JP2011219736A - Polyalkylene terephthalate resin composition and fiber comprising same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biomass-resource-derived polyester capable of considerably suppressing the use of fossil resources and the increase of carbon dioxide and of being developed into a wide range of applications because of its high melting point, and a fiber comprising the same.SOLUTION: The polyalkylene terephthalate resin composition is obtained by using, as raw materials, biomass-resource-derived glycol and biomass-resource-derived terephthalic acid and/or its ester-forming derivative, and comprises a phosphorus compound. The fiber comprising the polyalkylene terephthalate resin composition is also provided.

Description

  The present invention relates to a polyester obtained from a raw material derived from biomass resources and a fiber comprising the polyester. More specifically, a polyalkylene terephthalate resin composition comprising a glycol produced from a biomass resource and terephthalic acid produced from a biomass resource and / or an ester-forming derivative thereof as a raw material and containing a phosphorus compound. And a fiber made of the same.

  Petroleum, which is a fossil resource, is an important raw material for the chemical industry, but in the future there are concerns about depletion and a large amount of carbon dioxide is emitted during the manufacturing process and incineration and disposal. Is inviting problems. Under such circumstances, much attention has been paid to the use of recycled raw materials and materials with low environmental impact.

  Biomass resources are plants converted from water and carbon dioxide by photosynthesis, and include starch, carbohydrates, cellulose, and lignin. Since biomass resources use carbon dioxide as a raw material in the production process, even if materials using biomass resources are incinerated after use and decomposed into carbon dioxide and water, new carbon dioxide is generated. It is not a matter of fact, and it can be said that it is a renewable resource because it is taken up again by the plant. If these biomass resources can be used as an alternative to petroleum resources, the reduction of fossil resources will be suppressed.

  Polyester is one of the most commonly used synthetic resins in the world as various fibers, films, sheets, containers and the like because of its excellent mechanical strength, chemical stability, transparency, and low cost. Various attempts to synthesize such a large amount of polyester from renewable biomass resources have been studied. For example, it was reported on polypropylene terephthalate (PPT) containing non-petroleum-derived biomaterials by fermenting corn to obtain 1,3-PDO (1,3-propanediol) through biotechnological and chemical engineering processes. (Patent Document 1). Moreover, it reports on the polyethylene terephthalate (PET) which used ethylene glycol derived from biomass resources as a raw material (patent documents 2-4). However, the theoretical carbon atom biotinylation rate of these polymers is 36% (PPT) and 20% (PET), respectively. On the other hand, biodegradable polylactic acid (PLA) is produced from agricultural products as raw materials through processes of biotechnology and chemical engineering (Patent Document 5). PLA has a theoretical carbon atom bioavailability of 100%, but PLA has a fundamental problem that it has a low melting point and is unsuitable for use in applications that require thermal stability. Under such circumstances, it is demanded to obtain a polymer having a theoretical carbon atom biotinylation rate of 100% and a high melting point and high thermal stability.

Japanese translation of PCT publication No. 2007-502325 (Claims) Chinese Patent Publication 200710038144.6 (Claims) JP 2009-91694 A (Claims) International Publication No. 2009-72462 (Claims) JP-T-2007-530319 (Claims)

  The present invention relates to a polyalkylene terephthalate resin composition derived from a biomass resource that can greatly suppress the reduction of fossil resources and the increase of carbon dioxide, has a high bioavailability, has a high melting point, and can be developed for a wide range of uses. Is intended to provide a fiber.

  As a result of diligent studies to solve the above problems, a polyalkylene terephthalate resin composition containing a phosphorus compound using a biomass resource-derived glycol and a biomass resource-derived terephthalic acid and / or an ester-forming derivative thereof as raw materials As a result, it was found that a polyester having a high biogenic rate and a high melting point was obtained, and the above-mentioned problems were achieved.

  That is, an object of the present invention is to provide a polyalkylene terephthalate resin comprising a polyalkylene terephthalate resin and a phosphorus compound using a biomass resource-derived glycol and biomass resource-derived terephthalic acid and / or an ester-forming derivative thereof as raw materials. A solution is possible with the composition.

At that time, the proportion of carbon derived from biomass resources (measured bio-ization rate) obtained on the basis of the concentration of radioactive carbon ( ¹⁴ C) in circulating carbon in the 1950s with respect to all carbon atoms in the polymer is 60% or more. It can be suitably employed that the biomass resource-derived glycol is at least one selected from ethylene glycol, 1,3-propanediol, and 1,4-butanediol.

  Another object of the present invention can be solved by a fiber characterized by comprising the above-mentioned polyalkylene terephthalate resin composition.

  According to the present invention, it is possible to obtain a polyalkylene terephthalate resin composition having a high biogenic rate and a high melting point. Such a polyalkylene terephthalate resin composition is used in a wide range of applications, and is a conventional fossil resource with a large amount of use. It is a substitute for the polyester product, and can greatly reduce the reduction of fossil resources and the increase of carbon dioxide.

  The biomass resource-derived glycol of the present invention is not particularly limited as long as it is obtained from biomass resources. From the viewpoint of good physical properties of the obtained polyalkylene terephthalate resin composition, ethylene glycol, 1,3-propanediol. And at least one selected from 1,4-butanediol. In particular, ethylene glycol is preferred because the resulting polymer has a high melting point.

  Among the glycols used in the present invention, the proportion of biomass resource-derived glycol is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, based on the total glycol component.

  The method for obtaining these glycols from biomass resources is not particularly limited, and any method may be used. Examples thereof include the following methods.

  As a method of obtaining ethylene glycol, for example, there is a method of obtaining it from a biomass resource such as corn, sugarcane, wheat or crop stalk. These biomass resources are first converted to starch, starch is converted to glucose with water and enzymes, and then converted to sorbitol by hydrogenation reaction, which is subsequently subjected to hydrogenation reaction in the presence of a catalyst at a constant temperature and pressure. There is a method of obtaining ethylene glycol by purifying a mixture of various glycols. As another method, there is a method in which bioethanol is obtained from a carbohydrate crop such as sugar cane by a biological treatment method, then converted to ethylene, and further ethylene oxide is obtained via ethylene oxide. As yet another method, there is a method of obtaining glycerin from biomass resources and then obtaining ethylene glycol via ethylene oxide. The ethylene glycol thus obtained contains various impurities, and as impurities, 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, and 1,4-butanediol, respectively. It is preferably 1% by weight or less, more preferably 0.5% by weight or less from the viewpoint of physical properties of the obtained polyester, and more preferably 0.1% by weight or less from the viewpoint of the color tone of the obtained polyester. .

  Although it does not specifically limit as a method of obtaining 1, 3- propanediol from biomass resources, For example, it can obtain by fermentation from sugars, such as glucose, and subsequent refinement | purification.

  The method for obtaining 1,4-butanediol from biomass resources is not particularly limited. For example, succinic acid, succinic anhydride, succinic acid ester, maleic acid, maleic acid anhydride, maleic acid ester obtained by fermentation method, 1,4-butanediol can be obtained by chemical synthesis such as reduction from tetrahydrofuran, γ-butyrolactone and the like.

  On the other hand, the method for obtaining biomass resource-derived terephthalic acid is not particularly limited, and any method may be used. For example, isobutanol is obtained from corn, saccharides, or wood, and then converted to isobutylene. After isooctene was obtained by quantification, p-xylene was synthesized through a method known in the literature (Chemische Technik, vol. 38, No. 3, P116-119; 1986), that is, radical cleavage, recombination, and cyclization. A method of obtaining terephthalic acid by oxidation is mentioned. As another method, p-cymene is synthesized from cineol obtained from a plant of the genus Eucalyptus (Journal of Chemical Society of Japan, (2), P217-219; 1986), and then passed through p-methylbenzoic acid (Organic Synthesis, 27 1947), and a method for obtaining terephthalic acid. The biomass resource-derived terephthalic acid thus obtained may be further converted into an ester-forming derivative. The ester-forming derivatives mentioned here are lower alkyl esters, acid anhydrides, acyl chlorides and the like.

  These biomass resource-derived glycols, terephthalic acid and their ester-forming derivatives may contain various impurities, and colored substances are produced by the influence of impurities during the polyester production process, which deteriorates the color of the product. There is a case. For this reason, it is preferable to refine | purify so that an impurity may not be contained as much as possible. The biomass resource-derived terephthalic acid is also preferably converted to dimethyl ester or diethyl ester because distillation purification is possible and the purity can be improved.

  The proportion of the biomass resource-derived terephthalic acid and / or ester-forming derivative thereof used in the present invention is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, based on the total dicarboxylic acid component. .

  As a copolymerization component within the range in which the effect of the present invention is not substantially impaired, for example, a fragrance such as isophthalic acid, isophthalic acid-5-sulfonate, phthalic acid, naphthalene-2,6-dicarboxylic acid, bisphenol dicarboxylic acid, etc. Aliphatic dicarboxylic acid and its ester-forming derivatives, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, etc. Dicarboxylic acid components such as acids and ester-forming derivatives thereof, propanediol, butanediol, pentanediol, hexanediol, polyethylene glycol having a molecular weight of 500 to 20000, diethylene glycol, 2-methyl-1,3-propanediol, Polyoxytetramethylene glycol, Li oxy trimethylene glycol, may contain a diol component such as bisphenol A- ethylene oxide adducts. These copolymer components can be used alone or in combination of two or more.

  The most preferred embodiment of the present invention is a polyethylene terephthalate derived from a biomass resource consisting of only biomass-derived ethylene glycol as the glycol component, and only terephthalic acid derived from the biomass resource as the dicarboxylic acid component, and having a melting point of 240 ° C. or higher. is there.

  For example, in polyethylene terephthalate, the theoretical carbon atom bioreaction rate in the present invention, when ethylene glycol derived from biomass resources and terephthalic acid derived from fossil resources are used, with respect to carbon number 8 of terephthalic acid, Since ethylene glycol has 2 carbon atoms, 2 of the total carbon number of 10 is derived from biomass resources, the theoretical carbon atom biotinylation rate is 20%. Conversely, when biomass resource-derived terephthalic acid and fossil resource-derived ethylene glycol are used, the theoretical carbon atom bio-ization rate is 80%.

  The theoretical carbon atom bioreaction rate of the polyalkylene terephthalate resin composition of the present invention is preferably 60% or more, and more preferably 80% or more in order to further suppress the reduction of fossil resources and the increase of carbon dioxide. When there is no, it is more preferable that it is 95% or more.

On the other hand, regarding the “ratio of carbon derived from biomass resources (measured bio-ization rate) obtained based on the concentration of radioactive carbon ( ¹⁴ C) in circulating carbon in the 1950s relative to all carbon atoms in the polymer” This will be described below.

The concentration of radioactive carbon ¹⁴ C can be measured by the following radioactive carbon concentration measurement method. Radiocarbon concentration measurement method uses accelerator mass spectrometry (AMS) and uses carbon isotopes ( ¹² C, ¹³ C, ¹⁴ C) contained in the sample to be analyzed using atomic weight difference by accelerator Thus, it is physically separated and the abundance of each isotope atom is measured. The carbon atom is usually ¹² C, and the isotope ¹³ C is present in about 1.1%. ¹⁴ C is called a radioisotope and its half-life regularly decreases at about 5370 years. It takes 26,000 years for all of these to collapse. Cosmic rays are continuously radiated in the Earth's upper atmosphere, and even though the amount is very small, ¹⁴ C is constantly generated and balanced with radiation decay, and the concentration of ¹⁴ C is almost constant (the amount of carbon atoms in the atmosphere). It is about 1 trillionth). This ¹⁴ C immediately undergoes an exchange reaction with ¹² C of carbon dioxide, and carbon dioxide containing ¹⁴ C is generated. Since plants take in carbon dioxide in the atmosphere and grow by photosynthesis, ¹⁴ C is always contained at a constant concentration. In contrast, fossil resources such as oil, coal, and natural gas, which were originally included in ¹⁴ C, have already been destroyed over the years and are hardly included. Therefore, by measuring the concentration of ¹⁴ C, it is possible to determine how much biomass resource-derived carbon is contained and how much fossil resource-derived carbon is contained. In particular, the standard of making the ¹⁴ C concentration in the circulating carbon in the natural world in the 1950s 100% is usually used, and oxalic acid (supplied by the American Standards and Science and Technology Association NIST) is used as a standard substance. A value expressed as follows is obtained. As a unit of this ratio, pMC (percent modern carbon) is used.
pMC = ( ¹⁴ Csa / ¹⁴ C50) × 100
¹⁴ C50: ⁽¹⁴ C concentration in the circulation of carbon in the natural world of the 1950s) ¹⁴ C concentration of the standard substance
¹⁴ Csa: ¹⁴ C concentration of the measurement sample.

At present, the ¹⁴ C concentration in the atmosphere measured in this way is measured to be about 110 pMC (percent Modern Carbon), and if it is a substance derived from 100% biomass resources, the value of about 110 pMC is almost the same. It is known to show. The ratio (%) of the pMC of the target substance determined based on this value as 100% is referred to in the present invention as “the concentration of radioactive carbon ( ¹⁴ C) in circulating carbon in the 1950s relative to all carbon atoms in the polymer. “The ratio of carbon derived from biomass resources as a standard (measured bio-ization rate)”. On the other hand, it is known that the ¹⁴ C concentration (pMC) obtained by measuring a substance derived from a fossil resource is almost 0 pMC, and in this case, the actual bio-ization rate is 0%. In order to further suppress the decrease in fossil resources and the increase in carbon dioxide, the measured bioreaction rate in the present invention is preferably 60% or more, more preferably 70% or more, particularly preferably 85% or more, and 100%. Most preferred. When there is no copolymerization component, 95% or more is preferable.

  The polyalkylene terephthalate resin composition of the present invention is usually produced by any one of the following processes.

  That is, (A) a process in which terephthalic acid and alkylene glycol are used as raw materials, a low polymer is obtained by direct esterification reaction, and a high molecular weight polymer is obtained by subsequent polycondensation reaction, and (B) dimethyl terephthalate and alkylene glycol are used as raw materials. In this process, a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Here, the esterification reaction proceeds even without a catalyst, but a compound such as magnesium, manganese, calcium, cobalt, zinc, lithium, and titanium may be used as a catalyst as in the case of the transesterification catalyst. Moreover, as a catalyst used in the polycondensation, a titanium compound, an aluminum compound, a tin compound, an antimony compound, a germanium compound, or the like is used. Raw materials derived from biomass resources contain a large amount of impurities, and deposits around the base increase during spinning, which increases the number of times the base is washed and yarn breaks, reducing operability, but highly active titanium and aluminum compounds as catalysts. Is preferable because the amount of catalyst added can be reduced, and as a result, the deposit around the die can also be reduced. On the other hand, in solid phase polymerization, the catalyst is deactivated by impurities in the raw material derived from biomass resources, and the polymerization time may be extended. Therefore, it is preferable to use an antimony compound or a germanium compound that is difficult to deactivate.

  Titanium compounds include titanium complexes, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyl titanate tetramer, titanium alkoxides, titanium oxides obtained by hydrolysis of titanium alkoxides, titanium acetylacetonate Etc. Among these, a titanium complex having a polycarboxylic acid and / or a hydroxycarboxylic acid and / or a polyhydric alcohol as a chelating agent is preferable from the viewpoint of the thermal stability of the polymer, the color tone, and the small amount of deposit around the mouthpiece. Examples of the chelating agent for the titanium compound include lactic acid, citric acid, mannitol, tripentaerythritol and the like.

  Examples of the aluminum compound include aluminum carboxylate, aluminum alkoxide, aluminum chelate compound, basic aluminum compound, and the like, specifically, aluminum acetate, aluminum hydroxide, aluminum carbonate, aluminum ethoxide, aluminum isopropoxide, aluminum acetyl. Examples include acetonate and basic aluminum acetate.

  Examples of the tin compound include monobutyltin oxide, and examples of the antimony compound include antimony alkoxide and antimony trioxide.

  Biomass resource-derived glycol components and biomass resource-derived terephthalic acid components may contain a large amount of impurities, so the resulting polyalkylene terephthalate resin may generate impurities, and color and thermal stability may deteriorate. Is derived from biomass resources with low biogenic rate, such as polyalkylene terephthalate resin composed of biomass resource-derived glycol component and fossil resource-derived terephthalic acid component, and polyalkylene terephthalate resin composed of fossil resource-derived glycol component and biomass resource-derived terephthalic acid component Polyalkylene terephthalate resin was not a big problem.

  However, in the complete biomass resource-derived polyalkylene terephthalate resin consisting of biomass resource-derived glycol component and biomass resource-derived terephthalic acid component, the phenomenon appears remarkably, not only the color tone and thermal stability deteriorate, but also a large amount of foreign particles Occurs and the moldability is greatly deteriorated. It is estimated that this is because the impurities contained in the biomass resource-derived glycol component and the impurities contained in the biomass resource-derived terephthalic acid component react or form aggregates.

  As a result of earnestly studying such problems, the polyalkylene terephthalate resin composition containing a polyalkylene terephthalate resin containing a phosphorus compound suppresses the generation of foreign particles and has good color tone and thermal stability. It was found that a polyalkylene terephthalate resin composition was obtained. This effect is considered to be due to the phosphorus compound in the polyalkylene terephthalate resin composition suppressing reaction and aggregation caused by impurities. Therefore, in this invention, it is essential to make a polyalkylene terephthalate resin contain a phosphorus compound. By containing a phosphorus compound in the polyalkylene terephthalate resin composition, it can be easily processed into a fiber, a film and the like for the first time.

  Although it does not specifically limit as a phosphorus compound, It selects from 1 or more types of compounds chosen from a phosphite compound, a phosphate compound, a phosphonite compound, a phosphonate compound, a phosphinite compound, and a phosphinate compound. Examples of the phosphite compound include phosphorous acid, phosphorous acid monoalkyl ester, phosphorous acid dialkyl ester, phosphorous acid trialkyl ester, and alkali metal salts thereof. Specifically, phosphorous acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, etc., sodium phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol -Di-phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite and the like. Examples of the phosphate compound include phosphoric acid, phosphoric acid monoalkyl ester, phosphoric acid dialkyl ester, phosphoric acid trialkyl ester, and alkali metal salts thereof. Specific examples include phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and sodium phosphate. Examples of the phosphonite compound include phosphonous acid, phosphonous acid monoalkyl ester, phosphonous acid dialkyl ester, phosphonous acid trialkyl ester, and alkali metal salts thereof. Specifically, methylphosphonous acid, ethylphosphonous acid, propylphosphonous acid, isopropylphosphonous acid, butylphosphonous acid, phenylphosphonous acid, tetrakis (2,4-di-t-butylphenyl) [1 , 1-biphenyl] -4,4′-diylbisphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite Etc. Examples of the phosphonate compound include phosphonic acid, phosphonic acid monoalkyl ester, phosphonic acid dialkyl ester, phosphonic acid trialkyl ester, and alkali metal salts thereof. Specifically, sodium phosphonate, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthyl Phosphonic acid, anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2 , 5-dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid , 2, , 5-tricarboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, Methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethylphosphonic acid diethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, benzylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, benzylphosphonic acid Diphenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (3,5-di-tert-butyl-4-hydroxy) Loxybenzylphosphonate ethyl), magnesium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate) Diethylphosphonoacetic acid, methyl diethylphosphonoacetate, ethyl diethylphosphonoacetate and the like. Examples of the phosphinite compound include phosphinic acid, phosphinic acid monoalkyl ester, phosphinic acid dialkyl ester, phosphinic acid trialkyl ester, and alkali metal salts thereof. Specifically, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, Examples include diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid, and the like. Examples of the phosphinate compound include hypophosphorous acid, hypophosphorous acid monoalkyl ester, hypophosphorous acid dialkyl ester, hypophosphorous acid trialkyl ester, and alkali metal salts thereof. Specifically, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid, xylylphosphinic acid, biphenylylphosphinic acid, diphenyl Phosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, anthrylphosphinic acid, 2 -Carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-dicarboxyph Nylphosphinic acid, 2,5-dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenylphosphinic acid, 2,3,4- Tricarboxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxy Phenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxylphenyl) phosphinic acid, bis ( 2,4-dicarboxyphenyl) phosphinic acid, bis ( , 5-Dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3,4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4,4) 5-tricarboxyphenyl) phosphinic acid and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester, dimethylphosphinic acid ethyl ester, ethyl Phosphinic acid methyl ester, diethylphosphite Acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, diphenylphosphinic acid Examples include phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, and bisbenzylphosphinic acid phenyl ester. Among these, phosphoric acid, trimethyl phosphate, triethyl phosphate, ethyl ethyl diethylphosphonoacetate, and the like are preferable because they have a high effect of suppressing the generation of foreign particles, and the molding processability is improved. In addition, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite (PEP-36: manufactured by Asahi Denka Co.) represented by chemical formula (1) or chemical formula (2) Tetrakis (2,4-di-t-butyl-5-methylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite (GSY-P101: manufactured by Osaki Kogyo Co., Ltd.), Represented by chemical formula (3), bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite (PEP-24G: manufactured by Asahi Denka Co., Ltd. or IRGAFOS126: manufactured by Ciba Specialty Chemicals), Tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite (IRGAFOS) represented by the chemical formula (4) -EPQ: Ciba Japan Chemicals Inc. or SandostabP-EPQ: produced by Clariant) trivalent phosphorus compounds, such as, preferred in view of color tone and thermal stability improvement. These phosphorus compounds may be used alone or in combination of two or more.

  The amount of the phosphorus compound contained in the polyalkylene terephthalate resin composition of the present invention is not particularly limited, but in the range of 0.1 to 1000 ppm in total in terms of phosphorus atoms with respect to the polyalkylene terephthalate resin composition obtained. Preferably there is. When the addition amount is within the above range, a polyalkylene terephthalate resin composition having good moldability and excellent color tone and thermal stability can be obtained because the generation of foreign particles is suppressed. More preferably, it is the range of 1-300 ppm, Most preferably, it is the range of 5-100 ppm.

  In the present invention, the phosphorus compound is a polyalkylene terephthalate resin composition that undergoes a polycondensation reaction after esterifying or transesterifying the biomass resource-derived glycol and the biomass resource-derived terephthalic acid and / or its ester-forming derivative. It is preferable to add it when manufacturing. The addition time of the phosphorus compound is not particularly limited, but after the esterification or transesterification reaction until the start of the polycondensation reaction or until the polymerization reaches the target degree of polymerization after the start of the polycondensation reaction. It is preferable to add in between.

Moreover, it is preferable that intrinsic viscosity IV of the polyalkylene terephthalate resin obtained by this invention is 0.4-2.0 dlg- ¹ . Here, the intrinsic viscosity of the polyalkylene terephthalate resin is a value measured at 25 ° C. using orthochlorophenol as a solvent, and a polyalkylene terephthalate resin composition containing an additive such as a phosphorus compound added during polymerization is used. It is a measured value. When the polyalkylene terephthalate resin of the present invention is polyethylene terephthalate (PET) is more preferably the intrinsic viscosity IV is 0.4～1.5Dlg ^-1, it is 0.6～1.3Dlg ^-1 Is particularly preferred. When the polyalkylene terephthalate resin of the present invention is a polypropylene terephthalate (PPT) is more preferably the intrinsic viscosity IV is 0.6～2.0Dlg ^-1, it is 0.7～1.6Dlg ^-1 Is particularly preferred. When the polyalkylene terephthalate resin of the present invention is polybutylene terephthalate (PBT) is more preferably the intrinsic viscosity IV is 0.6～2.0Dlg ^-1, is 0.8～1.8Dlg ^-1 It is particularly preferred.

  In the polyalkylene terephthalate resin composition of the present invention, the filtration pressure increase index measured by the method described later is 10 MPa or less. Therefore, when molding is performed for a long period of time, the number of operations such as foreign matter filter replacement and die replacement is reduced. Therefore, it is preferable because the operability is improved. The filtration pressure increase index is more preferably 8 MPa or less, the filtration pressure increase index is more preferably 6 MPa or less, and the filtration pressure increase index is particularly preferably 4 MPa or less.

  In the polyalkylene terephthalate resin composition of the present invention, the number of foreign particles having a maximum diameter of 10 μm or more, measured by a method described later, is 10 / g or less. Therefore, yarn breakage during spinning and film formation during film formation This is preferable because it prevents tearing and the like. More preferably, the number of foreign particles having a maximum diameter of 10 μm or more is 8 particles / g or less, more preferably the number of foreign particles having a maximum diameter of 10 μm or more is 6 particles / g or less, and a foreign material having a maximum diameter of 10 μm or more. It is particularly preferable that the number of particles is 4 / g or less.

  The polyalkylene terephthalate resin composition of the present invention preferably contains a color tone adjusting agent. When a raw material derived from biomass resources is used, the polymer may be colored. In this case, it is preferable to use a color tone adjusting agent because the color tone is equivalent to that of the polymer derived from fossil resources. As the color tone adjusting agent, it is preferable to use a dye used for a resin or the like. In particular, COLOR INDEX GENERIC NAME includes SOLVENT BLUE 104, SOLVENT BLUE 45, SOLVENT BLUE 11, SOLVEN BLUE 25, SOLVEN BLUE 35, SOLVEN BLUE 35, SOLVEN BLUE 55, SOLVENT BLUE 36 83, SOLVENT BLUE 87, SOLVENT BLUE 94, SOLVENT BLUE 122 and other blue color adjusters, SOLVENT VIOLET 36, SOLVENT VIOLET 8, SOLVENT VIOLET 13, SOLVENT VIOLET 14S Purple color adjusting agents such as LVENT VIOLET 27, SOLVENT VIOLET 28, SOLVENT VIOLET 37, SOLVENT VIOLET 49, SOLVENT RED 24, SOLVENT RED 25, SOLVENT RED 25, SOLVENT RED 27, SOLVENT RED 27, SOLVENT RED 27, SOLVENT RED 27 SOLVENT RED 109, SOLVENT RED 111, SOLVENT RED 121, SOLVENT RED 135, SOLVENT RED 149, SOLVENT RED 168, SOLVENT RED 179, SOLVENT RED 195 A preparation is mentioned. Among them, blue-based color adjusting agents such as SOLVENT BLUE 104 and SOLVENT BLUE 45, and purple-based color adjusting agents such as SOLVENT VIOLET 36 do not contain halogen, which tends to cause corrosion of the apparatus, and have relatively high thermal stability at high temperatures. It is preferable because it has good color developability and has the same color tone as the polymer derived from fossil resources. These may be used alone or in combination of two or more.

  The amount of the color tone adjusting agent contained in the polyalkylene terephthalate resin composition of the present invention is not particularly limited, but is in the range of 0.1 to 100 ppm in total with respect to the obtained polyalkylene terephthalate resin composition, It is preferable because a polyalkylene terephthalate resin composition having high brightness can be obtained. More preferably, it is the range of 0.5-20 ppm, Especially preferably, it is the range of 1-5 ppm.

  In addition, the biomass resource-derived polyester of the present invention is blended with an antioxidant, an ultraviolet absorber, a flame retardant, a fluorescent whitening agent, a matting agent, a plasticizer or an antifoaming agent, or other additives as necessary. May be.

  In the present invention, in order to obtain a higher molecular weight polyalkylene terephthalate resin composition, the polyalkylene terephthalate resin composition obtained by the above method may be subjected to solid phase polymerization. The solid-state polymerization is not particularly limited in apparatus and method, but is carried out by heat treatment under an inert gas atmosphere or under reduced pressure. Any inert gas may be used as long as it is inert to the polyester, and examples thereof include nitrogen, helium, carbon dioxide, etc. Nitrogen is preferably used from the viewpoint of economy. Further, under reduced pressure, the pressure in the apparatus is preferably set to 133 Pa or less, and more reduced pressure is advantageous because the time required for the solid phase polycondensation reaction can be shortened.

  The biomass resource-derived polyalkylene terephthalate resin composition obtained in the present invention can also be recycled. Specifically, a biomass resource-derived polyalkylene terephthalate resin composition waste is used as a raw material, and a depolymerization reaction is performed with a biomass resource-derived or fossil resource-derived glycol component to obtain bis (hydroxyalkyl) terephthalate first. This may be polymerized again, but is preferably further transesterified with methanol or ethanol to give dimethyl terephthalate or diethyl terephthalate. These terephthalic acid dialkyl esters are preferred because they can be purified to high purity by distillation. Polymerization can be carried out again using the thus obtained biomass resource-derived terephthalic acid dialkyl ester.

  The polyester obtained in the present invention can be produced by batch polymerization, semi-continuous polymerization, or continuous polymerization.

  The polyester chip produced using the biomass resource-derived polyalkylene terephthalate resin composition obtained in the present invention can be processed by a normal polyester processing method. The polyalkylene terephthalate resin composition of the present invention can be used as molded articles such as fibers, films and resins, and can be produced into various final products. Among them, low environmental impact can be an important viewpoint, and therefore it is preferable to use it for automobile use fibers that require raw materials derived from biomass, for example, interior materials such as car seats, seat belts, ceiling materials, and tire rubber reinforcing fibers. . In particular, since the polyester derived from biomass resources of the present invention can suppress an increase in carbon dioxide even when incinerated, it is often incinerated as thermal recycling after use, and tires requiring high thermal stability are used. It is particularly preferable to use it for rubber reinforcing fibers such as carcass materials and cap materials. Further, the biomass resource-derived polyalkylene terephthalate resin composition of the present invention has better adhesion than petroleum-derived polyester, and is particularly preferably used for rubber reinforcing fibers of these tires. For these applications, existing theoretical polylactic acid fibers with 100% bioavailability of carbon atoms could not be used due to their low melting point and thermal stability.

  The method for obtaining the polyester fiber from the above-mentioned polyalkylene terephthalate resin composition can be applied with a normal melt spinning-stretching process. Specifically, after the polyalkylene terephthalate resin composition is heated to a melting point or higher and melted, it is discharged from the pores, cooled and solidified with cooling air, then applied with an oil agent, taken up by a take-up roller, and taken-up roller Undrawn yarn can be collected by winding with a winding device disposed later. In order to impart excellent mechanical properties such as the above-described industrial polyester fiber, it is preferable to use a high molecular weight polyalkylene terephthalate resin composition. To melt spin such a high molecular weight polymer, the molten polymer is spun. From the viewpoint of improving the spinnability, it is preferable to pass through a heating cylinder held at a high temperature during cooling and solidification with cold air. Here, from the viewpoint of alleviating rapid thinning of the polymer after melt spinning and improving spinnability, the temperature in the heating cylinder is preferably 280 ° C. to 330 ° C., and the heating cylinder length is 50 mm to 500 mm is preferable.

  The undrawn yarn wound in this way becomes a polyester fiber to which physical properties such as mechanical properties are applied by drawing with a pair of heated rollers and finally applying tension or relaxation heat treatment. . In addition, in this extending process, it can carry out continuously, without winding once after taking up in the above-mentioned melt spinning process, and it is preferable to set it as continuous extending | stretching from industrial viewpoints, such as productivity. Here, in performing this stretching-heat treatment, the stretching ratio, stretching temperature, and heat treatment conditions can be appropriately selected depending on the target fiber fineness, strength, elongation, shrinkage rate, etc. In order to obtain the polyester fiber for use, it is usually preferable to carry out the total draw ratio from 3.5 to 6.5 and from 2 to 3 steps. Here, it is general that the temperature of the first roller that performs the first stage of stretching is equal to or higher than the glass transition temperature, and the temperature of the rollers after the second stage of stretching is sequentially increased. In applications where heat treatment is applied during molding of a tire cord or the like, low shrinkage is preferable, and it is preferable to perform relaxation heat treatment in the heat treatment step.

  Hereinafter, the present invention will be described in more detail with reference to examples.

The raw materials used are as follows.
Biomass resource-derived ethylene glycol:
・ EG * 1: India glycol (purity 99.5%)
・ EG * 2: Made by Changchun Taisei Group (Purity 97.7%)
Biomass resource-derived 1,3-propanediol: Fermented glucose and then purified.
Biomass resource-derived 1,4-butanediol: Biomass resource-derived succinic acid was reduced.
-Fossil resource-derived ethylene glycol: manufactured by Nippon Shokubai Co., Ltd.
Biomass resource-derived terephthalic acid: Biomass resource-derived p-xylene was oxidized.
-Biomass resource-derived dimethyl terephthalate: Biomass resource-derived terephthalic acid was methyl esterified.
・ Fossil resource-derived terephthalic acid: manufactured by Mitsui Chemicals ・ Fossil resource-derived dimethyl terephthalate: manufactured by SK Chemical

  In addition, the physical-property value in an Example was measured by the method described below.

(1) Intrinsic viscosity IV of polyester
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.

(2) Melting point (Tm)
Using a DSC apparatus, first the temperature was raised from 40 ° C. to 280 ° C. at a rate of 16 ° C./min, then maintained for 3 minutes, the heat history was removed, and then the rate of temperature drop was 16 ° C./min. The temperature was maintained for 3 minutes after the temperature was lowered. Finally, the temperature was raised to 280 ° C. at a temperature raising rate of 16 ° C./min, and the melting temperature obtained during the second temperature raising process was defined as Tm.

(3) Color tone of polymer Using a color difference meter (SM color computer model SM-T45, manufactured by Suga Test Instruments Co., Ltd.), it was measured as a Hunter value (L, a, b value).

(4) Carboxyl terminal group amount of polymer The measurement was carried out by titrating with an automatic titrator (COM-550, manufactured by Hiranuma Sangyo Co., Ltd.) using orthocresol as a solvent and a 0.02 N aqueous NaOH solution at 25 ° C.

(5) Thermal stability index (Δ carboxyl end group 290, Δb value 290)
The polyalkylene terephthalate resin composition was dried under reduced pressure at 150 ° C. for 12 hours, heated and melted at 290 ° C. for 60 minutes in a nitrogen atmosphere, and then subjected to carboxyl end group amount and color tone by the methods (3) and (4). The difference between before and after heating and melting was measured as Δ carboxyl end group 290 and Δb value 290, respectively.

(6) Index of increase in filtration pressure After the polyalkylene terephthalate resin composition was dried under reduced pressure at 150 ° C. for 12 hours, an X4 type 20 μm Dynaloy filter (filtration area 4. 5 cm ² ), melt extrusion was performed at a temperature of 280 ° C. and a passing rate of 5 g / min, and the difference between the primary pressure and the secondary pressure of the filter was measured as a filtration pressure. In the present invention, the difference in filtration pressure between the elapse of 120 minutes and the elapse of 720 minutes from the start of melt extrusion of the polyalkylene terephthalate resin composition was measured as a filtration pressure increase index.

(7) Number of foreign particles After the polyalkylene terephthalate resin composition was dried under reduced pressure at 150 ° C. for 12 hours, it was melt extruded at 280 ° C. with a 20 mm diameter single screw extruder, discharged from a flat die at a width of 110 mm, and cooled. Cooling with a roll, an unstretched sheet having a thickness of 20 μm was formed at an average extrusion speed of 4 m / min. A CCD camera is installed between the film forming sheet cooling roll and the winder, and an image is taken into the image processing apparatus while performing a focus scan at a magnification of 40. Two points on the circumference of the particles recognized by the image processing apparatus. The maximum value of the linear distance between them is taken as the maximum diameter, and the measurement of counting particles having a maximum diameter of 10 μm or more as foreign particles is measured three times for 10 minutes, and the average value is converted to 1 g of polyalkylene terephthalate resin composition weight. did. The number of foreign particles was not evaluated at a level where titanium oxide particles were contained in the polyalkylene terephthalate resin composition.

(8) Polymer diethylene glycol content 1,6-Hexanediol / methanol mixed solution was added and cooled using monoethanolamine as a solvent, neutralized and centrifuged, and then the supernatant was gas chromatographed (manufactured by Shimadzu Corporation) GC-14A).

(9) Phosphorus content of polymer After a chip-like sample is heated and melted on an aluminum plate, a molded body having a flat surface is prepared by a compression press machine, and a fluorescent X-ray elemental analyzer (manufactured by Rigaku Corporation, System 3270) Determined by

(10) Measurement method for measuring bioavailability After pulverizing a sample with sandpaper and a pulverizer, the sample is heated with copper oxide, completely oxidized to carbon dioxide, and reduced to graphite with iron powder. Convert to a single compound. The obtained graphite was introduced into an AMS apparatus and measured. In addition, oxalic acid which is a standard substance (American Standards / Science and Technology Association NIST supply) was measured at the same time, and a ¹⁴ C concentration (pMC) was determined based on the ¹⁴ C concentration of the standard substance. On the other hand, the ¹⁴ C concentration (pMC) of 100% bio-derived polylactic acid was determined by the same method. Based on the ¹⁴ C concentration (pMC) of this polylactic acid as a reference of 100%, the measured bioavailability of the sample was determined. Rounded to the first decimal place. When it exceeded 100%, it was set as 100%.

(11) Deposit around the die and thread breakage frequency The amount of deposit around the die hole 72 hours after spinning of the fiber was observed using a long focus microscope. ◎ (Accepted / Good) when there is almost no deposit and no yarn breakage. ○ (Pass) when there is some deposit but no yarn breakage. The state that occurred was determined as x (disqualification).

(12) High elongation Using a Tensilon tensile tester manufactured by Toyo Boardwin, the SS curve was obtained at a sample length of 25 cm and a tensile speed of 30 cm / min, and the high elongation was calculated.

Example 1
Magnesium acetate equivalent to 10 ppm in terms of magnesium atom, 100 kg of biomass resource-derived dimethyl terephthalate and 58 kg of biomass resource-derived ethylene glycol (manufactured by India Glycol) were melted in a nitrogen atmosphere at 150 ° C. and stirred. Then, the temperature was raised to 230 ° C. over 3 hours, methanol was distilled off, and transesterification was performed to obtain bis (hydroxyethyl) terephthalate. This was transferred to a polycondensation tank.

  After the transfer, biomass resource-derived ethylene glycol (India) is added in another mixing tank 30 minutes before adding antimony trioxide equivalent to 250 ppm in terms of antimony atoms and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atoms to the resulting polymer. Glycol Co., Ltd.) was premixed and stirred at room temperature for 30 minutes, and then the mixture was added. Further, after 5 minutes, an ethylene glycol slurry (derived from biomass resource, manufactured by India Glycol) of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. After another 5 minutes, the reaction was started under reduced pressure. The reactor was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque is reached, the reaction system is purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged in the form of a strand, cooled, and immediately cut to obtain polyethylene terephthalate resin composition pellets. It was. The time from the start of decompression to the arrival of the predetermined stirring torque was 2 hours and 20 minutes. The obtained polyethylene terephthalate resin composition was good in both color tone and thermal stability. The polymer properties are summarized in Table 2.

Examples 2 and 3
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 1 except that 10 ppm in terms of titanium atom was used as a polymerization catalyst in place of antimony trioxide instead of the antimony trioxide. The polymerization time and polymer characteristics are summarized in Table 2.

Example 4
A citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atom, 82.5 kg of biomass resource-derived terephthalic acid and 49.1 kg of biomass resource-derived 1,3-propanediol, a temperature of 240 ° C. and a pressure of 1.2 to the obtained polymer. The esterification reaction was carried out in an esterification reaction tank maintained at × 10 ⁵ Pa until the temperature of the distillate fell below 90 ° C. 140 kg of the obtained esterification reaction product was transferred to a polycondensation tank.

  After transfer, 30 minutes before adding magnesium acetate equivalent to 10 ppm in terms of magnesium atom to the resulting polymer and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atom to the resulting polymer to the esterification reaction product The mixture was premixed in 1,3-propanediol derived from biomass resources in another mixing tank and stirred at room temperature for 30 minutes, and then the mixture was added. Further, after 5 minutes, 1,3-propanediol (derived from biomass resources) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. After another 5 minutes, the reaction system was decompressed to start the reaction. The temperature in the reactor was gradually raised from 240 ° C. to 280 ° C., and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque is reached, the reaction system is purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged in the form of strands, cooled, and then immediately cut to obtain polypropylene terephthalate resin composition pellets. It was. The time from the start of decompression to the arrival of the predetermined stirring torque was 2 hours and 9 minutes. The obtained polypropylene terephthalate resin composition was good in both color tone and thermal stability. The properties of the polypropylene terephthalate resin composition are summarized in Table 2.

Example 5
A citrate chelate titanium complex equivalent to 10 ppm in terms of titanium atoms, 82.5 kg of biomass resource-derived terephthalic acid and 89.5 kg of biomass resource-derived 1,4-butanediol, a temperature of 220 ° C. and a pressure of 1. In the esterification reaction tank held at 2 × 10 ⁵ Pa, the esterification reaction was performed until the temperature of the distillate fell below 90 ° C. 135 kg of the obtained esterification reaction product was transferred to a polycondensation tank.

  After transfer, 30 minutes before adding magnesium acetate equivalent to 10 ppm in terms of magnesium atom to the resulting polymer and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atom to the resulting polymer to the esterification reaction product The mixture was premixed in 1,4-butanediol derived from biomass resources in another mixing tank and stirred at room temperature for 30 minutes, and then the mixture was added. Further, after 5 minutes, 1,4-butanediol (derived from biomass resources) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. After another 5 minutes, the reaction system was decompressed to start the reaction. The reactor was gradually heated from 220 ° C. to 250 ° C., and the pressure was reduced to 60 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged in the form of strands, cooled, and immediately cut to obtain polymer pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 2 hours and 14 minutes. The obtained polybutylene terephthalate resin composition was good in both color tone and thermal stability. The properties of the polybutylene terephthalate resin composition are summarized in Table 2.

Example 6
About 100 kg of bis (hydroxyethyl) terephthalate with a 100% bio-measurement rate is charged in advance, and 82.5 kg of terephthalic acid derived from biomass resources in an esterification reaction tank maintained at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa. And 35.4 kg of biomass resource-derived ethylene glycol (manufactured by India Glycol Co., Ltd.) are sequentially supplied over 4 hours, and after completion of the supply, an esterification reaction is further performed over 1 hour, and the resulting esterification reaction product 101 is obtained. .5 kg was transferred to the polycondensation tank.

  After the transfer, the esterification reaction product is obtained by adding ethylene glycol of antimony trioxide equivalent to 250 ppm in terms of antimony atoms and trimethyl phosphate equivalent to 10 ppm in terms of phosphorus atoms to the resulting polymer (from biomass resources, manufactured by India Glycol) The solution was added. Further, after 5 minutes, an ethylene glycol (derived from biomass resource, manufactured by India Glycol) slurry of titanium oxide particles was added in an amount of 0.3% by weight in terms of titanium oxide particles to the obtained polymer. Thereafter, the reaction system was decompressed while stirring at 30 rpm to start the reaction. The reactor was gradually heated from 250 ° C. to 290 ° C., and the pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged in a strand form, cooled, and immediately cut to obtain polymer pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 2 hours 30 minutes. The obtained polyethylene terephthalate resin composition was good in both color tone and thermal stability. The properties of the polyethylene terephthalate resin composition are summarized in Table 2.

Example 7
As shown in Table 1, a polyethylene terephthalate resin composition was obtained in the same manner as in Example 6 except that phosphoric acid was used as shown in Table 1. Table 2 summarizes the polymerization time and the characteristics of the polyethylene terephthalate resin composition.

Examples 8-11
A magnesium acetate ethylene glycol (derived from biomass resources, manufactured by India Glycol) equivalent to 10 ppm in terms of magnesium atoms is added to the resulting polymer during polymerization, and the polymerization catalyst, the amount added, and the phosphorus compound are shown in Table 1. A polyethylene terephthalate resin composition was obtained in the same manner as in Example 6 except for changing as described above. Table 2 summarizes the polymerization time and the characteristics of the polyethylene terephthalate resin composition.

Examples 12 and 13
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the ratio between the biomass resource-derived ethylene glycol and the fossil resource-derived ethylene glycol was changed as shown in Table 1. Table 2 summarizes the polymerization time and the characteristics of the polyethylene terephthalate resin composition.

Examples 14 and 15
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the ratio of the biomass resource-derived terephthalic acid and the fossil resource-derived terephthalic acid was changed as shown in Table 1. Table 2 summarizes the polymerization time and the characteristics of the polyethylene terephthalate resin composition.

Examples 16 and 17
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the dicarboxylic acid copolymer component derived from the fossil resource was added as shown in Table 1. Table 2 summarizes the polymerization time and the characteristics of the polyethylene terephthalate resin composition.

Examples 18-22
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the phosphorus compound was changed as shown in Table 1. Table 4 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Examples 23 and 24
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the color modifier was added as an ethylene glycol (derived from biomass resources, manufactured by India Glycol) solution as shown in Table 1 during polymerization. Table 4 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 25
The pellet obtained in Example 6 was vacuum dried at 150 ° C. for 3 hours, and then solid phase polymerization was performed. The solid phase polymerization was carried out at 225 ° C. for 12 hours under a reduced pressure of 100 Pa using a tubular apparatus having a structure in which an inert gas or the like can flow from the lower part. The properties of the polyethylene terephthalate resin composition are summarized in Table 4.

Example 26
Solid phase polymerization was performed in the same manner as in Example 22 using the pellets obtained in Example 9. By carrying out at 225 degreeC for 15 hours, the same intrinsic viscosity as Example 22 was reached. The properties of the polyethylene terephthalate resin composition are summarized in Table 4.

Example 27
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 6 except that the biomass resource-derived ethylene glycol manufactured by Changchun Taisei Group was used. A slightly yellowish polyethylene terephthalate resin composition was obtained. Table 4 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 28
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the biomass resource-derived ethylene glycol manufactured by Changchun Taisei Group was used. A considerably yellowish polyethylene terephthalate resin composition was obtained. Table 4 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Examples 29-32
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 9 except that the addition amount of the phosphorus compound was changed as shown in Table 1. In Examples 29 and 30 in which the phosphorus content of the polyethylene terephthalate resin composition was low, the number of foreign particles was slightly high. Table 4 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 33 to Example 34
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 1 except that no titanium oxide particles were added, and in the same manner as in Example 2 in Example 34. Table 6 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Examples 35-36
Example 35 obtained a polypropylene terephthalate resin composition in the same manner as in Example 4 except that no titanium oxide particles were added, and Example 36 obtained a polybutylene terephthalate resin composition in the same manner as in Example 5. . Table 6 summarizes the polymerization time and the characteristics of the resin composition.

Examples 37-39
Example 37 was the same as Example 6, except that no titanium oxide particles were added, Example 38 was the same as Example 9, and Example 39 was the same as Example 11. Polyethylene terephthalate A resin composition was obtained. Table 6 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 40 to Example 45
Except for not adding titanium oxide particles, Examples 40 to 45 were respectively similar to Examples 18 to 23 to obtain polyethylene terephthalate resin compositions. Table 6 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 46
Using the pellets obtained in Example 38, solid phase polymerization was carried out in the same manner as in Example 22. By carrying out at 225 degreeC for 15 hours, the same intrinsic viscosity as Example 22 was reached. The properties of the polyethylene terephthalate resin composition are summarized in Table 6.

Examples 47-50
Except not adding titanium oxide particles, Examples 47 to 50 were obtained in the same manner as Examples 29 to 32 to obtain polyethylene terephthalate resin compositions. Table 6 summarizes the polymerization time and the properties of the polyethylene terephthalate resin composition.

Example 51
The polyethylene terephthalate resin composition obtained in Example 1 was vacuum-dried at 150 ° C. for 12 hours, melted at a spinning temperature of 285 ° C., and then discharged from a spinneret having a hole diameter of 0.18 mmφ and a number of holes of 36. An undrawn yarn was obtained by taking up with a take-up roller at 1000 m / min. At this time, although some deposits were observed around the nozzle holes during spinning, thread breakage hardly occurred and almost no increase in filtration pressure was observed. The obtained undrawn yarn was subjected to drawing-heat treatment at a drawing temperature of 90 ° C. and a heat treatment temperature of 140 ° C. with a hot roll drawing machine at a draw ratio of 3.0 times to obtain a drawn yarn. The results are summarized in Table 7.

Examples 52, 53
In the same manner as in Example 51, the polyethylene terephthalate resin compositions obtained in Examples 2 and 3 were spun and stretched, respectively. At this time, almost no deposit around the mouthpiece hole during spinning was observed, no thread breakage occurred, and almost no increase in filtration pressure was observed. The results are summarized in Table 7.

Example 54
The polypropylene terephthalate resin composition obtained in Example 4 was vacuum-dried at 150 ° C. for 12 hours, melted at a spinning temperature of 265 ° C., and then discharged from a spinneret having a hole diameter of 0.3 mmφ and 24 holes. An undrawn yarn was obtained by taking up with a take-up roller of 1500 m / min. At this time, almost no deposit around the mouthpiece hole during spinning was observed, no thread breakage occurred, and almost no increase in filtration pressure was observed. The obtained undrawn yarn was drawn with a hot roll drawing machine at a drawing temperature of 55 ° C. and a heat treatment temperature of 130 ° C. and subjected to drawing-heat treatment at a total draw ratio of 2.0 times to obtain a drawn yarn. The results are summarized in Table 7.

Example 55
The polybutylene terephthalate resin composition obtained in Example 5 was vacuum-dried at 150 ° C. for 12 hours, melted at a spinning temperature of 260 ° C., and then discharged from a spinneret having a hole diameter of 0.3 mmφ and 24 holes. An undrawn yarn was obtained by taking up with a take-up roller at a speed of 1500 m / min. At this time, almost no deposit around the mouthpiece hole during spinning was observed, no thread breakage occurred, and almost no increase in filtration pressure was observed. The obtained undrawn yarn was drawn at a drawing temperature of 65 ° C. and a heat treatment temperature of 130 ° C. with a hot roll drawing machine, and subjected to drawing-heat treatment at a total draw ratio of 2.0 times to obtain a drawn yarn. The results are summarized in Table 7.

Examples 56-74, 77-82
In the same manner as in Example 51, the polyethylene terephthalate resin compositions obtained in Examples 6 to 24 and 27 to 32 were spun and stretched, respectively. The results are summarized in Table 7. In Example 61, a slight amount of deposit was observed around the die hole during spinning, and a slight breakage of the yarn occurred.

Example 75
The solid state polymerization chip obtained in Example 25 was vacuum dried at 150 ° C. for 15 hours, then supplied to an extruder-type spinning machine and melted at a spinning temperature of 300 ° C., and then a hole diameter of 0.6 mmφ and 100 holes. It discharged from the spinneret. At this time, some deposits around the nozzle holes during spinning were observed, but yarn breakage hardly occurred and almost no increase in filtration pressure was observed. The molten polymer discharged from the spinneret passes through a 15 cm heating cylinder heated to 295 ° C., then cooled and solidified, and then taken up by a take-off roller, and subsequently heated to 90 ° C. and 140 ° C. Is stretched in two stages so that the total draw ratio becomes 5.0 times, and finally subjected to relaxation heat treatment with a roller heated to 230 ° C., and then wound up at a speed of 3000 m / min to obtain a drawn yarn. It was. As shown in Table 7, it was high in strength and had good physical properties. Moreover, the hydrolysis resistance was good.

Example 76
The solid phase polymerization chip obtained in Example 26 was spun and stretched in the same manner as in Example 75. The results are summarized in Table 7.

Examples 83-84, 87-94, 96-100
In the same manner as in Example 51, the polyethylene terephthalate resin compositions obtained in Examples 33 to 34, 37 to 44, and 46 to 50 were spun and stretched, respectively. The results are summarized in Table 8. In Example 97, a slight amount of deposit was observed around the die hole during spinning, and slight breakage of the yarn occurred.

Example 85
In the same manner as in Example 54, the polypropylene terephthalate resin composition obtained in Example 35 was spun and stretched, respectively. The results are summarized in Table 8.

Example 86
In the same manner as in Example 55, the polybutylene terephthalate resin composition obtained in Example 36 was spun and stretched, respectively. The results are summarized in Table 8.

Example 95
In the same manner as in Example 75, the polybutylene terephthalate resin composition obtained in Example 46 was spun and stretched, respectively. The results are summarized in Table 8.

Comparative Example 1
A polyethylene terephthalate resin composition was obtained in the same manner as in Example 6 except that ethylene glycol derived from fossil resources and terephthalic acid derived from fossil resources were used and the catalyst at the time of polymerization was changed as shown in Table 9. The actual bioconversion rate of the obtained polyethylene terephthalate resin composition was 0%. The properties of the polyethylene terephthalate resin composition are summarized in Table 10.

Comparative Example 2
A polypropylene terephthalate resin composition was obtained in the same manner as in Example 4 except that 1,3-propanediol derived from fossil resources and terephthalic acid derived from fossil resources were used and the catalyst at the time of polymerization was changed as shown in Table 7. . The actual bioconversion rate of the obtained polypropylene terephthalate resin composition was 0%. Table 10 summarizes the properties of the polypropylene terephthalate resin composition.

Comparative Example 3
Polybutylene terephthalate resin composition in the same manner as in Example 5 except that 1,4-butanediol derived from fossil resources and terephthalic acid derived from fossil resources were used, and the catalyst during the esterification reaction was changed as shown in Table 7. Got. The actual bioconversion rate of the obtained polybutylene terephthalate resin composition was 0%. Table 10 summarizes the properties of the polybutylene terephthalate resin composition.

Comparative Examples 4-7
The addition of the diol component and the phosphorus compound was changed as shown in Table 9. Comparative Examples 4 and 5 were the same as in Example 6 and the polyethylene terephthalate resin composition, and Comparative Example 6 was the same as in Example 4 and the polypropylene terephthalate resin. A polybutylene terephthalate resin composition was obtained in the same manner as in Example 5 in Comparative Example 7. The obtained polymer was found to have a bioconversion rate of 20 to 33%. The polymer properties are summarized in Table 10.

Comparative Examples 8-10
The addition of the dicarboxylic acid component and the phosphorus compound was changed as shown in Table 9. Comparative Example 8 was a polyethylene terephthalate composition as in Example 6, and Comparative Example 9 was a polypropylene terephthalate composition as in Example 4. In Comparative Example 10, a polybutylene terephthalate composition was obtained in the same manner as in Example 5. The obtained polymer was found to have a bioconversion ratio of 67 to 79%. The polymer properties are summarized in Table 10.

Comparative Examples 11-12
Except not adding a phosphorus compound, the comparative example 11 was carried out similarly to Example 6, and the comparative example 12 was carried out similarly to Example 27, and obtained the polyethylene terephthalate composition. The actual bioconversion rate of the obtained polyethylene terephthalate composition was 100%, but the number of foreign particles in the polyethylene terephthalate composition was very large. The polymer properties are summarized in Table 10.

Comparative Examples 13-14
Except not adding a phosphorus compound, the comparative example 13 obtained the polypropylene terephthalate resin composition like Example 4, and the comparative example 14 obtained the polybutylene terephthalate resin composition like Example 5. Although the obtained polymer was 100% biopolymerized, the number of foreign particles was very large. The properties of the resin composition are summarized in Table 10.

Comparative Examples 15-18
A polyethylene terephthalate resin composition, a polypropylene terephthalate resin composition, and a polybutylene terephthalate resin composition were obtained in the same manner as in Comparative Examples 11 to 14 except that no titanium oxide particles were added. Although the obtained resin composition had a substantial bioconversion rate of 100%, the filtration pressure increase index was high, and the number of foreign particles was very large. The properties of the resin composition are summarized in Table 10.

Comparative Examples 19, 22-23, 26, 29-30, 33-34
In the same manner as in Example 51, the polyethylene terephthalate resin compositions obtained in Comparative Examples 1, 4 to 5, 8, 11 to 12, and 15 to 16 were spun and stretched, respectively. At this time, deposits were observed around the nozzle holes during spinning, and yarn breakage and increased filtration pressure occurred. The results are summarized in Table 11.

Comparative Examples 20, 24, 27, 31, 35
In the same manner as in Example 54, the polypropylene terephthalate resin compositions obtained in Comparative Examples 2, 6, 9, 13, and 17 were spun and stretched, respectively. At this time, deposits were observed around the nozzle holes during spinning, and yarn breakage and increased filtration pressure occurred. The results are summarized in Table 11.

Comparative Examples 21, 25, 28, 32, 36
In the same manner as in Example 55, the polybutylene terephthalate resin compositions obtained in Comparative Examples 3, 7, 28, 32, and 36 were spun and stretched, respectively. At this time, deposits were observed around the nozzle holes during spinning, and yarn breakage and increased filtration pressure occurred. The results are summarized in Table 11.

Claims (9)

A polyalkylene terephthalate resin composition comprising a polyalkylene terephthalate resin and a phosphorus compound, each of which uses biomass resource-derived glycol and biomass resource-derived terephthalic acid and / or an ester-forming derivative thereof as raw materials. 2. The polyalkylene terephthalate resin composition according to claim 1, wherein the content of the phosphorus compound is in the range of 0.1 to 1000 ppm in terms of phosphorus atoms based on the polyalkylene terephthalate resin composition. 3. The polyalkylene terephthalate resin composition according to claim 1, wherein the phosphorus compound is at least one selected from phosphoric acid, trimethyl phosphate, triethyl phosphate, and ethyl diethylphosphonoacetate. The polyalkylene terephthalate resin composition according to any one of claims 1 to 3, wherein the phosphorus compound is at least one selected from phosphorus compounds represented by formulas (1) to (4).

The proportion of carbon derived from biomass resources (measured bio-ization rate) is 60% or more based on the concentration of radioactive carbon ( ¹⁴ C) in circulating carbon in the 1950s relative to all carbon atoms of polyalkylene terephthalate resin. The polyalkylene terephthalate resin composition according to claim 1, wherein the composition is a polyalkylene terephthalate resin composition. The polyalkylene terephthalate resin composition according to any one of claims 1 to 5, wherein the biomass resource-derived glycol is at least one selected from ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The polyalkylene terephthalate resin composition according to claim 1, further comprising a color tone adjusting agent. A fiber comprising the polyalkylene terephthalate resin composition according to any one of claims 1 to 7. When a polyalkylene terephthalate resin composition is produced by subjecting a biomass resource-derived glycol and a biomass resource-derived terephthalic acid and / or an ester-forming derivative thereof to esterification or transesterification, followed by a polycondensation reaction. A process for producing a polyalkylene terephthalate resin composition, comprising adding