JP4380653B2 - Polyester and method for producing the same - Google Patents

Description

  The present invention relates to a polyester containing a diol unit and a dicarboxylic acid unit as constituent components and a method for producing the same.

  In modern society, paper, plastic, aluminum foil, etc. are used in a wide range of applications such as liquids and powders for various foods, medicines, miscellaneous goods, packaging materials for solids, agricultural materials, and building materials. . In particular, plastics are excellent in strength, water resistance, moldability, transparency, cost, etc., and are used in many applications as bags and containers. Examples of plastics currently used for these applications include polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate. However, molded products made of the above plastics are not biodegraded or hydrolyzed in the natural environment, or the degradation rate is extremely slow, so when they are buried after use, they remain in the soil or are discarded. In some cases, the landscape may be damaged. In addition, even when incinerated, there are problems such as generating harmful gases and damaging the incinerator.

  Therefore, as a means for solving the above-mentioned problems, many studies have been made on biodegradable materials that are decomposed into carbon dioxide gas and water by microorganisms in soil or water. Typical examples of the biodegradable material include aliphatic polyester resins such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate, and aromatic-aliphatic copolyester resins such as polybutylene adipate terephthalate.

  Among them, polylactic acid is one of the most representative polyesters, but the major problem is that the biodegradability rate is extremely slow (Reference Non-Patent Document 1). On the other hand, polybutylene succinate, polybutylene succinate adipate, etc. with mechanical properties similar to polyethylene are aliphatic polyesters with a relatively fast biodegradability rate, biodegrading used molded products, Although there is an advantage that it is easy to compost, the speed is not yet sufficient, and a method for controlling the speed has not been developed.

  By the way, such polyesters are currently produced by polycondensation of raw materials derived from fossil fuel resources, but there are concerns about the recent depletion of fossil fuel resources and an increase in carbon dioxide in the atmosphere on a global scale. From the background of the problem, attention has been focused on methods for deriving these polymer raw materials from biomass resources. These methods are expected to become a particularly important process from the viewpoint of carbon neutral since this resource is a renewable resource.

So far, technologies for producing dicarboxylic acids such as succinic acid and adipic acid from glucose, glucose, cellulose, oils and fats derived from biomass resources using fermentation methods have been developed (Patent Document 1, Non-Patent Document 1, 2 and 3).
However, these processes are processes for producing the desired dicarboxylic acid through steps such as neutralization, extraction, and crystallization after once obtaining the dicarboxylic acid as an organic acid salt by fermentation. In addition to nitrogen atoms contained in biomass resources, there are features that many impurities such as nitrogen atoms derived from fermentation bacteria, ammonia and metal cations are mixed.
Future Materials, Vol. 1, No. 11, p. 31 (2001) Japanese Patent Laid-Open No. 2005-27533 Biotechnology and Bioengineering Symp. No. 17 (1986) 355-363 Journal of the American Chemical Society No. 116 (1994) 399-400 Appl. Microbiol Biotechnol No. 51 (1999) 545-552

  The present inventors have obtained knowledge that conventional biodegradable polyesters do not have sufficient biodegradable speed as biodegradable resins. In addition, regarding the polyester produced from a specific raw material, the present inventors may greatly contribute to environmental problems by developing a method for freely controlling the biodegradability rate according to the use of the polyester. Thought. An object of the present invention is to provide a high-molecular-weight polyester with less coloration that has practical physical properties and can control the biodegradability rate.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the presence of sulfur atoms in a specific range in polyester improves the biodegradation rate of the resin. This means that the biodegradability rate of the resin can be controlled by controlling the content of sulfur atoms in the polyester.
That is, the first feature of the present invention is a polyester comprising a diol unit and a dicarboxylic acid unit as constituents, wherein at least the dicarboxylic acid unit is derived from biomass resources, and the sulfur atom in the polyester It is a biomass resource-derived polyester whose content is 0.0001 ppm or more and 50 ppm or less by mass ratio with respect to the polyester.
The second is the biomass resource-derived polyester according to the first aspect, wherein the content of sulfur atom in the polyester is 0.0001 ppm or more and 5 ppm or less by mass ratio with respect to the polyester.
Third, the biomass resource-derived polyester according to the first or second aspect, wherein the biomass resource is a plant resource.
The fourth is the biomass resource-derived polyester according to any one of the first to third aspects, wherein the reduced viscosity (ηsp / c) of the polyester is 0.5 or more.
The fifth is 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 1.0 or more.

Sixth, the biomass resource-derived polyester according to any one of the first to fifth aspects , wherein the polyester has a YI value of −10 or more and 30 or less.
Seventh, the polyester comprises 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 any one of the first to sixth aspects, wherein the polyester is contained .
Eighth, 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 as described in 7 above .
Ninth is the biomass resource-derived polyester according to any one of the first to eighth aspects , wherein the dicarboxylic acid unit is a succinic acid unit derived from a biomass resource .

Tenth, in a method for producing a polyester by reaction of a dicarboxylic acid and a diol, the dicarboxylic acid used for the reaction is derived from biomass resources, and the sulfur atom content in the dicarboxylic acid is reduced to the dicarboxylic acid. On the other hand, the method for producing a biomass resource-derived polyester according to the first aspect, wherein the mass ratio is 0.01 ppm or more and 100 ppm or less.

The eleventh aspect is the method for producing a biomass resource-derived polyester according to the tenth aspect, wherein the sulfur atom content in the dicarboxylic acid is 0.01 ppm or more and 20 ppm or less by mass ratio with respect to the dicarboxylic acid. is there.
The twelfth 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 oxycarboxylic acid. A method for producing a biomass resource-derived polyester as described in 10 or 11 above, wherein
13th is the biomass resource origin polyester obtained by the manufacturing method in any one of the said 10th-12th .
14th is a thermoplastic resin, biodegradable resin, natural resin, or polysaccharide with respect to 99.9-0.1 weight% of biomass resource origin polyesters in any one of said 1st-9th and 13th. Is a biomass resin- derived polyester resin composition characterized by containing 0.1 to 99.9% by weight.
15th is a molded object formed by shape | molding the biomass resource origin polyester in any one of the said 1st-9th and 13th .
16th is a molded object formed by shape | molding the biomass resource origin polyester resin composition of the said 14th .

  According to the present invention, it is possible to provide a high molecular weight polyester that can control the biodegradability rate, has little coloration, has excellent mechanical properties, and can be used in various applications. In addition, the development of this technique greatly contributes to solving environmental problems, fossil fuel resource depletion problems, etc., and can provide a resin having practical physical properties. In particular, since a so-called diol unit or dicarboxylic acid unit obtained from a natural material vegetated under the present global environment in the atmosphere by a technique such as fermentation is used as a polyester monomer, the raw material can be obtained very inexpensively. 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 carbon dioxide absorption and emission 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 is to provide a new polyester manufacturing process 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 the soil dumping is stopped and incinerated.

Hereinafter, the present invention will be described in detail.
<Polyester>
The polyester which is the subject of the present invention comprises a dicarboxylic acid unit and a diol unit as essential components. In the present invention, at least one of the dicarboxylic acid and diol constituting the dicarboxylic acid unit and the diol unit is preferably derived from biomass resources.
-Dicarboxylic acid unit Examples of the dicarboxylic acid constituting the dicarboxylic acid unit include aliphatic dicarboxylic acids or mixtures thereof, aromatic dicarboxylic acids or mixtures thereof, and mixtures of aromatic dicarboxylic acids and aliphatic dicarboxylic acids. . Among these, those containing an aliphatic dicarboxylic acid as a main component are preferable. The main component referred to in the present invention usually represents 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more with respect to 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, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable from the viewpoint of physical properties of the obtained polymer, and those having succinic acid as a main component are particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more 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, a more preferable biomass resource is a plant resource. , Buckwheat, soybeans, fats and oils, 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 such as Escherichia (US Pat. No. 5,770,435), aerobic bacteria such as Corynebacterium (JP-A-11-113588), Bacillus genus, Rizobium genus, Brevibacterium genus, Arthrobacter genus Anaerobic bacteria (Japanese Patent Application Laid-Open No. 2003-235593), Bacteroides ruminicola, Bacteroides amylophilus, etc. Rumen bacteria, E. coli. coli (J. Bacteriol., 57: 147-158) or E. coli. E. coli strains (Japanese Patent Publication No. 2000-500333, US Pat. No. 6,159,738) 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 its mutant MJ-233 AB-41 strain are respectively 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 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 the electrodialysis of the succinate produced by the fermentation method as described in JP-A-2-283289 or the method of treating with a basic ion exchange resin, 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 JP-A 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 documents such as washing, filtration, drying, etc. 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 nitrogen atoms as impurities due to the purification process including the biomass resource origin, fermentation treatment and neutralization step with acid. Specifically, nitrogen atoms 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-described method is, in terms of atoms, in the dicarboxylic acid, the upper limit is usually 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, Most preferably, it is 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 process.

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. It is a 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.
Moreover, when using the dicarboxylic acid manufactured by the fermentation method, a sulfur atom may be contained by the refinement | purification process including the neutralization process by an acid. Specifically, examples of the impurities containing sulfur atoms include sulfuric acid, sulfate, sulfurous acid, organic sulfonic acid, and organic sulfonate.

  The sulfur atom content contained in the dicarboxylic acid is, in terms of atoms in the dicarboxylic acid, the upper limit is usually 100 ppm or less, preferably 20 ppm or less, more preferably the upper limit is 10 ppm or less, and particularly preferably, the upper limit is 5 ppm or less. Most preferably, the upper limit is 0.5 ppm or less. On the other hand, the lower limit is usually 0.001 ppm or more, preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and particularly preferably 0.1 ppm or more. When the amount is too large, the polymerization reaction tends to be delayed, the resulting polymer partially gels, and the stability of the produced polymer decreases. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous. The sulfur atom content is a value measured by a known elemental analysis method.

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 tanks 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).

The dicarboxylic acid used in the present invention is usually preferably one with little coloring. 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 an extremely high capital investment for its production and requires a great amount of production time. In the present invention, the YI value is a value measured by a method based on JIS K7105.
(2) Diol unit 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- And cyclohexanedimethanol. 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, and these In particular, a mixture mainly composed of 1,4-butanediol or 1,4-butanediol is particularly preferable. The main component here is usually 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more with respect to all diol units.

  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-end 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 a 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, 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 process. .

When using the diol manufactured by the fermentation method, a sulfur atom may be contained by the refinement | purification process including the neutralization process by an acid. In this case, specific examples of impurities containing sulfur atoms include sulfuric acid, sulfurous acid, and organic sulfonates.
The sulfur atom content contained in the diol is, in terms of atoms, in the diol, the upper limit is usually 100 ppm or less, preferably 20 ppm or less, more preferably the upper limit is 10 ppm or less, and particularly preferably, the upper limit is 5 ppm or less. Preferably, the upper limit is 0.5 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually 0.001 ppm or more, preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and particularly preferably 0.1 ppm or more. When the amount is too large, the polymerization reaction tends to be delayed, the resulting polymer partially gels, and the stability of the resulting polymer decreases. On the other hand, the smaller the sulfur atom content, the more preferable it is. However, the purification process becomes complicated and economically disadvantageous. The sulfur atom content is a value measured by a known elemental analysis method.

  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 impurities themselves and the oxidation reaction of the diol promoted by the impurities are suppressed. For example, when 1,4-butanediol is used, diol oxidation production such as 2- (4-hydroxybutyloxy) tetrahydrofuran It is possible to prevent the polyester from being colored by an object.

  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 diol storage temperature 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.

  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, but the polyesters of the present invention are typical ones. As specific examples, the following polyesters can be exemplified.

Polyesters using succinic acid include succinic acid and ethylene glycol polyester, succinic acid and 1,3-propylene glycol polyester, succinic acid and neopentyl glycol polyester, succinic acid and 1,6-hexamethylene glycol. And polyesters of succinic acid and 1,4-butanediol, polyesters of succinic acid and 1,4-cyclohexanedimethanol, and the like.
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 And polyester of oxalic acid and 1,4-butanediol, polyester of oxalic acid and 1,4-cyclohexanedimethanol, and the like.

Examples of polyesters using adipic acid include 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 And polyester of adipic acid and 1,4-butanediol and 1,4-cyclohexanedimethanol of adipic acid.
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.
Specific examples of the bifunctional oxycarboxylic acid include lactic acid, glycolic acid, hydroxybutyric acid, hydroxycaproic acid, 2-hydroxy3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, and 2-hydroxyisocaprone. Examples include acids and caprolactones, and these may be esters of oxycarboxylic acids, lactones, or derivatives of oxycarboxylic acid polymers. These oxycarboxylic acids can be used alone or as a mixture of two or more. 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, readily available lactic acid or glycolic acid is particularly preferable. The form is preferably 30 to 95% because an aqueous solution can be easily obtained. When a bifunctional oxycarboxylic acid is used as a copolymerization component for the purpose of easily producing a polyester having a high degree of polymerization, a desired copolymerized polyester can be produced by adding any bifunctional oxycarboxylic acid during polymerization. Specifically, the lower limit of the amount used to achieve the effect is usually 0.02 mol% or more, preferably 0.5 mol% or more, more preferably 1.0 mol%, based on the raw material monomer. That's it. On the other hand, the upper limit of the amount used is usually 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less.
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.

Specific examples of the trifunctional or higher polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol and the like, and they can be used alone or as a mixture of two 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.
Specific examples of the tri- or higher functional polycarboxylic acid or anhydride thereof include propanetricarboxylic acid, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, and the like. It can also be used as a mixture of two or more.

Specific examples of the tri- or higher functional oxycarboxylic acid include malic acid, hydroxyglutaric acid, hydroxymethylglutaric acid, tartaric acid, citric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, and the like. It can also be used as a mixture of In particular, malic acid, tartaric acid, citric acid and a mixture thereof are preferable because of easy availability.
Specifically, when the embodiment of the polyester is shown, when malic acid is used as the trifunctional oxycarboxylic acid of the copolymer component, for example, a copolymer polyester of succinic acid-1,4-butanediol-malic acid, succinic acid- Adipic acid-1,4-butanediol-malic acid copolyester, succinic acid-1,4-butanediol-malic acid-tartaric acid copolyester, succinic acid-adipic acid-1,4-butanediol-apple Acid-tartaric acid copolyester, succinic acid-1,4-butanediol-malic acid-citric acid copolyester, succinic acid-adipic acid-1,4-butanediol-malic acid-citric acid copolyester It becomes. 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 ,

  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 the polyester of the present invention, a chain extender such as a carbonate compound or a diisocyanate compound can also be used, but the amount thereof is usually a carbonate bond and a urethane bond with respect to all monomer units constituting the polyester, It is 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less. 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 0.06 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 13C 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.

Thus, the polyester of the present invention is a generic term for polyesters, polyesters, copolymer polyesters, chain-extended (coupled) high molecular weight polyesters, and modified polyesters.
In the present invention, a polyester containing substantially no chain extender is preferred. 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.
In the present invention, the polyester terminal group may be sealed with carbodiimide, an epoxy compound, a monofunctional alcohol or carboxylic acid.

<Production method of polyester>
Production of a polyester mainly composed of a diol unit and a dicarboxylic acid unit can be performed by a known technique for producing a polyester. However, it is essential that the polyester in the present invention contains a sulfur atom within a specific range. The polymerization reaction at the time of producing this polyester can set appropriate conditions conventionally employed and is not particularly limited. Specifically, in the case of introducing the dicarboxylic acid component and the diol component, and further an oxycarboxylic acid unit or a trifunctional or higher component, an esterification reaction between the dicarboxylic acid component including these components and the diol component, and It can be produced by a general method of melt polymerization, such as a polycondensation reaction under reduced pressure after transesterification, or a known solution heating dehydration condensation method using an organic solvent. From the viewpoints of performance and simplicity of the production process, a melt polymerization method performed in the absence of a solvent is preferable.

As a method of incorporating a sulfur atom in the polyester, (i) a method of adding a sulfur atom-containing compound to the polymerization reaction system, (ii) a method of using a dicarboxylic acid and / or diol containing a sulfur component as a raw material monomer, etc. However, the method (ii) is preferable for the reason of simplifying the production process.
(I) When using the method which adds the compound containing a sulfur atom to a polymerization reaction system, the timing which mixes the compound containing a sulfur atom will not be specifically limited if polyester is extracted from a polymerization reaction tank. In this case, the sulfur atom-containing compound includes sulfuric acid, sulfate, sulfurous acid, organic sulfonic acid, organic sulfonate, and the like. The amount of the compound used is an amount corresponding to the amount of sulfur atom contained in the polyester. is there.

(Ii) About the method using the dicarboxylic acid and / or diol containing a sulfur component as a raw material monomer, the method using the biomass resource-derived dicarboxylic acid and / or diol described above can be mentioned.
In order to control the sulfur atom content in the polyester, (i) and (ii) may be used in combination.

  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 tank in which the oxygen concentration during the polyester production reaction is controlled to a specific value or less. Polyester may be produced with 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 tube due to impurities such as sulfur components 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.

The amount of diol used in the production of the polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof, but in general during the esterification and / or transesterification and / or polycondensation reactions. Is used in excess of 0.1 to 20 mol%.
The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction.

  As the polymerization catalyst, in general, a compound containing a group 1 to group 14 metal element excluding hydrogen and carbon in the periodic table can be used. 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.

  In these, the metal compound containing titanium, a zirconium, germanium, zinc, aluminum, magnesium, and calcium, and those mixtures are preferable, and especially a titanium compound, a zirconium compound, and a germanium compound are 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.

  Specific examples of the germanium compound include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. In view of price and availability, germanium oxide, tetraethoxygermanium, tetrabutoxygermanium, and the like are preferable, and germanium oxide is particularly preferable.

  The amount of the catalyst used in the case of using a metal compound as these polymerization catalysts, 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 1000 ppm or less, as the amount of metal relative to the produced polyester. More preferably, it is 250 ppm or less, Especially preferably, it is 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.

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 ° C or lower. 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 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 pellets>
After the completion of the polymerization reaction, the polyester extracted in a strand form from the polymerization reaction tank is pelletized using a known fixed or rotary cutter or pelletizer while being cooled or cooled with water, air, or the like, May be stored.

The pellet shape is usually formed into a cylindrical shape or a spherical shape having a circular or elliptical cross section.
The diameter of the polyester pellet is adjusted by adjusting the outlet diameter from the polymerization tank, the strand drawing speed, the take-up speed, the cutting speed, and the like. Specifically, for example, it is adjusted by adjusting the pressure of the reaction tank at the time of extracting the polymer or adjusting the cutting speed of the rotary strand cutter.

  The lower limit (minimum diameter) of the obtained polyester pellets is usually 0.1 mm or more, preferably 0.2 mm or more, more preferably 0.5 mm or more, most preferably 1 mm or more, and the upper limit ( The maximum diameter) is 20 mm or less, preferably 10 mm or less, more preferably 7 mm or less, and most preferably 4 mm or less. If the diameter is too small, deterioration due to hydrolysis during storage of the pellet tends to be remarkable, and if the diameter is too large, the bite during molding tends to be poor and unevenness of the product tends to occur.

  In the polyester pellet of the present invention, the proportion of the powdery body having a diameter of less than 1 mm is preferably 2.0% by weight or less, and the proportion of the powdery body having a diameter of less than 1 mm is 1.0% by weight or less. Is more preferable. When the ratio of the powdery body having a diameter of less than 1 mm is large, the powdery body has poor penetration into the molding machine screw at the time of melt molding, and the residence time in the molding machine becomes long, and the surface area is large. Thermal degradation is likely to occur, and it is mixed as foreign matter such as burns or bumps in the molded body, leading to problems such as a decrease in mechanical strength and poor appearance of the molded body.

In addition, the diameter of the polyester pellet here shows the diameter or length of the cross section of the polyester pellet. Moreover, the cross section of a polyester pellet shows the cross section where the cross-sectional area of the obtained polyester pellet becomes the largest.
In the present invention, the water content in the polyester pellets during storage 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 become complicated and economically disadvantageous, but it will take much time for the drying time, and deterioration of the coloring of the polyester and the formation of bumps will occur. There is a tendency to be caused. On the other hand, when the amount is too large, the polyester tends to be significantly deteriorated due to hydrolysis during storage of the pellets.

  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.

Furthermore, in the present invention, the polyester pellets may be stored in a sealed state because the polyester is easily hydrolyzed by moisture and the properties of the polyester are lowered. The sealed state here means a state in which the dried state of the polyester is maintained.
The sealing method is a method of storing in a space having a sealing function, a method of storing in a bag having a sealing function, a method of covering a sheet having a sealing function with polyester pellets, and a dry atmosphere (dry air And a method of storing in a silo). Among these, it is preferable to store in a bag having a sealing function.

  The bag material is preferably highly airtight, and is preferably a synthetic resin film or sheet. Specific examples include sheets made of polyolefin resins such as polyethylene and polypropylene, and vinyl chloride resins, or those sheets reinforced with films such as polyester and polyamide, and various fiber substrates. These sheets may be laminated with a barrier layer that shields water vapor, oxygen, and the like, if necessary. Examples thereof include a composite film such as polyester / aluminum / polyethylene.

Various packaging materials having such characteristics are commercially available, but those that can be easily sealed by heat sealing are preferable, and are formed into a packaging bag by means of heat fusion and / or sewing.
There is no restriction | limiting in particular in the shape of a packaging bag, Well-known packaging bag shapes, such as flexible containers, such as a flat bag, a gusset bag, a square bottom bag, and a flexible container, are employable. Among these, it is preferable to have a bottom surface in consideration of making the cross-sectional shape of the body portion of the package into a substantially rectangular shape, and gusset bags, square bottom bags, flexible containers, and the like are preferable. And it is more preferable that the shape of the bottom surface is generally rectangular because a package having a substantially rectangular cross-sectional shape can be easily obtained.

Moreover, since the polyester pellet derived from biomass resources is easily contaminated with impurities because it is mixed with impurities, it may be stored in the dark.
The method of shielding light is not particularly limited as long as the polyester is shielded from light. Specifically, the polyester is stored in a space having a light shielding function, or stored in a bag having a light shielding function. The method, the method of covering the sheet | seat provided with the light-shielding function on the polyester pellet, etc. are mentioned. Among these, it is preferable to store in a bag having a light shielding function.

As the degree of light shielding, the upper limit of the illuminance of the space is usually 300 lux or less, preferably 70 lux or less, more preferably 1 lux or less, most preferably 0.001 lux or less, and the lower limit is particularly limited. Not. If the illuminance is too high, the coloring of the polyester tends to be remarkable, and if it is too low, the control is difficult and economically disadvantageous.
The lower limit of the temperature when storing the polyester pellets is −50 ° C. or higher, preferably −30 ° C. or higher, more preferably 0 ° C. or higher, and the upper limit is 80 ° C. or lower, preferably 50 ° C. or lower. More preferably, it is 30 ° C. or lower, but it is most preferable to store at room temperature because a management step is not necessary. If the temperature is too low, the management process becomes complicated and tends to be economically disadvantageous. If it is too high, the polyester tends to deteriorate significantly.

Although the external pressure at the time of storing a polyester pellet is not specifically limited, Usually, it is atmospheric pressure (normal pressure).
You may pelletize the polyester composition mentioned later and preserve | save on the above-mentioned conditions.
<Physical properties of polyester>
In addition, the polyester pellet of this invention is obtained from polyester which shows the following physical properties, and even when it stores, there is little deterioration of the physical property.
The polyester of the present invention not only has many uses to replace general-purpose polymer materials, but also has physical properties such as aliphatic diols and aliphatic dicarboxylic acids such as polybutylene succinate and polybutylene succinate adipate. In the case of polyester, the density is 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. It possesses properties of general-purpose polymers such as strength of 30 to 40 MPa, impact test strength of about 5 to 20 kJ / m ² , and glass transition point of −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.

Here, 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. The presence of the polyester can be evaluated from many viewpoints such as protection and the direction of new technology 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 sense of crisis of wasting and depleting petroleum resources, and, in recent years, the remarkable development of biotechnology such as fermentation technology in recent years Advances in technology have made it possible. First, a method that relies 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 heat energy are released in the stages of plant processing, fermentation, treatment, etc., 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.

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, the sulfur atom is one of the causative substances that particularly affect the acceleration of biodegradation. The present inventors have found the fact that, as a practical polyester, the acceptable sulfur atom content of the polyester is 0.0001 ppm to 50 ppm in terms of atoms.
In view of the fact that the polyester raw material is derived from biomass resources, it is due to a specific situation that some sulfur may be mixed in many processes such as neutralization and purification in the production stage. The presence of sulfur compounds may have a subtle effect on the coloration of polyester and the promotion of biodegradability. On the other hand, sulfur compounds remain in the soil after biodegradation, which may cause soil acidity or environmental pollution. It may not be appropriate. In addition, when the material collected by the separate collection system established in the current consumer society is reused, the mixture of sulfur also affects the coloring and mechanical properties of the polyester. Like other general-purpose plastics, incineration can cause generation of sulfur dioxide, etc., and the presence of sulfur is also restricted in terms of toxicity and bad odor. Considering such a comprehensive situation, it can be said that the maximum allowable sulfur atom content is about 50 ppm.

The reason why the sulfur atom content present in the polyester is 0.0001 ppm to 50 ppm in terms of atoms will be described in more detail. This is because the sulfur atoms mixed in this polyester remain in the polyester, which mainly contains diol units and dicarboxylic acid units derived from biomass resources. Reducing the sulfur content is a preferred embodiment in increasing the polymerization rate and degree of polymerization in polyester polymerization. On the other hand, in order to remove the sulfur amount to a very small amount, for example, 0.0001 or less, not only a very high level of technical operation is required, but also the manufacturing cost is very high. If the influence of the amount of sulfur remaining in the polyester is analyzed, a very small amount of sulfur shows a behavior related to the promotion of biodegradation. Therefore, it is an important problem to be solved for the invention to search for an acceptable range for sulfur mixed in polyester.
When this sulfur compound is present in the polyester as sulfate or sulfite, if the sulfur-containing polyester is biodegraded in a large amount or continuously in the soil, it accumulates due to accumulation. As acidification proceeds monotonically, there are concerns about the effects on microorganisms, the effects on animals and plants, and the environmental pollution of water quality. As a result of analyzing and studying a safe range without losing trust such as safety and security as a green plastic, in the normal use state of the polyester of the present invention, about 0.0001 to 50 ppm is the pH of sulfur. Is found to be in an appropriate range that naturally disappears or recovers by natural purification, and eventually, the maximum is 50 ppm. For example, in a polyester containing about 120 ppm of sulfur atoms, when the polyester containing 300 ppm of sulfur atoms is biodegraded under the condition that the pH of the soil is lowered by 0.2, the pH value is reduced by about 0.5. The soil tends to be significantly acidified according to the atomic content.

  Although the polyester of the present invention has biodegradable properties, the product is recovered by a separate collection system established in the current consumer society in the normal distribution process, and incinerated. May cause generation of SOx such as sulfur dioxide peculiar to sulfur compounds. Therefore, it is necessary to consider the mixing of sulfur atoms from the environmental viewpoint such as toxic and bad odor. When the amount of sulfur contained in the polyester is large, SOx such as sulfur dioxide is generated monotonically in proportion to the amount of sulfur. Even in such incineration disposal, the existence of sulfur atoms can lead to pollution of animals, plants, air, soil, and water quality, so the effects of so-called sulfur naturally disappear or are restored by natural purification. The fact that the appropriate amount of the range is 0.0001 to 50 ppm is found. From the viewpoint of social common sense, sulfur content exceeding 50 ppm, for example, 100 ppm, 250 ppm, etc., is a source of many SOx harmful gases such as sulfur dioxide and is not in an acceptable range.

  More importantly, safety such as taste and toxicity when the polyester of the present invention is used in a bottle, a container, a packaging material of a food product such as a luxury product or a beverage must be considered. 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, sulfur compounds do not act as toxic to the human body in trace amounts, but there is also concern about the effects on odor and taste, so it is necessary to consider the trust of consumers to the maximum. The polyester of the present invention is a material devised to ensure its reliability in consideration of all cases such as molding, molding safety, biodegradation, recovery, and incineration from such production. Considering such circumstances, taking into account such comprehensive circumstances such as polymerization, molding, use of molded articles, biodegradation, and incineration of polyester, it is safe and reliable for people's lives. In order to provide a product, the acceptable range of the sulfur atom content is 30 ppm, 40 ppm, etc., but it can be said that the maximum is about 50 ppm.

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

The melting point of the polyester of the present invention is not particularly limited, but is usually 40 ° C to 270 ° C, preferably 50 ° C to 230 ° C, and more preferably 60 ° C to 130 ° C. These are determined by the above-described components, and it is possible to produce a polyester having a melting point within the above range by appropriately selecting the components.
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 upper limit of the sulfur atom content in the polyester of the present invention is 50 ppm or less, preferably 5 ppm or less, more preferably 3 ppm or less, and most preferably 0.3 ppm or less in terms of atoms. On the other hand, the lower limit is not particularly limited, but is 0.0001 ppm or more, preferably 0.001 ppm or more, more preferably 0.01 ppm or more, particularly preferably 0.05 ppm or more, and most preferably 0. .1 ppm or more.

If the sulfur content is too high, the thermal stability and hydrolysis resistance of the polyester tend to be reduced, and if the amount is too low, the purification cost becomes remarkably high and the polyester tends to be economically disadvantageous.

  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 10,000 ppm or less, preferably 3000 ppm or less, more preferably 1000 ppm or less, and most preferably 500 ppm or less in the polyester. 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.

  The reduced viscosity (ηsp / c) value of the polyester produced according to the present invention is 0.5 or more, and preferably 1.0 or more, more preferably 1.8 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.

  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.

<Polyester composition>
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, a succinic acid unit, an oxalic acid unit, a malonic acid unit, a glutaric acid unit, an adipic acid unit, 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 oxycarboxylic acid units such as lactic acid units and 6-hydroxycaproic acid units. 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 with respect to 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 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. In addition, aliphatic oxycarboxylic acid 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 crosslinking 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 the polysaccharide include cellulose, modified cellulose such as cellulose acetate, chitin, chitosan, starch, and modified starch.
Other degradable resins include polyalkylene glycols such as polyvinyl alcohol, modified polyvinyl alcohol, polyethylene glycol, and polypropylene glycol.

  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. Will increase 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 increases its 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 and 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 products such as staples, crimped fibers, drawn tapes and bands, striped tapes, split yarns, composite fibers, blow bottles, foams, and the like can be obtained. In addition, the obtained molded products are various films such as shopping bags, garbage bags, agricultural films, various containers such as cosmetic containers, detergent containers, food containers, bleach 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 t0 (sec) during which only the solvent falls was measured, and the reduced viscosity ηsp / C (= (t−t0) / t0 · C) at 30 ° C. was calculated (C is the concentration of the solution).

  Sulfur content: About 0.1 g of sample was collected in a platinum boat and burned in a quartz tube tubular furnace (AQF-100 (concentration system) manufactured by Mitsubishi Chemical Corporation). The sulfur content in the combustion gas was 0.1%- Absorbed with hydrogen peroxide. Thereafter, sulfate ions in the absorbing solution were measured using an ion chromatograph (ICS-1000 type, manufactured by Dionex).

Terminal carboxyl group amount: The value obtained by dissolving the obtained polyester in benzyl alcohol and titrating with 0.1N 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 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 E. 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 NOs: 3 and 4 as primers. Went by.
Composition of reaction solution: Template DNA 1 ng, Pyrobest DNA polymerase (Takara Shuzo) 0.1 μL, 1-fold concentration buffer, 0.5 μM each primer and 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, 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 ligation kit ver. 2 (manufactured by Takara Shuzo), 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 0.5 g, FeSO ₄ · 7H ₂ O 6 mg, MnSO ₄ · 4-5H ₂ O 6 mg, biotin 200 μg, thiamine 100 μg, yeast extract 1 g, casamino acid 1 g, glucose 20 g, dissolved in 1 L of distilled water] Bacterium flavum strain MJ-233 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 a synthetic DNA designed based on the base sequence of the gene described in JP-A-11-206385 ( It was performed by PCR using 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 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 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 lactate dehydrogenase gene disruption The pGEMT / CgLDH prepared in (B) above was cleaved with restriction enzymes EcoRV and XbaI to cut out the coding region of lactate dehydrogenase consisting of about 0.25 kb. 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 in which an insertion fragment of about 0.75 kb was recognized 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 [
10 g of tryptone, 5 g of yeast extract, 5 g of NaCl, 20 g of glucose, and 15 g of agar were dissolved in 1 L of distilled water.

  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 sucrose-insensitive strain 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, as an absorbance change at 340 nm, that the coenzyme NADH was oxidized to NAD + with the production of lactic acid using pyruvic acid 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 consists 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 digested with the restriction enzyme PstI, blunted with Klenow fragment, and then cleaved with the restriction enzyme KpnI. Separated and collected by 0% agarose gel electrophoresis.

(B) Construction of Coryneform Bacterial Expression Vector A pHSG298par-rep described in JP-A-12-93183 is used as a plasmid that can stably replicate independently in a coryneform bacterium. 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, 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 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 the 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 SONIFIER 350 (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 The reaction was carried out at 25 ° C. in a reaction solution containing 20 units / 1.5 ml malate dehydrogenase (manufactured by WAKO, derived from yeast) and the enzyme. 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 this was 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.

<Polyester using biomass resource-derived succinic acid with a sulfur atom content of 0.2 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 with a sulfur atom content of 0.2 ppm (YI = 2.5), Mitsubishi Chemical 88.5 parts by weight of industrial grade 1,4-butanediol, 0.37 parts by weight of malic acid, and 5.4 parts by weight of 88% lactic acid aqueous solution in which 0.98% by weight of germanium dioxide was previously dissolved as a catalyst were charged. The inside of the system was put into 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. A white polyester (yellowness YI of 11) was obtained.
The obtained polyester had a sulfur atom content of 0.1 ppm, a polyester reduced viscosity (ηsp / c) 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 0.2 ppm of sulfur atom of 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 aqueous solution of 88% lactic acid dissolved by 98% by weight was charged, and the inside of the system was put into 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 0.2 ppm of the sulfur atom 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 of Example 2 except that 5.4 parts by weight of an aqueous 88% lactic acid solution in which 0.98% by weight of germanium dioxide was dissolved in advance was used as a catalyst. A white polyester similar to that in 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 biomass resources containing 0.2 ppm of the sulfur atom 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 an aqueous 88% 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 0.2 ppm of sulfur atom of 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-reduced pressure 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, 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 sulfur atom content of 2 ppm>

Example 7
As a raw material, succinic acid derived from a biomass resource containing 2 ppm of sulfur atoms instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of the sulfur atom of Example 1 (yellowness YI is 3) 100 weights A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that the parts were used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.1 hours.
In the obtained polyester (yellowness YI is 19), the sulfur atom content was 1.4 ppm, the reduced viscosity (ηsp / c) of the polyester was 2.4, and the amount of terminal carboxyl groups was 15 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 sulfur atom content of 5 ppm>

Example 8
As a raw material, succinic acid derived from a biomass resource containing 5 ppm of sulfur atoms instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of the sulfur atom of Example 1 (yellowness YI is 7) 100 weight A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that the parts were used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2 hours.
In the obtained polyester (yellowness YI is 22), the sulfur atom content was 2.6 ppm, the reduced viscosity (ηsp / c) of the polyester was 2.3, and the terminal carboxyl group content was 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 sulfur atom content of 18 ppm>

Example 9
Implemented except that 100 parts by weight of succinic acid derived from a biomass resource containing 18 ppm of sulfur atoms was used as a raw material instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of the sulfur atom of Example 1. A polyester was produced under the same polycondensation reaction conditions as in Example 1. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 3.3 hours.
The resulting brown polyester (yellowness YI was 42) had a reduced viscosity (ηsp / c) of 2.4, and the amount of terminal carboxyl groups was 18 equivalents / ton. The obtained polyester (0.5 g) was dissolved almost uniformly in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixture) at room temperature, but a trace amount of insoluble matter was observed.

  <Polyester using biomass resource-derived succinic acid with a sulfur atom content of 34 ppm>

Example 10
Implemented except that 100 parts by weight of succinic acid derived from biomass resources containing 34 ppm of sulfur atoms was used as a raw material instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of sulfur atoms in Example 1 A polyester was produced under the same polycondensation reaction conditions as in Example 1. The polymerization reaction time under a reduced pressure of 0.07 × 10 ³ Pa was 7 hours.
The resulting brown polyester (yellowness YI was 38) had a reduced viscosity (ηsp / c) of 2.4 and a terminal carboxyl group content of 30 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 sulfur atom content of 290 ppm>

Comparative example a
As a raw material, succinic acid derived from a biomass resource containing 290 ppm of sulfur atoms (yellowness YI is 8) instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of the sulfur atom of Example 1 100 weight A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that the parts 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 dark brown tea had a sulfur atom content of 16 ppm, a polyester reduced viscosity (ηsp / c) of 1.1, and a terminal carboxyl group content of 69 equivalents / ton.

<Polyester using biomass resource-derived succinic acid with a sulfur atom content of 330 ppm>

Comparative Example b
100% by weight of succinic acid derived from a biomass resource containing 330 ppm of sulfur atoms instead of 100 parts by weight of succinic acid derived from biomass resources containing 0.2 ppm of the sulfur atom of Example 1 as a raw material (yellowness YI is 8) A polyester was produced under the same polycondensation reaction conditions as in Example 1 except that the parts 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 dark brown tea had a sulfur atom content of 16 ppm, a reduced viscosity (ηsp / c) of 0.7 and a terminal carboxyl group content of 139 equivalents / ton.

  In the examination of this example, it was found that the higher the sulfur atom content in the polyester, the higher the biodegradability. On the other hand, it can be seen that the higher the sulfur atom content, the more likely the coloration and polymerization inhibition of the polyester tend to become remarkable. In addition, the higher the sulfur atom content, the more insolubles in organic solvents, which are thought to have been generated by some gelation, tend to increase. Decrease is caused.

<Polyester using petroleum-derived succinic acid containing no sulfur atom>

Comparative Example 1
Instead of succinic acid derived from biomass resources containing 0.2 ppm of sulfur atoms of Example 1, succinic acid containing no petroleum-derived sulfur atoms (Kawasaki Chemical Co., Ltd., industrial grade (yellowness YI is 1.5) )) Was used in the same manner as in Example 1 except that the same polyester was produced. The obtained polyester did not contain sulfur.

  The obtained polyester was tested in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2
A reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and an exhaust port for decompression has a succinic acid containing no petroleum-derived sulfur atoms (Kawasaki Chemical Co., Ltd., industrial grade (yellowness YI is 1). .5)) 100 parts by weight, 88.5 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation, 0.37 parts by weight of malic acid, 0.06 parts by weight of p-toluenesulfonic acid hydrate and catalyst 5.4 parts by weight of an aqueous 88% lactic acid solution in which 0.98% by weight of germanium dioxide was dissolved in advance was charged, and the system was placed in a nitrogen atmosphere by nitrogen-reduced pressure 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. No increase in viscosity was observed. The reduced viscosity (ηsp / c) of the polyester was 0.2, and the sulfur atom content was 54 ppm.

  From Table 1, it was confirmed that the polyester using succinic acid derived from biomass resources 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
Moreover, the compositions 3-5 were prepared with the compounding ratio (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.

(Ii) Polylactic acid: “Lacia H-400” manufactured by Mitsui Chemicals, Inc.
<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.

(Ii) Tensile test: JIS K7113 compliant
No. 2 dumbbell used (Pulling speed: 50 mm / min)
Bending test: JIS K7203 compliant MD: Flow direction during sheet forming TD: Direction perpendicular to flow <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.

(Ii) Tensile test: JIS Z1702 compliant MD: Flow direction during film formation TD: Direction perpendicular to flow

<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, and after 2 hours, the valve of the pressure vessel 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.

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 (16)

  A polyester having a diol unit and a dicarboxylic acid unit as constituents, wherein at least the dicarboxylic acid unit is derived from a biomass resource, and the sulfur atom content in the polyester is a mass ratio with respect to the polyester. A biomass resource-derived polyester having a content of 0.0001 ppm to 50 ppm. 2. The biomass resource-derived polyester according to claim 1, wherein the content of sulfur atom in the polyester is 0.0001 ppm or more and 5 ppm or less by mass ratio with respect to the polyester. The biomass resource-derived polyester according to claim 1 or 2, wherein the biomass resource is a plant resource. The biomass resource-derived polyester according to any one of claims 1 to 3, wherein the polyester has a reduced viscosity (ηsp / c) of 0.5 or more. The biomass resource-derived polyester according to any one of claims 1 to 4, 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 5, wherein the YI value of the polyester is -10 or more and 30 or less. 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 any one of claims 1 to 6, 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 7. The biomass resource-derived polyester according to any one of claims 1 to 8, wherein the dicarboxylic acid unit is a succinic acid unit derived from a biomass resource . In the method for producing a polyester by reaction of a dicarboxylic acid and a diol, the dicarboxylic acid used for the reaction is derived from biomass resources, and the sulfur atom content in the dicarboxylic acid is in a mass ratio with respect to the dicarboxylic acid. It is 0.01 ppm or more and 100 ppm or less by the manufacturing method of biomass resource origin polyester of Claim 1 characterized by the above-mentioned . The method for producing a biomass resource-derived polyester according to claim 10, wherein the sulfur atom content in the dicarboxylic acid is 0.01 ppm or more and 20 ppm or less in terms of mass ratio with respect to the dicarboxylic acid. 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 claim 10 or 11. A biomass resource-derived polyester obtained by the production method according to any one of claims 10 to 12. A thermoplastic resin, a biodegradable resin, a natural resin, or a polysaccharide is 0.1% with respect to 99.9 to 0.1% by weight of the biomass resource-derived polyester according to any one of claims 1 to 9 and 13. 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 1-9 and 13. The molded object formed by shape | molding the biomass resource origin polyester resin composition of Claim 14.