressed, and the stabilization at the time of forming the molten G becomes possible. In the case where the atmosphere under the polycondensation reaction is acidic, it is known that diethylene glycol is produced due to the presence of the acidic compound catalyst. Accordingly, the method for improving the heat resistance of the polyester is carried out by adding a basic compound to suppress the production of diethylene glycol during the polycondensation reaction. However, the added basic compound is a compound containing a metal element, and the metal element component thereof becomes a catalyst and has a reverse reaction for promoting a polycondensation reaction in a high temperature atmosphere. As a result, even if a basic compound is added, the inherent viscosity of the polyester is lowered. In the past, polyesters were produced by polycondensation of a raw material mainly derived from petroleum, -5-200938563, but in recent years, the reduction of petrochemical fuel and the environmental problem of increase of oxygen in the atmosphere have intensified, so countermeasures corresponding to this problem have been made. . Therefore, there is a demand for a polyester which is used as a raw material of a polyester which is not derived from a petrochemical fuel to reduce environmental load (for example, Document 1). Patent Document 1: JP-A-2006-32 No. 995 SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a polyester having improved heat resistance. Still another object is to provide a method of producing the polyester. [Method for Solving the Problem] The inventors of the present invention have actively reviewed the polyester in order to eliminate the problems of the above-mentioned prior art. As a result, it has been found that polyester is produced by using glycol produced from biomass as a glycol component, and heat resistance in a molten state can be improved as compared with a conventional ester. More specifically, the melting point of the poly(aromatic dicarboxylic acid ethylene glycol) resin + 3 0 ° C in the molten state is small in the intrinsic viscosity of the polyester, and the polyester is improved to complete the present invention. That is, the object of the present invention is to provide a poly(aromatic diester) resin characterized by poly (a total carbon atom contained in an ethylene dicarboxylate, which is 100 in the recycled carbon at a point of 1950). The basis of %, the 14C concentration ratio (hereinafter, the carbon content becomes a necessary raw material. Referring to the point of the patent of the present invention, the heat-resistant dicarboxylic acid B resin which is melted at a temperature is found for the conventional polymerization of resources) The medium 14c concentration is referred to as the biological 200938563 conversion rate) of 11% or more, whereby the above problems can be solved. Further, the present invention is a poly(aromatic dicarboxylic acid ethylene glycol) resin having an intrinsic viscosity of 〇.5 〇 to 1. 〇〇dL/g. Preferably, in the present invention, the poly(aromatic dicarboxylic acid ethylene glycol) resin has a 14C concentration ratio of 16% or more when the concentration of the circulating carbon in the cycle of 1950 is used as the basis of loo%. Polyethylene terephthalate or a polyethylene naphthalate having a ratio of 14C in a concentration of 14C in the recycled carbon at 1950 as a basis of 100%, which is 11% or more. The purpose can be achieved by using dimethyl aromatic dicarboxylate as the main raw material of the acid component, and using 14C of the total carbon atoms contained in the ethylene glycol in the circulating carbon at the time of 1950 as the benchmark of 100%. The ethylene glycol having a concentration ratio of 80% or more is obtained as a method for producing any of the above poly(aromatic dicarboxylic acid ethylene glycol) resins as a diol component. Further, the aromatic dicarboxylic acid dimethyl ester is preferably dimethyl terephthalate or dimethyl naphthalene dicarboxylate. In addition, the dimethyl terephthalate is preferably obtained by a step of depolymerizing a reaction step by using an alkanediol, preferably ethylene glycol, using polyethylene terephthalate as a raw material. Ethylene terephthalate is depolymerized, followed by transesterification using methanol to obtain dimethyl terephthalate. [Effects of the Invention] According to the present invention, it is possible to provide a polyester having improved heat resistance, i.e., a polyester having a low inherent viscosity reduction at 28 ° C. 200938563 [Embodiment]

In the present invention, the bioavailability is 11% or more, and as described later, the measurement of the 14C concentration with respect to the radiocarbon constituting the total carbon amount is as described in the case where the concentration of the substance based on the 14C concentration is 107.44 pMC. The ratio is 10%, and the ratio with respect to the reference concentration (107.44 pMC) is at least 1%. Further, the term "biomass glycol" means ethylene glycol produced from biomass resources, and ethylene glycol having a biodegradation ratio of 80% or more as measured by a method described later. Q The term “biomass resource” here refers to the use of solar energy, a renewable carbon-derived carbon neutral carbon (Carbon Neutral) organic resource, and is derived from petrochemical resources such as coal, oil and natural gas. Resources. The biomass resources of the present invention can be classified into three types: a waste system, an unused system, and a resource crop system. Biomass resources are specifically cellulose-based crops (pulp, kenaf, wheat straw, rice straw, old paper, paper residue, etc.), lignin, charcoal, compost, natural rubber, cotton, sugar cane, oil, fat (vegetables) Oil, cottonseed oil, soybean oil, coconut oil, etc.), glycerin, carbohydrate crops (corn, taro, wheat, rice, sweet potato, etc.), gansu residue, terpene compound, pulp black liquor, kitchen waste , drainage sludge, etc. The method for producing the diol compound from the biomass resource is not particularly limited, but may be exemplified by a biological treatment method using a microorganism such as a fungus or a bacterium, and chemical treatment using an acid, a base, a catalyst, thermal energy or light energy. The method, or a known method such as physical processing methods such as miniaturization, compression, microwave processing, or electromagnetic wave treatment. -8- 200938563 Various methods are available for the conversion of biomass resources to ethylene glycol. The production method is not particularly limited, but first, a biological treatment method using a microorganism or the like from a biomass resource, or a chemical treatment method using an acid, a base, a catalyst, a thermal energy or a light energy, or a fine Known methods such as physical processing methods such as chemical conversion, compression, microwave processing, or electromagnetic wave processing. Further, a method in which the product obtained by the above methods is subjected to a hydrogen heating decomposition reaction and purified by using a catalyst is used. 〇 One of the other methods is, for example, a method in which ethanol is produced by a biological treatment method from sugar cane, sugar cane, and other carbohydrate-based crops, and then the epoxide is purified from the ethanol. A method of purifying by a distillation process or the like may also be employed. Alternatively, other methods of obtaining ethylene glycol from biomass resources can be exemplified by the following methods. That is, from biomass resources to glycerol, sorbitol, xylitol, glycol, fructose or cellulose, etc., and then using a catalyst to heat decomposition reaction by hydrogen, from which ethylene glycol and 1,2- are produced. A method of mixing a mixture of propylene glycol. Other methods are examples: ethanol is produced by biological treatment from sugar cane, bagasse, carbohydrate crops, etc., followed by ethylene oxide to form a mixture of ethylene glycol, diethylene glycol, and triethylene glycol. Method, etc. In the present invention, the rate of biochemistry is 14c when the concentration of the radioactive carbon 14C in the circulating carbon at the time of the 1985 point in the total carbon atoms of ethylene glycol or polyester is used as a reference (the enthalpy is set to 100%). Concentration ratio. The concentration of the radioactive carbon 14c can be determined by the following measurement method (radiation carbon concentration measurement). That is, the 14C concentration measurement is performed by combining the Tandem accelerator and the mass spectrometer accelerator mass analysis method (AMS : Accelerator 200938563)

Mass Spectrometry), using the weight of the atom by the accelerator

The isotope of carbon contained in the sample analyzed by the separation (specific examples are 12C, 13c, 14c), and the method of measuring the presence of one atom of the isotope is one of the molar carbon atoms (6.02x1 023). Typically about one-tenth of a carbon atom is about 6.02 x 1011 14C. 14C is called a radioactive isotope and has a half-life of 573 years and is regularly reduced. It takes 226,000 years to make such a complete collapse. In the past, carbon dioxide and the like in the atmosphere have been absorbed and fixed by plants, etc., and it is considered that the 14c elements contained in the first stage of immobilization, etc., have been collapsed in the petrochemical fuels such as soot, oil, and natural gas after 26,000 years or more. . Therefore, in the 21st century, fossil fuels such as soot, petroleum, and natural gas are completely free of 14C elements. Therefore, the chemical substances produced using these fossil fuels as raw materials are completely free of 14C. On the other hand, the 14C cosmic ray is subjected to nuclear reactions in the atmosphere, and is continuously generated. Since the rest of the radiation is reduced, the amount of 14C becomes a certain amount in the earth's atmosphere. On the other hand, when carbon dioxide in the atmosphere is inhaled and immobilized by plants or animals that eat this plant, 14C is not newly added in the state of inhalation, and the 14C concentration is relatively constant with the time of 14C. The ratio is reduced. Therefore, by analyzing the 14C concentration in the diol compound, it is possible to easily determine a diol compound which uses petrochemical resources such as petrochemical fuel as a raw material or a biomass resource as a raw material. Further, the 14C concentration is referred to as a modern standard as the 14c concentration in the circulating carbon in the natural world at the time of 1950 years, and the 14C concentration is 100% as a standard. Now, the concentration of 14c thus measured is -10°Pp (the percentage of modern carbon) as measured by -10-200938563, and it is assumed that if the plastic used as a sample is made of a substance derived from 100% natural (biological), 11 The OpMC is around. This 値 corresponds to the aforementioned biochemical rate of 1%. On the other hand, when the 14C concentration is measured using a chemical substance derived from a fossil fuel such as petroleum, it is also known that OpMC is roughly displayed. This 値 corresponds to the aforementioned biochemical rate of 0%. Using these enthalpy, a compound derived from a natural resource (a compound derived from biomass φ) - a mixture ratio of a compound derived from a petrochemical resource can be calculated. Furthermore, the 14C concentration is used as a reference for modern standards, and the use of the oxalic acid standard by NIST (National Institute of Standards and Technology) is preferably used. The radiant energy of the carbon in the oxalic acid (the intensity of the 14c radiant energy per gram of carbon) is corrected to 13C per carbon isotope for each of the carbon isotope's use of the attenuation correction from 1950 to the measurement date. Concentration 値. Detailed analysis method of 14C concentration in diol compound First, it is necessary to pretreat the glycolated φ compound. Specifically, the carbon contained in the diol compound is oxidized and all converted into carbon dioxide. Further, the obtained carbon dioxide is separated from water and nitrogen, and the carbon dioxide is subjected to a reduction treatment to be converted into solid carbon graphite. The graphite thus obtained is irradiated with a cation such as Cs + to form an anion of carbon. Next, the carbon ions were accelerated using a Tandem accelerator, and the negative ion crystal charges were converted into cations 'the orbital separation of 12C3+, 13C3+, and 14C3+ by mass spectrometry'. The separated 14C3+ was measured by an electrostatic analyzer. In the present invention, the poly(aromatic dicarboxylic acid ethylene glycol) tree-11 - 200938563 which is produced by polymerization can be used as a main raw material by using dimethyl aromatic dicarboxylate as a main raw material, and a biochemical ratio of 80% or more is used. A diol is obtained as a method of producing a glycol component. Dimethyl terephthalate or dimethyl naphthalate may be preferably used as the aromatic dicarboxylic acid dimethyl ester. Other types of aromatic dicarboxylic acid dimethyl esters are relatively easy to obtain, and therefore are industrially easy to implement. The dimethyl naphthalene dicarboxylate has a plurality of structural isomers, but is preferably dimethyl 2,6-naphthalene dicarboxylate or dimethyl 2,7-naphthalene dicarboxylate. The term "as a main raw material" means that an acid component other than dimethyl terephthalate or the like may be polymerized in a range that does not substantially impair the effects of the present invention. Specifically, it means the total amount of the aromatic dicarboxylic acid component (derivative containing an aromatic dicarboxylic acid) with respect to the poly (aromatic dicarboxylic acid ethylene glycol) resin (hereinafter referred to as polyester). 80% or more of the ratio is used. More preferably, it is used in a ratio of 90 mol% or more. As the dicarboxylic acid component other than dimethyl terephthalate or dimethyl naphthalate, a lower dibasic aromatic dicarboxylic acid and an aromatic dicarboxylic acid as a derivative of an aromatic dicarboxylic acid can be exemplified. Alkyl ester. Specifically, it can be exemplified by aromatic 0 aromatic dicarboxylic acid diethyl ester, aromatic dicarboxylic acid dipropyl ester, and aromatic dicarboxylic acid dibutyl ester. The aromatic dicarboxylic acid can be exemplified by isophthalic acid, phthalic acid, biphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfide dicarboxylic acid, diphenylmethane dicarboxylic acid, Diphenoxymethane dicarboxylic acid, diphenoxyethane dicarboxylic acid, benzophenone dicarboxylic acid, diphenylphosphonium dicarboxylic acid. Further, one or two or more hydrogen atoms may be directly substituted on the aromatic ring of the aromatic dicarboxylic acid to be substituted into a halogen atom, an amine group, a decyl group, a carboxyl group, an ester group, an ether group or a sulfonate. Acid metal salt based 'sulfonate ammonium salt, sulfonic acid money base -12- 200938563 compound. Further, the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention can be produced by using dimethyl dicarboxylate as a raw material instead of the above aromatic dicarboxylic acid. Alternatively, an aromatic dicarboxylic acid can be used for esterification reaction with ethylene glycol having a biochemical ratio of 80% or more, followed by polycondensation of the obtained esterification reaction product. Further, in the polyester of the present invention, regenerated terephthalic acid or regenerated dimethyl terephthalate is preferably used as the above-mentioned terephthalic acid or dimethyl terephthalate. As a countermeasure against the problem of decomposing fossil fuels in recent years, it is possible to provide a polyester having a reduced environmental load by regenerating dimethyl terephthalate and biomass glycol. The term "regenerated dimethyl terephthalate" means dimethyl terephthalate obtained by, for example, the following method. Namely, the raw material is a polyester waste containing polyethylene terephthalate as a main component, and depolymerization is carried out using ethylene glycol, and bis(2-hydroxyethyl)terephthalate is first obtained. Next, methanol hydrazine was added to the obtained bis(2-hydroxyethyl) bis(terephthalate) to carry out a transesterification reaction to obtain a mixture containing dimethyl terephthalate, methanol and ethylene glycol. High purity terephthalate can be obtained by purifying the finally produced dimethyl terephthalate-containing mixture by distillation or the like. The dimethyl terephthalate thus obtained is an example of regenerated dimethyl terephthalate. Further, the regenerated terephthalic acid system represents a terephthalic acid obtained by subjecting the dimethyl terephthalate to a hydrolysis reaction and purifying. The above polyester can be produced by any method known in the art of polyester production other than biomass glycol. Specifically, the direct alkylation of terephthalic acid with terephthalic acid and bio-glycol is carried out to directly react a lower alkyl ester of terephthalic acid such as terephthalic acid terpolymer T-13-200938563 with biomass glycol. The transesterification reaction 'produces a first-stage reaction of ethylene glycol terephthalate and/or its oligomer. Then, it can be produced by subjecting the reaction product of the first stage to heating under reduced pressure in the presence of a polycondensation reaction catalyst to carry out a second-stage reaction until the desired degree of polymerization. In the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention, polyethylene terephthalate is obtained by using dimethyl terephthalate or terephthalic acid as an acid component in the raw material. The ratio of total carbon in the repeating unit is composed of 80% (8) of carbon atoms derived from dimethyl terephthalate or the like, and 20% (two) of carbon atoms derived from ethylene glycol. The use of ethylene glycol as a glycol component having a biochemical rate of 80% or more represents the total carbon atom derived from ethylene glycol in the entire carbon atom constituting polyethylene terephthalate, that is, polyparaphenylene. The repeating unit of ethylene diformate is 20% of carbon atoms in the entire carbon atom, but more than 80% of it is a 14C-derived carbon atom derived from biomass. Therefore, theoretically, the biochemical rate of polyethylene terephthalate in this case is 16% or more. ◎ In the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention, poly(2,6-naphthalenedicarboxylic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid or the like) is used as an acid component to obtain a poly component. The ratio of all carbon atoms in the repeating unit of ethylene terephthalate is 86% (12) from the carbon atom derived from 2,6-naphthalenedicarboxylic acid, etc., and the carbon atom derived from ethylene glycol is 1 4% (2). The use of ethylene glycol having a biochemical ratio of 80% or more as a glycol component means that all carbon atoms derived from ethylene glycol are all carbon atoms constituting a repeating unit of polyethylene naphthalate, that is, polynaphthalene is formed. The repeating unit of ethylene diester is 14% of carbon atoms in the total carbon-14-200938563, but more than 80% of it is a 14C-derived carbon atom derived from biomass. Therefore, theoretically, the biochemical rate of polyethylene terephthalate in this case is more than 11%. Unexpectedly, when the poly(aromatic dicarboxylic acid ethylene glycol) resin having a biochemical ratio of 11% or more was produced using ethylene glycol having a biochemical ratio of 80% or more as described above, the inventors found that heat resistance was improved. That is, the inherent viscosity reduction during melting is small. At this time, since the melting point of the polyester obtained by selecting the aromatic dicarboxylic acid or the like is changed, the temperature at the time of moderate melting in the evaluation of the heat resistance may be selected from the melting point of the obtained polyester + 10 to 40 ° C, preferably the melting point + 30 °c. The inherent viscosity of the resulting poly(ethylene dicarboxylate) resin is preferably in the range of 0.50 to 1.0 〇dL/g. When the intrinsic viscosity is less than 0.5 OdL/g, the strength of the obtained polyester molded article is extremely weak, and it is difficult to use it as a molded article. On the other hand, when the intrinsic viscosity exceeds l_〇0dL/g, the melt viscosity becomes too large to deteriorate the formability extremely. The intrinsic viscosity is preferably in the range of 0_60 to 0.70 dL/g. When the poly(aromatic dicarboxylic acid ethylene glycol) resin is produced, the pH of the ethylene glycol used may be preferably from 5.5 to 7.6, more preferably from 6. to 7. The pH is measured by diluting ethylene glycol in water having the same capacity as described later, and measuring it using a commercially available pH meter. In general, the polyester polymerization reaction uses a vinegar exchange reaction catalyst or a polycondensation reaction catalyst, and mainly uses a heavy metal such as a fission, a chain or a wrong. More examples of the carcass are acetic acid, antimony trioxide, and antimony oxide. Since heavy metals generally have a large environmental load, the catalyst for both the vinegar exchange reaction catalyst and the polycondensation reaction catalyst in the present invention is suitably used as a catalyst for the environmentally less hydrazine -15-200938563. The use of recycled dimethyl terephthalate or biomass glycol as the acid component and glycol component used in the polyester raw material, and the use of a titanium compound as a catalyst for the polycondensation reaction catalyst can further improve the global environment. The problem of polyester.

Further, as the titanium compound used for the polycondensation reaction catalyst, generally commercially available titanium tetrachloride such as titanium acetate or tetrabutyltitanium oxide or tetraisopropoxide titanium oxide can be used. Further, a titanium compound represented by the following formula (I) and a phosphorus compound represented by the following formula (II) can be used, and the ratio (P/Ti) of the molar number of the phosphorus element to the molar number of the titanium element (P/Ti) becomes 1.0. The titanium/phosphorus reactant reacted as a composition of the range of ~4.0 as a polymerization catalyst.

[In the above formula, R1,! ^2! ^3 and R4 are each the same or different and represent an alkyl group or a phenyl group, m represents an integer of 1 to 4, and when m is 2 to 4, each of 2 to 4 R2 and R3 respectively represent the same group or a different group] . More specifically, R1, R2, R3 and R4 are preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. [Chemical 2] R50-P- (OH) a (Μ)

II ο [In the above formula, R5 represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 to 16 to 200938563 carbon atoms]. When the ratio of the molar number of the phosphorus element to the molar number of the titanium element (P/Ti) is less than 1.0, the resulting polyester has a poor color tone and is inferior in heat resistance. On the other hand, when the ratio is more than 4.0, the catalyst activity in the polyester production step is insufficient for the transesterification reaction or the polycondensation reaction. The ratio of the molar number of the phosphorus element to the molar number of the titanium element (P/Ti) is preferably in the range of 1 · 2 to 3.5, more preferably in the range of 1 5 to 3 〇, and φ is preferably 1.8 to 〜 The scope of 2.8. Further, as an example, the reaction product of the titanium compound represented by the formula (I) and the phosphorus compound represented by the formula (II) can be obtained by heating a reaction in an alkanediol, preferably ethylene glycol. The reaction method of the two compounds can be exemplified by the following methods. For example, a component composed of the phosphorus compound represented by the formula (II) is mixed with ethylene glycol to obtain a mixed solution in which part or all of the phosphorus compound is dissolved in ethylene glycol. Next, a titanium compound represented by the formula (I) (which may also be a ruthenium solution using ethylene glycol or the like as a solvent) is added dropwise to the mixed solution to make the reaction mixture at a temperature of from 0 ° C to 200 ° C. It is preferably heated for 30 minutes or more, preferably at a temperature of 60 to 150 ° C for 40 to 90 minutes. The reaction pressure in the reaction is not particularly limited and is usually carried out under normal pressure. The titanium compound represented by the above formula (I) can be exemplified by titanium tetrachloride such as tetrabutyl titanate, titanium tetraisopropoxide, tetra-n-titanium-titanium oxide, tetra-titanium oxide or tetra-titania, or four. Benzene oxide, octadecyl trititanate, hexaalkyl dititanate, octaphenyl trititanate, or hexaphenyl dititanate. Further, the titanium compound other than the titanium compound represented by the above formula (I) may, for example, be titanium acetate, titanium propionate or titanium benzoate. Further, the phosphorus compound represented by the above formula (II) can be exemplified by, for example, monomethyl phosphate, monoethyl phosphate, mono-n-propyl phosphate, monoisopropyl phosphate, mono-n-butyl phosphate, and second-butyl phosphate. Ester, monobutyl butyl phosphate, monoamyl phosphate, monohexyl phosphate, monoheptyl phosphate, monooctyl phosphate, monodecyl phosphate, monodecyl phosphate, monoundecyl phosphate, mono-phosphoric acid Alkyl ester, monotridecyl phosphate, monotetradecyl phosphate, monopentadecanoate phosphate, monohexadecyl phosphate, monoheptadecanophosphate, monooctadecyl phosphate, monobasic phosphate Ester, monobenzyl phosphate, mono(4-methylphenyl) phosphate, mono(4-ethylphenyl) phosphate, mono(4-propylphenyl) phosphate, mono(4-butylphenyl) phosphate , mono(4-pentylphenyl) phosphate, mono(4-hexylphenyl) phosphate, mono(4-octylphenyl) phosphate, mono(4-mercaptophenyl phosphate), phosphoric acid single (4-ten) Dialkyl phenyl ester), monomethyl phosphate, monodextyl phosphate, monophenyl phosphate, mononaphthyl phosphate, monodecyl phosphate, and the like. The titanium compound represented by the above formula (I) is also preferably used by a method in which an aromatic polyvalent carboxylic acid represented by the following formula (III) and/or an acid anhydride thereof are used in advance. The reaction molar ratio of the titanium compound to the aromatic polyvalent carboxylic acid and/or its anhydride in this case is preferably in the range of (2:1) to (2:5), preferably (1:1) to (1). : 2) The scope. 〔化3〕

Ph-(COOH) „ (III> [where η represents an integer of 2 to 4]. The amount of the soluble titanium element contained in the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention is The poly(aromatic dicarboxylic acid ethylene glycol) resin is preferably in the range of 5 to 70 ppm based on the weight of -18 to 200938563. The so-called polyester soluble titanium element means that it is formulated as an inorganic particle such as titanium dioxide. In the poly(aromatic dicarboxylic acid ethylene glycol) resin, the polyester is not mixed with a molecular grade and corresponds to a Ti element in the polyester. More specifically, a catalyst composed of an organic titanium compound or the like is used. The titanium element contained is equivalent to the titanium element which is soluble in the polyester. That is, the titanium compound represented by the above formula (I) and the titanium element of titanium acetate correspond to the soluble titanium element of the polyester. When the amount of the polyester soluble titanium element in the carboxylic acid ethylene glycol) resin is less than 500 ppm, the polycondensation reaction becomes slow, and when it exceeds 70 ppm, the obtained polyester has a poor color tone and the heat resistance is lowered. The amount is preferably in the range of 7 to 60 ppm, more In the range of i〇~5〇ppm, it is also possible to additionally use a compound containing a titanium compound selected from the above formula (I) and a compound represented by the following formula (I) (III) A compound of at least one of the group consisting of a mixture of aromatic polyvalent carboxylic acids or an anhydride thereof, which is a polycondensation reaction catalyst, or the following formula (1) (2) The next preparation is a catalyst for a polycondensation reaction consisting essentially of a catalyst compound composed of a mixture of the titanium compound and a dish represented by the following formula (Iv).

ReOOC-X-P-(〇RT) s , II (lv) ο [In the above formula, R6 and R7 represent the same or different alkyl groups having 1 to 4 carbon atoms, and X represents -CH2- or -CHPh-]. -19- 200938563 0.65 ^ P/Ti ^5.0 ( 1 ) 1 0 ^ P + Ti ^200 ( 2 ) [In the above formula, Ti represents the concentration of the polyester soluble titanium metal element contained in the polyester (ppm by weight) , p represents the phosphorus element concentration (weight PPm) of the phosphorus compound contained in the polyester]. Among them, when (P/Ti) is less than 0.65, the hue of the obtained polyester is less preferable with the case of yellowing. Further, when (P/Ti) exceeds 5.0, the polymerization rate of the polyester is drastically lowered, and it is difficult to obtain a polyester having a sufficiently high intrinsic viscosity. The appropriate range of the (P/Ti) is characterized by being narrower than the catalytic compound containing a metal element which has been conventionally used in the past, but in the case of an appropriate range, the present invention can obtain an effect which has not been conventionally obtained. On the other hand, when (Ti + P) is less than 10, the productivity in the forming step such as the spinning process is drastically lowered, and the obtained molded article cannot obtain sufficient performance for practical use. Further, when (Ti + P ) exceeds 200, there is a case where a small amount of foreign matter is caused by the contact with the medium. The range of (P/Ti) 値 in the formula (1) is preferably in the range of 1.0 to 4.5, more preferably in the range of 2.0 to 4.0. The range of (P + Ti ) 値 in the formula (2) is preferably in the range of 12 to 150, more preferably in the range of 15 to 100. In the production of the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention, the titanium compound component used as a catalyst in the polycondensation reaction can also reduce the amount of foreign matter caused by the catalyst. A titanium compound of an ester-soluble titanium element. The titanium compound-20-200938563 containing a polyester-soluble titanium element is exemplified by a titanium compound represented by the following general formula (I), or a titanium compound represented by the general formula (I) and a fragrance of the following general formula (III). A product of the reaction of a polyvalent carboxylic acid or an anhydride thereof. 〔化5〕

[In the above formula, 'R1, R2, R3 and R4 each represent the same or different alkyl group or phenyl group. m represents an integer of 1 to 4, and when m is 2 to 4, each of 2 to 4 R2 and R3 represent the same or different groups, respectively. [6]

Ph —(COOH) n (III) [wherein η represents an integer of 2 to 4]. Here, as the titanium compound represented by the general formula (I), a titanium compound or the like which is described in detail in the above general formula (I) is preferably used. Further, in the production of the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention, the aromatic polyvalent carboxylic acid represented by the formula (III) is reacted with the titanium compound represented by the above formula (I) or The acid anhydride thereof preferably uses phthalic acid, trimellitic acid, hemitritic acid, pyromellitic acid, and the like, that is, phthalic anhydride, trimellitic anhydride, and trimellitic anhydride. When the titanium compound is reacted with an aromatic polyvalent carboxylic acid or an anhydride thereof, a part or all of the aromatic polyvalent carboxylic acid or an anhydride thereof is dissolved in a solvent, and the mixture is dissolved in a solvent. The titanium compound is added dropwise and heated at a temperature of 0 to 200 ° C for at least 30 minutes, preferably at a temperature of 30 to 150 ° C for 40 to 90 minutes. The reaction pressure at this time is not particularly limited and is sufficient under normal pressure. Further, as the solvent for dissolving the aromatic polyvalent carboxylic acid or its anhydride, any of ethanol, ethylene glycol, propylene glycol, butylene glycol, benzene, and xylene may be used as needed. The reaction molar ratio of the titanium compound to the aromatic polyvalent carboxylic acid or its anhydride is not particularly limited. However, when the proportion of the titanium compound is too high, the color tone of the obtained poly Q ester deteriorates and the softening point may decrease. On the contrary, if the proportion of the titanium compound is too low, the aggregation condensation reaction is difficult to progress. Therefore, the reaction molar ratio of the titanium compound to the aromatic polyvalent carboxylic acid or its anhydride is preferably in the range of 2/1 to 2/5. The other catalyst compound used as a polycondensation reaction catalyst in the production of the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention may be the above-mentioned titanium compound component and phosphorus represented by the following general formula (IV). The unreacted mixture of compounds consists essentially of. © 〔化7〕

ReOOC-X-p- (0RT) 2 (IV)

II 0 [In the above formula, R6 and R7 represent the same or different alkyl groups having 1 to 4 carbon atoms, and X represents -CH2- or -CHPh-]. The compound (phosphate compound) represented by the above formula (IV) is preferably selected from the group consisting of carbonylmethoxymethanephosphoric acid, carbonylethoxymethanephosphoric acid, carbonylpropoxymethanephosphoric acid, carbonylpropoxymethanephosphoric acid, and carbonylmethyl Oxy-phosphonium-phenyl-22- 200938563 acetic acid, ethoxylated-disc-phenylacetic acid, ortho-oxy-phosphonium-phenylacetic acid and carbon-butoxy-phosphonium- Dimethyl esters of phenylacetic acid, diethyl esters, dipropyl esters and dibutyl esters. More preferably, these compounds are carbonylmethoxymethanephosphoric acid, dimethyl carbonylmethoxymethane phosphate, diethyl carbonyl methoxymethane phosphate, carbonyl ethoxymethane phosphate, dimethyl carbonyl ethoxymethane phosphate. Or carbonyl ethoxymethane diethyl phosphate. The phosphoric acid ester compound described above is relatively slow in chemical reaction with the titanium compound as compared with the phosphonium compound which is usually used as a stabilizer, and the duration of the catalytic activity of the titanium compound can be maintained long in the chemical reaction. As a result, even if the amount of the titanium compound added to the polyester is reduced, the necessary catalyst activity can be maintained. Further, even if a large amount of a stabilizer is added to the catalyst compound containing the phosphorus compound represented by the formula (IV), the thermal stability of the obtained polyester is not lowered, and the color tone is not deteriorated. A phosphorus compound represented by the formula (IV) is also preferably used in this point. Further, the catalytic compound containing the phosphorus compound represented by the above formula (IV) preferably satisfies the following formulas (1) and (2): 0.65 SP/Ti guest 5.0 ( 1 ) 1 0 ^ P + Ti ^ 200 ( 2 ) [In the above formula, Ti represents the concentration (weight ppm) of the polyester soluble barium metal element contained in the polyester, and P represents the phosphorus element concentration of the phosphorus compound contained in the polyester ( Weight ppm)]. Here, when (P/Ti) is less than 0.65, the hue of the obtained polyester is not preferable with the case of -23-200938563 yellow. Further, when the (P/Ti) exceeds 5.0, the polymerization rate is drastically lowered, and it is difficult to obtain the target polyester having a viscosity. The appropriate range of the (p/Ti) is characterized by being narrower than the catalyst compound containing a metal element, but as appropriate, the present invention can obtain effects which have not been conventionally obtained. On the other hand, when (Ti + P) is less than 10, the productivity in the spinning step is drastically lowered, and the obtained molded article cannot be used with sufficient performance. In addition, when (Ti + P ) exceeds 200, foreign matter caused by a small amount is not preferable. The range of (p/Ti) 値 in the formula (1) is preferably in the range of from 1 to 1, more preferably from 2.0 to 4.0. In the formula (2) (the range is preferably in the range of 12 to 150, more preferably 15 to 100 f. The poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention is polycondensed using the above catalyst compound The reaction, at a temperature, under normal pressure or reduced pressure, preferably in 〇. 5Pa, preferably in combination with the conditions of the polymerization reaction for 15 to 300 minutes of the present invention poly (aromatic dicarboxylic acid B The amount of the soluble titanium element of the diester) resin is as described above in terms of the amount of poly(ethylene dicarboxylate, preferably in the range of 5 to 70 ppm. Here, the soluble titanium element) is as described above. When the ester solubility is less than 50 pm, the polycondensation reaction rate becomes slow. When the amount of the polyester exceeds 70 ppm, the color of the obtained polyester is poor, and the heat resistance is not good. The obtained polyester soluble titanium is 7 to 60 pm. The range is preferably in the range of 10 to 50 ppm. When the polyester is sufficiently high, it is inherently used in the conventional process, and the forming process is actually obtained, because of the catalyst. 0~4.5 of the formula P + Ti) Scope. In the manufacture, 2 3 0 ~ 320 〇 C ~ 0.2MPa T ο polyester contained in the resin) "The amount of the polyester of the polyester obtained by the amount of the soluble titanium element is preferably good. 200938563 In addition, the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention can be formulated with an antioxidant, an ultraviolet absorber, and the like. A fuel, a fluorescent whitening agent, a deodorant, a coloring agent or an antifoaming agent or other additives, etc. The present invention is specifically described by the following examples, but the present invention is not limited to the examples. The parts and % in the examples are shown in parts by weight and % by weight unless otherwise specified. The respective measurements are determined according to the following methods. Examples 1 to 3 are glycols using biomass ethylene glycol as a raw material for polyester. In the components, in Comparative Examples 1 to 3, ethylene glycol produced from petrochemical resources was used as a glycol component of the polyester raw material. As a result of measuring the biochemical rate of ethylene glycol, the bioavailability of biomass ethylene glycol was 90. On the other hand, the bioavailability of ethylene glycol produced by petrochemical resources is less than 0.06%. Here, ethylene glycol produced by petrochemical resources refers to petrochemical resources such as petroleum, natural gas or coal produced by general industry. The ethylene glycol produced by using the component as a raw material. The dimethyl terephthalate which is regenerated is used to depolymerize polyester waste mainly containing polyethylene terephthalate by using ethylene glycol. The obtained bis(2-hydroxyethyl terephthalate) is added with methanol for transesterification, and the resulting dimethyl terephthalate is distilled and purified to obtain dimethyl terephthalate. The intrinsic viscosity of the viscosity polyester is determined in a solution of o-chlorophenol at 35 ° C. (2 ) Diethylene glycol (DEG) content The obtained polyester is pulverized, and the obtained pulverized material is decomposed with hydrazine to give a gas-25 - 200938563 The phase chromatography method was used to analyze the quantitative solution. (3) Evaluation of heat resistance First, the case where the polyester is polyethylene terephthalate will be described. The polyester pellets were dried by hot air at 160 ° C for 6 hours, and then placed in a nitrogen atmosphere at a normal pressure and a temperature of 28 ° C for 60 minutes, and the polyester pellets were taken out immediately after 60 minutes. Next, the intrinsic viscosity of each polyester pellet before and after heat treatment at 285 °C was measured in a 35 t o-chlorophenol solution. The temperature of 2 85 ° C is the temperature at which the polyethylene terephthalate polymerized in each of the examples and the comparative examples has a melting point of +30 ° C. The intrinsic viscosity before being dried by hot air and placed in an atmosphere at a temperature of 285 °C was used as a reference, and the decrease in the intrinsic viscosity after treatment at 285 °C for 60 minutes was expressed by AIV. It was maintained at 285 ° C for 60 minutes in a nitrogen atmosphere, and it was judged to have good heat resistance in the case where the Λιν before and after the heat treatment was 0.1 00 dL/g or less. Further, in the case where the AIV is 0.08 5 dL/g or less, it is judged to have excellent heat resistance, and then the polyester is polyethylene naphthalate, except that the melting point of the polyethylene naphthalate for the application of 0 is also considered. 3 0. (: The temperature was measured by using the same procedure as in the case of polyethylene terephthalate except for 295 t. (4) Evaluation of biological rate (measurement of 14 C concentration) 14 C concentration measurement by combination The above-described Tandem accelerator and mass spectrometer accelerator mass analysis method measures the concentration of the measured sample relative to the radiocarbon 14C constituting the total carbon amount. Then, based on the case of 1〇7 44 pMc, the bioavailability is taken as a reference. The biochemical rate was calculated as the ratio of the concentration of 値-26-200938563. (5) pH measurement The pH of the ethylene glycol used in the comparative example of the example was diluted with water of the same capacity, and used. The pH meter (D-25 type) produced by Horiba, Ltd. was measured and measured. Each PH was measured and corrected by three pH calibration solutions of 4.01, 6.86, and 9.18. [Example 1] 100 parts of regeneration was performed. Dimethyl terephthalate, 60 parts of biomass glycol (ρΗ = 6.1), 0.03 1 part of manganese acetate 4 hydrate were fed into a transesterification tank, and under nitrogen gas atmosphere for about 3 hours. Warm up from 140 °C to 24 (TC The transesterification reaction was carried out while distilling the produced methanol out of the transesterification tank. After the transesterification reaction, 0.004 parts of a phosphoric acid compound as a stabilizer and 0.04 part of antimony trioxide as a polycondensation catalyst were immediately added. The temperature was raised to 285 ° C, and a polycondensation reaction was carried out under reduced pressure to obtain a polyester. The diethylene glycol content of the obtained polyester was measured. As a result, the content of diethylene glycol was 0.72% by weight. The intrinsic viscosity before and after the treatment was measured in a nitrogen atmosphere at a temperature of 285 ° C for 60 minutes. As a result, the intrinsic viscosity reduction range (AIV ) after the heat treatment for 60 minutes was 〇.〇79dL/ g»The bioavailability of the obtained polyester was 18%. The evaluation results are shown in Table 1. The regenerated dimethyl terephthalate used in this example was a dimethyl terephthalate obtained by the following operation. 1 part of polyparaphenylene phthalate-27-200938563 acid ethylene diester, 360 parts of ethylene glycol and 2.7 parts of sodium carbonate were supplied to the depolymerization tank, and the polymerization was carried out at 180 ° C under stirring. 4 hours. The resulting depolymerization reaction The liquid is subjected to hot filtration. The residue on the filter is washed with 90 parts of ethylene glycol heated to 170 ° C. The obtained washing liquid is mixed with the depolymerization treatment liquid, and the depolymerization reaction is mixed with the washing liquid. The liquid was concentrated by distillation under reduced pressure of 6.65 kPa, and 270 parts of ethylene glycol was recovered. 2.7 parts of sodium carbonate and 180 parts of methanol were added to the obtained concentrate and put into a transesterification reaction tank, and the liquid temperature was maintained at 75 ° under normal pressure with stirring. C-hour transesterification anti-Q. The mixture of the obtained dimethyl terephthalate, methanol and ethylene glycol is cooled to 40 ° C, and solid-liquid separation is carried out by a centrifugal separation device to obtain solid terephthalic acid. Dimethyl ester. The obtained dimethyl terephthalate was put into 180 parts of methanol and washed at 4 (TC) with stirring, and then subjected to solid-liquid separation by a centrifugal separation device to obtain dimethyl terephthalate obtained by solid-liquid separation. The residual methanol was simultaneously distilled at 160 ° C. The molten dimethyl terephthalate was distilled into a distillation column, and distilled under reduced pressure of 6.65 kPa to obtain 83 parts of dimethyl terephthalate. Distillate. © [Comparative Example 1] Except for Example 1, except that further purified ethylene glycol (pH = 6.1) manufactured by petrochemical resources was used instead of biomass glycol, the remainder was as in Example 1. The operation was carried out to obtain a polyester. The evaluation results are shown in Table 1. [Example 2] 1 part by weight of dimethyl terephthalate regenerated, 60 parts of biomass ethylene-2-28-200938563 alcohol (pH = 6.1) And 0.0012 parts of titanium trimellitate was fed into a transesterification tank, and the transesterification tank was pressurized at 0.08 MPa, and heated from 140 ° C to 240 ° C in a nitrogen gas atmosphere for about 3 hours. The resulting methanol is distilled off the transesterification tank and subjected to a transesterification reaction. After completion of the transesterification reaction, 0.012 parts of a phosphoric acid compound as a stabilizer was added, and the temperature was immediately raised to 28 5 ° C, and a polycondensation reaction was carried out under reduced pressure to obtain a polyester. Further, dimethyl terephthalate was used for regeneration. The same as the dimethyl terephthalate used in Example 1. The diethylene glycol content of the obtained polyester was measured. As a result, the content of diethylene glycol was 0.84% by weight. The intrinsic viscosity before and after the treatment was measured in a nitrogen atmosphere at a temperature of 285 ° C for 60 minutes. As a result, the intrinsic viscosity reduction range (AIV ) after the heat treatment for 60 minutes was 〇. 7 5 dL/g. The bioavailability of the obtained polyester was 17%. The evaluation results are shown in Table 1. ® [Comparative Example 2] In addition to the second example, ethylene glycol (ρΗ = 6·) which was previously purified from petrochemical resources was used. 1) Instead of using biomass ethylene glycol, the operation was carried out as in Example 2 to obtain a polyester. The evaluation results are shown in Table 1. [Example 3] '100 of terephthalic acid purified from petroleum resources in the past Dimethyl ester, 60 parts of bio-diol ΡΗ = 6.1), 0.0012 parts of titanium trimellitate was fed into the transesterification tank, and the transesterification tank was pressurized at 0.08 MPa, and heated from 140 °C in about 3 hours under nitrogen gas -29-200938563 atmosphere. At 240 ° C, the produced methanol was distilled off the transesterification tank to carry out a transesterification reaction. After the transesterification reaction was completed, 0.012 parts of a phosphoric acid compound as a stabilizer was added, and the temperature was immediately raised to 28 5 ° C under reduced pressure. The polycondensation reaction was carried out to obtain a polyester. The diethylene glycol content of the obtained polyester was measured, and as a result, the content of diethylene glycol was 0.81 wt%. Further, the polyester was exposed to a nitrogen atmosphere at a temperature of 285 ° C for 60 minutes to measure the intrinsic viscosity before and after the treatment. As a result, the intrinsic viscosity drop Q degree (Δίν ) after the above heat treatment for 60 minutes was 〇.〇7 5dL/g. The bioavailability of the obtained polyester was also 18%. The evaluation results are shown in Table 1. [Comparative Example 3] Except that ethylene glycol (ρΗ = 6.1) which was previously purified by petrochemical resources was used instead of biomass glycol in Example 3, the operation was carried out as in Example 3, Polyester. The evaluation results are shown in Table 1. [Example 4] 100 parts of dimethyl 2,6-naphthalene dicarboxylate, 50 parts of biomass ethylene glycol (ρΗ = 6. 1 ), and 0.03 part of manganese acetate tetrahydrate were fed into a transesterification tank. The temperature was raised from 140 ° C to 240 ° C in a nitrogen atmosphere for about 3 hours, and the produced methanol was distilled off the transesterification tank to carry out a transesterification reaction. After the end of the transesterification, 0.005 parts of a phosphoric acid compound as a stabilizer and 0.024 parts of antimony trioxide as a polycondensation catalyst were immediately added to 285. (: The polycondensation reaction was carried out under reduced pressure to obtain a polyester. The results of evaluation of the content of the alcohol, the evaluation of the heat resistance, and the bioavailability of the polyester are shown in Table 1. [Comparative Example 4] The polyester was obtained as in Example 4 except that ethylene glycol (ΡΗ = 6.1), which was previously purified from petrochemical resources, was used in the same manner as in Example 4 to obtain a polyester. The results are shown in Table 1. [Example 5] The polyester obtained in Example 2 was subjected to crystallization treatment at 160 ° C for 1 hour, fed into a sealed container, and solidified in a vacuum at 220 ° C for 8 hours. The phase polymerization was carried out until 0.75 dL/g. The evaluation results are shown in Table 1. [Example 6] In addition to the use of biomass glycol in Example 1, and further purified ethylene glycol previously produced by petrochemical resources © pH = 6.1) A mixture of the weight ratio of 2:1 was used instead of the biomass glycol, and the operation was carried out as in Example 1 to obtain a polyester. The evaluation results are shown in Table 1. [Example 7] 225 parts were used. Biomass glycol obtained by transesterification of Example 1 and regenerated p-benzene The polyester oligomer obtained by using ethylene formate as a raw material is retained in the reactor, and is supplied with a mixture of 1,79 parts of high-purity p-benzene at a constant speed under a nitrogen gas atmosphere maintained at 255 ° C under normal pressure. -31 - 200938563 Dicarboxylic acid and 95 parts of biomass glycol. The water produced by the esterification reaction and the biomass glycol are distilled off to the reactor for esterification for 4 hours. Esterification reaction: 225 parts of the polyester oligomer obtained in the esterification reaction was transferred to a polycondensation reaction tank to obtain 9 parts of the same antimony trioxide and 0.009 parts as in Example 1 as a polymerization catalyst. The phosphorus compound and 2.45 parts of an aqueous solution containing 20% tetraethylammonium hydroxide are poured into a polycondensation reaction tank, and then the temperature in the polycondensation reaction tank is raised from 255 ° C to 285 ° C, and the reaction in the polycondensation reaction tank is carried out. The pressure is reduced from atmospheric pressure to 30 Pa or less, and water and ethylene glycol generated in the polycondensation reaction are removed from the polycondensation reaction tank while being heated and reduced in pressure at each stage, and a polycondensation reaction is carried out to obtain an intrinsic viscosity. .63dL/g, diethylene glycol containing The polyester was granulated in an amount of 1.0% by weight. The polyester was further granulated by a conventional method. The evaluation results are shown in Table 1. [Comparative Example 5] In the same manner as in Example 7, a further purified ethylene glycol manufactured by a petrochemical resource was used. (pH = 6.1) The procedure of Example 7 was followed except that the biomass glycol was used instead, and the polyester was obtained. The evaluation results are shown in Table 1. -32- 200938563 [Table 1] EG EG of the acid raw material of the raw material DEG content of bio-polyester heat resistance evaluation: intrinsic viscosity (dL/g) ingredient surface type rate (%) physicochemical rate (%) (wt%) 60 minutes after 60 minutes ΔIV Example 1 R-DMT B- EG 90 17 0.72 0.641 0.562 0.079 Example 2 R-DMT B-EG 90 18 0.84 0.642 0.567 0.075 Example 3 N-DMT B-EG 90 18 0.81 0.648 0.573 0.075 Example 4 NDC B-EG 90 13 0.45 0.640 0.547 0.093 Example 5 R-DMT B-EG 90 17 0.72 0.750 0.685 0.065 Example ό R-DMT B-EG 90 12 0.85 0.629 0.539 0.090 Example 7 ΡΤΑ B-EG 90 18 0.95 0.630 0.552 0.078 Comparative Example 1 R-DMT N -EG <0.06 0 0.90 0.639 0.512 0.127 Comparative Example 2 R-DMT N-EG <0.06 0 0.92 0.643 0.524 0.119 Comparative Example 3 N-DMT N-EG < 0.06 0 0.88 0.637 0.521 0.116 Comparative Example 4 NDC N-EG < 0.06 0 0.55 0.620 0.514 0.106 Comparative Example 5 ΡΤΑ N-EG < 0.06 0 0.98 0.627 0.526 0.101

Remarks: R-DMT: Regenerated ethylene terephthalate N-DMT: Non-regenerated ethylene terephthalate NDC manufactured from petrochemical resources: Dimethyl 2,6-naphthalene dicarboxylate PTA: Terephthalic acid EG: Ethylene glycol B-EG: Ethylene glycol N-EG manufactured from biomass-derived raw materials: Ethylene glycol DEG manufactured from petrochemicals: Diethylene glycol [Industrial use Possibility According to the present invention, it is possible to provide a polyester having improved heat resistance, that is, a polyester having a low inherent viscosity reduction in the case of 2 8 5 t. Further, a ratio of 14C in which dimethyl terephthalate is used as a main acid component and a concentration of 14C in the recycled carbon at the time of the all-carbon atom contained in ethylene glycol is used as a reference of 100% is provided. More than 80% of ethylene glycol is used as a method of producing a polyester from -33 to 200938563, which is capable of producing an improved heat resistance, that is, a polyester having a low inherent viscosity reduction when placed at 285 t. The method. These findings are of great significance in the development of the industry. -34-

Claims (1)

200938563 X. Patent application scope 1. Poly (aromatic dicarboxylic acid ethylene glycol) resin' characterized by all carbon atoms contained in poly(ethylene dicarboxylate) resin '1950' The 14C concentration in the recycled carbon at the time point is a ratio of 14C of the ratio of iOO% of 11% or more. 2. The poly(aromatic dicarboxylic acid ethylene glycol) resin as claimed in claim 1 has an intrinsic viscosity of 0.5 0 to 1. 〇〇dL/g. 0 3. The poly(aromatic dicarboxylic acid ethylene glycol) resin according to claim 1 or 2, wherein the poly(aromatic ethylene dicarboxylate) resin is in the recycled carbon at the time of 1950 years. 14C concentration is 14% concentration of 14C concentration ratio of 14% or more of polyethylene terephthalate' or 14c concentration of circulating carbon in 1950's point as the basis of 1%% of 14c concentration Polyethylene naphthalate having a ratio of 11% or more. 4. A method for producing a poly(ethylene dicarboxylate) resin according to item 1 of the patent application, characterized in that an aromatic dicarboxylic acid dicarboxylate is used as a main acid component raw material, and an ethylene compound is used. Among the all carbon atoms contained in the alcohol, ethylene glycol is used as a diol component in a 14 C concentration ratio of 80% or more based on a 14 C concentration of recycled carbon at a temperature of 1950. 5. A method for producing a poly(ethylene dicarboxylate) resin according to item 4 of the patent application, wherein the dimethyl aromatic dicarboxylate is dimethyl terephthalate or naphthalene dicarboxylate ester. 6. The method for producing a poly(ethylene dicarboxylate) resin according to claim 5, wherein dimethyl terephthalate is obtained by using polyethylene terephthalate as a raw material Step of depolymerization step -35- 200938563 obtained dimethyl terephthalate. 7. The method for producing a poly(ethylene dicarboxylate) resin according to claim 6 wherein dimethyl terephthalate is obtained by using polyethylene terephthalate as a raw material. Dimethyl terephthalate obtained by the step of depolymerizing the ethylene glycol. -36- 200938563 VII. Designated representative map: (1) The designated representative figure of this case is: None (2), the symbol of the representative figure is simple: no 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none -4-