TWI485178B - Use of ethylene glycol to improve the heat resistance of the polyester - Google Patents

Description

Polyester using biomass glycol to improve heat resistance

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.

Polyester, especially polyethylene terephthalate, is widely used in various applications such as fibers and films because it has many 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 high temperature atmosphere gas, but the thermal deterioration of the polyester is considered to be related to the diethylene 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 melt molding is made possible. In the case where the atmosphere gas in the polycondensation reaction is acidic, it is known that diethylene glycol is produced due to the presence of an 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, there is a case where the inherent viscosity of the polyester is lowered.

Conventional polyesters are produced by polycondensing a raw material mainly derived from petroleum. However, in recent years, environmental problems such as a decrease in petrochemical fuel and an increase in the amount of carbon dioxide in the atmosphere have increased, and therefore countermeasures against this problem have become necessary. Therefore, a polyester which uses a plant-derived raw material which is not derived from a fossil fuel as a raw material of a polyester to reduce an environmental load is required (for example, refer to Patent Document 1).

Patent Document 1: JP-A-2006-321995

The object of the present invention is to provide a polyester having improved heat resistance. Still another object of the present invention is to provide a method of producing the polyester.

The present inventors conducted an active review of polyester in order to eliminate the problems of the above-described prior art. As a result, it has been found that polyester is produced by using ethylene glycol produced from biomass resources as a glycol component, and heat resistance in a molten state can be improved as compared with a conventional polyester. More specifically, it has been found that the polyester has a low inherent viscosity reduction in the molten state of the melting point of the poly(aromatic dicarboxylic acid ethylene glycol) resin + 30 ° C, and the heat resistance of the polyester is improved. this invention.

That is, the object of the present invention is to provide a poly(aromatic dicarboxylic acid ethylene glycol) resin characterized by containing all carbon atoms in a poly(aromatic dicarboxylic acid ethylene glycol) resin at a time of 1950 The ¹⁴ C concentration in the recycled carbon is 100%, and the ¹⁴ C concentration ratio (hereinafter sometimes referred to as the biochemical rate) is 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 0.50 to 1.00 dL/g. Preferably, in the present invention, the poly(aromatic dicarboxylic acid ethylene glycol) resin has a ¹⁴ C concentration ratio of 16% or more when the ¹⁴ C concentration in the recycled carbon at the time of 1950 is 100%. terephthalate, or cyclic carbon C concentration of point 1950 as a ratio of the ¹⁴ C concentration of ¹⁴ to 100% of the baseline of not less than 11% of polyethylene terephthalate and polyethylene naphthalate.

Another object of the present invention is to use a dimethyl ester of an aromatic dicarboxylic acid as a main raw material of the acid component, and to use a ¹⁴ C concentration in the circulating carbon of the 1950-year point in the total carbon atoms contained in the ethylene glycol. A method of producing a poly(aromatic dicarboxylic acid ethylene glycol) resin in which any of the above-mentioned polyethylene glycols having a ¹⁴ C concentration ratio of 100% or more is 100% or more as a diol component. Further, the aromatic dicarboxylic acid dimethyl ester is preferably dimethyl terephthalate or dimethyl naphthalate. Further, dimethyl terephthalate is preferably obtained by a step of depolymerizing a reaction step comprising a polyethylene terephthalate as a raw material by an alkanediol, preferably ethylene glycol. Ethylene phthalate is depolymerized, followed by transesterification using methanol to obtain dimethyl terephthalate.

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 at 285 °C.

The present invention, the biochemical rate of 11% or more are diagrams described later as measured with respect to the concentration of C constituting the total carbon amount of radioactive carbon of ^14, the ¹⁴ C concentration as a reference of the concentration of the substance in the case 107.44pMC it as The biochemical rate is 100%, and the ratio with respect to the reference concentration (107.44 pMC) is 11% or more. Further, the term "biomass glycol" refers to ethylene glycol produced from biomass resources, and ethylene glycol having a biodegradation rate of 80% or more as measured by a method described later.

The biomass resource here uses solar energy, a renewable carbon-derived carbon neutral carbon (Carbon Neutral) organic resource, and is derived from petrochemical resources such as coal, oil, natural gas, etc. 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 (canola oil, Cottonseed oil, soybean oil, coconut oil, etc., glycerin, carbohydrate crops (corn, taro, wheat, rice, sweet potato, etc.), bagasse, terpene compounds, pulp black liquor, kitchen waste, drainage Mud and so on. 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.

Various methods are available for the conversion of biomass resources to ethylene glycol. The production method is not particularly limited, but firstly, a biological treatment method using microorganisms such as bacteria or bacteria such as biomass resources, a chemical treatment method using acid, alkali, catalyst, heat or light energy, or 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 heat decomposition reaction and purified by using a catalyst is used.

Still another method is exemplified by a method of producing ethanol from a sugar cane, a bagasse, and other carbohydrate-based crops by a biological treatment method, and then subjecting the ethanol to epoxide and purification. 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. Still another method is a method for producing ethanol from a sugar cane, a bagasse, a carbohydrate crop, or the like by a biological treatment method, followed by passing through ethylene oxide to form a mixture of ethylene glycol, diethylene glycol, and triethylene glycol. Wait.

The present invention represents a so-called bio-based configuration rate of ¹⁴ C when the total carbon atoms of ethylene glycol, the polyester in the concentration of the carbon cycle 1950 of the radiation point of ¹⁴ C carbon as the reference (the value set to 100%) Concentration ratio. The concentration of the radioactive carbon ¹⁴ C can be determined by the following measurement method (radiation carbon concentration measurement). That is, the concentration measurement of ¹⁴ C is performed by a combination of Tandem accelerator and mass spectrometer mass spectrometry (AMS: Accelerator Mass Spectrometry), and the carbon contained in the sample analyzed by the accelerator is physically separated by the weight difference of the atoms. The isotope (specifically, ¹² C, ¹³ C, ¹⁴ C) is a method for measuring the presence of one atom of an isotope.

In a mole of carbon atoms (6.02 x 10 ²³ ), there are about 6.02 x ^{10 11 14} C of about one megagram of a typical carbon atom. ¹⁴ C is called a radioactive isotope and has a half-life of 5730 years and is regularly reduced. It takes 226,000 years to make such a complete collapse. In the past, it was considered that the carbon dioxide in the atmosphere was absorbed and fixed by plants, etc., and it was considered that all of the ¹⁴ C elements contained in the first stage of the immobilization were collapsed in the petrochemical fuel such as the medium carbon, oil, and natural gas after 226,000 years or more. Therefore, in the 21st century, fossil fuels such as soot, oil, and natural gas are completely free of ¹⁴ C elements. Therefore, the chemical substances produced from these fossil fuels as raw materials are completely free of ¹⁴ C. On the other hand, the ¹⁴ C-series cosmic rays undergo nuclear nuclear reactions in the atmosphere, and are continuously generated. The rest of the radiation is reduced by radiation decay, and the amount of ¹⁴ C 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, ¹⁴ C is not newly added in the state of inhalation, and ¹⁴ C is passed along with the half-life of ¹⁴ C. The concentration is reduced by a certain ratio. Therefore, by analyzing the ¹⁴ C concentration in the diol compound, it is possible to easily determine whether a petrochemical resource such as a fossil fuel is used as a raw material or a diol compound using a biomass resource as a raw material. And, the C concentration at ¹⁴ C concentration point 1950 of the nature of the carbon cycle of the modern standard reference ^14, this ¹⁴ C as 100% concentration is generally carried out by reference. The value of the ¹⁴ C concentration is about 110 pMC (the percentage of the modern carbon), and it is assumed that the value of 110 pMC is displayed when the plastic used as the sample is made of a substance derived from 100% natural (biological). . This value corresponds to 100% of the aforementioned biochemical rate. On the other hand, when the ¹⁴ C concentration is measured using a chemical substance derived from a fossil fuel such as petroleum, it is also known that 0pMC is roughly displayed. This value corresponds to the aforementioned biochemical rate of 0%. Using these values, a compound derived from a natural resource (a biomass-derived compound) - a mixture ratio of a compound derived from a petrochemical resource can be calculated.

Furthermore, the ¹⁴ C 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 carbon in oxalic acid (the intensity of ¹⁴ C radiant energy per gram of carbon) is corrected to a certain value for each carbon isotope with respect to ¹³ C, and the value of the attenuation correction is used as the standard from 1950 to the measurement date. The ¹⁴ C concentration value.

Detailed analysis method of ¹⁴ C concentration in the diol compound First, it is necessary to pretreat the diol 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 obtained therefrom is irradiated with a cation such as Cs ⁺ to form an anion of carbon. Next, the Tandem accelerator is used to accelerate the carbon ions, and the negative ion crystal charges are converted into cations, and the orbital separation of ¹² C ³⁺ , ¹³ C ³⁺ , and ¹⁴ C ^{3+ is} performed by mass analysis of the electromagnets, and the measurement is performed by an electrostatic analyzer. Separated ¹⁴ C ³⁺ .

In the present invention, the poly(aromatic dicarboxylic acid ethylene glycol) resin produced by polymerization can be obtained by using dimethyl aromatic dicarboxylate as a main raw material and using ethylene glycol having a biochemical ratio of 80% or more as a binary material. Obtained by the method of producing an alcohol 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 easy to industrially 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, diethyl aromatic dicarboxylate, dipropyl aromatic dicarboxylic acid, and dibutyl aromatic dicarboxylic acid can be exemplified. 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 which are directly bonded to the aromatic ring of the aromatic dicarboxylic acid may be substituted with a halogen atom, an amine group, a mercapto group, a carboxyl group, an ester group, an ether group or a sulfonate. A compound of an acid metal salt group, an ammonium sulfonate group, or a phosphonium sulfonate group. 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 environmental problems of the recent years and the problem of depletion of fossil fuels, 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. That is, 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 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 terephthalic acid 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 using a polyester production method other than biomass glycol. Specifically, the transesterification reaction of a lower alkyl ester of terephthalic acid such as dimethyl terephthalate with biomass glycol is carried out by directly reacting terephthalic acid with biomass ethylene glycol. Thereby, a first-stage reaction of ethylene glycol terephthalate and/or its oligomer is produced. Then, it can be produced by heating the reaction product of the first stage in the presence of a polycondensation reaction catalyst under reduced pressure and polycondensing to a desired second polymerization stage.

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% (2) of carbon atoms derived from ethylene glycol. The use of ethylene glycol as a glycol component having a biochemical rate of 80% or more means that all carbon atoms derived from ethylene glycol are all carbon atoms constituting polyethylene terephthalate, that is, polyparaphenylene is formed. The repeating unit of ethylene diformate is 20% of carbon atoms in the entire carbon atom, but more than 80% of it is a ¹⁴ C-containing 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, a pair of polymers is obtained as an acid component using dimethyl 2,6-naphthalene dicarboxylate or 2,6-naphthalenedicarboxylic acid as a raw material. The ratio of all carbon atoms in the repeating unit of ethylene phthalate is 86% (12) from the carbon atom derived from 2,6-naphthalenedicarboxylic acid, and the carbon atom derived from ethylene glycol is 14 % (2). The use of ethylene glycol having a biochemical rate of 80% or more as a diol 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 entire carbon atom, but more than 80% of it is a ¹⁴ C-containing carbon atom derived from biomass. Therefore, theoretically, the biochemical rate of polyethylene terephthalate in this case is 11% or more.

Unexpectedly, when the poly(aromatic dicarboxylic acid ethylene glycol) resin having a biochemical rate of 11% or more was produced by 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 an aromatic dicarboxylic acid or the like is changed, the temperature at the time of moderate melting in the evaluation of 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 1.00 dL/g. When the intrinsic viscosity is less than 0.50 dL/g, the strength of the obtained polyester molded article is extremely weak, and it is difficult to use it as a molded product. On the other hand, when the intrinsic viscosity exceeds 1.00 dL/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 6.0 to 7.0. The pH is as follows, and ethylene glycol can be diluted with water of the same capacity and measured using a commercially available pH meter.

In general, the polyester polymerization reaction uses a transesterification reaction catalyst or a polycondensation reaction catalyst, and mainly uses heavy metals such as manganese, ruthenium and osmium. More specifically, manganese acetate, antimony trioxide, and antimony oxide can be exemplified. Since the heavy metal generally has a large environmental load, the catalyst for the transesterification reaction catalyst and the polycondensation reaction catalyst in the present invention is preferably used for titanium compound having less environmental load. As a catalyst. 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 for the polycondensation reaction catalyst, generally commercially available titanium tetrachloride such as titanium acetate or tetrabutyl titanate 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 is used as a polymerization catalyst.

[In the above formula, R ¹ , R ² , R ³ and R ^{4 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 R ² and R ³ represent the same or different groups, respectively.

More specifically, R ¹ , R ² , R ³ and R ^{4 are} preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

[In the above formula, R ⁵ represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 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 3.0, and most preferably in the range of 1.8 to 2.8.

Further, the reaction product of the titanium compound represented by the formula (I) and the phosphorus compound represented by the formula (II) may be, for example, one obtained by heating 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 a phosphorus compound represented by the general 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 be a solution using ethylene glycol or the like as a solvent) is added dropwise to the mixed solution, and the reaction mixture is heated at a temperature of 0 ° C to 200 ° C for 30 minutes or longer. It is preferably heated 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-propoxide-titania, tetra-titanium oxide or tetra-titanium oxide, 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 Alkane ester, monotridecyl phosphate, monotetradecyl phosphate, monopentadecanoate phosphate, monohexadecyl phosphate, monoheptadecanoate phosphate, monooctadecyl phosphate, monophenyl phosphate, Monobenzyl phosphate, mono(4-methylphenyl) phosphate, mono(4-ethylphenyl) phosphate, mono(4-propylphenyl) phosphate, mono(4-butylphenyl) phosphate, phosphoric acid Mono(4-pentylphenyl ester), mono(4-hexylphenyl phosphate), mono(4-octylphenyl phosphate), mono(4-mercaptophenyl phosphate), mono(4-dodecyl phosphate) Phenyl 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 reacting an aromatic polyvalent carboxylic acid represented by the following formula (III) and/or an anhydride thereof. 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.

[Chemical 3]

Ph-(COOH) _n (III)

[In the above formula, n 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 from 5 to 70 ppm based on the weight of the poly(aromatic dicarboxylic acid ethylene glycol) resin. The range is better. The term "polyester-soluble titanium element" as used herein means that the inorganic particles such as titanium dioxide are blended in a poly(aromatic dicarboxylic acid ethylene glycol) resin, and the polyester is not mixed in a molecular grade and is equivalent to Ti in the polyester. The element exists. More specifically, the titanium element contained in a catalyst composed of an organic titanium compound or the like corresponds to a titanium element whose polyester is soluble. That is, the titanium compound represented by the above formula (I) and the titanium element of titanium acetate correspond to a soluble titanium element. When the amount of the polyester soluble titanium element in the poly(aromatic dicarboxylic acid ethylene glycol) resin is less than 500 ppm, the polycondensation reaction becomes slow, and when it exceeds 70 ppm, the color of the obtained polyester is poor, and the heat resistance thereof is lowered. Not appropriate. The amount of titanium element is preferably in the range of 7 to 60 ppm, more preferably in the range of 10 to 50 ppm.

Further, an aromatic polyvalent carboxylic acid selected from the group consisting of a titanium compound represented by the above formula (I) and a titanium compound represented by the following formula (I) and the above formula (III) or A titanium compound component of at least one of the group consisting of product components of an acid anhydride reaction serves as a polycondensation reaction catalyst. Further, a catalyst compound consisting essentially of an unreacted mixture of the titanium compound component and the phosphorus compound represented by the following formula (IV) may be prepared as a polymerization under the following formulas (1) and (2). Condensation reaction catalyst.

[Chemical 4]

[In the above formula, R ⁶ and R ⁷ represent the same or different alkyl groups having 1 to 4 carbon atoms, and X represents -CH ₂ - or -CHPh-].

0.65≦P/Ti≦5.0 (1)

10≦P+Ti≦200 (2)

[In the above formula, Ti represents the concentration (ppm by weight) of the polyester soluble titanium metal element contained in the polyester, and P represents the phosphorus element concentration (ppm by weight) 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 yellowish and is not preferable. 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 catalyst 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 in practical use. Further, when (Ti + P) exceeds 200, there is a case where a small amount of foreign matter is caused by the catalyst.

The range of the (P/Ti) value 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 the (P+Ti) value 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 component containing the 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 an aromatic compound represented by the following general formula (III). A product of the reaction of a polyvalent carboxylic acid or its anhydride.

[Chemical 5]

[In the above formula, R ¹ , R ² , R ³ and R ⁴ 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 R ² and R ³ respectively represent the same or different basis].

[Chemical 6]

Ph-(COOH) _n (III)

[In the above formula, n represents an integer of 2 to 4].

Here, as the titanium compound represented by the general formula (I), a titanium compound or the like detailed in the above 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 is preferably phthalic acid, trimellitic acid, hemitritic acid, pyromellitic acid or the like, that is, phthalic anhydride, trimellitic anhydride or benzenetricarboxylic anhydride.

When the titanium compound is reacted with an aromatic polyvalent carboxylic acid or an anhydride thereof, a titanium compound is added dropwise to the mixed solution by partially or completely dissolving one or both of the aromatic polyvalent carboxylic acid or an anhydride thereof in a solvent. And heating 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, the solvent in which the aromatic polyvalent carboxylic acid or its anhydride is dissolved may be any of ethanol, ethylene glycol, propylene glycol, butanediol, benzene, and xylene, 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 polyester is deteriorated, and the softening point may be lowered. Conversely, 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.

[Chemistry 7]

[In the above formula, R ⁶ and R ⁷ represent the same or different alkyl groups having 1 to 4 carbon atoms, and X represents -CH ₂ - 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-phenylacetic acid, carbonylethoxy-phosphonium-phenylacetic acid, carbonylpropoxy-phosphonium-phenylacetic acid and carbonylbutoxy-phosphonium-phenylacetic acid Dimethyl esters, 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 phosphorus 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 the stabilizer is added to the catalyst compound containing the phosphorus compound represented by the general formula (IV), the thermal stability of the obtained polyester is not lowered, and the color tone is not deteriorated. From this point, the phosphorus compound represented by the formula (IV) is also preferably used.

Further, the catalyst compound containing the phosphorus compound represented by the above formula (IV) preferably satisfies the following formulas (1) and (2):

0.65≦P/Ti≦5.0 (1)

10≦P+Ti≦200 (2)

[In the above formula, Ti represents the concentration (ppm by weight) of the polyester-soluble titanium metal element contained in the polyester, and P represents the phosphorus element concentration (ppm by weight) of the phosphorus compound contained in the polyester].

Here, when (P/Ti) is less than 0.65, the hue of the obtained polyester is not preferable. Further, when (P/Ti) exceeds 5.0, the polymerization reaction rate of the polyester is drastically lowered, and it is difficult to obtain a target polyester having a sufficiently high intrinsic viscosity. The appropriate range of the (P/Ti) is characterized by being narrower than the conventional catalyst element containing a metal element, 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 greatly lowered, and the obtained molded article cannot obtain sufficient performance in practical use. In addition, when (Ti + P) exceeds 200, foreign matter due to the catalyst is less likely to occur in a small amount.

The range of the (P/Ti) value 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 the (P+Ti) value 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 polycondensation reaction using the above catalyst compound is carried out at a temperature of 230 to 320 ° C under normal pressure or reduced pressure. Preferably, at 0.05 Pa to 0.2 MPa, the polymerization is preferably carried out for 15 to 300 minutes under the combination of the conditions.

The amount of the polyester soluble titanium element contained in the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention is preferably from 5 to 70 ppm based on the weight of the poly(aromatic dicarboxylic acid ethylene glycol) resin. range. Here, the details of the "polyester soluble titanium element" are as described above. When the amount of the soluble titanium element of the polyester is less than 50 pm, the polycondensation reaction rate is slow, and when the amount of the soluble titanium element of the polyester exceeds 70 ppm, the color tone of the obtained polyester is poor, and the heat resistance of the obtained polyester is not good. . The amount of the soluble titanium element of the obtained polyester is preferably in the range of 7 to 60 pm, more preferably in the range of 10 to 50 ppm.

In addition, the poly(aromatic dicarboxylic acid ethylene glycol) resin of the present invention may be formulated with an antioxidant, a UV absorber, a flame retardant, a fluorescent whitening agent, a deodorant, a coloring agent or an antifoaming agent, or Other additives, etc.

Example

The invention is specifically illustrated by the following examples, but the invention is not limited to the examples. Further, parts and % in the examples are parts by weight and % by weight unless otherwise specified, and each measured value is measured by the following method.

In Examples 1 to 3, biomass glycol was used as the glycol component of the polyester raw material, and in Comparative Examples 1 to 3, ethylene glycol produced from petrochemical resources was used as the glycol component of the polyester raw material. As a result of measuring the bioavailability of ethylene glycol, the bioavailability of biomass glycol was 90%. On the other hand, the bioavailability of ethylene glycol produced from petrochemical resources is less than 0.06%. Here, the ethylene glycol produced from the petrochemical resources refers to ethylene glycol produced by using a component obtained from a petrochemical resource such as petroleum, natural gas or coal which is generally produced in the industry as a raw material. Further, the regenerated terephthalic acid terephthalate is obtained by depolymerizing polyester waste mainly containing polyethylene terephthalate by using ethylene glycol, and producing the terephthalic acid bis(2- Hydroxyethyl ester) The methanol was added for transesterification, and the resulting dimethyl terephthalate was distilled to obtain dimethyl terephthalate.

(1) Intrinsic viscosity

The intrinsic viscosity of the polyester was determined in an o-chlorophenol solution at 35 °C.

(2) Diethylene glycol (DEG) content

The obtained polyester was pulverized, and the obtained pulverized product was decomposed with hydrazine, and the obtained supernatant was quantitatively analyzed by gas chromatography.

(3) Heat resistance evaluation

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 left in a nitrogen atmosphere at a normal pressure of 285 ° 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 an o-chlorophenol solution at 35 ° C. The 285 ° C system is a temperature at which the melting point of the polymerized polyethylene terephthalate in each of the examples ‧ comparative examples is +30 ° C. The intrinsic viscosity before drying 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 represented by ΔIV. It was maintained at 285 ° C for 60 minutes in a nitrogen atmosphere, and it was judged to have good heat resistance when the ΔIV before and after the heat treatment was 0.100 dL/g or less. Further, when ΔIV was 0.085 dL/g or less, it was judged to have excellent heat resistance.

Then, in the case where the polyester is polyethylene naphthalate, except for the temperature of the applicable polyethylene naphthalate melting point + 30 ° C, the temperature is 295 ° C, and the polyethylene terephthalate is used. In the same manner, heat resistance evaluation was performed.

(4) Evaluation of biological rate ( ¹⁴ C concentration measurement)

^{The 14} C concentration measurement was performed by measuring the concentration of the radioactive carbon ¹⁴ C with respect to the total carbon content by combining the accelerator mass analysis method of the Tandem accelerator and the mass spectrometer as described above. Next, in the case of 107.44 pMC, the 100% biochemical rate was used as a reference, and the bioavailability was calculated as the concentration ratio for the value.

(5) pH measurement

The pH of the ethylene glycol used in the Example ‧ Comparative Example was diluted with water of the same capacity, and the pH was measured using a pH meter (D-25 type) manufactured by Horiba, Ltd. Each pH of the assay was determined by calibration with three pH calibration solutions of 4.01, 6.86, and 9.18.

[Example 1]

100 parts of regenerated dimethyl terephthalate, 60 parts of biomass glycol (pH=6.1), and 0.031 parts of manganese acetate tetrahydrate were fed into a transesterification tank under a nitrogen gas atmosphere at about 3 The temperature was raised from 140 ° C to 240 ° C in an hour, and the produced methanol was distilled off the transesterification tank to carry out a transesterification reaction. After completion of the transesterification reaction, 0.004 parts of a phosphoric acid compound as a stabilizer and 0.04 part of antimony trioxide as a polymerization reaction catalyst were added, and the temperature was immediately 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. 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 reduction range (?IV) after the heat treatment for 60 minutes was 0.079 dL/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 obtained by using dimethyl terephthalate obtained as follows. 100 parts of polyethylene terephthalate, 360 parts of ethylene glycol, and 2.7 parts of sodium carbonate were supplied to the depolymerization reaction tank, and depolymerization was carried out at 180 ° C for 4 hours while stirring. The obtained depolymerization treatment liquid was subjected to hot filtration, and the residue on the filter was washed with 90 parts of ethylene glycol heated to 170 ° C. The obtained cleaning liquid was mixed with the depolymerization treatment liquid, and the depolymerization treatment liquid mixed with the cleaning liquid was concentrated by distillation under reduced pressure of 6.65 kPa, and 270 parts of ethylene glycol was recovered. To the obtained concentrate, 2.7 parts of sodium carbonate and 180 parts of methanol were added and put into a transesterification reaction tank, and the mixture was stirred under a normal pressure to maintain the liquid temperature at 75 ° C for one hour to carry out a transesterification reaction. A mixture of the obtained dimethyl terephthalate, methanol, ethylene glycol or the like was cooled to 40 ° C, and subjected to solid-liquid separation by a centrifugal separator to obtain solid dimethyl terephthalate. The obtained dimethyl terephthalate was placed in 180 parts of methanol and washed at 40 ° C with stirring, and then subjected to solid-liquid separation by a centrifugal separator. The dimethyl terephthalate obtained by solid-liquid separation was melted at 160 ° C while distilling off residual methanol. The molten dimethyl terephthalate obtained by distilling off methanol was put into a distillation column, and distilled under reduced pressure at a pressure of 6.65 kPa to obtain 83 parts of a dimethyl terephthalate fraction.

[Comparative Example 1]

Except in Example 1, except that ethylene glycol (pH = 6.1) which was previously purified by petrochemical resources was used instead of biomass glycol, the operation was carried out as in Example 1 to obtain a polyester. The evaluation results are shown in Table 1.

[Embodiment 2]

100 parts of regenerated dimethyl terephthalate, 60 parts of biomass glycol (pH=6.1), and 0.0012 parts of titanium trimellitate were fed into a transesterification tank, and the transesterification tank was pressurized at 0.08 MPa. The temperature was raised from 140 ° C to 240 ° C in a nitrogen gas atmosphere for about 3 hours, and the produced methanol was distilled off the transesterification tank to carry out 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 285 ° C, and a polycondensation reaction was carried out under reduced pressure to obtain a polyester. Further, the regenerated terephthalic acid terephthalate was used in the same manner 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. 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 reduction range (?IV) after the heat treatment for 60 minutes was 0.075 dL/g. The bioavailability of the obtained polyester was also 17%. The evaluation results are shown in Table 1.

[Comparative Example 2]

The polyester was obtained as in Example 2 except that ethylene glycol (pH = 6.1) which was previously purified from petrochemical resources was used instead of the biomass glycol in Example 2. The evaluation results are shown in Table 1.

[Example 3]

100 dimethyl terephthalate purified from petrochemical resources, 60 parts of biomass glycol (pH=6.1), and 0.0012 parts of titanium trimellitate were fed into a transesterification tank and pressurized at 0.08 MPa. The transesterification tank was heated from 140 ° C to 240 ° C in a nitrogen gas atmosphere for about 3 hours, and the produced methanol was distilled off the transesterification tank to carry out 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 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 0.81% by weight. 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 reduction range (?IV) after the heat treatment for 60 minutes was 0.075 dL/g. The bioavailability of the obtained polyester was also 18%. The evaluation results are shown in Table 1.

[Comparative Example 3]

The polyester was obtained as in Example 3 except that ethylene glycol (pH = 6.1) which was previously purified from petrochemical resources was used instead of the biomass glycol in Example 3. The evaluation results are shown in Table 1.

[Example 4]

100 parts of dimethyl 2,6-naphthalenedicarboxylate, 50 parts of biomass glycol (pH=6.1), and 0.030 parts of manganese acetate tetrahydrate were fed into a transesterification tank under a nitrogen atmosphere. The temperature was raised from 140 ° C to 240 ° C in 3 hours, and the produced methanol was distilled off the transesterification tank to carry out a transesterification reaction. After completion of the transesterification, 0.005 parts of a phosphoric acid compound as a stabilizer and 0.024 parts of antimony trioxide as a polymerization reaction catalyst were added, and the temperature was immediately raised to 285 ° C, and a polycondensation reaction was carried out under reduced pressure to obtain a polyester. The evaluation results of the content of diethylene glycol, 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 (pH = 6.1) which was previously purified from petrochemical resources was used instead of the biomass glycol in Example 4. The evaluation 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 subjected to solid phase polymerization in a vacuum at 220 ° C for 8 hours until it became 0.75 dL / g. The evaluation results are shown in Table 1.

[Embodiment 6]

Except that the biomass glycol was used in Example 1 and the further purified ethylene glycol (pH=6.1) manufactured by petrochemical resources was used in place of the biomass glycol in a mixture of 2:1 by weight, The operation was carried out in the same manner as in Example 1 to obtain a polyester. The evaluation results are shown in Table 1.

[Embodiment 7]

225 parts of the polyester oligomer obtained by using the biomass ethylene glycol obtained by the transesterification reaction of Example 1 and the regenerated ethylene terephthalate as a raw material are retained in the reactor, and a nitrogen gas atmosphere is stirred under stirring. The slurry prepared by mixing 179 parts of high-purity terephthalic acid and 95 parts of biomass glycol was supplied at a constant speed under the condition of normal pressure at 255 °C. The water produced by the esterification reaction and the biomass glycol were distilled off to the outside of the reactor, and the esterification reaction was carried out for 4 hours to complete the esterification reaction.

225 parts of the polyester oligomer obtained in the esterification reaction was transferred to a polycondensation reaction tank, and 0.09 parts of the same antimony trioxide, 0.009 parts of phosphorus compound, and 2.45 parts of 20 as the polymerization catalyst were used as a polymerization catalyst. An aqueous solution of % tetraethylammonium hydroxide is poured into a polycondensation reaction tank. Then, the temperature in the polycondensation reaction tank is raised from 255 ° C to 285 ° C, and the reaction pressure in the polycondensation reaction tank is reduced from atmospheric pressure to 30 Pa or less, and the temperature is raised and reduced in each stage to generate a polycondensation reaction. The water, ethylene glycol, and the like are removed to the outside of the polycondensation reaction tank, and a polycondensation reaction is carried out to obtain a polyester having an intrinsic viscosity of 0.63 dL/g and a diethylene glycol content of 1.0% by weight. Further, the polyester is pelletized by a conventional method. The evaluation results are shown in Table 1.

[Comparative Example 5]

The polyester was obtained as in Example 7 except that ethylene glycol (pH = 6.1) which was previously purified from petrochemical resources was used in the same manner as in Example 7 except that the biomass glycol was used. The evaluation results are shown in Table 1.

[Possibility of industrial use]

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 at 285 °C. Further, the ratio of the ¹⁴ C concentration when the dimethyl terephthalate is used as the main acid component and the ¹⁴ C concentration in the recycled carbon at the point of 1950 in the total carbon atoms contained in the ethylene glycol is used as the basis of 100% is A method of producing a polyester by using 80% or more of ethylene glycol as a glycol component, which is a method for producing a polyester having an improved heat resistance, that is, a polyester having a low inherent viscosity when placed at 285 ° C. These findings are of great significance in the development of the industry.

Claims (7)

A poly(aromatic dicarboxylic acid ethylene glycol) resin characterized by dimethyl aryl dicarboxylate and ¹⁴ C concentration in recycled carbon from biomass resources (except petrochemical resources) at 1950 100% of the ¹⁴ C concentration ratio of 80% or more of ethylene glycol, and the poly (aromatic dicarboxylic acid ethylene glycol) resin contained in the total carbon atoms, in the 1950's point of circulating carbon ¹⁴ C concentration as a 100% reference ¹⁴ C concentration ratio of 11% or more, its intrinsic viscosity is in the range of 0.50 to 1.00 dL / g, and contains manganese acetate, barium compound, titanium acetate, titanium trimellitate, tetradecane Titanium oxide or a titanium compound represented by the following formula (I) and a phosphorus compound represented by the following formula (II), the ratio of the molar number of the phosphorus element to the molar number of the titanium element (P/Ti) is 1.0. a titanium/phosphorus reactant that reacts with a composition of the range of ~4.0, [In the above formula, R ¹ , R ² , R ³ and R ^{4 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 R ² and R ³ respectively represent the same base or a different base], [In the above formula, R ⁵ represents an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 20 carbon atoms]. The poly(aromatic dicarboxylic acid ethylene glycol) resin according to claim 1, wherein the antimony compound is antimony trioxide. The poly(aromatic dicarboxylic acid ethylene glycol) resin according to claim 1 or 2, wherein the poly(aromatic dicarboxylic acid ethylene glycol) resin is a ¹⁴ C concentration in the recycled carbon at the time of 1950. 100% of the ¹⁴ C concentration ratio of 14% or more of polyethylene terephthalate, or the ¹⁴ C concentration of recycled carbon in the 1950's point as a 100% basis for the ¹⁴ C concentration ratio of 11% The above polyethylene naphthalate. A method for producing a poly(ethylene dicarboxylate) resin according to item 1 of the patent application, characterized in that dimethyl aromatic dicarboxylate is used as a raw material of a main acid component, and ethylene glycol is used. having total carbon atoms at the C concentration in the carbon cycle of the 1950 point of ¹⁴ C as ¹⁴ to 100% of the reference concentration ratio of 80% or more of ethylene glycol as a diol component. A method for producing a poly(ethylene dicarboxylate) resin according to claim 4, wherein the dimethyl aromatic dicarboxylate is dimethyl terephthalate or dimethyl naphthalene dicarboxylate. The method for producing a poly(ethylene dicarboxylate) resin according to claim 5, wherein the dimethyl terephthalate is depolymerized by using polyethylene terephthalate as a raw material. The dimethyl terephthalate obtained in the step of the reaction step. A method for producing a poly(ethylene dicarboxylate) resin according to item 6 of the patent application, wherein dimethyl terephthalate is included The dimethyl terephthalate obtained by the step of depolymerizing the ethylene glycol using polyethylene terephthalate as a raw material.