JP4380654B2 - Polyester and method for producing the same - Google Patents

Description

  The present invention relates to a polyester produced from a raw material derived from biomass resources. Specifically, the present invention relates to a polyester derived from biomass resources containing a diol unit and a dicarboxylic acid unit as constituents and a method for producing the same.

  Conventional polyesters are produced by polycondensing petroleum-derived raw materials for any of aromatic polyesters, aliphatic polyesters, wholly aromatic polyesters, semi-aromatic polyesters, and polycarbonates. However, in recent years, environmental issues have been emphasized, and countermeasures against global environmental load problems such as fossil fuel depletion and increased carbon dioxide in the atmosphere are required. On the other hand, by using raw materials derived from plants as raw materials for polyester, these raw materials are raw materials that can be renewed every year, so the supply of raw materials is irrelevant to fossil fuel depletion, and carbon dioxide is absorbed by plant growth. Therefore, it can greatly contribute to the reduction of carbon dioxide.

  Various methods for producing dicarboxylic acids such as succinic acid and adipic acid from glucose using a fermentation method are known (see Patent Document 1, Non-Patent Documents 1 and 2). However, according to these production methods, since the dicarboxylic acid obtained by the fermentation method is obtained as an organic acid salt, ammonia or a metal cation is mixed as an impurity as an impurity. This is a process for producing the target dicarboxylic acid through steps such as neutralization, extraction and crystallization after obtaining the dicarboxylic acid as an organic acid salt by fermentation. This is because, in addition to the nitrogen element contained, many impurities such as nitrogen element derived from fermentation bacteria, ammonia and metal cations are mixed.

Diols such as 1,4-butanediol, 1,3-propanediol, and ethylene glycol are obtained directly from plant-derived raw materials by fermentation, and the corresponding dicarboxylic acid is produced by fermentation, and then this is reduced with a reduction catalyst. There is a method obtained by hydrogenation (Non-patent Document 3).
Japanese Patent Laid-Open No. 2005-27533 Journal of the American Chemical Society No. 116 (1994) 399-400 Appl. Microbiol Biotechnol No. 51 (1999) pp. 545-552 Biotechnology and Bioengineering Symp. No. 17 (1986) 355-363

  When trying to produce polyester using dicarboxylic acid or diol derived from biomass resources produced by conventional technology, the polymerization reaction is usually hindered by ammonia salts or metal cations contained as impurities in the raw material. It has been clarified by the inventor's research that there is a problem that a polyester having an appropriate molecular weight cannot be obtained or the obtained polyester is colored.

  Accordingly, an object of the present invention is to provide a practical biomass resource-derived polyester having a high molecular weight and little coloration using a raw material obtained by fermentation and a method for producing the same. Furthermore, the fact that the polyester produced from a biomass resource having a specific nitrogen atom content of the present invention is excellent in biodegradability has been investigated.

  As a result of analyzing and examining the behavior of impurities present in polyesters polymerized using dicarboxylic acids or diols produced from biomass resources, the nitrogen atom content contained as impurities in the raw materials and in the polyesters is The knowledge that it has a great influence on the coloring and biodegradability of the resin has been obtained and the present invention has been achieved.

According to a first aspect of the present invention, in the polyester whose main repeating unit is a dicarboxylic acid unit and a diol unit, at least one of the dicarboxylic acid and diol which are raw materials of the polyester is obtained from biomass resources, Biomass characterized in that the nitrogen atom content in the polyester excluding the nitrogen atom contained in the functional group covalently bonded in the molecule is 0.01 ppm or more and 1000 ppm or less by mass ratio with respect to the polyester It is a resource-derived polyester.
Second, the biomass resource-derived polyester described in the first item, wherein the biomass resource is a plant resource.
Third, the biomass resource-derived polyester according to the first or second aspect, wherein the nitrogen atom content in the polyester is 0.01 ppm to 100 ppm by mass ratio with respect to the polyester. .
Fourthly, the nitrogen atom content in the polyester is 0.01 ppm to 50 ppm in terms of mass ratio with respect to the polyester, derived from the biomass resource according to any one of the above first to third features Polyester.

Fifth, the biomass resource-derived polyester according to any one of the first to fourth aspects, wherein the reduced viscosity (ηsp / c) of the polyester is 0.5 or more.
Sixth, the biomass resource-derived polyester according to any one of the first to fifth aspects, wherein the reduced viscosity (ηsp / c) of the polyester is 1.0 or more.
Seventh, the biomass resource-derived polyester according to any one of the first to sixth aspects , wherein the polyester has a YI value of −10 or more and 30 or less.
Eighth, the biomass resource-derived polyester according to any one of the first to seventh aspects , wherein the dicarboxylic acid is succinic acid derived from biomass resources .

Ninth, the polyester is a trifunctional or higher polyfunctional compound unit selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher oxycarboxylic acid. It is what is called biomass resource origin polyester in any one of the said 1st-8th characterized by containing.
Tenth, the content of the trifunctional or higher polyfunctional compound unit is 0.0001 mol% or more and 0.5 mol% or less with respect to 100 mol% of all the monomer units constituting the polyester. The biomass resource-derived polyester according to the ninth aspect, which is characterized.
11thly, in the method for producing polyester by reaction of dicarboxylic acid and diol, at least one of dicarboxylic acid raw material and diol raw material to be used for the reaction is derived from biomass resources, and is derived from the biomass resources. nitrogen content of the dicarboxylic acid material and the diol in the raw material, the manufacturing method of a biomass-resource-derived polyester according to the first, characterized in that at 0.01ppm than 2000ppm or less in mass ratio with respect to the total sum of the raw material Is.
Twelfth, the method for producing a biomass resource-derived polyester according to the eleventh aspect, wherein the nitrogen atom content is 0.01 ppm or more and 1000 ppm or less by mass ratio with respect to the total of the raw materials. .
Thirteenth, the method for producing a biomass resource-derived polyester according to the eleventh or twelfth aspect, wherein the nitrogen atom content is 0.01 ppm or more and 100 ppm or less by mass ratio with respect to the total of the raw materials. Is.
Fourteenth, in the presence of at least one trifunctional or higher polyfunctional compound selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher oxycarboxylic acid. It is made to react, It is a manufacturing method of the biomass resource origin polyester in any one of the said 11th-13th characterized by the above-mentioned .
Fifteenth is a biomass resource-derived polyester obtained by the production method according to any one of the above 11th to 14th .
Sixteenth, a general-purpose thermoplastic resin, biodegradable resin, natural resin with respect to 99.9 to 0.1% by weight of the biomass resource-derived polyester according to any one of the first to tenth and fifteenth aspects, Or it is a biomass resource origin polyester resin composition characterized by mix | blending 0.1-99.9 weight% of polysaccharides.
Seventeenth is a molded body obtained by molding the biomass resource-derived polyester according to any one of the first to tenth and fifteenth aspects .
Eighteenth is a molded article formed by molding the biomass resource-derived polyester resin composition described in the sixteenth aspect .

  In the present invention, at least one of a dicarboxylic acid and a diol constituting a main repeating unit of a polyester is obtained from a biomass resource, and nitrogen contained in a functional group covalently bonded in the molecule of the polyester is removed. Provided is a polyester characterized in that the nitrogen atom content in the polyester is 0.01 ppm or more and 1000 ppm or less in terms of nitrogen atoms with respect to the total mass of the polyester.

The present invention contributes to solving environmental problems, fossil resource problems, and the like, and can provide a resin having practical physical properties, and its industrial utility value is extremely large. In addition, the polyester of the present invention produced from biomass resources is surprisingly better biodegradable than the polyester produced from petroleum-derived raw materials having the same structure. Thus, it is possible to provide a high molecular weight polyester that is excellent in biodegradability, has little coloration, and has excellent mechanical properties and can be used in various applications.
In addition, since a so-called diol or dicarboxylic acid obtained by a method such as fermentation from a natural material vegetated under the present global environment in the atmosphere is used as a polyester monomer, the raw material can be obtained at a very low cost. Since plant raw material production can be dispersed and diversified in various places, the supply of raw materials is very stable, and the difference in the mass balance of absorption and release of carbon dioxide is made because it is done in the global environment of the atmosphere. It is relatively balanced. Moreover, it can be recognized as an environmentally friendly and safe polyester. Such a polyester of the present invention not only can be evaluated in the physical properties, structure and function of the material, but also potentially has the feasibility of a recycling society including recycling that cannot be expected at all from polyester derived from fossil fuels. Have advantages. This provides a polyester manufacturing process from a new perspective that is different from conventional fossil fuel-dependent orientation, so the use of plastic materials from a completely new perspective, a new second stage plastic. And contribute significantly to development. The polyester of the present invention is less likely to generate harmful substances and offensive odors even if it is discarded from soil and incinerated.

The polyester which is the subject of the present invention contains a dicarboxylic acid unit and a diol unit as main essential components. Moreover, in the present invention, at least one of the dicarboxylic acid and diol constituting the dicarboxylic acid unit and diol unit is derived from biomass resources.
The polyester of the present invention is a polyester obtained by polycondensation of dicarboxylic acid and / or diol produced from biomass resources, in a polyester excluding nitrogen contained in the functional group covalently bonded in the polyester molecule. By making the nitrogen atom content of 0.01 ppm or more and 1000 ppm or less, predetermined functions and properties of the polyester can be enhanced. In the present invention, ppm means ppm by mass.

-Dicarboxylic acid As dicarboxylic acid which comprises a dicarboxylic acid unit, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, or a mixture thereof is mentioned. Among these, those containing an aliphatic dicarboxylic acid as a main component are preferable. The main component referred to in the present invention is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, particularly preferably 90% mol or more, based on all dicarboxylic acid units.

  Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters. Among these, terephthalic acid is preferable as the aromatic dicarboxylic acid, and dimethyl terephthalate is preferable as the derivative of the aromatic dicarboxylic acid. Even when the aromatic dicarboxylic acid disclosed in the present specification is used, a desired aromatic polyester can be produced by using any aromatic dicarboxylic acid such as polyester of dimethyl terephthalate and 1,4-butanediol. it can.

  As the aliphatic dicarboxylic acid component, an aliphatic dicarboxylic acid or a derivative thereof is used. Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. Examples include chain or alicyclic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester, and butyl ester of the aliphatic dicarboxylic acid, and cyclic acid anhydrides of the aliphatic dicarboxylic acid such as succinic anhydride. Can be used. Among these, the aliphatic dicarboxylic acid is preferably adipic acid, succinic acid, dimer acid or a mixture thereof from the viewpoint of the physical properties of the resulting polymer. The aliphatic dicarboxylic acid derivatives are adipic acid and succinic acid. The methyl esters of these, or mixtures thereof, are preferred. Among these, those containing succinic acid as a main component are particularly preferable.

These dicarboxylic acids can be used alone or in combination of two or more.
In the present invention, these dicarboxylic acids are preferably derived from biomass resources.
Biomass resources as used in the present invention are those in which solar light energy is converted into a form such as starch or cellulose by the photosynthetic action of plants, animals that grow by eating plants, plants or animals Includes products made by processing the body. Among these, more preferable biomass resources include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugarcane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, potato, buckwheat, soybean, fat and oil. Waste paper, papermaking residue, marine product residue, livestock excrement, sewage sludge, food waste and the like. Among these, plant resources such as wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil residue, buckwheat, soy, fat, waste paper, paper residue Wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, papermaking residue, most preferably corn, sugar cane, cassava, sago palm. These biomass resources generally contain many alkali metals and alkaline earth metals such as nitrogen atoms, Na, K, Mg, and Ca.

  These biomass resources are not particularly limited, but are induced to carbon sources through known pretreatment and saccharification processes such as chemical treatment with acids and alkalis, biological treatment with microorganisms, physical treatment, and the like. Is done. The process usually includes, for example, a micronization process by pretreatment such as chipping, scraping, or crushing biomass resources, although it is not particularly limited. If necessary, a grinding process is further included with a grinder or a mill. The biomass resources refined in this way are further guided to a carbon source through pretreatment and saccharification processes, and specific methods include acid treatment and alkali treatment with strong acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid. , Chemical methods such as ammonia freezing steam explosion method, solvent extraction, supercritical fluid treatment, oxidant treatment, etc., physical methods such as fine grinding, steam explosion method, microwave treatment, electron beam irradiation, microorganisms and enzyme treatment Biological treatment such as hydrolysis may be mentioned.

  Carbon sources derived from the above biomass resources usually include hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose, pentoses such as arabinose, xylose, ribose, xylulose, ribulose, pentose, saccharose, starch, cellulose Disaccharides and polysaccharides such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monoctinic acid, arachidic acid, eicosene Fermentation of fats and oils such as acids, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid, ceracolonic acid, polyalcohols such as glycerin, mannitol, xylitol, ribitol Carbohydrate are used, these glucose, fructose, xylose are preferred, and glucose is particularly preferred. As a carbon source derived from a broader plant resource, cellulose which is a main component of paper is preferable.

Using these carbon sources, dicarboxylic acids can be produced by microbial conversion fermentation methods, chemical conversion methods including hydrolysis, dehydration reaction, hydration reaction, oxidation reaction, etc., and combinations of these fermentation methods and chemical conversion methods. Synthesized. Among these, the fermentation method by microbial conversion is preferable.
The microorganism used for microbial conversion is not particularly limited as long as it has the ability to produce dicarboxylic acid. For example, anaerobic bacteria such as Anaerobiospirillum (US Pat. No. 5,143,833), Actinobacillus (US Pat. No. 5,504,004) ), Facultative anaerobic bacteria (E. coli (J. Bacteriol., 57: 147-158)) such as the genus Escherichia (US Pat. No. 5,770,435) or mutants of E. coli strains (Special Table 2000) Aerobic bacteria such as Corynebacterium genus (Japanese Patent Laid-Open No. 11-113588), Bacillus genus, Rizobium genus, Brevibacterium genus, Arthro, etc. Anaerobic rumen bacteria such as aerobic bacteria belonging to the genus Bacter (Japanese Patent Laid-Open No. 2003-235593), Bacteroides ruminicola, Bacteroides amylophilus, and the like can be used.

More specifically, the parent strain of bacteria that can be used in the present invention is preferably a coryneform bacterium, a Bacillus bacterium, or a Rhizobium bacterium, and more preferably a coryneform bacterium. These bacteria have the ability to produce succinic acid by microbial conversion.
Examples of coryneform bacteria include microorganisms belonging to the genus Corynebacterium, microorganisms belonging to the genus Brevibacterium, or microorganisms belonging to the genus Arthrobacter, and among these, those belonging to the genus Corynebacterium or Brevibacterium And more preferably, Corynebacterium glutamicum, Brevibacterium flavum, Brevibacterium amniagenes or Brementac fermentum bacterium. And microorganisms belonging to

  Particularly preferred specific examples of the above-mentioned bacterial parent strains include Brevibacterium flavum MJ-233 (FERM BP-1497), MJ-233 AB-41 (FERM BP-1498), Brevibacterium ammoniagenes ATCC6872, Coryne And bacteria glutamicum ATCC 31831 and Brevibacterium lactofermentum ATCC 13869. Brevibacterium flavum is currently sometimes classified as Corynebacterium glutamicum (Lielbl, W., Ehrmann, M., Ludwig, W. and Schleiffer, K. H., International Journal). of Systemic Bacteriology, 1991, vol. 41, p255-260), Brevibacterium flavum MJ-233 strain, and mutant MJ-233 AB-41 strain thereof are each represented by Corynebacterium glutamicum MJ. -233 strain and MJ-233 AB-41 strain.

  Brevibacterium flavum MJ-233 was released on April 28, 1975 at the Institute of Biotechnology, National Institute of Technology, Ministry of International Trade and Industry (currently the National Institute of Advanced Industrial Science and Technology, Patent Deposit Center). Deposited under the deposit number FERM P-3068 in Tsukuba City, 1-1-1 Higashi 1-chome, Ibaraki, Japan, and transferred to an international deposit under the Budapest Treaty on May 1, 1981, with the deposit number FERM BP-1497 Has been granted.

Reaction conditions such as reaction temperature and pressure in microbial conversion will depend on the activity of microorganisms such as selected cells and molds, but suitable conditions for obtaining dicarboxylic acids should be selected in each case. That's fine.
In microbial conversion, neutralizing agents are usually used because the metabolic activity of microorganisms decreases or the activity of microorganisms stops when pH decreases, and the production yield deteriorates or the microorganisms die. To do. Usually, the pH in the reaction system is measured by a pH sensor, and the pH is adjusted by adding a neutralizing agent so as to be in a predetermined pH range. There is no restriction | limiting in particular about the addition method of a neutralizing agent, Continuous addition or intermittent addition may be sufficient.

Examples of the neutralizing agent include ammonia, ammonium carbonate, urea, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, and alkaline earth metal carbonate. Ammonia, ammonium carbonate and urea are preferred. Examples of the alkali (earth) metal hydroxide include NaOH, KOH, Ca (OH) ₂ , Mg (OH) ₂ , or a mixture thereof. Examples of the alkali (earth) metal carbonate include _{is, Na 2 CO 3, K 2} CO 3, CaCO 3, MgCO 3, NaKCO 3 etc., or the like and mixtures thereof.

The pH value is adjusted to a range in which the activity is most effectively exhibited depending on the type of microorganisms such as fungus bodies and molds to be used. In general, the pH value is about 4 to 10, preferably about 6 to 9. It is a range.
As a method for purifying a dicarboxylic acid obtained by a production method including a fermentation method, a method using electrodialysis, a method using an ion exchange resin, a salt exchange method and the like are known. For example, it can be produced by using a combination of electrodialysis and water splitting steps to separate the dicarboxylate salt to produce pure acid, and further purification can be achieved by passing the product stream through a series of ion exchange columns. Alternatively, hydrolytic electrodialysis for conversion to a supersaturated solution of dicarboxylic acid may be used (US Pat. No. 5,034,105). Further, as a salt exchange method, for example, dicarboxylic acid and ammonium sulfate may be mixed and reacted with ammonium hydrogen sulfate and / or sulfuric acid at a sufficiently low pH to produce dicarboxylic acid and ammonium sulfate (Japanese Patent Publication No. 2001-514900). Publication). As a specific method using an ion exchange resin, after removing solids such as bacterial cells from a dicarboxylic acid solution by centrifugation, filtration, etc., desalting with an ion exchange resin and crystallization or column chromatography from the solution. And a method of separating and purifying dicarboxylic acid. As another purification method, as described in JP-A-3-30685, fermented with calcium hydroxide as a neutralizing agent, precipitated and removed calcium sulfate with sulfuric acid, then strongly acidic ion exchange resin, weak base After electrodialyzing a succinate produced by a method of treatment using a basic ion exchange resin or a fermentation method as described in JP-A-2-283289, a strongly acidic ion exchange resin, a weakly basic ion exchange resin The method of processing using is illustrated. Furthermore, the methods described in US Pat. No. 6,284,904 and Japanese Patent Application Laid-Open No. 2004-196768 are also preferably used. That is, in the present invention, any purification method may be used, such as the method using electrodialysis, the method using ion exchange resin, the method of treating with an acid such as sulfuric acid, water, alcohol, carvone. By repeating the crystallization using an acid or a mixture thereof and any unit operations described in the above-mentioned known literatures such as washing, filtration, and drying and the reference examples of the present invention in any combination, and repeatedly as necessary. A purified monomer raw material suitable for the present invention can be produced. Among these, the ion exchange method or the salt exchange method is particularly preferable in terms of cost and efficiency, and the salt exchange method is particularly preferable in terms of industrial productivity.

It is usually necessary to reduce the amount of impurity nitrogen compounds and metal cations contained in the dicarboxylic acid by purification in order to obtain a practical polymer.
The dicarboxylic acid derived from the biomass resource by the above-mentioned method contains elemental nitrogen as an impurity due to the purification process including the biomass resource origin, fermentation treatment and neutralization step with acid. Specifically, nitrogen elements such as amino acids, proteins, ammonium salts, urea, and fermenting bacteria are included.

  The nitrogen atom content contained in the dicarboxylic acid derived from the biomass resource by the above-mentioned method is usually 2000 ppm or less, preferably 1000 ppm or less with respect to the carboxylic acid, in terms of nitrogen atom, in the carboxylic acid. More preferably, it is 100 ppm or less, and most preferably 50 ppm or less. The lower limit is usually 0.01 ppm or more, preferably 0.05 ppm or more, more preferably 0.1 ppm or more, still more preferably 1 ppm or more, particularly preferably 10 ppm or more for reasons of economic efficiency of the purification step. If the amount is too large, the polymerization reaction may be delayed, the resulting polymer may be colored, partially gelled, and the stability may be lowered. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.

The nitrogen atom content is measured by a known method such as elemental analysis or an amino acid analyzer and a method of separating amino acids and ammonia in a sample under biological amino acid separation conditions and detecting them by ninhydrin color development. Value.
Use of a dicarboxylic acid having a nitrogen atom content in the above range is advantageous in reducing the coloring of the resulting polyester. It also has the effect of suppressing the delay of the polyester polymerization reaction.

As a specific method for efficiently reducing the amount of impurity ammonia contained in the dicarboxylic acid, there is a reaction crystallization method using a weakly acidic organic acid having a pH higher than that of the target dicarboxylic acid.
In the present invention, when using the dicarboxylic acid derived from biomass resources obtained by the above-mentioned method as a polyester raw material, the oxygen concentration in the tank for storing the dicarboxylic acid connected to the polymerization system is controlled to a certain value or less. Also good. Thereby, coloring by the oxidation reaction of the nitrogen source which is an impurity of polyester can be prevented.

  A tank is usually used to control the oxygen concentration and store the raw material. However, the apparatus is not particularly limited as long as the apparatus can control the oxygen concentration other than the tank. The type of the storage tank is not specifically limited, and a known metal or those whose inner surfaces are lined with glass, resin, or the like, or a glass or resin container is used. From the viewpoint of strength, etc., those made of metal or those lining them are preferably used. As the material for the metal tank, known materials are used. Specifically, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic stainless steel such as SUS310, SUS304, and SUS316, clad Steel, cast iron, copper, copper alloy, aluminum, inconel, hastelloy, titanium and the like can be mentioned.

  The lower limit of the oxygen concentration in the dicarboxylic acid storage tank is not particularly limited with respect to the total volume of the storage tank, but is usually 0.00001% or more, preferably 0.01% or more. On the other hand, the upper limit is 16% or less, preferably 14% or less, and more preferably 12% or less. When the oxygen concentration is too low, the equipment and the management process become complicated, which is economically disadvantageous. On the other hand, when the oxygen concentration is too high, coloring of the produced polymer tends to increase.

  The lower limit of the temperature in the dicarboxylic acid storage tank is usually −50 ° C. or higher, preferably 0 ° C. or higher. On the other hand, the upper limit is usually 200 ° C. or lower, preferably 100 ° C. or lower, and more preferably 50 ° C. or lower. However, the method of storing at room temperature is most preferable because there is no need for temperature control. When the temperature is too low, the storage cost tends to increase. When the temperature is too high, the dehydration reaction of carboxylic acid tends to occur simultaneously.

The lower limit of the humidity in the dicarboxylic acid storage tank is not particularly limited, but is usually 0.0001% or more, preferably 0.001% or more, and more preferably 0.01%. Thus, most preferably, it is 0.1% or more, and the upper limit is 80% or less, preferably 60% or less, more preferably 40% or less. When the humidity is too low, the management process tends to be complicated and economically disadvantageous. When it is too high, the dicarboxylic acid adheres to the storage tank and piping, the dicarboxylic acid is blocked, and the storage tank. When the metal is made of metal, tank corrosion tends to be a problem.
The pressure in the dicarboxylic acid storage tank is usually atmospheric pressure (normal pressure).

  In general, the dicarboxylic acid used in the present invention is preferably less colored. The upper limit of the yellowness (YI value) of the dicarboxylic acid used in the present invention is usually 50 or less, preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, and particularly preferably 4 or less. On the other hand, the lower limit thereof is not particularly limited, but is usually −20 or more, preferably −10 or more, more preferably −5 or more, particularly preferably −3 or more, and most preferably −1 or more. The use of dicarboxylic acids exhibiting a high YI value has a significant drawback in the coloration of the polymer produced. On the other hand, a dicarboxylic acid exhibiting a low YI value is a more preferable form, but it is economically disadvantageous in that it requires a very large capital investment for its production and requires a large production time. In the present invention, the YI value is a value measured by a method based on JIS K7105.

-Diol In the present invention, the diol unit is derived from an aromatic diol and / or an aliphatic diol, and a known compound can be used, but an aliphatic diol is preferably used.
The aliphatic diol is not particularly limited as long as it is an aliphatic and alicyclic compound having two OH groups, but the lower limit of the carbon number is 2 or more, and the upper limit is usually 10 or less, preferably 6 The following aliphatic diols are mentioned. Among these, an even number of diols or a mixture thereof is preferable because a polymer having a higher melting point can be obtained.

Specific examples of the aliphatic diol include, for example, ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol and 1,4-cyclohexanedi Methanol etc. are mentioned. These may be used alone or as a mixture of two or more.
Among these, ethylene glycol, 1,4-butanediol, 1,3-propylene glycol and 1,4-cyclohexanedimethanol are preferable, and among them, ethylene glycol and 1,4-butanediol are preferable. 4-butanediol is particularly preferred. In the present invention, the content when 1,4-butanediol is used as a main component is not particularly limited, but is usually 50 mol% or more, preferably 60 mol% or more, based on all diol units. More preferably, it is 70 mol% or more, Most preferably, it is 90 mol% or more.

  The aromatic diol is not particularly limited as long as it is an aromatic compound having two OH groups, and examples thereof include aromatic diols having a lower limit of 6 or more carbon atoms and an upper limit of usually 15 or less. . Specific examples of the aromatic diol include, for example, hydroquinone, 1,5-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, bis (p-hydroxyphenyl) methane and bis (p-hydroxyphenyl) -2,2-propane. Etc. In the present invention, the content of the aromatic diol in the total amount of diol is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.

Further, both terminal hydroxy polyethers may be used by mixing with the above aliphatic diol. As both-terminal hydroxy polyether, the lower limit is usually 4 or more, preferably 10 or more, and the upper limit is usually 1000 or less, preferably 200 or less, more preferably 100 or less.
Specific examples of both terminal hydroxy polyethers include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, poly 1,3-propanediol, and poly 1,6-hexamethylene glycol. . In addition, a copolymerized polyether of polyethylene glycol and polypropylene glycol can be used. The use amount of these both terminal hydroxy polyethers is an amount calculated as a content in the polyester of usually 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less.

In the present invention, these diols may be derived from biomass resources. Specifically, the diol compound may be produced directly from a carbon source such as glucose by a fermentation method, or the dicarboxylic acid, dicarboxylic acid anhydride, or cyclic ether obtained by the fermentation method is converted into a diol compound by a chemical reaction. May be.
For example, 1,4-butanediol is produced by chemical synthesis from succinic acid, succinic anhydride, succinic acid ester, maleic acid, maleic anhydride, maleic acid ester, tetrahydrofuran, γ-butyrolactone, etc. obtained by fermentation. Alternatively, 1,4-butanediol may be produced from 1,3-butadiene obtained by a fermentation method. Among these, a method of hydrogenating succinic acid with a reduction catalyst to obtain 1,4-butanediol is efficient and preferable.

Examples of catalysts for hydrogenating succinic acid include Pd, Ru, Re, Rh, Ni, Cu, Co and compounds thereof, and more specifically, Pd / Ag / Re, Ru / Ni / Co / ZnO. Cu / Zn oxide, Cu / Zn / Cr oxide, Ru / Re, Re / C, Ru / Sn, Ru / Pt / Sn, Pt / Re / alkali, Pt / Re, Pd / Co / Re, Cu / Si, Cu / Cr / Mn, ReO / CuO / ZnO, CuO / CrO, Pd / Re, Ni / Co, Pd / CuO / CrO ₃ , phosphoric acid Ru, Ni / Co, Co / Ru / Mn, Cu / Pd / KOH and Cu / Cr / Zn are mentioned. Among these, Ru / Sn or Ru / Pt / Sn is preferable in terms of catalytic activity.

Furthermore, a method of producing a diol compound from biomass resources by a combination of known organic chemical catalytic reactions is also actively used. For example, when pentose is used as a biomass resource, a diol such as butanediol can be easily produced by a combination of a known dehydration reaction and catalytic reaction.
The diol derived from the biomass resource may contain nitrogen atoms as impurities due to the purification process including the biomass resource origin, fermentation process, and neutralization step with acid. In this case, specifically, amino acids, proteins, ammonia, urea, and nitrogen atoms derived from fermentation bacteria are included.

The upper limit of the nitrogen atom content contained in the diol produced by the fermentation method is usually 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less in terms of atoms in the diol. The lower limit is not particularly limited, but is usually 0.01 ppm or more, preferably 0.05 ppm or more, and more preferably 0.1 ppm or more for reasons of economic efficiency of the purification process. If the amount is too large, the polymerization reaction tends to be delayed, the resulting polymer may be colored, partially gelled, and the stability may be lowered. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.
Further, as another aspect, the nitrogen atom content contained in the dicarboxylic acid raw material and the diol is a mass ratio with respect to the above-mentioned total raw material, and the upper limit is usually 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm. Hereinafter, it is most preferably 50 ppm or less. The lower limit is not particularly limited, but is usually 0.01 ppm or more, preferably 0.05 ppm or more and 0.1 ppm or more.

  In the present invention, when using the biomass resource-derived diol obtained by the above-mentioned method as a polyester raw material, in order to suppress the coloration of the polyester due to the impurities, in the tank for storing the diol linked to the polymerization system The oxygen concentration and temperature may be controlled. By this control, the coloring of the impurity itself and the oxidation reaction of the diol promoted by the impurity are suppressed. For example, diol oxidation such as 2- (4-hydroxybutyloxy) tetrahydrofuran when 1,4-butanediol is used. Coloring of the polyester by the product can be prevented.

  A tank is usually used to control the oxygen concentration and store the raw material. However, the apparatus is not particularly limited as long as the apparatus can control the oxygen concentration other than the tank. The type of the storage tank is not specifically limited, and a known metal or those whose inner surfaces are lined with glass, resin, or the like, or a glass or resin container is used. From the viewpoint of strength, etc., those made of metal or those lining them are preferably used. As the material for the metal tank, known materials are used. Specifically, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic stainless steel such as SUS310, SUS304, and SUS316, clad Steel, cast iron, copper, copper alloy, aluminum, inconel, hastelloy, titanium and the like can be mentioned.

  The lower limit of the diol concentration in the storage tank is not particularly limited with respect to the total volume of the storage tank, but is usually 0.00001% or more, preferably 0.0001% or more, more preferably 0.001%. Thus, most preferably, it is 0.01% or more, and the upper limit is usually 10% or less, preferably 5% or less, more preferably 1% or less, and most preferably 0.1% or less. If the oxygen concentration is too low, the management process becomes complicated and tends to be economically disadvantageous. If it is too high, the coloring of the polymer by the oxidation reaction product of the diol tends to increase.

  The lower limit of the storage temperature of the diol in the storage tank is usually 15 ° C. or higher, preferably 30 ° C. or higher, more preferably 50 ° C. or higher, most preferably 100 ° C. or higher, and the upper limit is 230 ° C. or lower. Is 200 ° C. or lower, more preferably 180 ° C. or lower, and most preferably 160 ° C. or lower. If the temperature is too low, it takes time to raise the temperature during the production of the polyester, and the polyester production tends to be economically disadvantageous, and may solidify depending on the type of diol. On the other hand, if it is too high, the diol vaporization requires a high-pressure storage facility, which is not only economically disadvantageous but also tends to increase the degradation of the diol.

The pressure in the diol storage tank is usually atmospheric pressure (normal pressure). If the pressure is too low or too high, the management facilities become complicated and economically disadvantageous.
In the present invention, the upper limit of the content of the oxidation product of the diol used for producing a polymer having a good hue is usually 10,000 ppm or less, preferably 5000 ppm or less, more preferably 3000 ppm or less, most preferably 2000 ppm or less in the diol. is there. On the other hand, the lower limit is not particularly limited, but is usually 1 ppm or more, preferably 10 ppm or more, more preferably 100 ppm or more for reasons of economic efficiency of the purification step.
In the present invention, the diol is usually used as a polyester raw material after a purification step by distillation.

<Production method of polyester>
The production of the polyester mainly composed of the diol unit and the dicarboxylic acid unit of the present invention can be carried out by a known technique for producing a polyester, other than controlling the amount of nitrogen in the polymerization reaction solution. The polymerization reaction at the time of producing this polyester can set appropriate conditions conventionally employed and is not particularly limited.
The amount of the diol used in producing the polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof, but generally 1 to 20 mol since there is distillation during esterification. % Excess is used. The amount used when the aliphatic oxycarboxylic acid described later is used is preferably 0 to 60 mol, more preferably 1.0 to 40 mol, and particularly preferably 2 to 20 mol per 100 mol of the aliphatic dicarboxylic acid or derivative thereof. Is a mole.

  The timing and method of addition when using oxycarboxylic acid to be described later are not particularly limited as long as it is before the polycondensation reaction. For example, (1) The catalyst is added in a state dissolved in an aliphatic oxycarboxylic acid solution in advance. (2) A method of adding a catalyst at the same time as adding a catalyst at the time of raw material charging. The polyester of the present invention is preferably produced by polymerizing the above raw materials in the presence of a polymerization catalyst. As a catalyst, a titanium compound and a germanium compound are suitable. In particular, a germanium compound is preferable. The germanium compound is not particularly limited, and examples thereof include organic germanium compounds such as germanium oxide and tetraalkoxygermanium, and inorganic germanium compounds such as germanium chloride. In view of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium and the like are preferable, and germanium oxide is particularly preferable. Moreover, unless the objective of this invention is impaired, combined use of another catalyst is not prevented. The usage-amount of a catalyst is 0.001 to 3 weight% normally with respect to the amount of monomer to be used, More preferably, it is 0.005 to 1.5 weight%. The catalyst addition time is not particularly limited as long as it is before polycondensation, but it may be added when the raw materials are charged, or may be added at the start of pressure reduction. It is preferable to add the oxycarboxylic acid such as lactic acid or glycolic acid at the time of charging the raw material or to dissolve the catalyst in the oxycarboxylic acid aqueous solution and add the oxycarboxylic acid, particularly in terms of improving the storage stability of the catalyst. A method in which the catalyst is dissolved in an aqueous acid solution and added is preferred.

In the present invention, the polycondensation reaction may be performed in the presence of a polymerization catalyst other than germanium. The timing for adding these polymerization catalysts is not particularly limited as long as it is before the polycondensation reaction, and may be added when the raw materials are charged, or may be added at the start of pressure reduction.
Therefore, in the present invention, the polymerization catalyst generally includes a compound containing a group 1 to group 14 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. And compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. These catalyst components may be contained in a polyester raw material derived from biomass resources for the reasons described above. In that case, the raw material may be used as it is as a raw material containing a metal without purification. However, depending on the polyester to be produced, a polyester having a high degree of polymerization may be easier to produce as the content of a group 1 metal element such as sodium or potassium contained in the polyester raw material is smaller. In such a case, the raw material refine | purified to the grade which does not contain a group 1 metal element substantially is used preferably.

  Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferable, and among these, titanium compounds and germanium compounds are particularly preferable. In addition, the catalyst is preferably a compound that is liquid at the time of polymerization or that dissolves in an ester low polymer or polyester because the polymerization rate increases when it is melted or dissolved at the time of polymerization.

  The titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof. In addition, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate) diisopropoxide, titanium (triethanolaminate) ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide and composite oxides containing titanium and silicon (for example, titania / silica composite oxide (product name: C-94) manufactured by Acordis Industrial Fibers) are preferably used. Among these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate Rate, titanium lactate, butyl titanate dimer, titanium oxide, titania / silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers), tetra-n-butyl titanate, titanium (oxy) acetylacetate Nate, titanium tetraacetylacetonate, polyhydroxytitanium stearate, titanium lactate, butyl titanate dimer, titania / silica composite oxide (for example, Aco Rdis Industrial Fibers, product name: C-94) is more preferable, and in particular, tetra-n-butyl titanate, polyhydroxytitanium stearate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titania / silica composite An oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) is preferable.

  Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetylate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, and polyhydroxyzirconium. Examples include stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Furthermore, zirconium oxide and composite oxides containing, for example, zirconium and silicon are also preferably used. Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate acetate, zirconium ammonium oxalate, zirconium potassium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n- Propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide are preferred, zirconyl diacetate, zirconium tetraacetate, zirconium acetate acetate hydroxide, zirconium tris (butoxy) stearate, sulphur Zirconium ammonium acid, zirconium tetra-n-propoxide, zirconium tetra-n-butoxide are more preferred, Preferred for reasons of zirconium tris (butoxy) stearate is easily obtained polyester having a high degree of polymerization without colored.

  The amount of catalyst used in the case of using a metal compound as a polymerization catalyst other than germanium, the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably as the amount of metal relative to the polyester to be produced. 1000 ppm or less, more preferably 250 ppm or less, particularly preferably 130 ppm or less. If too much catalyst is used, it is not only economically disadvantageous but also lowers the thermal stability of the polymer. Conversely, if it is too little, the polymerization activity is lowered, and as a result, the polymer decomposes during polymer production. Is more likely to be triggered.

Conditions such as temperature, time, and pressure for producing the polyester of the present invention are selected in the range of 150 to 260 ° C., preferably 180 to 230 ° C., and the polymerization time is 2 hours or more, preferably 4 It is better to choose in the range of ~ 15 hours. The degree of vacuum should be 10 mmHg or less, more preferably 2 mmHg or less.
More specifically, the lower limit of the esterification reaction and / or transesterification reaction temperature between the dicarboxylic acid component and the diol component is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250. It is below ℃. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. The reaction pressure is usually normal pressure to 10 kPa, but normal pressure is preferred.

The lower limit of the reaction time is usually 1 hour or longer, and the upper limit is usually 10 hours or shorter, preferably 4 hours or shorter.
In the polycondensation reaction after the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the diol component, the lower limit is usually 0.01 × 10 ³ Pa or more, preferably 0.05 × 10 ³ Pa or more. Yes, the upper limit is usually 1.4 × 10 ³ Pa or less, preferably 0.4 × 10 ³ Pa or less. At this time, the lower limit of the reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and the upper limit is usually 260 ° C. or lower, preferably 250 ° C. or lower. The lower limit of the reaction time is usually 2 hours or more, and the upper limit is usually 15 hours or less, preferably 10 hours or less.

  In the present invention, a known vertical or horizontal stirred tank reactor can be used as a reaction apparatus for producing polyester. For example, using the same or different reaction apparatus, it is carried out in two stages, that is, a step of esterification and / or transesterification of melt polymerization and a step of polycondensation under reduced pressure. A method of using a stirred tank reactor equipped with a evacuation pipe for decompression to be connected can be mentioned. In addition, a method in which a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and the volatile components and unreacted raw materials generated during the polycondensation reaction in the condenser is preferably used. It is done.

  In the present invention, as a method for producing a polyester, after performing an esterification reaction and / or transesterification reaction of a conventional dicarboxylic acid component containing an aliphatic dicarboxylic acid and an aliphatic diol component, under reduced pressure, A method of increasing the degree of polymerization of the polyester while distilling off the diol produced by the transesterification reaction at the alcohol end of the polyester, or distilling the aliphatic dicarboxylic acid and / or its acid anhydride ring from the end of the aliphatic carboxylic acid of the polyester. A method of increasing the degree of polymerization of the polyester while leaving is used. In the latter case, the removal of the aliphatic carboxylic acid and / or its anhydride ring is usually carried out during the polycondensation reaction under reduced pressure in the latter stage of the melt polymerization step. Although the method of distilling the body by heating is employed, since the aliphatic dicarboxylic acid easily becomes an acid anhydride ring under the polycondensation reaction conditions, it may be distilled by heating in the form of an acid anhydride ring. Many. At this time, the linear or cyclic ether derived from the diol and / or the diol may also be removed together with the aliphatic dicarboxylic acid and / or the anhydride cyclic product thereof. Furthermore, the method of distilling off both the dicarboxylic acid component and the diol component of the cyclic monomer is a preferred embodiment because the polymerization rate is improved.

  In the present invention, the dicarboxylic acid and / or diol derived from biomass resources obtained by the above-described method is used as a polyester raw material in a reaction vessel in which the oxygen concentration during the polyester production reaction is controlled to a specific value or less. May be manufactured. As a result, 2- (4-hydroxybutyloxy) produced by coloring of polyester by oxidation reaction of nitrogen compounds as impurities, or oxidation reaction of 1,4-butanediol when 1,4-butanediol is used as a diol, for example. ) Since the coloring of the polyester by the diol oxidation reaction product such as tetrahydrofuran can be suppressed, a polyester having a good hue can be produced.

The production reaction here refers to the preparation of a polymer having a desired viscosity under reduced pressure in a polycondensation reaction tank from the time when the raw material is charged into the esterification reaction tank, and the temperature rise is started. It is defined as the period until the pressure is restored.
The lower limit of the oxygen concentration in the reaction tank during the production reaction is not particularly limited, but is usually 1.0 × 10 ⁻⁹ % or more, preferably 1.0 × 10 ⁻⁷ % or more, and the upper limit is usually 10% or less. , Preferably 1% or less, more preferably 0.1% or less, and most preferably 0.01% or less. When the oxygen concentration is too low, the management process tends to be complicated, and when it is too high, the polyester obtained for the above reason tends to become colored.

In the present invention, when the dicarboxylic acid and / or diol derived from biomass resources obtained by the above-described method is used as a polyester raw material, the stirring speed before stopping the polymerization reaction under reduced pressure may be controlled. Thereby, the polyester derived from the biomass resource with a high viscosity in which decomposition | disassembly was suppressed can be manufactured.
The “final stirring speed” here refers to the minimum number of stirring rotations of the stirring device when a polymer having a desired viscosity is produced during the condensation polymerization reaction described later. However, the operation of stopping the stirrer accompanying the production polymer extraction operation or the like is not included in the definition during the condensation polymerization reaction.

  The lower limit of the stirring speed before stopping the reaction at the time of the polymerization reaction under reduced pressure is usually 0.1 rpm or more, preferably 0.5 rpm or more, more preferably 1 rpm or more, and the upper limit is 10 rpm or less, preferably 7 rpm. Hereinafter, it is more preferably 5 rpm or less, and most preferably 3 rpm or less. When the stirring rate is too slow, the polymerization rate tends to be slow or the viscosity of the produced polymer tends to be uneven, and when it is too fast, in the production of polymers derived from biomass resources that have many impurities due to shearing heat generation. In particular, the polymer tends to decompose easily. In the present invention, it is usually preferable to produce the desired polyester by stirring at a rotational speed of at least 10 rpm for at least 5 minutes, preferably at least 10 minutes, more preferably at least 30 minutes.

  The lower limit of the stirring speed at the start of polymerization under reduced pressure is usually 10 rpm or more, preferably 20 rpm or more, more preferably 30 rpm or more, and the upper limit is 200 rpm or less, preferably 100 rpm or less, more preferably. Is 50 rpm or less. When the stirring speed is too slow, the polymerization speed tends to be slow or the viscosity of the produced polymer tends to be uneven, and when it is too fast, during the production of a polymer derived from biomass resources having many impurities due to shearing heat generation. Tends to degrade the polymer in particular.

  Here, the stirring speed at the time of the polymerization reaction under reduced pressure may be reduced continuously or in multiple stages in consideration of an increase in the viscosity of the polyester. More preferably, it is important that the average stirring speed for 10 minutes before stopping the polycondensation reaction under reduced pressure is lower than the average stirring speed for 30 minutes after starting the polycondensation reaction under reduced pressure. By performing this adjustment, the thermal decomposition during the production of the biomass resource-derived polyester that contains many impurities and is easily thermally decomposed is suppressed, and the polymer can be produced stably.

In addition, by controlling the stirring speed during the esterification reaction and / or transesterification reaction, for example, by-production of tetrahydrofuran when 1,4-butanediol is used as the diol, the polymerization rate is improved. Can do.
The lower limit of the stirring speed during the esterification reaction is usually 30 rpm or more, preferably 50 rpm or more, more preferably 80 rpm or more, and the upper limit is 1000 rpm or less, preferably 500 rpm or less. When the stirring speed is too slow, the distillation efficiency is poor and the esterification reaction tends to be slow, and for example, the diol dehydration reaction or dehydration cyclization tends to be caused. As a result, the ratio of the diol / dicarboxylic acid collapses and the polymerization rate is reduced, and it is necessary to charge an excessive amount of the diol. Disadvantageous.

  Moreover, when using dicarboxylic acid derived from biomass resources as a polyester raw material, the oxygen concentration and humidity when transferring the dicarboxylic acid from the storage tank to the reactor may be controlled. As a result, corrosion in the transfer pipe due to impurities can be prevented, and further, coloring due to the oxidation reaction of the nitrogen source can be suppressed, and a polyester having a good hue can be produced.

  Specifically, the transfer pipe is made of a commonly known metal, or an inner surface of which a lining such as glass or resin is applied, or a glass or resin container. From the viewpoint of strength, etc., those made of metal or those lining them are preferably used. As the material for the metal tank, known materials are used. Specifically, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic stainless steel such as SUS310, SUS304, and SUS316, clad Steel, cast iron, copper, copper alloy, aluminum, inconel, hastelloy, titanium and the like can be mentioned.

  The lower limit of the oxygen concentration in the transfer pipe is not particularly limited with respect to the total volume of the transfer pipe, but is usually 0.00001% or more, preferably 0.01% or more. On the other hand, the upper limit is usually 16% or less, preferably 14% or less, and more preferably 12% or less. When the oxygen concentration is too low, the capital investment and the management process become complicated, which is economically disadvantageous. On the other hand, when the oxygen concentration is too high, coloring of the produced polymer tends to increase.

  The lower limit of the humidity in the transfer pipe is not particularly limited, but is usually 0.0001% or more, preferably 0.001% or more, more preferably 0.01% or more, and most preferably 0.1% or more. The upper limit is 80% or less, preferably 60% or less, and more preferably 40% or less. If the humidity is too low, the management process tends to be cumbersome and economically disadvantageous. If it is too high, corrosion of the storage tank and piping tends to be a problem. Furthermore, when the humidity is too high, problems such as adhesion of dicarboxylic acid to storage tanks and piping, blocking of dicarboxylic acid, and the like occur, and corrosion of piping tends to be promoted by these adhesion phenomena.

The lower limit of the temperature in the transfer tube is usually −50 ° C. or higher, preferably 0 ° C. or higher. On the other hand, the upper limit is usually 200 ° C. or lower, preferably 100 ° C. or lower, more preferably 50 ° C. or lower. If the temperature is too low, the storage cost tends to increase, and if it is too high, the dicarboxylic acid dehydration reaction tends to occur simultaneously.
The pressure in the transfer pipe is usually from 0.1 kPa to 1 MPa, but is used at a pressure of about 0.05 MPa to 0.3 MPa from the viewpoint of operability.

  In addition, various additives such as plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorizers in the course of the polyester production process, or within the range where the properties of the produced polyester are not impaired. If necessary, inorganic fine particles or organic compounds may be added as agents, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, ion exchange agents, or coloring pigments. Color pigments include carbon black, titanium oxide, zinc oxide, iron oxide, and other inorganic pigments, as well as cyanine, styrene, phthalocyanine, anthraquinone, perinone, isoindolinone, quinophthalone, and quinocridone. Organic pigments such as those based on thioindigo can be used. Moreover, modifiers such as calcium carbonate and silica can also be used.

In this invention, you may control the temperature of the polyester at the time of extracting from a polymerization reaction tank after completion | finish of a polymerization reaction. Thereby, thermal decomposition at the time of extraction of high-viscosity polyester can be suppressed and taken out.
The temperature of the polyester when it is withdrawn from the polymerization reaction tank is (Te-50) ° C., where Te is the resin temperature when the pressure in the reaction tank is restored from reduced pressure to normal pressure or higher after completion of polymerization. Above, preferably (Te-30) ° C. or higher, more preferably (Te-20) ° C. or higher, most preferably (Te-10) ° C. or higher, and the upper limit is (Te + 20) ° C. or lower, preferably (Te + 10) ° C. or lower, more preferably Te ° C. or lower. If the temperature is too low, the viscosity of the polyester at the time of extraction will increase, making it difficult to extract and tend to cause problems with productivity. If it is too high, the thermal decomposition of the polyester will tend to be significant. .

Here, the temperature of the polyester at the time of extraction can be measured by a thermocouple or the like attached for the purpose of measuring the temperature in the polymerization reaction layer.
Moreover, in this invention, after completion | finish of a polymerization reaction, you may make the strand-shaped polyester extracted from the polymerization reaction tank contact the aqueous medium below a specific temperature. Thereby, it can obtain, suppressing decomposition | disassembly of highly viscous polyester.

The medium for cooling the polyester is not particularly limited, and examples thereof include diols such as ethylene glycol, alcohols such as methanol and ethanol, acetone, and water. Among these, water is most preferable. Two or more of these aqueous solvents may be used in combination.
The lower limit of the solvent temperature is usually −20 ° C. or higher, preferably −10 ° C. or higher, more preferably 0 ° C. or higher, most preferably 4 ° C. or higher, and the upper limit is usually 20 ° C. or lower. Is 15 ° C. or lower, more preferably 10 ° C. or lower. If the temperature is too low, the operating cost of the medium cooling equipment tends to be high and economically disadvantageous. On the other hand, if the temperature is too high, the thermal decomposition of the polyester tends to become noticeable when the strand is pulled out. is there.

  As for the time for cooling the polyester, the lower limit is usually 0.1 second or more, preferably 1 second or more, more preferably 5 seconds or more, most preferably 10 seconds or more, and the upper limit is usually 5 minutes or less, preferably Is 2 minutes or less, more preferably 1 minute or less, and most preferably 30 seconds or less. If the time is too short, fusion between strands tends to be remarkable or pelletization tends to be difficult, and if too long, productivity tends to be disadvantageous.

Although it does not specifically limit as a method to cool, For example, the method of taking out polyester in a strand form from a polymerization tank and submerging in a cooling medium, and the method of dropping a cooling medium on a strand in a shower form etc. are mentioned, for example.
<Polyester>
The polyester of the present invention includes all polyesters produced by the reaction of components mainly composed of various compounds belonging to the categories of dicarboxylic acid units and diol units listed above. As specific examples, the following polyesters can be exemplified.

As polyesters using succinic acid, polyesters of succinic acid and ethylene glycol, polyesters of succinic acid and 1,3-propylene glycol, polyesters of succinic acid and neopentyl glycol, polyesters of succinic acid and 1,6-hexamethylene glycol Examples thereof include polyesters of succinic acid and 1,4-butanediol and polyesters of succinic acid and 1,4-cyclohexanedimethanol.
As polyesters using oxalic acid, oxalic acid and ethylene glycol polyester, oxalic acid and 1,3-propylene glycol polyester, oxalic acid and neopentyl glycol polyester, oxalic acid and 1,6-hexamethylene glycol polyester Examples thereof include polyesters of oxalic acid and 1,4-butanediol, and polyesters of oxalic acid and 1,4-cyclohexanedimethanol.

As a polyester using adipic acid, adipic acid and ethylene glycol polyester, adipic acid and 1,3-propylene glycol polyester, adipic acid and neopentyl glycol polyester, adipic acid and 1,6-hexamethylene glycol polyester Examples thereof include polyesters of adipic acid and 1,4-butanediol and polyesters of adipic acid 1,4-cyclohexanedimethanol.
In addition, a polyester in which the above dicarboxylic acid is combined is also a preferable combination, a polyester of succinic acid, adipic acid and ethylene glycol, a polyester of succinic acid, adipic acid and 1,4-butanediol, a terephthalic acid, adipic acid and 1, Examples include 4-butanediol polyester and terephthalic acid, succinic acid, and 1,4-butanediol polyester.

  The present invention is also directed to a copolymer polyester in which a copolymer component is added as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid and / or an anhydride thereof to form a crosslinked structure, and Examples thereof include at least one polyfunctional compound selected from the group consisting of trifunctional or higher functional oxycarboxylic acids. Among these copolymer components, a bifunctional and / or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolymer polyester having a high degree of polymerization tends to be easily produced. Among them, the use of a trifunctional or higher functional oxycarboxylic acid is the most preferable method because a polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

  In the composition ratio of the structural unit of the polyester of the present invention, the molar ratio of the diol unit and the dicarboxylic acid unit is substantially equal, but the polyester may contain an oxycarboxylic acid unit as a copolymerization component. The amount of the oxycarboxylic acid unit is usually 0 to 30 mol per 100 mol of the dicarboxylic acid unit. The upper limit of the oxycarboxylic acid unit is preferably 20 mol%, more preferably 10 mol%, and the lower limit is preferably 0.5 mol%, more preferably 1 mol%.

As the oxycarboxylic acid unit, a corresponding oxycarboxylic acid and a derivative thereof are used as a raw material. Specific examples include p-hydroxybenzoic acid, lactic acid, lactide, glycolic acid, glycolide, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, caprolactone, 2-hydroxy3,3-dimethyl. Examples include butyric acid, 2-hydroxy-3-methylbutyric acid, 2-hydroxyisocaproic acid, or esters thereof, cyclic monomer esters, cyclic dimer esters, and mixtures thereof. When optical isomers exist in these, any of D-form, L-form, and racemic form may be sufficient, and a form may be a solid, a liquid, or aqueous solution. Of these, lactic acid or glycolic acid is preferred, and particularly preferred is lactic acid or glycolic acid, which is particularly prominent in increasing the polymerization rate during use and is readily available. The form is preferably 30 to 95% because an aqueous solution can be easily obtained. These aliphatic oxycarboxylic acids can be used alone or as a mixture of two or more.
Specifically, when the polyester is used, when lactic acid is used as the bifunctional oxycarboxylic acid, for example, a copolymer polyester of succinic acid-1,4-butanediol-lactic acid or succinic acid-adipic acid-1,4 is used. -Copolymerized polyester of butanediol-lactic acid. When glycolic acid is used, for example, it is a copolyester of succinic acid-1,4-butanediol-glycolic acid. For the oxycarboxylic acid unit, other corresponding oxycarboxylic acids and derivatives thereof are also used as raw materials. Specific examples include p-hydroxybenzoic acid, 2-hydroxy-n-butyric acid, 2-hydroxycaproic acid, 6-hydroxycaproic acid, caprolactone, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methyl. A predetermined copolyester can be produced by arbitrarily changing a bifunctional oxycarboxylic acid such as butyric acid or 2-hydroxyisocaproic acid.

The polyester of the present invention may be copolymerized with a tri- or higher functional alcohol or carboxylic acid. Specifically, trifunctional or more polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, propanetricarboxylic acid, malic acid, citric acid, tartaric acid, hydroxyglutaric acid, hydroxymethylglutaric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, etc. , Polyvalent carboxylic acid and polyvalent oxycarboxylic acid may be copolymerized. Since the amount of the above trifunctional or higher polyfunctional compound unit causes the generation of gel, the upper limit is usually 5 mol% or less, preferably 100 mol% of all monomer units constituting the polyester. Is 1 mol% or less, more preferably 0.50 mol% or less, particularly preferably 0.3 mol% or less. On the other hand, when a trifunctional or higher functional compound is used as a copolymerization component for the purpose of easily producing a polyester having a high degree of polymerization, the lower limit of the amount used to exert its effect is usually 0.0001 mol% or more, Preferably, it is 0.001 mol% or more, more preferably 0.005 mol% or more, and particularly preferably 0.01 mol% or more.
When pentaerythritol is used as the trifunctional or higher functional polyhydric alcohol of the copolymer component, for example, succinic acid-1,4-butanediol-pentaerythritol copolymerized polyester or succinic acid-adipic acid-1,4-butanediol- It becomes a copolyester of pentaerythritol. A desired copolyester can be produced by arbitrarily changing a trihydric or higher polyhydric alcohol. High molecular weight polyesters obtained by chain extending (coupling) these copolymerized polyesters also belong to the category of the polyester of the present invention.
When malic acid is used as the trifunctional oxycarboxylic acid of the copolymerization component, for example, copolymer polyester of succinic acid-1,4-butanediol-malic acid, succinic acid-adipic acid-1,4-butanediol-apple Acid copolyester, succinic acid-1,4-butanediol-malic acid-tartaric acid copolyester, succinic acid-adipic acid-1,4-butanediol-malic acid-tartaric acid copolyester, succinic acid- A copolymer polyester of 1,4-butanediol-malic acid-citric acid and a copolymer polyester of succinic acid-adipic acid-1,4-butanediol-malic acid-citric acid are obtained. A desired copolyester can be produced by arbitrarily changing the trifunctional oxycarboxylic acid.

Of course, in combination with a bifunctional oxycarboxylic acid, for example, copolymer polyester of succinic acid-1,4-butanediol-malic acid-lactic acid, succinic acid-adipic acid-1,4-butanediol-malic acid -Copolyester of lactic acid, copolymer polyester of succinic acid-1,4-butanediol-malic acid-tartaric acid-lactic acid, copolymer of succinic acid-adipic acid-1,4-butanediol-malic acid-tartaric acid-lactic acid Polyester, copolyester of succinic acid-1,4-butanediol-malic acid-citric acid-lactic acid, and copolyester of succinic acid-adipic acid-1,4-butanediol-malic acid-citric acid-lactic acid .
The physical properties of the polyester of the present invention will be explained by taking an example of a polyester of an aliphatic diol and an aliphatic dicarboxylic acid such as polybutylene succinate or polybutylene succinate adipate, and a density of 1.2 to 1.3 g / cm ^3. The melting point is 80 to 120 ° C., the tensile strength is 30 to 80 Mpa, the ultimate elongation is 300 to 600%, the tensile modulus is 400 to 700 Mpa, the tensile yield point strength is 30 to 40 Mpa, the impact test strength is about 5 to ²⁰ kJ / m ² , the glass transition point. It possesses the properties of general-purpose polymers such as −45 to −25 ° C. Moreover, when targeting a specific use, it can be set as the polyester which has the characteristics of arbitrary wide ranges beyond the range of the above ranges. Furthermore, it can have the melting point, melt index, and melt viscoelasticity properties so that a molded product can be produced by various molding means. These characteristics can be arbitrarily adjusted by changing the types of polyester raw materials and additives, polymerization conditions, molding conditions and the like according to the purpose of use.

The range of the typical physical property value which the polyester of this invention has in detail is disclosed below.

  The number average molecular weight of the polyester of the present invention is usually at least 5000, preferably 10,000 or more, more preferably 15,000 or more in terms of polystyrene, and the upper limit is usually 500,000 or less, preferably 300,000. It is as follows.

  As for the composition ratio of the polyester copolymer, the molar ratio of the diol unit and the dicarboxylic acid unit needs to be substantially equal.

The reduced viscosity (ηsp / c) value of the polyester produced in the present invention is 0.5 or more, and preferably 1.0 or more, more preferably 1.5 because practically sufficient mechanical properties can be obtained. The above is preferable, and 2.0 or more is particularly preferable. The upper limit of the reduced viscosity (ηsp / c) value is usually 6.0 or less, preferably 5.0 or less, from the viewpoint of operability such as ease of extraction after the polyester polymerization reaction and ease of molding. Preferably it is 4.0 or less.

The reduced viscosity as used in the present invention is measured under the following measurement conditions.
[Reduced viscosity (ηsp / c) measurement conditions]
Viscosity tube: Ubbelohde viscosity tube Measurement temperature: 30 ° C
Solvent: Phenol / tetrachloroethane (1: 1 weight ratio) solution Polyester concentration: 0.5 g / dl
The polyester of the present invention is preferably a polyester that dissolves uniformly when a polyester (0.5 g) is dissolved in a phenol / tetrachloroethane (1: 1 weight ratio) solution (volume: 1 dl) at room temperature. In general, the amount of insoluble components in the total polyester is preferably 1% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0.01% by weight or less.

The terminal carboxyl group concentration of the polyester of the present invention is usually 100 equivalents / ton or less, more preferably, the concentration is 50 equivalents / ton or less, particularly 35 equivalents / ton or less, and more preferably 25 equivalents / ton. Or less, preferably 0.1 equivalent / ton or more, preferably 0.5 equivalent / ton or more, particularly preferably 1 equivalent / ton or more. When this amount increases, the thermal stability during molding of the polymer and the hydrolysis resistance during relatively long-term use / storage tend to decrease, and a polymer having too few carboxyl groups is a more preferable form, In order to produce such a polymer, in addition to requiring a very high capital investment, it requires a lot of production time, which is an economical disadvantage. The amount of terminal carboxyl group is usually calculated by a known titration method. In the present invention, the obtained polyester is dissolved in benzyl alcohol and titrated with 0.1 N NaOH, and 1 × 10 ⁶ g The equivalent carboxyl group equivalent.

  In the polymer of the present invention, in particular, in the case of a polyester using a raw material derived from biomass resources, for example, volatile organic components such as tetothehydrofuran and acetaldehyde tend to be easily contained in the polyester. The upper limit of the content thereof is usually 10000 ppm or less, preferably 3000 ppm or less, more preferably 1000 ppm or less, and most preferably 500 ppm or less, based on the polyester mass. On the other hand, the lower limit is not particularly limited, but is usually 1 ppb or more, preferably 10 ppb or more, more preferably 100 ppb or more. When the volatile content is large, it may cause odor and may cause foaming during melt molding and deterioration of storage stability. On the other hand, an excessively small system is a preferred form, but it is economically disadvantageous to produce such a polymer, such as requiring a very large capital investment and requiring a large production time.

  In the present invention, the water content of the polyester may be adjusted. The lower limit of the water content is not particularly limited, but is usually 0.1 ppm or more, preferably 0.5 ppm or more, more preferably 1 ppm or more, most preferably 10 ppm or more, and the upper limit is usually 3000 ppm or less. Preferably it is 2000 ppm or less, More preferably, it is 1000 ppm or less, Especially preferably, it is 800 ppm or less, Most preferably, it is 500 ppm or less. If the water content is too low, not only will the equipment and management process be complicated and economically disadvantageous, but it will take a long time to dry, so deterioration of the coloring of the polyester and the formation of crumbs will occur. There is a tendency to be caused. On the other hand, when it is too much, there is a tendency that the deterioration of the polyester due to hydrolysis during storage becomes remarkable.

  As a method for measuring the water content (water content), a water vaporizer (VA-100 model manufactured by Mitsubishi Chemical Corporation) was used to heat and melt a sample of 0.5 g at 200 ° C. to vaporize water in the sample. After that, the total amount of water vaporized is quantified by a coulometric titration method based on the principle of Karl Fischer reaction using a trace moisture measuring device (CA-100 model manufactured by Mitsubishi Chemical Corporation) to determine the amount of moisture in the sample. Just decide.

  The polyester produced in the present invention is usually preferably a polyester with little coloring. The upper limit of the yellowness (YI value) of the polyester of the present invention is usually 50 or less, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, particularly preferably 10 or less, The lower limit is not particularly limited, but is usually −20 or more, preferably −10 or more, more preferably −5 or more, particularly preferably −3 or more, and most preferably −1 or more. Polyesters exhibiting high YI values have the disadvantage that their use applications such as films and sheets are limited. On the other hand, polyesters exhibiting a low YI value are a more preferred form, but there are economical disadvantages in producing such polymers, such as complicated manufacturing processes and very high capital investment. In the present invention, the YI value is a value measured by a method based on JIS K7105.

Moreover, the minimum of melting | fusing point of polyester is 50 degreeC or more normally, Preferably, it is 60 degreeC or more, More preferably, it is 80 degreeC or more. In the case of aliphatic polyester, the upper limit is 140 ° C. or lower, preferably 130 ° C. or lower.
The polyester of the present invention has a biodegradation rate in the soil of 1.01 times or more, preferably 1.05 times the biodegradation rate of the polyester having the same chemical structure obtained from the petroleum resources. As mentioned above, More preferably, it is 1.1 times or more.

The biodegradation rate is the rate at which polyester is decomposed by physiologically active substances possessed by living organisms and microorganisms, and is represented by the following formula.
That is, in a biodegradability test conducted under the same conditions, the weight loss rate after one month in the soil of the polyester A obtained from the raw material of petroleum resources is a (%), the same chemical structure as the polyester A and the raw material If the weight loss rate after one month in the soil of the polyester B of the present invention, a part of which is a plant-derived material, is b (%), preferably b / a ≧ 1.1, more preferably b / a ≧ 1.2, more preferably 1.5 times or more.

a (%) = 100 × (A ₀ −A ₁ ) / A ₀
A ₀ : Weight of polyester A before being buried in soil A ₁ : Weight of polyester A one month after being buried in soil b (%) = 100 × (B ₀ -B ₁ ) / B ₀
B ₀ : Weight of polyester B before embedding in soil B ₁ : Weight of polyester B after 1 month of embedding in soil In addition, other copolymer components are introduced into the polyester of the present invention as long as the effects of the present invention are not impaired. can do. As other copolymer components, a carbonate ester component, an ether component, an amide component, or the like may be copolymerized. A chain extender may be used such as carbonate or diisocyanate. Further, the end group may be sealed with carbodiimide, an epoxy compound, a monofunctional alcohol or carboxylic acid.

  Examples of the carbodiimide compound include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, as the monocarbodiimide compound, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, Examples include dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-2,6-diisopropylphenylcarbodiimide and the like. As the polycarbodiimide compound, those having a degree of polymerization of usually 2 or more, preferably 4 or more and an upper limit of usually 40 or less, preferably 30 or less, are used, U.S. Pat. No. 2,941,956, Japanese Patent Publication No. 47-33279, J. Pat. Org. Chem. 28, p2069-2075 (1963), and Chemical Review 1981, 81, No. 4, p. And those produced by the method described in 619-621 and the like.

  Examples of the organic diisocyanate that is a raw material for producing the polycarbodiimide compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof. Specifically, 1,5-naphthalene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 A mixture of tolylene diisocyanate and 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate And 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-diisocyanate, etc. .

Specific examples of industrially available polycarbodiimides include Carbodilite HMV-8CA (Nisshinbo), Carbodilite LA-1 (Nisshinbo), Starbazole P (Rhein Chemie), Starbazole P100 (Rhein Chemie) and the like. Is done.
The carbodiimide compound can be used alone, but a plurality of compounds can also be mixed and used.

The polyester of the present invention can also use chain extenders such as carbonate compounds and diisocyanate compounds. The amount of use thereof is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, with respect to all monomer units constituting the polyester. However, when the polyester of the present invention is used as a biodegradable resin, the presence of diisocyanate or carbonate bond may inhibit biodegradability. The carbonate bond is less than 1 mol%, preferably 0.5 mol% or less, more preferably 0.1 mol% or less, and the urethane bond is less than 0.06 mol%, preferably less than 0.1 mol%, based on the body unit. It is at most 01 mol%, more preferably at most 0.001 mol%. The carbonate bond amount and the urethane bond amount are calculated by NMR measurement such as ¹³ C NMR.

  Specific examples of the carbonate compound include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, and dicyclohexyl. Examples include carbonate. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

  Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and xylylene. Examples include known diisocyanates such as range isocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

Production of high molecular weight polyesters using these chain extenders (coupling agents) can be made using conventional techniques. After the completion of polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation.
More specifically, the end group obtained by catalyzing a diol and dicarboxylic acid (or its anhydride) has a hydroxyl group substantially, and the weight average molecular weight (Mw) is 20,000 or more, preferably Can be obtained by reacting the above chain extender with 40,000 or more polyester to obtain a higher molecular weight polyester resin. A prepolymer having a weight average molecular weight of 20,000 or more is not affected by the remaining catalyst even under severe conditions such as a molten state by using a small amount of a coupling agent. Molecular weight polyesters can be produced.

Therefore, for example, when the above-described diisocyanate is used as a chain extender to further increase the molecular weight, a prepolymer having a weight average molecular weight of 20,000 or more, preferably 40,000 or more, consisting of a diol and a dicarboxylic acid A polyester having a linear structure linked through a urethane bond derived from diisocyanate is produced.
The pressure during chain extension is usually 0.01 MPa or more and 1 MPa or less, preferably 0.05 MPa or more and 0.5 MPa or less, more preferably 0.07 MPa or more and 0.3 MPa or less. Most preferred.

  The lower limit of the reaction temperature during chain extension is usually 100 ° C or higher, preferably 150 ° C or higher, more preferably 190 ° C or higher, most preferably 200 ° C or higher, and the upper limit is usually 250 ° C or lower, preferably 240 ° C or lower. More preferably, it is 230 degrees C or less. If the reaction temperature is too low, the viscosity is high and uniform reaction is difficult, and high stirring power tends to be required. If it is too high, gelation and decomposition of the polyester tend to occur simultaneously.

  As for the time for chain extension, the lower limit is usually 0.1 minutes or more, preferably 1 minute or more, more preferably 5 minutes or more, and the upper limit is usually 5 hours or less, preferably 1 hour or less, more preferably 30 minutes or less, and most preferably 15 minutes or less. If the time is too short, the effect of addition tends to be lost, and if it is too long, gelation and decomposition of the polyester tend to occur simultaneously.

Moreover, you may use a dioxazoline, a silicate ester, etc. as another chain extender. Specific examples of the silicate ester include tetramethoxysilane, dimethoxydiphenylsilane, dimethoxydimethylsilane, and diphenyldihydroxylane.
Silicate esters are not particularly limited in terms of use for reasons of environmental protection and safety, but they are used in small quantities because they can be cumbersome and affect the polymerization rate. Sometimes it is better. Therefore, this content is preferably 0.1 mol% or less, more preferably 10 ⁻⁵ mol% or less, based on all monomer units constituting the polyester.

In the present invention, a polyester containing substantially no chain extender is most preferable. However, in order to increase the melt tension, a small amount of peroxide may be added as long as a low toxicity compound is added.
Thus, the polyester of the present invention is a generic term for polyesters, polyesters, copolyesters, chain extended (coupled) high molecular weight polyesters, and modified polyesters.

  The nitrogen atom content other than the functional group covalently bonded to the polyester of the present invention is 1000 ppm or less with respect to the polyester mass. The nitrogen atom content other than the functional group covalently bonded in the polyester is preferably 500 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, of which 40 ppm or less is preferable, and 30 ppm or less is more preferable. 20 ppm or less is most preferable. The nitrogen atom content other than the functional group covalently bonded to the polyester in the polymer is mainly derived from the nitrogen element in the raw material, but is included other than the functional group covalently bonded to the polyester. When the nitrogen atom content is 1000 ppm or less, it is preferable that coloring and generation of foreign matters during molding are small, and that the product after molding is less susceptible to deterioration such as heat or light and hydrolysis. Moreover, it is more preferable depending on a use that there is little coloring of a polyester and generation | occurrence | production of a foreign material that nitrogen atom content contained other than the functional group covalently bonded in polyester is 100 ppm or less. The effect becomes remarkable when the content is smaller. The nitrogen atom content contained in the polyester other than the covalently bonded functional group is preferably 0.01 ppm or more. More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, Most preferably, it is 1 ppm or more. If the nitrogen atom content is less than 0.01 ppm, a burden is imposed upon purification of the raw material, which is disadvantageous in terms of energy, and the influence on the environment cannot be ignored. Moreover, when the nitrogen atom content is 1 ppm or more, the biodegradation rate in the soil is accelerated, which is preferable. By using a raw material having a nitrogen atom content in the above range, usually, the polymerization rate of the polyester can be reduced in the polymerization reaction, and the biodegradability of the resulting polyester can be promoted.

The inventor has obtained more practical biodegradability rate, impact strength, tensile yield strength, tensile breaking strength, tensile breaking elongation, physical strength such as bending elastic modulus, coloration, yellowness (YI) of the polyester of the present invention. Value) and physical properties, such as the generation of harmful substances in the atmosphere or soil, as a result of comprehensive analysis and evaluation, as a result of the unique circumstances derived from biomass resources, so-called polyester Among the many causative substances that are mixed in, it has been found that nitrogen element is one of causative substances that particularly affects the promotion of biodegradation. And, as a practical polyester, the present inventors said that the nitrogen atom content in the polyester excluding nitrogen contained in the functional group covalently bonded in the acceptable polyester molecule is 0.01 ppm or more and 1000 ppm or less. It is a fact that has been found. In view of the fact that the polyester raw material is derived from biomass resources, it is due to a specific situation that some nitrogen elements may be mixed in many processes such as neutralization and purification in the production stage.

The reason why the nitrogen atom content in the polyester excluding nitrogen contained in the functional group covalently bonded in the molecule of the acceptable polyester as the practical polyester is 0.01 ppm or more and 1000 ppm or less will be described in more detail. Nitrogen atoms mixed into this polyester are not only those that contain diol units and dicarboxylic acid units derived mainly from biomass resources, as they are derived from biomass resources. In many processes such as neutralization and purification, it is possible that some elemental nitrogen such as ammonia, urea, amino acid, protein, and nitric acid may be mixed in even though the amount is extremely small. This elemental nitrogen has an advantageous effect on biodegradation and, as seen in Example 1 and Comparative Example 1, may have an advantageous effect on the biodegradation characteristics. On the other hand, if the nitrogen atom is 1000 ppm or more, for example, 5000 ppm, it becomes a hindrance in increasing the polymerization rate and the degree of polymerization related to the polymerization of the polyester, and causes a weak material property of the polyester.
However, what is important in the polyester of the present invention is to ensure the so-called green plastic reliability such as safety, security and harmlessness. In order for the biodegradable polyester of the present invention to ensure reliability, the presence of nitrogen atoms has a subtle effect.

  In order to remove a very small amount of nitrogen atoms, such as 0.01 ppm or less, not only a very high level of technical operation is required, but also the price is very high, which is an obstacle to the practice of the present invention. Analyzing the effect of the amount of nitrogen atoms remaining in the polyester, it can be understood that a very small amount of nitrogen atoms does not interfere with biodegradability but rather participates in the promotion of biodegradation. Show. Then, it is an important problem to be solved for the invention to find an acceptable range for nitrogen atoms mixed in the polyester. If this nitrogen atom-containing polyester biodegrades in the soil, especially if it is biodegraded in one place at a large amount or at a time, it will have a subtle effect on the pH of the soil due to accumulation, Concerning the accumulation, there is concern that environmental pollution such as impact on microorganisms, impact on animals and plants, and impact on water quality will progress. As a result of analyzing the range where reliability such as safety and security as a green plastic is not lost, in the normal use state of the polyester of the present invention, about 0.01 to 1000 ppm of nitrogen atoms is affected by nitrogen atoms. To the extent that the effects of pH are naturally extinguished or can be restored naturally by natural remediation, and more importantly, the effects on the plant due to soil enrichment can be prevented It is an acceptable range.

  More importantly, when the polyester of the present invention is used as a luxury product, a food bottle such as a beverage, a container, a food packaging material, etc., the polyester containing a large amount of nitrogen atoms has a taste, discomfort, toxicity, etc. We must also consider trust in the effects of In order to ensure the reliability as a green plastic, not only the impact on the environment, but also the impact on the human body, animals and plants as food must be highly considered. Of course, compounds containing nitrogen atoms do not act as toxic to the human body in trace amounts, but there is a concern that they may affect the senses of taste, odor, discomfort, and so on. Must be considered to the utmost. The polyester of the present invention not only analyzes material behavior, but also assumes all cases from production to molding, distribution, and safety of articles, biodegradation, recovery, and incineration. It is a material devised to ensure reliability. In view of such circumstances, the maximum allowable nitrogen atom content is considered, taking into account such comprehensive circumstances such as polyester polymerization, molding, use of molded articles, biodegradation, and incineration. It can be said that it is about 1000 ppm.

The nitrogen atom content can be measured by a chemiluminescence method which is a conventionally known method as described later.
In the present invention, the functional group covalently bonded in the polyester is a urethane functional group derived from the above diisocyanate compound or carbodiimide compound, an unreacted isocyanate functional group, a urea functional group, an isourea functional group, and Refers to an unreacted carbodiimide functional group. Therefore, in the present invention, the nitrogen atom content other than the functional group covalently bonded in the polyester is the above-mentioned urethane functional group, unreacted isocyanate functional group, from the total nitrogen atom content contained in the polyester, This is a value obtained by subtracting the nitrogen atom content attributed to the urea functional group, the isourea functional group and the unreacted carbodiimide functional group. Content of urethane functional group, unreacted isocyanate functional group, urea functional group, isourea functional group and unreacted carbodiimide functional group is the amount charged in spectroscopic measurement such as ¹³ C NMR and IR, and the production of polyester Is calculated from

The ratio of the nitrogen content contained in the polyester other than the functional group covalently bonded to the polyester of the present invention and the nitrogen content contained in the raw material is preferably larger than 0 and smaller than 0.9, more Preferably it is larger than 0 and smaller than 0.6.
The method for controlling the content of nitrogen atoms in the reaction solution is not limited as long as the polyester to be produced has the necessary properties. Examples thereof include a method for removing nitrogen atom-containing substances during the polymerization.

  It is preferable that the nitrogen atom-containing material is removed in the polyester polymerization step in order to reduce the load on purification for removing the nitrogen atom-containing material in the raw material. The range in which the amount of the nitrogen-containing compound in the reaction solution should be controlled varies depending on the properties of the target polyester, the polymerization conditions, etc., but usually the nitrogen atom amount is 1000 ppm or less, preferably 900 ppm or less, more preferably Is 800 ppm or less.

The polyester obtained by the above-described method is blended (kneaded) with various conventionally known resins to obtain a polyester composition. As such a resin, various conventionally known general-purpose thermoplastic resins, biodegradable resins, and natural resins can be used, and preferred examples include biodegradable polymers and general-purpose thermoplastic resins. These may be used alone or in combination of two or more. Various resins may be resins obtained from biomass resources.
The polyester of the present invention can be made into a polyester composition having an arbitrary wide range of properties by blending (kneading) with various known resins. For example, although the physical property value varies greatly depending on the blend ratio, it is not particularly limited. However, in a system in which polybutylene succinate and polylactic acid described later are blended, the tensile strength is 30 to 60 Mpa, the ultimate elongation is 3 to 400%, General-purpose polymers such as an elastic modulus of 500 to 3000 Mpa, a tensile yield strength of 30 to 50 Mpa, a bending strength of 30 to 100 Mpa, a bending elastic modulus of 600 to 4000 Mpa, and an impact test strength of about 5 to ²⁰ kJ / m ² can be possessed. Similarly, a blend system with a soft aromatic polyester can have the characteristics of general-purpose polymers such as a tensile strength of 30 to 70 Mpa, an ultimate elongation of 400 to 800%, and a tensile yield point strength of 10 to 30 Mpa. Furthermore, the density is 1 to 1.4 g / cm ³ , the melting point is 150 to 270 ° C., the tensile strength is 30 to 80 Mpa, and the ultimate elongation is 100 to 100% by combining with general-purpose resins such as nylon, polycarbonate, polyacetal, ABS, PET, and polystyrene. The properties of a general-purpose polymer such as 600% and glass transition point of −85 to 150 ° C. can be retained. These characteristics can be arbitrarily adjusted by changing the types of polyester raw materials and various resins, blend amount ratios, molding conditions and the like according to the purpose of use.

  As the general-purpose thermoplastic resin to be blended with the biomass-derived polyester of the present invention, any of the following general-purpose thermoplastic resins such as petroleum-derived polyester, polyvinyl acetate, polyvinyl alcohol, polyester, polycarbonate, and polyamide can be selected. In this case, it is necessary to consider compatibility with biomass-derived polyester. Furthermore, in order to properly maintain the properties of the biomass-derived polyester of the present invention, the blending amount is also important. Usually, a biomass-derived polyester is 99.9 to 20% by weight, and a general-purpose plastic resin can be blended in an amount of about 0.1 to 80% by weight. However, when the purpose is to maintain the biodegradable characteristics of the biomass-derived polyester, the blend amount of a general-purpose thermoplastic resin is 50 to 1% by weight, depending on the purpose, preferably 30 to When the content is about 3% by weight, predetermined physical properties can be obtained while maintaining biodegradability.

Examples of the biodegradable polymer include aliphatic polyester resins, polycaprolactone, polylactic acid, polyvinyl alcohol, polyethylene succinate, polybutylene succinate, polysaccharides, and other biodegradable resins.
The amount of blend of these biodegradable polymers is 99.9 to 0.1% by weight of the biomass-derived polyester of the present invention, given that both are biodegradable resins for the purpose of biodegradation. %, The biodegradable polymer can be properly expressed even when blended with about 0.1 to 99.9% by weight of the biodegradable polymer. However, from the viewpoint of the biomass-derived polyester of the present invention, a blend of 99.9 to 40% by weight of the polyester derived from biomass and about 0.1 to 60% by weight of the biodegradable polymer is preferable. A blend of about 5 to 50% by weight of the biodegradable polymer is more preferable.

Examples of natural resins and polysaccharides to be blended with the biomass-derived polyester of the present invention include cellulose acetate, chitosan, cellulose, chromanindene, rosin, lignin, and casein. This kind of natural resin or polysaccharide has the property of being naturally spoiled in the presence of water or air and returning to the soil or becoming a fertilizer. A natural resin and a polysaccharide can be blended in an amount of about 0.1 to 99.9% by weight with respect to 99.9 to 0.1% by weight of the biomass-derived polyester of the present invention. However, in order to maintain not only the biodegradability of the biomass-derived polyester but also various properties such as mechanical properties, water resistance, and weather resistance required for the original plastic, 5 to 50 natural resins and polysaccharides are used. It is more preferable to blend about% by weight.
There is also a problem of compatibility between the biomass-derived polyester of the present invention and natural resins and polysaccharides. If these are solved, the material consisting of the composition of the biomass-derived polyester and natural resin of the present invention can be used as long as the used material is discarded, the natural resin and polysaccharide are It is also effective as a soil conditioner and compost after rotting. This type of polyester composition may be encouraged to be actively and naturally dumped, especially in the soil, which will increase its significance as a green plastic product. Although the specific composition of each resin is disclosed below, it is not specifically limited.
Examples of the aliphatic polyester-based resin include aliphatic polyester-based resins, aliphatic oxycarboxylic acid-based resins, etc., which have aliphatic and / or alicyclic diol units and aliphatic and / or alicyclic dicarboxylic acid units as essential components. Can be mentioned.

  Specific examples of the aliphatic and / or alicyclic diol unit constituting the aliphatic polyester resin include, for example, an ethylene glycol unit, a diethylene glycol unit, a triethylene glycol unit, a polyethylene glycol unit, a propylene glycol unit, and a dipropylene glycol. Unit, 1,3-butanediol unit, 1,4-butanediol unit, 3-methyl-1,5-pentanediol unit, 1,6-hexanediol unit, 1,9-nonanediol unit, neopentyl A glycol unit, a polytetramethylene glycol unit, a 1,4-cyclohexanedimethanol unit, etc. are mentioned. Moreover, these can also be used in mixture of 2 or more types.

  Specific examples of the aliphatic and / or alicyclic dicarboxylic acid units constituting the aliphatic polyester resin include, for example, succinic acid units, oxalic acid units, malonic acid units, glutaric acid units, adipic acid units, and pimelic acid. Examples include units, suberic acid units, azelaic acid units, sebacic acid units, undecanedioic acid units, dodecanedioic acid units, and 1,4-cyclohexanedicarboxylic acid units. Moreover, these can also be used in mixture of 2 or more types.

  Specific examples of the aliphatic oxycarboxylic acid unit constituting the aliphatic oxycarboxylic acid resin include, for example, a glycolic acid unit, a lactic acid unit, a 3-hydroxybutyric acid unit, a 4-hydroxybutyric acid unit, and a 4-hydroxyvaleric acid unit. , 5-hydroxyvaleric acid units and 6-hydroxycaproic acid units. Moreover, these can also be used in mixture of 2 or more types.

  The aliphatic polyester resin may be copolymerized with an oxycarboxylic acid unit such as a lactic acid unit or a 6-hydroxycaproic acid unit. The upper limit of the oxycarboxylic acid unit described above is usually 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, and most preferably based on 100 mol% of all monomer units constituting the polyester. Is 10 mol% or less.

  The aliphatic polyester resin may be copolymerized with a tri- or higher functional alcohol or carboxylic acid. Specifically, trifunctional or more polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, propanetricarboxylic acid, malic acid, citric acid, tartaric acid, hydroxyglutaric acid, hydroxymethylglutaric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, etc. , Polyvalent carboxylic acid and polyvalent oxycarboxylic acid may be copolymerized. Since the amount of the above-mentioned trifunctional or higher polyfunctional compound unit causes generation of gel, the upper limit is usually 5 mol% or less, preferably 100 mol% of all monomer units constituting the polyester. Is 1 mol% or less, more preferably 0.50 mol% or less, and particularly preferably 0.3 mol% or less. On the other hand, when a tri- or higher functional compound is used as a copolymerization component for the purpose of easily producing a polyester having a high degree of polymerization, the lower limit of the amount used to achieve its effect is usually 0.0001 mol% or more, Preferably, it is 0.001 mol% or more, more preferably 0.005 mol% or more, and particularly preferably 0.01 mol% or more. In addition, aliphatic oxycarboxylic acid-based resins include aliphatic and / or alicyclic diol units such as 1,4-butanediol units, succinic acid units, and adipic acid units, and aliphatic and / or alicyclic dicarboxylic acids. Units, trimethylolpropane units, glycerin units, pentaerythritol units, propanetricarboxylic acid units, malic acid units, citric acid units, tartaric acid units and other trifunctional or higher aliphatic polyhydric alcohol units, aliphatic polycarboxylic acid units, Aliphatic polyvalent oxycarboxylic acid units may be copolymerized. The upper limit of the amount of the units described above is usually 90 mol% or less, preferably 70 mol% or less, more preferably 50 mol% or less, based on 100 mol% of all monomer units constituting the polyester.

  In addition, the diol (polyhydric alcohol) unit, dicarboxylic acid (polycarboxylic acid) unit, and oxycarboxylic acid unit constituting the aliphatic polyester-based resin are mainly aliphatic, but biodegradable. Contains a small amount of other components such as aromatic diol (polyhydric alcohol) units, aromatic dicarboxylic acid (polyhydric carboxylic acid) units, aromatic oxycarboxylic acid units, etc. May be. Specific examples of aromatic diol (polyhydric alcohol) units include bisphenol A units and 1,4-benzenedimethanol units. Specific examples of aromatic dicarboxylic acid (polyhydric carboxylic acid) units include terephthalate. Examples thereof include an acid unit, an isophthalic acid unit, a trimellitic acid unit, a pyromellitic acid unit, a benzophenone tetracarboxylic acid unit, a phenyl succinic acid unit, and a 1,4-phenylenediacetic acid unit. Specific examples of the aromatic oxycarboxylic acid unit include a hydroxybenzoic acid unit. The introduction amount of these aromatic compound units is 50 mol% or less, preferably 30 mol% or less in the total polymer.

  The manufacturing method of the aliphatic polyester-based resin can employ a publicly known method, and is not particularly limited. In addition, a urethane bond, an amide bond, a carbonate bond, an ether bond, a ketone bond, or the like may be introduced into the aliphatic polyester resin within a range that does not affect biodegradability. In addition, as the aliphatic polyester, for example, those obtained by increasing the molecular weight or cross-linking using an isocyanate compound, an epoxy compound, an oxazoline compound, an acid anhydride, a peroxide, or the like may be used. Furthermore, the terminal group may be sealed with carbodiimide, an epoxy compound, a monofunctional alcohol or carboxylic acid.

  Examples of polysaccharides include cellulose, modified cellulose such as cellulose acetate, chitin, chitosan, starch, and modified starch. Other degradable resins include polyalkylenes such as polyvinyl alcohol, modified polyvinyl alcohol, polyethylene glycol, and polypropylene glycol. Glycol and the like.

  General-purpose thermoplastic resins include, for example, polyolefin resins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-α-olefin copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyolefin, and polyfluoride. Halogen-containing resins such as vinylidene, styrene resins such as polystyrene and acrylonitrile-butadiene-styrene copolymers, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyisoprene, polybutadiene, acrylonitrile-butadiene copolymer rubber, styrene In addition to elastomers such as butadiene copolymer rubber and styrene-isoprene copolymer rubber, polyamide resins such as nylon 6, 6, nylon 6, polyvinyl acetate, methacrylate resins, polycarbonate Sulfonate-based resin, polyacetal, polyphenylene oxide, polyurethane, and the like. Various properties can also be prepared by using various compatibilizers.

The mixing ratio (weight ratio) of the above-mentioned resin with respect to the polyester of the present invention in the polyester composition is described in detail above, but if the general blending amount common to various resins is clarified as a general term, the present invention The polyester / resin is preferably 99.9 / 0.1 or more and 0.1 / 99.9 or less, more preferably 99/1 or more and 1/99 or less, and most preferably 98/2. It is 2/98 or less.
Moreover, a conventionally well-known various additive can be mix | blended and it can also be set as a composition.
Additives include, for example, crystal nucleating agents, antioxidants, anti-blocking agents, ultraviolet absorbers, light proofing agents, plasticizers, heat stabilizers, colorants, flame retardants, mold release agents, antistatic agents, antifogging agents. And additives for resins such as surface wetting improvers, incineration aids, pigments, lubricants, dispersion aids and various surfactants. These addition amounts are usually 0.01 to 5% by weight in the whole composition. These can also be used as one kind or a mixture of two or more kinds.

Moreover, a conventionally well-known various filler can be mix | blended and it can also be set as a composition. As functional additives, chemical fertilizers, soil conditioners, plant activators and the like can also be added. The filler is roughly classified into an inorganic filler and an organic filler. These can also be used as one kind or a mixture of two or more kinds.
Inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, wallastenite Baked perlite, silicates such as calcium silicate and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate and barium sulfate Is mentioned. Content of an inorganic type filler is 1-80 weight% normally in all the compositions, Preferably it is 3-70 weight%, More preferably, it is 5-60 weight%. Some inorganic fillers, such as calcium carbonate and limestone, have properties of soil improvers, and if a biomass-derived polyester composition containing a large amount of these inorganic fillers is dumped in the soil, Since the inorganic filler after biodegradation remains and functions as a soil conditioner, the significance as a green plastic is increased. In the case of applications such as agricultural materials and civil engineering materials that are dumped in the soil, it is the present invention that polyesters with added chemical fertilizers, soil conditioners, plant activators, etc. are used as molded articles. This greatly increases the usefulness of polyester.

Examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These can be used as one kind or a mixture of two or more kinds. The addition amount of the organic filler is usually 0.01 to 70% by weight in the entire composition. In particular, this organic filler filler has a role as a green plastic because the organic filler remains in the soil after biodegradation of the polyester composition and also serves as a soil conditioner and compost.
For the preparation of the composition, all conventionally known mixing / kneading techniques can be applied. As the mixer, a horizontal cylindrical type, V-shaped, double-cone type mixer, a blender such as a ribbon blender or a super mixer, various continuous mixers, or the like can be used. Moreover, as a kneading machine, a batch type kneading machine such as a roll or an internal mixer, a single-stage type, a two-stage type continuous kneading machine, a twin screw extruder, a single screw extruder, or the like can be used. Examples of the kneading method include a method in which various additives, fillers, and thermoplastic resins are added and blended when heated and melted. In addition, blending oils and the like can be used for the purpose of uniformly dispersing the various additives.

  The polyester and the composition thereof according to the present invention can be subjected to various molding methods applied to general-purpose plastics. For example, compression molding (compression molding, laminate molding, stampable molding), injection molding, extrusion molding or coextrusion molding (film molding by inflation method or T-die method, laminate molding, sheet molding, pipe molding, electric wire / cable molding, irregular shape Material molding), hollow molding (various blow molding), calendar molding, foam molding (melt foam molding, solid phase foam molding), solid molding (uniaxial stretch molding, biaxial stretch molding, roll rolling molding, stretch-oriented nonwoven fabric molding, Examples thereof include thermoforming [vacuum forming, pressure forming], plastic working), powder forming (rotary forming), various non-woven fabric forming (dry method, adhesion method, entanglement method, spunbond method, etc.).

In addition, for various purposes such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction / wear / lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. It is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.).
By such a molding method, single layer film, multilayer film, stretched film, shrink film, laminate film, single layer sheet, multilayer sheet, stretched sheet, pipe, electric wire / cable, monofilament, multifilament, various nonwoven fabrics, flat yarn, Various molded articles such as staples, crimped fibers, drawn tapes and bands, striped tapes, split yarns, composite fibers, blow bottles, foams, and the like can be obtained. Molded products obtained include various types of films such as shopping bags, garbage bags, agricultural films, cosmetic containers, detergent containers, food containers, bleach containers, and other containers, fishing lines, fishing nets, ropes, binding materials, surgical threads. It is expected to be used for applications such as sanitary cover stock materials, cold storage boxes, cushioning materials, medical materials, electrical equipment materials, home appliance housings, and automotive materials.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples, unless the summary is exceeded.
The characteristic values in the following examples were measured by the following method. Moreover, ppm in this invention is mass ppm.
Dilute solution viscosity (reduced viscosity): Polyester is dissolved in phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) to a concentration of 0.5 g / dL, and the solution is a viscosity tube in a thermostatic bath at 30 ° C. The time t (sec) for dropping was measured. Further, the time t ₀ (sec) during which only the solvent falls was measured, and the reduced viscosity η _sp / C (= (t−t ₀ ) / t ₀ · C) at 30 ° C. was calculated (C is the concentration of the solution).

Nitrogen atom content: A sample of 10 mg was taken into a quartz boat, the sample was burned using a total nitrogen analyzer (TN-10 manufactured by Mitsubishi Chemical Corporation), and determined by a chemiluminescence method.
Terminal carboxyl group amount: The value obtained by dissolving the obtained polyester in benzyl alcohol and titrating with 0.1 N NaOH, which is the carboxyl group equivalent per 1 × 10 ⁶ g.
YI value: Measured based on the method of JIS K7105.

Reference example 1
<Construction of vector for gene disruption>
(A) Extraction of Bacillus subtilis genomic DNA In 10 mL of LB medium [composition: tryptone 10 g, yeast extract 5 g, NaCl 5 g dissolved in distilled water 1 L], Bacillus subtilis ISW1214 is cultured until the late logarithmic growth phase, The cells were collected. The obtained cells were suspended in 0.15 mL of a 10 mM NaCl / 20 mM Tris buffer (pH 8.0) / 1 mM EDTA · 2Na solution containing lysozyme at a concentration of 10 mg / mL.

  Next, proteinase K was added to the suspension so that the final concentration was 100 μg / mL, and the mixture was incubated at 37 ° C. for 1 hour. Further, sodium dodecyl sulfate was added to a final concentration of 0.5%, and the mixture was incubated at 50 ° C. for 6 hours for lysis. To this lysate, add an equal amount of phenol / chloroform solution, shake gently at room temperature for 10 minutes, and then centrifuge (5,000 × g, 20 minutes, 10-12 ° C.) to obtain a supernatant. The fraction was collected and sodium acetate was added to a concentration of 0.3 M, and then twice as much ethanol was added and mixed. The precipitate collected by centrifugation (15,000 × g, 2 minutes) was washed with 70% ethanol and then air-dried. To the obtained DNA, 5 mL of a 10 mM Tris buffer (pH 7.5) -1 mM EDTA · 2Na solution was added and left overnight at 4 ° C., and used as template DNA for subsequent PCR.

(B) Amplification and cloning of SacB gene by PCR The acquisition of Bacillus subtilis SacB gene is based on the already reported base sequence of the gene (GenBank Database Accession No. X02730) using the DNA prepared in (A) as a template. This was performed by PCR using the synthetic DNAs (SEQ ID NO: 1 and SEQ ID NO: 2) designed in (1).

Composition of reaction solution: Template DNA 1 μL, Pfx DNA polymerase (manufactured by Invitrogen) 0.2 μL, 1 × concentration attached buffer, 0.3 μM each primer, 1 mM MgSO ₄ , 0.25 μM dNTPs were mixed to make a total volume of 20 μL.
Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds and 68 ° C. for 2 minutes was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 68 ° C. in the final cycle was 5 minutes.

  Confirmation of the amplified product was carried out by separating by 0.75% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and then visualized by ethidium bromide staining, and a fragment of about 2 kb was detected. The DNA fragment of interest was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN).

  The recovered DNA fragment was phosphorylated at the 5 ′ end with T4 polynucleotide kinase (T4 Polynucleotide Kinase: manufactured by Takara Shuzo), and then ligated with a ligation kit ver. 2 (manufactured by Takara Shuzo Co., Ltd.) was used to bind to the EcoRV site of the E. coli vector (pBluescript II: manufactured by STRATEGENE), and E. coli (DH5α strain) was transformed with the resulting plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium [10 g tryptone, 5 g yeast extract, 5 g NaCl, and 15 g agar dissolved in 1 L distilled water] containing 50 μg / mL ampicillin and 50 μg / mL X-Gal. .

  Clones that formed white colonies on this medium were then transferred to LB agar medium containing 50 μg / mL ampicillin and 10% sucrose and cultured at 37 ° C. for 24 hours. Among these clones, those that could not grow on a medium containing sucrose were subjected to liquid culture by a conventional method, and then plasmid DNA was purified. Strains in which the SacB gene is functionally expressed in E. coli should be unable to grow on sucrose-containing media. The obtained plasmid DNA was cleaved with restriction enzymes SalI and PstI, whereby an inserted fragment of about 2 kb was observed, and the plasmid was named pBS / SacB.

(C) Construction of chloramphenicol resistant SacB vector 500 ng of E. coli plasmid vector pHSG396 (Takara Shuzo: Chloramphenicol resistant marker) was reacted with a restriction enzyme PshBI10 unit at 37 ° C. for 1 hour, followed by phenol / chloroform extraction and ethanol precipitation. It was collected by. After smoothing both ends with Klenow Fragment (manufactured by Takara Shuzo), ligation kit ver. MluI linker (Takara Shuzo) was ligated and circularized using 2 (Takara Shuzo), and Escherichia coli (DH5α strain) was transformed. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 34 μg / mL chloramphenicol. Plasmid DNA was prepared from the obtained clones by a conventional method, and a clone having a restriction enzyme MluI cleavage site was selected and named pHSG396Mlu.

  On the other hand, pBS / SacB constructed in (B) above was cleaved with restriction enzymes SalI and PstI, and the ends were blunted with Klenow fragment. Ligation kit ver. After linking the MluI linker using 2 (Takara Shuzo), a DNA fragment of about 2.0 kb containing the SacB gene was separated and recovered by 0.75% agarose gel electrophoresis. This SacB gene fragment was cleaved with the restriction enzyme MluI, and then the pHSG396Mlu fragment was dephosphorylated with alkaline phosphatase (Alkaline Phosphatase Calf intestine) and ligation kit ver. 2 (manufactured by Takara Shuzo) and transformed into E. coli (DH5α strain). The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 34 μg / mL chloramphenicol. The colonies thus obtained were then transferred to an LB agar medium containing 34 μg / mL chloramphenicol and 10% sucrose and cultured at 37 ° C. for 24 hours. Among these clones, plasmid DNA was purified by a conventional method for those that could not grow on a medium containing sucrose. As a result of analyzing the plasmid DNA thus obtained by MluI digestion, it was confirmed that it had an inserted fragment of about 2.0 kb, and this was named pCMB1.

(D) Acquisition of kanamycin resistance gene The kanamycin resistance gene is obtained by PCR using the DNA of E. coli plasmid vector pHSG299 (Takara Shuzo: Kanamycin resistance marker) as a template and the synthetic DNAs shown in SEQ ID NO: 3 and SEQ ID NO: 4 as primers. Went by.
Composition of reaction solution: Template DNA 1 ng, Pyrobest DNA polymerase (Takara Shuzo) 0.1 μL, 1 × concentration buffer, 0.5 μM each primer, 0.25 μM dNTPs were mixed to make the total volume 20 μL.

Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 62 ° C. for 15 seconds and 72 ° C. for 1 minute 20 seconds was repeated 20 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C. in the final cycle was 5 minutes.
Confirmation of the amplification product was carried out by separating by 0.75% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and then visualized by ethidium bromide staining, and a fragment of about 1.1 kb was detected. The target DNA fragment was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN). The recovered DNA fragment was phosphorylated at the 5 'end with T4 polynucleotide kinase (T4 Polynucleotide Kinase: manufactured by Takara Shuzo).

(E) Construction of kanamycin-resistant SacB vector The approximately 3.5 kb DNA fragment obtained by cleaving pCMB1 constructed in (C) above with restriction enzymes Van91I and ScaI was separated and recovered by 0.75% agarose gel electrophoresis. did. This was mixed with the kanamycin resistance gene prepared in (D) above, and ligated kit ver. 2 (Takara Shuzo) was used for ligation, and Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL kanamycin.

  It was confirmed that the strain grown on this kanamycin-containing medium was unable to grow on the sucrose-containing medium. Moreover, the plasmid DNA prepared from the same strain produced fragments of 354, 473, 1807, and 1997 bp by digestion with the restriction enzyme HindIII. Therefore, it was determined that the structure shown in FIG. 1 was correct, and the plasmid was designated as pKMB1. Named.

Reference example 2
<Preparation of LDH gene disruption strain>
(A) Extraction of Brevibacterium flavum MJ233-ES genomic DNA A medium [urea 2 g, (NH ₄ ) ₂ SO ₄ 7 g, KH ₂ PO ₄ 0.5 g, K ₂ HPO ₄ 0.5 g, MgSO _{4. 7H 2 O 0.5g, FeSO 4 ·} 7H 2 O 6mg, MnSO 4 · 4-5H 2 O6mg, biotin 200 [mu] g, thiamine 100 [mu] g, yeast extract 1g, casamino acid 1g, glucose 20g, dissolved in distilled water 1L] in 10mL Brevibacterium flavum MJ-233 strain was cultured until the late logarithmic growth phase, and genomic DNA was prepared from the obtained cells by the method shown in (A) of Reference Example 1 above.

(B) Cloning of lactate dehydrogenase gene The MJ233 strain lactate dehydrogenase gene was obtained by using the DNA prepared in (A) above as a template and designing it based on the nucleotide sequence of the gene described in JP-A-11-206385. This was performed by PCR using DNA (SEQ ID NO: 5 and SEQ ID NO: 6).
Composition of reaction solution: Template DNA 1 μL, Taq DNA polymerase (Takara Shuzo) 0.2 μL, 1 × concentration attached buffer, 0.2 μM each primer, 0.25 μM dNTPs were mixed to make a total volume of 20 μL.

Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 55 ° C. for 20 seconds and 72 ° C. for 1 minute was repeated 30 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C. in the final cycle was 5 minutes.
Confirmation of the amplification product was performed by separating by 0.75% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and then visualized by ethidium bromide staining, and a fragment of about 0.95 kb was detected. The target DNA fragment was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN).

  The recovered DNA fragment was mixed with a PCR product cloning vector pGEM-TEasy (Promega) and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL ampicillin and 50 μg / mL X-Gal.

Clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then plasmid DNA was purified. By cutting the obtained plasmid DNA with restriction enzymes SacI and SphI, an insert fragment of about 1.0 kb was recognized, and this was named pGEMT / CgLDH.
(C) Construction of plasmid for disrupting lactate dehydrogenase gene The coding region of lactate dehydrogenase consisting of about 0.25 kb was excised by cutting the pGEMT / CgLDH prepared in (B) above with restriction enzymes EcoRV and XbaI. The ends of the remaining approximately 3.7 kb DNA fragment were blunted with Klenow fragment, and ligated kit ver. 2 (manufactured by Takara Shuzo Co., Ltd.) and transformed into E. coli (DH5α strain). The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL ampicillin. The strain grown on this medium was subjected to liquid culture by a conventional method, and then the plasmid DNA was purified. By cutting the obtained plasmid DNA with restriction enzymes SacI and SphI, a clone in which an insert fragment of about 0.75 kb was recognized was selected and named pGEMT / ΔLDH.

  Next, a DNA fragment of about 0.75 kb generated by cleaving the above pGEMT / ΔLDH with restriction enzymes SacI and SphI is separated and recovered by 0.75% agarose gel electrophoresis, and a lactate dehydrogenase gene fragment containing a defective region Was prepared. This DNA fragment was mixed with pKMB1 constructed in Reference Example 1 cut with restriction enzymes SacI and SphI, and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL kanamycin and 50 μg / mL X-Gal.

  Clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then plasmid DNA was purified. The obtained plasmid DNA was cleaved with restriction enzymes SacI and SphI, and a plasmid with an inserted fragment of about 0.75 kb was selected and named pKMB1 / ΔLDH (FIG. 2).

(D) Preparation of lactate dehydrogenase gene disruption strain derived from Brevibacterium flavum MJ233-ES strain Plasmid DNA used for transformation of Brevibacterium flavum MJ-233 strain was obtained by the calcium chloride method (Journal of) using pKMB1 / ΔLDH. (Molecular Biology, 53, 159, 1970).

  The Brevibacterium flavum MJ233-ES strain was transformed by the electric pulse method (Res. Microbiol., Vol. 144, p. 181-185, 1993), and the obtained transformant was treated with 50 μg / mL of kanamycin. LBG agar medium containing [tryptone 10 g, yeast extract 5 g, NaCl 5 g, glucose 20 g, and agar 15 g dissolved in 1 L of distilled water] was smeared.

  Since the strain grown on this medium is a plasmid in which pKMB1 / ΔLDH cannot be replicated in Brevibacterium flavum MJ233-ES, the lactate dehydrogenase gene of the plasmid and Brevibacterium flavum MJ-233 strain As a result of homologous recombination with the same gene on the genome, the kanamycin resistance gene and SacB gene derived from the plasmid should be inserted on the same genome.

Next, the homologous recombination strain was subjected to liquid culture in an LBG medium containing kanamycin 50 μg / mL. A portion equivalent to about 1 million cells of this culture was smeared on a 10% sucrose-containing LBG medium. As a result, about 10 strains that were considered to be sucrose-insensitive due to elimination of the SacB gene by the second homologous recombination were obtained.
Among the strains thus obtained, those in which the lactate dehydrogenase gene is replaced with a mutant derived from pKMB1 / ΔLDH and those in which the wild type is restored are included. Confirmation of whether the lactate dehydrogenase gene is mutant or wild type can be easily confirmed by subjecting the cells obtained by liquid culture in LBG medium to direct PCR reaction and detecting the lactate dehydrogenase gene. it can. When the lactate dehydrogenase gene is analyzed using primers (SEQ ID NO: 7 and SEQ ID NO: 8) for PCR amplification, a wild-type DNA fragment of 720 bp and a mutant type having a deletion region should have a DNA fragment of 471 bp.

  As a result of analyzing the strain that became insensitive to sucrose by the above method, a strain having only the mutant gene was selected, and the strain was named Brevibacterium flavum MJ233 / ΔLDH.

(E) Confirmation of lactate dehydrogenase activity The Brevibacterium flavum MJ233 / ΔLDH strain prepared in (D) above was inoculated in medium A and cultured with shaking aerobically at 30 ° C. for 15 hours. The obtained culture was centrifuged (3,000 × g, 4 ° C., 20 minutes) to recover the bacterial cells, and then sodium-phosphate buffer [composition: 50 mM sodium phosphate buffer (pH 7.3)]. Washed with.

  Next, 0.5 g (wet weight) of washed cells was suspended in 2 mL of the sodium-phosphate buffer, and the cells were crushed by applying an ultrasonic crusher (manufactured by Branson) under ice cooling. The crushed material was centrifuged (10,000 × g, 4 ° C., 30 minutes), and the supernatant was obtained as a crude enzyme solution. As a control, a crude enzyme solution of Brevibacterium flavum MJ233-ES strain was similarly prepared and subjected to the following activity measurement.

Confirmation of the lactate dehydrogenase enzyme activity was carried out by measuring the oxidation of coenzyme NADH to NAD ⁺ as a change in absorbance at 340 nm with the production of lactic acid using pyruvate as a substrate for both crude enzyme solutions [L. Kanarek and R.K. L. Hill, J.M. Biol. Chem. 239, 4202 (1964)]. The reaction was carried out at 37 ° C. in the presence of 50 mM potassium-phosphate buffer (pH 7.2), 10 mM pyruvic acid and 0.4 mM NADH. As a result, the lactate dehydrogenase activity in the crude enzyme solution prepared from Brevibacterium flavum MJ233 / ΔLDH was 10 minutes compared to the lactate dehydrogenase activity in the crude enzyme solution prepared from Brevibacterium flavum MJ233-ES strain. 1 or less.

Reference example 3
<Construction of Coryneform Bacterial Expression Vector>
(A) Preparation of promoter fragment for coryneform bacteria A DNA fragment (hereinafter referred to as TZ4 promoter) described in SEQ ID NO: 4 of JP-A-7-95891 reported to have a strong promoter activity in coryneform bacteria. I decided to use it. This promoter fragment was obtained by using the Brevibacterium flavum MJ233 genomic DNA prepared in (A) of Reference Example 2 as a template and designing it based on the sequence described in SEQ ID NO: 4 of JP-A-7-95891. This was performed by PCR using DNA (SEQ ID NO: 9 and SEQ ID NO: 10).

Composition of reaction solution: Template DNA 1 μL, PfxDNA polymerase (manufactured by Invitrogen) 0.2 μL, 1 × concentration attached buffer, 0.3 μM each primer, 1 mM MgSO ₄ , 0.25 μM dNTPs were mixed to make a total volume of 20 μL.
Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds, and 72 ° C. for 30 seconds was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute and 20 seconds, and the heat retention at 72 ° C. in the final cycle was 2 minutes.

  The amplification product was confirmed by separation by 2.0% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and visualization by ethidium bromide staining, and a fragment of about 0.25 kb was detected. The DNA fragment of interest was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN).

  The recovered DNA fragment was phosphorylated at the 5 ′ end with T4 polynucleotide kinase (T4 Polynucleotide Kinase: manufactured by Takara Shuzo), and then ligated with a ligation kit ver. 2 (Takara Shuzo) was used to bind to the SmaI site of E. coli vector pUC19 (Takara Shuzo), and Escherichia coli (DH5α strain) was transformed with the resulting plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL ampicillin and 50 μg / mL X-Gal.

Six clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then the plasmid DNA was purified and the nucleotide sequence was determined. Among them, a clone in which the TZ4 promoter was inserted so as to have a transcriptional activity in the reverse direction to the lac promoter of pUC19 was selected and named pUC / TZ4.
Next, a DNA fragment prepared by cleaving pUC / TZ4 with restriction enzymes BamHI and PstI is composed of synthetic DNA (SEQ ID NO: 11 and SEQ ID NO: 12) phosphorylated at the 5 ′ end, and BamHI and A DNA linker having a sticky end against PstI was mixed, and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. This DNA linker contains a ribosome binding sequence (AGGAGG) and a cloning site (PacI, NotI, ApaI in this order from the upstream).

Clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then plasmid DNA was purified. From the obtained plasmid DNA, one that was cleaved by the restriction enzyme NotI was selected and named pUC / TZ4-SD.
The thus constructed pUC / TZ4-SD was cleaved with the restriction enzyme PstI, blunted with Klenow fragment, and then cleaved with the restriction enzyme KpnI to give a promoter fragment of about 0.3 kb. Separated and collected by 0% agarose gel electrophoresis.

(B) Construction of Coryneform Bacterial Expression Vector pHSG298par-rep described in JP-A-12-93183 is used as a plasmid that can stably replicate independently in coryneform bacteria. This plasmid comprises a replication region and a region having a stabilizing function of the natural plasmid pBY503 possessed by Brevibacterium stachynis IFO12144, a kanamycin resistance gene derived from the Escherichia coli vector pHSG298 (Takara Shuzo), and a replication region of Escherichia coli. The DNA prepared by cleaving pHSG298par-rep with the restriction enzyme SseI, blunting the ends with Klenow fragment, and then cleaving with the restriction enzyme KpnI is mixed with the TZ4 promoter fragment prepared in (A) above and ligated. Kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL kanamycin.
The strain grown on this medium was subjected to liquid culture by a conventional method, and then the plasmid DNA was purified. From the obtained plasmid DNA, one that was cleaved by the restriction enzyme NotI was selected, and the plasmid was named pTZ4 (construction procedure is shown in FIG. 3).

Reference example 4
<Preparation of a strain with enhanced pyruvate carboxylase activity>
(A) Acquisition of pyruvate carboxylase gene The acquisition of pyruvate carboxylase gene derived from Brevibacterium flavum MJ233 strain is a corynebacteria in which the entire genome sequence has been reported using the DNA prepared in (A) of Reference Example 2 as a template. Um Glutamicum It was performed by PCR using a synthetic DNA (SEQ ID NO: 13 and SEQ ID NO: 14) designed based on the sequence of the gene of ATCC13032 strain (GenBank Database Accession No. AP005276).

Composition of reaction solution: Template DNA 1 μL, PfxDNA polymerase (manufactured by Invitrogen) 0.2 μL, 1 × concentration attached buffer, 0.3 μM each primer, 1 mM MgSO ₄ , 0.25 μM dNTPs were mixed to make a total volume of 20 μL.
Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds and 68 ° C. for 4 minutes was repeated 35 times. However, the heat retention at 94 ° C in the first cycle was 1 minute 20 seconds, and the heat retention at 68 ° C in the final cycle was 10 minutes. After completion of the PCR reaction, 0.1 μL of Takara Ex Taq (Takara Shuzo) was added, and the mixture was further incubated at 72 ° C. for 30 minutes.

  Confirmation of the amplification product was carried out by separating by 0.75% agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis and then visualized by ethidium bromide staining, and a fragment of about 3.7 kb was detected. The DNA fragment of interest was recovered from the gel using a QIAQuick Gel Extraction Kit (manufactured by QIAGEN).

  The recovered DNA fragment was mixed with a PCR product cloning vector pGEM-TEasy (Promega) and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL ampicillin and 50 μg / mL X-Gal.

Clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then plasmid DNA was purified. By cutting the obtained plasmid DNA with restriction enzymes PacI and ApaI, an insertion fragment of about 3.7 kb was observed, which was designated as pGEM / MJPC.
The base sequence of the insert fragment of pGEM / MJPC was determined using a base sequencing device (Model 377XL) manufactured by Applied Biosystems and a Big Dye Terminator cycle sequence kit ver3. The resulting DNA base sequence and deduced amino acid sequence are set forth in SEQ ID NO: 15. Only the amino acid sequence is shown in SEQ ID NO: 16. Since this amino acid sequence shows extremely high homology (99.4%) with that derived from Corynebacterium glutamicum ATCC13032, the insert of pGEM / MJPC is a pyruvate carboxylase gene derived from Brevibacterium flavum MJ233. I determined that there was.

(B) Construction of Pyruvate Carboxylase Activity Enhancement Plasmid A pyruvate carboxylase gene fragment consisting of about 3.7 kb generated by cleaving the pGEM / MJPC prepared in (A) above with restriction enzymes PacI and ApaI It was separated and collected by% agarose gel electrophoresis.
This DNA fragment was mixed with pTZ4 constructed in Reference Example 3 cleaved with restriction enzymes PacI and ApaI, and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL kanamycin.

The strain grown on this medium was subjected to liquid culture by a conventional method, and then the plasmid DNA was purified. The obtained plasmid DNA was cleaved with restriction enzymes PacI and ApaI, and a plasmid with an inserted fragment of about 3.7 kb was selected and named pMJPC1 (FIG. 4).
(C) Transformation into Brevibacterium flavum MJ233 / ΔLDH strain Plasmid DNA for transformation with pMJPC1 capable of replicating in Brevibacterium flavum MJ233 strain is the Escherichia coli (DH5α strain transformed with (B) above. ).

  Transformation into Brevibacterium flavum MJ233 / ΔLDH strain was performed by the electric pulse method (Res. Microbiol., Vol. 144, p. 181-185, 1993), and the obtained transformant was kanamycin 50 μg / mL. In an LBG agar medium [tryptone 10 g, yeast extract 5 g, NaCl 5 g, glucose 20 g, and agar 15 g dissolved in 1 L of distilled water].

From the strain grown on this medium, liquid culture was performed by a conventional method, and then plasmid DNA was extracted and analyzed by restriction enzyme digestion. As a result, it was confirmed that the strain retained pMJPC1. The strain was named as bacterial flavum MJ233 / PC / ΔLDH strain.
(D) Pyruvate carboxylase enzyme activity The transformant Brevibacterium flavum MJ233 / PC / ΔLDH strain obtained in (C) above was cultured overnight in 100 ml of A medium containing 2% glucose and 25 mg / L kanamycin. . The obtained cells were collected, washed with 50 ml of 50 mM potassium phosphate buffer (pH 7.5), and resuspended in 20 ml of the same composition. The suspension was crushed with SONIFIER350 (manufactured by BRANSON), and the centrifuged supernatant was used as a cell-free extract. The pyruvate carboxylase activity was measured using the obtained cell-free extract. Measurement of enzyme activity is 100 mM Tris / HCl buffer (pH 7.5), 0.1 mg / 10 ml biotin, 5 mM magnesium chloride, 50 mM sodium hydrogen carbonate, 5 mM sodium pyruvate, 5 mM sodium adenosine triphosphate, 0.32 mM NADH , 20 units / 1.5 ml malate dehydrogenase (manufactured by WAKO, derived from yeast) and a reaction solution containing the enzyme at 25 ° C. 1 U was defined as the amount of enzyme that catalyzes the decrease of 1 μmol NADH per minute. The specific activity in the cell-free extract in which pyruvate carboxylase was expressed was 0.2 U / mg protein. It should be noted that pyruvate carboxylase activity was not detected by this activity measurement method in cells obtained by similarly culturing the parent strain MJ233 / ΔLDH strain using A medium.

Reference Example 5
<Preparation of fermentation broth>
Urea: 4 g, ammonium sulfate: 14 g, monopotassium phosphate: 0.5 g, dipotassium phosphate 0.5 g, magnesium sulfate heptahydrate: 0.5 g, ferrous sulfate heptahydrate: 20 mg, sulfuric acid Manganese hydrate: 20 mg, D-biotin: 200 μg, thiamine hydrochloride: 200 μg, yeast extract: 1 g, casamino acid: 1 g, and distilled water: 1000 mL of medium in a 500 mL Erlenmeyer flask, 120 ° C., 20 minutes Heat sterilized. This was cooled to room temperature, 4 mL of 50% glucose aqueous solution sterilized in advance and 50 μL of sterile 5% kanamycin aqueous solution were added, and inoculated with Brevibacterium flavum MJ233 / PC / ΔLDH prepared in Reference Example 4 (C). The seed culture was performed at 30 ° C. for 24 hours.

  Urea: 12 g, ammonium sulfate: 42 g, monopotassium phosphate: 1.5 g, dipotassium phosphate 1.5 g, magnesium sulfate heptahydrate: 1.5 g, ferrous sulfate heptahydrate: 60 mg, sulfuric acid Manganese hydrate: 60 mg, D-biotin: 600 μg, thiamine hydrochloride: 600 μg, yeast extract 3 g, casamino acid 3 g, antifoaming agent (Adecanol LG294: manufactured by Asahi Denka): 1 mL and distilled water: 2500 mL of a medium of 5 L It put into the fermenter and sterilized by heating at 120 ° C for 20 minutes. After cooling this to room temperature, 500 mL of a 12% aqueous glucose solution sterilized in advance was added, and the whole amount of the above-mentioned seed culture solution was added thereto, and the mixture was kept at 30 ° C. Main culture was performed at aeration of 500 mL / min and stirring at 500 rpm. After 12 hours, glucose was almost consumed.

Magnesium sulfate heptahydrate: 1.5 g, ferrous sulfate heptahydrate: 60 mg, manganese sulfate hydrate: 60 mg, D-biotin: 600 μg, thiamine hydrochloride: 600 μg, antifoam (Adecanol LG294 : Manufactured by Asahi Denka): 5 ml and distilled water: 1.5 L of a medium was placed in a 3 L Erlenmeyer flask and sterilized by heating at 120 ° C. for 20 minutes. After cooling to room temperature, microbial cells collected by centrifugation at 10,000 g for 5 minutes were added to the culture solution obtained by the above main culture. D. It was resuspended so that (660 nm) was 60. 1.5 L of this suspension and 1.5 L of a 20% glucose solution sterilized in advance were mixed in a 5 L jar fermenter, and kept at 35 ° C. The pH was kept at 7.6 using 2M ammonium carbonate, and the reaction was conducted with aeration at 500 mL / min and stirring at 300 rpm. About 50 hours after the start of the reaction, glucose was almost consumed. 57 g / L of succinic acid was accumulated. This fermentation broth was separated into cells and supernatant by centrifugation at 10,000 g for 5 minutes and ultrafiltration (NTU-3000-C1R manufactured by Nitto Denko Corporation).
By performing the above operation 30 times, 103 L of succinic acid fermentation broth supernatant could be obtained.

<Purification of succinic acid from succinic acid fermentation broth>
103 L (succinic acid content 5.87 kg) of the succinic acid fermentation supernatant obtained as described above was concentrated in a stirred tank equipped with a jacket while reducing the pressure, and the concentration of succinic acid was 32.9% and ammonia. 11.9% concentrate: 17.8 kg (calculated value) was obtained. To this, 8.58 kg of acetic acid (manufactured by Daicel Chemical Industries) was added and cooled to 30 ° C., 4.0 kg of methanol (manufactured by Kishida Chemical Co., Ltd.) was added, cooled to 15 ° C. and stirred for 1 hour, and then at 20 ° C. Stirring was continued for 4 hours.

Crystals were precipitated and filtered with a centrifugal filter to obtain 4.95 kg of crystals containing 74.6% oxalic acid, 3.5% acetic acid and 12.2% ammonia.
4.9 kg of crystals obtained in 11.3 kg of acetic acid were added, dissolved at 85 ° C., and immediately cooled to 20 ° C. Crystals were already precipitated, but the mixture was further stirred for 3 hours, and then filtered with a centrifugal filter. Crystals containing oxalic acid 87.9%, acetic acid 8.4%, and ammonia 0.6% 2.44 kg was obtained.

The obtained crystals were washed with 3.5 L of demineralized water cooled to 5 ° C., and filtered through a centrifugal filter. As a result, 90% oxalic acid, 1.7% acetic acid, 0.05% ammonia (approximately 500 ppm) ) Containing 2.08 kg of crystals was obtained.
This crude oxalic acid crystal (2.0 kg) was dissolved in 28.5 L of demineralized water, and passed through a tower filled with 1 L of ion exchange resin (SK1BH, manufactured by Mitsubishi Chemical Corporation) at SV = 2, and approximately 33 L of processing solution. Got. This was concentrated to approximately 5.2 L while continuously feeding it to a rotary evaporator under reduced pressure. Crystals had already precipitated at this stage. Further, after cooling to 5 ° C. and continuing stirring for 2 hours, this was filtered to obtain 1.76 kg of crystals of 96.7% oxalic acid. When this was dried with a vacuum dryer, 1.68 kg of oxalic acid could be obtained.

<Production of 1,4-butanediol>
1,4-butanediol was obtained by a known method using the biomass resource-derived succinic acid obtained by the method as described above. Such 1,4-butanediol was obtained, for example, by the following method.
A mixed solution of 100 parts by weight of biomass resource-derived succinic acid, 317 parts by weight of methanol and 2 parts by weight of concentrated sulfuric acid (97%) was stirred for 2 hours under reflux. After cooling the reaction solution, 3.6 parts by weight of sodium bicarbonate was added, and the reaction solution was stirred at 60 ° C. for 30 minutes. Distillation under normal pressure and the distillation residue were filtered and then distilled under reduced pressure to obtain dimethyl succinate (yield 93%). In the presence of 15 parts by weight of CuO-ZnO catalyst (T-8402, manufactured by Zude Chemie), 100 parts by weight of the obtained dimethyl succinate was added to an autoclave (Hastelloy C) having a volume capacity about 4 times that of the charged dimethyl succinate. The temperature was raised to 230 ° C. over 1 hour while stirring under pressure of 5 MPa using hydrogen. Thereafter, the reaction solution was stirred for 9 hours at 230 ° C. under a hydrogen pressure of 15 MPa. After the reaction solution was cooled, degassing was performed. The catalyst was removed from the reaction solution by filtration. The filtrate was distilled under reduced pressure to obtain purified 1,4-butanediol (yield 81%). The produced purified 1,4-butanediol contained 0.7 ppm of nitrogen atoms, but did not contain sulfur atoms. Further, 1,4-butanediol contained 1000 ppm of 2- (4-hydroxybutyloxy) tetrahydrofuran as an oxidation product.

In the present invention, the reduced viscosity was measured under the following measurement conditions.
[Reduced viscosity (ηsp / c) measurement conditions]
Viscosity tube: Ubbelohde viscosity tube Measurement temperature: 30 ° C
Solvent: Phenol / tetrachloroethane (1: 1 weight ratio) solution Polyester concentration: 0.5 g / dl

<Production of polyester using biomass resource-derived succinic acid with a nitrogen atom content of 5 ppm>
Example 1
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression, 100 parts by weight of biomass resource-derived succinic acid having a nitrogen atom content of 5 ppm (YI = 2.5), manufactured by Mitsubishi Chemical Corporation Nitrogen was charged with 88.5 parts by weight of technical grade 1,4-butanediol, 0.37 parts by weight of malic acid, and 5.4 parts by weight of an aqueous 88% lactic acid solution in which 0.98% by weight of germanium dioxide was previously dissolved as a catalyst. -The inside of the system was put into a nitrogen atmosphere by vacuum replacement.

Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 30 minutes, and at the same time, the pressure was reduced to 0.07 × 10 ³ Pa over 1.5 hours. A white polyester (yellowness YI of 11) was obtained.
The obtained polyester had a nitrogen atom content of 2 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.5, and a terminal carboxyl group content of 26 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

  The obtained polyester was film-formed using an inflation molding machine at a molding temperature of 160 ° C., a blow ratio of 2.5, and a thickness of 20 μm. The formed film was cut into a size of 5 cm × 18 cm and embedded in soil. The weight loss rate of the film at 1 month, 2 months, 3 months, and 6 months was measured, and a biodegradation test was performed. The results are shown in Table 1.

Example 2
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression, 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1, Asahi Kasei Corporation ) Industrial grade adipic acid 32 parts by weight, Mitsubishi Chemical Corporation industrial grade 1,4-butanediol 111.6 parts by weight, malic acid 0.48 parts by weight, and germanium dioxide as the catalyst in advance. 7.2 parts by weight of an 88% aqueous lactic acid solution with 98% by weight dissolved was charged, and the system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution.
Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, the temperature was raised to 230 ° C. over 30 minutes, and at the same time, the pressure was reduced to 0.07 × 10 ³ Pa over 1.5 hours. As a result, the same white polyester as in Example 1 (yellowness YI is 13) was obtained.
The polyester obtained had a reduced viscosity (ηsp / c) of 2.4 and a terminal carboxyl group content of 22 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

Example 3
As raw materials, 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of the nitrogen atom content of Example 1, 81.4 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation, ethylene glycol 6.3 parts by weight, malic acid 0.37 parts by weight, and polycondensation similar to that in Example 2 except that 5.4 parts by weight of 88% aqueous lactic acid solution in which 0.98% by weight of germanium dioxide was previously dissolved was used as a catalyst. A white polyester similar to that of Example 2 was obtained depending on the reaction conditions (reduced viscosity (ηsp / c) was 2.4. The amount of terminal carboxyl groups was 21 equivalents / ton). The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

Example 4
As raw materials, 100 parts by weight of succinic acid derived from a biomass resource containing 5 ppm of the nitrogen atom content of Example 1, 81.4 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation, 1, Example 2 except that 12.3 parts by weight of 4-cyclohexanedimethanol, 0.37 parts by weight of malic acid, and 5.4 parts by weight of 88% aqueous lactic acid solution in which 0.98% by weight of germanium dioxide was dissolved in advance were used as a catalyst. The same white polyester as in Example 2 was obtained under the same polycondensation reaction conditions as described above (reduced viscosity (ηsp / c) was 2.6, terminal carboxyl group content was 17 equivalents / ton). The polymerization reaction time under a reduced pressure of 0.07 × 10 ³ Pa took 3.8 hours. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

Example 5
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression, 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atom in Example 1, Mitsubishi Chemical ( 80.4 parts by weight of industrial grade 1,4-butanediol and 0.37 parts by weight of malic acid were charged, and the system was placed in a nitrogen atmosphere by nitrogen-reduction under reduced pressure.
Next, the temperature in the system was increased to 220 ° C. while stirring, and the reaction was performed at this temperature for 1 hour. Next, after adding a catalyst solution obtained by diluting 0.11 part by weight of tetra-n-butyl titanate to 0.4 part by weight of butanol to the reaction system, the temperature was raised to 230 ° C. over 30 minutes, The pressure was reduced to 0.07 × 10 ³ Pa over time, the reaction was performed at the same degree of pressure for 2 hours to complete the polymerization, and a white polyester similar to Example 1 was obtained (reduced viscosity (ηsp / c ) Is 2.5, and the amount of terminal carboxyl groups is 11 equivalents / ton.) The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

Example 6
In Example 1, a polyester was produced under the same polycondensation reaction conditions as Example 1 except that 0.74 parts by weight of malic acid was charged instead of 0.37 parts by weight of malic acid. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 1.1 hours. The polyester obtained had a reduced viscosity (ηsp / c) of 3.2 and a terminal carboxyl group content of 63 equivalents / ton. The obtained polyester (0.5 g) was dissolved almost uniformly in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature, but a small amount of insoluble matter was observed.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 12 ppm>
Example 7
As a raw material, instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1, 100 parts by weight of succinic acid derived from biomass resources containing 12 ppm of nitrogen atoms (yellowness YI is 7) A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that they were used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2 hours.
The obtained polyester (yellowness YI was 22) had a nitrogen atom content of 3.6 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.3, and a terminal carboxyl group content of 19 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 19 ppm>
Example 8
As a raw material, instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1, 100 parts by weight of succinic acid (yellowness YI is 8) derived from biomass resources containing 19 ppm of nitrogen atoms A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that they were used. The polymerization reaction time under a reduced pressure of 0.07 × 10 ³ Pa was 2.4 hours.
The obtained polyester (yellowness YI was 18) had a nitrogen atom content of 14 ppm, a reduced viscosity (ηsp / c) of 2.5 and a terminal carboxyl group content of 19 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 115 ppm>
Example 9
Example 1 except that 100 parts by weight of succinic acid derived from biomass resources containing 115 ppm of nitrogen atoms was used as a raw material instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1. A polyester was produced under the same polycondensation reaction conditions. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.9 hours.
The obtained polyester (yellowness YI was 23) had a nitrogen atom content of 19 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.5, and a terminal carboxyl group content of 19 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 180 ppm>
Example 10
Example 1 except that 100 parts by weight of succinic acid derived from biomass resources containing 180 ppm of nitrogen atoms was used as a raw material instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1. A polyester was produced under the same polycondensation reaction conditions. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.6 hours.
The obtained polyester (yellowness YI was 37) had a nitrogen atom content of 22 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.6, and a terminal carboxyl group content of 19 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 230 ppm>
Example 11
As a raw material, instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1, 100 parts by weight of succinic acid (yellowness YI is 11) derived from biomass resources containing 230 ppm of nitrogen atoms A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that they were used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.6 hours.
The obtained polyester (yellowness YI was 39) had a nitrogen atom content of 27 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.4, and a terminal carboxyl group content of 19 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using biomass resource-derived succinic acid with a nitrogen atom content of 660 ppm>
Example 12
As a raw material, instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen atoms in Example 1, 100 parts by weight of succinic acid (yellowness YI is 8) derived from biomass resources containing 660 ppm of nitrogen atoms A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that they were used. The polymerization reaction was carried out under reduced pressure of 0.07 × 10 ³ Pa for 2.5 hours, but the resulting polyester was colored dark brown (yellowness YI was 60 or more).
The obtained brown tea had a nitrogen atom content of 54 ppm, a reduced viscosity (ηsp / c) of 0.7, and a terminal carboxyl group content of 139 equivalents / ton. An attempt was made to dissolve the obtained polyester (0.5 g) in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixture) at room temperature, but a considerable amount of undissolved residue was observed.

<Polyester using polyester using biomass resource-derived 1,4-butanediol containing succinic acid derived from a biomass resource with a nitrogen atom content of 5 ppm and nitrogen atom 0.7 ppm>
Example 13
As a raw material, 88.5 parts of 1,4-butanediol derived from biomass resources containing 0.7 ppm of nitrogen atoms instead of 88.5 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation in Example 1 A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that parts by weight were used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 3 hours.
The obtained polyester (yellowness YI was −1) had a nitrogen atom content of 2.1 ppm, a reduced viscosity (ηsp / c) of the polyester of 2.5, and a terminal carboxyl group content of 21 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using petroleum-derived succinic acid not containing nitrogen atoms and biomass resource-derived 1,4-butanediol containing 0.7 ppm nitrogen atoms>
Example 14
As a raw material, instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm of nitrogen in Example 1, petroleum-derived succinic acid (Kawasaki Chemical Co., Ltd., industrial grade (yellowness YI is 2) In place of 88.5 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation in 100 parts by weight, 1,4-butanediol 88.5 derived from a biomass resource containing 0.7 ppm of nitrogen atom A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that parts by weight were used, and the polymerization reaction time under a reduced pressure of 0.07 × 10 ³ Pa was 3.4 hours.
In the obtained polyester (yellowness YI is 7), the nitrogen atom content was 0.5 ppm, the reduced viscosity (ηsp / c) of the polyester was 2.5, and the amount of terminal carboxyl groups was 28 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

<Polyester using petroleum-derived dimethyl terephthalate containing no nitrogen atom and biomass resource-derived 1,4-butanediol containing 0.7 ppm of nitrogen atom>
Example 15
1,4-butanediol 74 derived from biomass resources containing 132 parts by weight of dimethyl terephthalate and 0.7 ppm of nitrogen atoms in a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a vacuum outlet. In addition, 1.7 parts by weight of a 1,4-butanediol solution in which 6% by weight of tetrabutyl titanate was previously dissolved as a catalyst and a catalyst were charged, and the system was placed in a nitrogen atmosphere by nitrogen-vacuum substitution.
Next, the system was heated to 150 ° C. with stirring, and then reacted for 3 hours while raising the temperature to 215 ° C. Next, the temperature was raised to 245 ° C., and the pressure was reduced to 0.07 × 10 ³ Pa at the same time over 1.5 hours. (Yellowness YI is 0.4).
The obtained polyester had a nitrogen atom content of 0.4 ppm, a reduced viscosity (ηsp / c) of the polyester of 1.2, and a terminal carboxyl group content of 21 equivalents / ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.
In the examination of this example, it was found that the higher the nitrogen atom content in the polyester, the higher the biodegradability. On the other hand, it can be seen that as the content of nitrogen atoms increases, the coloration and polymerization inhibition of the polyester tend to become remarkable. In addition, the higher the nitrogen atom content, the more insolubles in organic solvents that are thought to have been generated by some gelation tend to increase. Decrease is caused.

Comparative Example 1
Instead of succinic acid produced by a fermentation method with a nitrogen atom content of 5 ppm in Example 1, polyester was produced using petroleum-derived commercial raw materials. Succinic acid was the same as Example 1 except that Kawasaki Kasei Co., Ltd. industrial grade (Yellowness YI was 2) was used, and 1,4-butanediol was Mitsubishi Chemical Co., Ltd. industrial grade. The polyester similar to Example 1 was manufactured by the method. Nitrogen atoms were not detected in the produced polyester. The obtained polyester was tested in the same manner as in Example 1. The results are shown in Table 1.

<Biodegradability test in soil>
The film produced by the above method was cut into a size of 5 cm × 18 cm and embedded in soil. The weight loss rate of the film at 1 month, 2 months, 3 months, and 6 months was measured. The results are shown in the table.

Comparative Example 2
Example 1 except that 100 parts by weight of succinic acid derived from a biomass resource containing 5000 ppm of nitrogen atoms was used as a raw material instead of 100 parts by weight of succinic acid derived from a biomass resource containing 5 ppm of nitrogen atoms in Example 1. A polyester was produced under the same polycondensation reaction conditions. The polymerization reaction was carried out for 2.5 hours under a reduced pressure of 0.07 × 10 ³ Pa, but no increase in the viscosity of the polyester was observed. The reduced viscosity (ηsp / c) of the polyester was 0.3, and the content of nitrogen atoms was 1200 ppm. An attempt was made to dissolve the obtained polyester (0.5 g) in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixture) at room temperature, but a considerable amount of undissolved residue was observed.

From Table 1, it was confirmed that the polyester using fermented succinic acid has a high biodegradation rate in soil.

Reference Example 6
Examples of molding and physical properties of the polyester and various compositions of the present invention are shown below as reference examples.
<Preparation of composition>
Compositions 1 and 2 were prepared at a blending ratio (% by weight) shown in Table 2. The composition was prepared using a twin-screw extruder (KZW15) manufactured by Technobel at a kneading temperature of 190 ° C.

(Ii) Talc: “PKP-53S” manufactured by Fuji Talc Industry Co., Ltd.
Ecoflex: manufactured by BASF Japan Compositions 3 to 5 were prepared at the blending ratios (% by weight) shown in Table 3. The composition was prepared at a kneading temperature of 190 ° C. using a lab plast mill manufactured by Toyo Seiki Co., Ltd.

<Injection molding>
The samples shown in Table 4 were injection molded using a tabletop injection molding machine and a minimax molding machine manufactured by CSI. The molding temperature was 200 ° C. The physical property evaluation results are also shown in Table 4. All the evaluations were performed in an environment of 23 ° C. and 50% RH.

<Sheet molding>
Using a T-die molding machine, the sheets shown in Table 5 were molded. The molding temperature was 200 ° C., the roll temperature was 30 ° C., and the sheet thickness was 500 μm. The physical property evaluation results are also shown in Table 5. All the evaluations were performed in an environment of 23 ° C. and 50% RH.

<Film forming>
Inflation molding was performed using the samples shown in Table 6. The molding temperature was 160 ° C., the blow ratio was 2.5, and the film thickness was 20 μm. The physical property evaluation results are also shown in Table 6. All the evaluations were performed in an environment of 23 ° C. and 50% RH.

<Foam molding>
The polyester of the present invention was press-molded at 190 ° C. and 10 MPa to produce a sheet having a thickness of 1 mm. The obtained sheet was charged in a pressure vessel with a valve in a solid state, and the temperature in the pressure vessel was heated to 100 ° C. using an external heat source, and at the same time, carbon dioxide was charged in the pressure vessel. At this time, the pressure was increased to 15 MPa by pressurizing with a pump. Thereafter, a constant temperature of 100 ° C. and a constant pressure of 15 MPa were maintained for 2 hours. After 2 hours, the pressure vessel valve was fully opened to rapidly release the pressure in the pressure vessel to obtain a foam. The obtained foam had a high closed cell ratio and no foam was produced even when pressed in water.

The birth of the polyester of the present invention and its background will be described in detail. In a large cycle on the ground, in the atmosphere, the birth of the polyester of the present invention is the preservation of the global environment, resource saving, pollution prevention, aesthetic environment protection, new The presence of the polyester can be evaluated from many viewpoints such as the direction of technical development.
The characteristics of the polyester of the present invention are completely different from conventional recognition in terms of its presence in the global environment, compared to conventional underground fossil fuel dependent type, for example, petroleum resource dependent polyester. To do.
In particular, since a so-called diol unit or dicarboxylic acid unit obtained from a natural material vegetated under the global environment of the present atmospheric atmosphere by a method such as fermentation is used as a polyester monomer, the raw material can be obtained very inexpensively. Moreover, since plant production can be artificially and arbitrarily increased, plant raw material production can be dispersed and diversified in various regions and countries, so that there is no risk in raw material supply and stable supply can be achieved. Furthermore, because the cycle from the raw material stage of polyester to the final stage of waste disposal, which is monomer acquisition, polyester synthesis, and biodegradation, is exclusively based on the natural process of the global environment in the atmosphere. The polyester of the invention provides a cycle that gives reliability and a sense of security. It is clear that this is an important background that cannot be ignored in the technological development of polyester, industrial development and expansion of consumer society.

  However, it can be said that the main reason contributing to the birth of the polyester of the present invention is the background that can be said to be a request of an era based on technological progress. Countermeasures against the deterioration of the global environment, including the so-called greenhouse effect caused by carbon dioxide, countermeasures against the danger of oil resources being wasted and depleted, and the extremely important developments in recent years, such as the remarkable development of biotechnology such as fermentation technology Advances in technology have made it possible. First, a method that depends on vegetation in the atmosphere is to absorb a large amount of carbon dioxide in the production of a plant as a raw material, and this absorption amount is defined as Abs. Although some carbon dioxide and thermal energy are released in stages such as plant processing, fermentation, and treatment, diol units or dicarboxylic acid units can be easily produced. Furthermore, when the polymerized polyester of the present invention is buried in the ground, left in water, or left in seawater, it substantially releases water and carbon dioxide by decomposition by microorganisms. Become. If this released amount is Rel, the difference between Abs and Rel is very small. In this sense, the mass balance of carbon dioxide in the atmosphere may be relatively small. Thus, not only is the mass balance of carbon dioxide absorption and release balanced, but it is also advantageous in terms of energy balance. In particular, the vegetation-dependent oriented present invention can suppress the problem of increasing new carbon dioxide in the atmosphere as much as the conventional oriented fossil fuel dependent type.

  Moreover, as a secondary effect, the polyester material of the present invention can be recognized not only in physical properties, structure and function, but also as an environmentally friendly and safe polyester. The process leading to the disappearance of vegetation raw materials, which cannot be expected at all from such fossil fuel-derived polyester, is characterized by potentially holding the feasibility of a recycling society including recycling. This is to provide a polyester manufacturing process with a new circulation type viewpoint, which is different from the conventional fossil fuel-dependent orientation in the manufacturing process of plastic called polyester. This essentially changes the perception of the so-called plastics industry in response to the demands and progress of the times. It can be said that this is a revolution that can be said to be the beginning of a new second-stage plastic era in response to the remarkable development of biotechnology in recent years. This polyester of the present invention greatly enhances the potential evaluation and value, and from a completely new point of view, it contributes significantly to the further expansion, development and consumption of typical polyesters for plastic materials It is.

The polyester of the present invention has an excellent biodegradable function, but is not a material developed only for the purpose of actively dumping it into the ground. It also means that it can be dumped in the soil without hindrance to the environment. For example, it also includes the meaning of changing to soil if left untreated, such as agricultural, forestry and fishery materials such as transplanting seedling pots and civil engineering and building materials such as temporary sandbags. Although the polyester of the present invention has biodegradable properties, it also has the property that it can be recovered as waste plastic by fractional collection and used again as a molding material, which is established in the current consumer society. Of course, even if the molded product molded by using the recovered polyester again as a molding material is dumped into the soil, the biodegradable function appears as in the first molded product. Furthermore, when recovered by a separate recovery system and incinerated, it can be used as a fuel and as a heat energy source without generating harmful substances and odors. Even if consumption increases further, the polyester of the present invention can also take measures against an increase in carbon dioxide and air pollution.

An outline of the construction of pKMB1 is shown. An outline of the construction of pKMB1 / ΔLDH is shown. An outline of the construction of the pTZ vector is shown. An outline of the construction of pMJPC1 is shown.

Claims (18)

In the polyester in which the main repeating unit is a dicarboxylic acid unit and a diol unit, at least one of the dicarboxylic acid and diol, which are raw materials of the polyester, is obtained from biomass resources, and is covalently bonded to the polyester molecule. A biomass resource-derived polyester, wherein a nitrogen atom content in a polyester excluding nitrogen atoms contained in a functional group is 0.01 ppm or more and 1000 ppm or less by mass with respect to the polyester. The biomass resource-derived polyester according to claim 1, wherein the biomass resource is a plant resource. 3. The biomass resource-derived polyester according to claim 1, wherein a nitrogen atom content in the polyester is 0.01 ppm or more and 100 ppm or less by mass ratio with respect to the polyester. The biomass resource-derived polyester according to any one of claims 1 to 3, wherein the nitrogen atom content in the polyester is 0.01 ppm to 50 ppm in terms of mass ratio with respect to the polyester. The biomass resource-derived polyester according to any one of claims 1 to 4, wherein the polyester has a reduced viscosity (ηsp / c) of 0.5 or more. 6. The biomass resource-derived polyester according to any one of claims 1 to 5, wherein the polyester has a reduced viscosity (ηsp / c) of 1.0 or more. The biomass resource-derived polyester according to any one of claims 1 to 6, wherein the YI value of the polyester is -10 or more and 30 or less. The biomass resource-derived polyester according to any one of claims 1 to 7, wherein the dicarboxylic acid is succinic acid derived from biomass resources . The polyester contains at least one trifunctional or higher polyfunctional compound unit selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher oxycarboxylic acid. The biomass resource-derived polyester according to claim 1, wherein the polyester is derived from biomass resources . The content of the trifunctional or higher polyfunctional compound unit is 0.0001 mol% or more and 0.5 mol% or less with respect to 100 mol% of all monomer units constituting the polyester. The biomass resource-derived polyester according to 9, In a method for producing a polyester by reaction of a dicarboxylic acid and a diol, at least one of a dicarboxylic acid raw material and a diol raw material used for the reaction is derived from biomass resources, and the dicarboxylic acid raw material and diol derived from the biomass resources 2. The method for producing a biomass resource-derived polyester according to claim 1, wherein the nitrogen atom content in the raw material is 0.01 ppm or more and 2000 ppm or less in a mass ratio with respect to the total of the raw materials. The method for producing a biomass resource-derived polyester according to claim 11, wherein the nitrogen atom content is 0.01 ppm or more and 1000 ppm or less by mass ratio with respect to the total of the raw materials. The method for producing a biomass resource-derived polyester according to claim 11 or 12, wherein the nitrogen atom content is 0.01 ppm or more and 100 ppm or less by mass ratio with respect to the total of the raw materials.   The reaction is performed in the presence of at least one trifunctional or higher polyfunctional compound selected from the group consisting of a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher functional oxycarboxylic acid. The method for producing a biomass resource-derived polyester according to any one of claims 11 to 13.   The biomass resource origin polyester obtained by the manufacturing method of any one of Claims 11-14. Thermoplastic resin, biodegradable resin, natural resin, or polysaccharide is 0.1 with respect to 99.9 to 0.1 weight% of biomass resource origin polyesters of any one of Claims 1-10 and 15. A biomass resource-derived polyester resin composition characterized by containing ˜99.9% by weight. The molded object formed by shape | molding the biomass resource origin polyester of any one of Claims 1-10 and 15. The molded object formed by shape | molding the biomass resource origin polyester resin composition of Claim 16.