JP2008094886A - Foamed article made from biomass resource-derived polyester, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamed article produced by a polyester derived from a biomass resource, having practical physical properties and greatly contributing to solve problems such as an environmental problem, a problem of the starvation of fossil fuel, etc. <P>SOLUTION: This foamed article produced by the polyester derived from the biomass resource and having the main recurring units of a dicarboxylic acid unit and diol unit is characterized in that at least one of the dicarboxylic acid and diol which are the raw materials of the polyester, is obtained from the biomass resource and the terminal carboxyl group amount in the polyester is ≤50 equivalent/ton. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a foam using a biomass resource-derived polyester having a diol unit and a dicarboxylic acid unit as a constituent unit, a method for producing the same, and a cushioning material comprising the foam.

  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. Moreover, 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 typical polyesters, but the big problem is that the biodegradability rate is extremely slow. 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.
These processes are processes for producing the target 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 the elemental nitrogen contained in resources, there are features that many impurities such as nitrogenous elements derived from fermentation bacteria, ammonia and metal cations are mixed.
Moreover, the manufacturing method of biomass resource origin polyester is disclosed (patent document 1).
JP 2005-139287 A

  The dicarboxylic acids and diols derived from biomass resources containing a large amount of impurities as described above are usually used after further reducing the amount of impurities by a purification treatment. In addition to nitrogen elements contained in biomass resources, acids and diols include nitrogen elements derived from microorganisms and enzymes, nitrogen elements such as ammonia used in purification processes, sulfur elements, inorganic acids and organic acids, metal cations, etc. Therefore, when such a dicarboxylic acid component and / or diol component derived from a biomass resource is used as a raw material, the obtained polyester has poor properties such as hydrolysis resistance, and the hydrolysis of the polymer during storage becomes remarkable. The knowledge that there is a problem that the molding process becomes difficult was obtained. Further, the polyester disclosed in Patent Document 1 has a high nitrogen atom content in the polyester as high as 44 ppm, so the amount of terminal carboxyl groups in the polyester is high and the stability is poor, and foreign matter is easily generated during molding. The problem of exhibiting the characteristics of the present invention has also been clarified by the present inventors' research.

  Therefore, in the case of such a polyester having poor physical properties or moldability, naturally, when it is attempted to produce a foam using this polyester, a foamed molded product having good physical properties cannot be obtained, or when it is remarkable. The foam molding itself becomes impossible.

  An object of the present invention is to provide a good biomass resource-derived polyester foam by suppressing hydrolysis in the case of using a biomass resource-derived dicarboxylic acid component and / or diol component as a raw material.

As a result of diligent research to solve the above problems, the present inventors have found that when dicarboxylic acid and / or diol derived from biomass resources is used as a polyester raw material, water in the polyester or water in the polyester during the foaming step is used. It was found that decomposition is significantly accelerated by impurities contained in the raw material, and various physical properties (viscoelasticity and molecular weight) of the polymer required at the time of foaming are significantly reduced. Therefore, when foam-molding polyester derived from biomass resources, if the amount of terminal carboxyl groups in the polyester is reduced to 50 equivalents / ton or less after reducing the amount of specific impurities in the polyester, these problems occur. Has been found to be solved, and the present invention has been completed.
That is, the gist of the present invention is as follows.

[1] In a foam obtained from a polyester whose main repeating unit is a dicarboxylic acid unit and a diol unit, at least one of a dicarboxylic acid and a diol as a raw material of the polyester is obtained from a biomass resource, A biomass resource-derived polyester foam, wherein the amount of terminal carboxyl groups in the polyester is 50 equivalents / ton or less.

[2] The biomass resource-derived polyester foam according to [1], wherein the reduced viscosity (ηsp / C) of the polyester is 1.5 dL / g or more.

[3] The nitrogen atom content in the polyester excluding nitrogen atoms contained in the functional group covalently bonded in the molecule of the polyester is 0.01 ppm or more and 50 ppm or less by mass ratio with respect to the polyester. The biomass resource-derived polyester foam according to [1] or [2], wherein:

[4] The biomass resource-derived polyester according to any one of [1] to [3], wherein a content of sulfur atom in the polyester is 0.0001 ppm to 10 ppm by mass with respect to the polyester. Made of foam.

[5] The biomass resource according to any one of [1] to [4], wherein the dicarboxylic acid unit constituting the main repeating unit of the polyester is an aliphatic dicarboxylic acid unit derived from a biomass resource. Polyester foam.

[6] The biomass resource-derived polyester foam according to [5], wherein the dicarboxylic acid unit constituting the main repeating unit of the polyester is a succinic acid unit derived from biomass resources.

[7] Any one of [1] to [6], wherein the polyester is modified with a modifier of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyester. A biomass resource-derived polyester foam according to crab.

[8] The biomass resource-derived polyester foam according to [7], wherein the modifier has a carbodiimide group.

[9] In a method for producing a foam using a polyester obtained by reacting a raw material containing at least a dicarboxylic acid and a diol, at least one of a dicarboxylic acid raw material and a diol raw material used for a polyester production reaction is derived from biomass resources. And the nitrogen atom content in the dicarboxylic acid raw material and the diol raw material is 0.01 ppm or more and 500 ppm or less in terms of mass ratio with respect to the total of the raw materials, and the terminal carboxyl group content in the polyester is 50 equivalents. A method for producing foam of a biomass resource-derived polyester foam, characterized in that a material having a capacity of / ton or less is used.

[10] In a method for producing a foam using a polyester obtained by reacting a raw material containing at least a dicarboxylic acid and a diol, at least one of a dicarboxylic acid raw material and a diol raw material used for the polyester production reaction is derived from biomass resources. And a biomass resource-derived polyester foam characterized in that the sulfur atom content in the raw material is 0.01 ppm to 100 ppm by mass ratio with respect to the total of the raw materials. Method.

[11] The biomass resource as described in [10], wherein a nitrogen atom content in the dicarboxylic acid raw material and / or diol raw material is 0.01 ppm or more and 500 ppm or less in a mass ratio with respect to the total of the raw materials. A method for producing a polyester foam.

[12] At least one trifunctional or more polyfunctional 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 with the dicarboxylic acid and diol. The method for producing a biomass resource-derived polyester foam according to any one of [9] to [11], wherein the reaction is carried out in the presence of a compound.

[13] At least one selected from the group consisting of thermoplastic resins, biodegradable resins, natural resins, and polysaccharides is used in an amount of 0.1 to 99.9 with respect to 99.9 to 0.1% by weight of the polyester. The method for producing a biomass-resource-derived polyester foam according to any one of [9] to [12], wherein a polyester composition blended by weight% is used.

[14] The method for producing a biomass resource-derived polyester foam according to [13], wherein the biodegradable resin is an aliphatic polyester.

[15] The method for producing a biomass resource-derived polyester foam according to [13] or [14], wherein the biodegradable resin is an aliphatic oxycarboxylic acid resin.

[16] The method for producing a biomass-resource-derived polyester foam according to any one of [13] to [15], wherein the biodegradable resin is an aromatic / aliphatic copolyester resin.

[17] The method for producing a biomass resource-derived polyester foam according to [15] or [16], wherein the biodegradable resin is an aromatic / aliphatic copolymer polyester resin.

[18] The method for producing a biomass resource-derived polyester foam according to any one of [9] to [17], wherein a chain extender is allowed to act on the polyester.

[19] A biomass resource-derived polyester foam according to any one of [9] to [18], wherein a polyester containing 0.01 to 10 parts by weight of a carbodiimide compound is used per 100 parts by weight of the polyester. Manufacturing method.

[20] The method for producing a biomass resource-derived polyester foam according to [19], wherein the carbodiimide compound is a polycarbodiimide compound having a polymerization degree of 2 to 40.

[21] A biomass resource-derived polyester foam obtained by the production method according to any one of [9] to [20].

[22] A cushioning material comprising a biomass resource-derived polyester foam according to any one of [1] to [8] and [21].

According to the present invention, in the case where a dicarboxylic acid and / or diol derived from biomass resources is used as a raw material for polyester, the physical properties of the product obtained during the manufacturing process of the foam and by suppressing hydrolysis promoted by impurities. Deterioration can be prevented and a good polyester foam can be provided.
Development of this method greatly contributes to solving environmental problems, fossil fuel resource depletion problems, and the like, 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. Because plant raw material production can be dispersed and diversified in various places, the supply of raw materials is very stable, and the difference in the mass balance of absorption and release of carbon dioxide is made because it is done in the global environment of the atmosphere. It is relatively balanced. Moreover, it can be recognized as an environmentally friendly and safe polyester foam.

Such a biomass resource-derived polyester foam of the present invention can be evaluated not only in the physical properties, structure and function of materials, but also in the feasibility of a recycling society including recycling, which cannot be expected at all from polyester derived from fossil fuels. Has the advantage of potentially holding. This is to provide a polyester manufacturing process from a new perspective, which is different from conventional fossil fuel-dependent orientation. Contributes significantly to the use and development of
The biomass resource-derived polyester foam of the present invention is less likely to generate harmful substances and offensive odors even if the soil dumping is stopped and incinerated.

Below, the typical aspect for implementing this invention is demonstrated concretely, However, This invention is not limited to the following aspects, unless the summary is exceeded.
First, polyester (hereinafter may be referred to as “polyester of the present invention”) as a raw material of the biomass resource-derived polyester foam of the present invention will be described.

[polyester]
The polyester of the present invention contains 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 derived from biomass resources.

<Dicarboxylic acid unit>
Examples of the dicarboxylic acid constituting the dicarboxylic acid unit include an aliphatic dicarboxylic acid or a mixture thereof, an aromatic dicarboxylic acid or a mixture thereof, and a mixture of an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid. Among these, those containing an aliphatic dicarboxylic acid as a main component are preferable. The main component in the present invention refers to a component that occupies 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 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, an aliphatic dicarboxylic acid or a derivative thereof is used. Specific examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which are usually chains having 2 to 40 carbon atoms. 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, more preferable biomass resources are 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 cass, straw , Buckwheat, soybeans, fats and oils, waste paper, papermaking residue, marine product residue, livestock excrement, sewage sludge, food waste and the like. Among them, 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, oil, waste paper, paper residue Preferred are wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, papermaking residue, and most preferred are corn, sugar cane, cassava, sago palm. These biomass resources generally contain a large amount of alkali metals and alkaline earth metals such as nitrogen element, 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. For example, the process is usually not particularly limited, but includes a refinement process by pretreatment such as chipping, scraping, or crushing biomass resources. If necessary, a grinding process by a grinder or a mill is further included. 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 treatments such as hydrolysis can be mentioned.

  Carbon sources derived from the above biomass resources include hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose, pentoses such as arabinose, xylose, ribose, xylulose, ribulose, pentose, saccharose, starch, cellulose, etc. Disaccharides / polysaccharides, 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, eicosenoic acid Fermentability of oils and fats such as arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid, and ceracolonic acid, and polyalcohols such as glycerin, mannitol, xylitol, and ribitol Quality is 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. ), Facultative anaerobes such as Escherichia (US Pat. No. 5,770,435) (E. coli (J. Bacteriol., 57: 147-158) or mutants of E. coli strains (special table 2000) -50033, US Pat. No. 6,159,738), aerobic bacteria such as Corynebacterium (Japanese Unexamined Patent Publication No. 11-113588), Bacillus genus, Rizobium genus, Brevibacterium genus, Arthrobac er belonging to the genus aerobic bacteria (JP 2003-235593), Bacteroidesruminicola, or the like can be used anaerobic rumen bacteria such Bacteroidesamylophilus. These references are incorporated herein by reference.

  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 are preferred. And more preferably Corynebacterium glutamicum, Brevibacterium flavum, Brevibacterium ammoniagenes or Brevibacterium cerium bacterium. Examples include microorganisms.

  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 Schleifer, K. H., International Journal). of Systemic Bacteriology, 1991, vol. 41, p255-260), Brevibacterium flavum MJ-233 strain, and mutant MJ-233 AB-41 strain thereof are 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.

  In addition, Brevibacterium flavum MJ-233-AB-41 was established on November 17, 1976 at the Institute of Biotechnology, Institute of Industrial Science and Technology, Ministry of International Trade and Industry (currently the National Institute of Advanced Industrial Science and Technology, Patent Deposit Center) ( Deposit number FERM P-3812 at Tsukuba City, Ibaraki Prefecture, Japan 305-8586 Japan, No. 6) and transferred to the international deposit under the Budapest Treaty on May 1, 1981. BP-1498 is assigned.

  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 adjust pH. Specifically, 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 may be produced by using a combination of electrodialysis and water splitting steps to separate the dicarboxylate salt to produce pure acid, and further purification may be performed 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). In addition, as a salt exchange method, for example, an ammonium salt of dicarboxylic acid may be mixed with ammonium hydrogen sulfate and / or sulfuric acid at a sufficiently low pH and reacted to produce dicarboxylic acid and ammonium sulfate (JP 2001-514900). Issue gazette).

  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. Can be used to separate and purify the 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 As described in JP-A-2-283289, a succinate produced by fermentation is electrodialyzed, followed by a strongly acidic ion exchange resin or a weakly basic ion exchange. The method of processing using resin 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, and drying and the reference examples of the present invention in any combination and repeatedly as necessary. A purified monomer raw material suitable for the present invention can be produced. Among these, the ion exchange method or the salt exchange method is particularly preferable in terms of cost and efficiency, and the salt exchange method is particularly preferable in terms of industrial productivity.

  By carrying out such purification, it is usually necessary to reduce the amount of impurity nitrogen compounds and metal cations contained in the dicarboxylic acid in order to obtain a practical polyester.

  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 biomass resources by the above-mentioned method is a mass ratio with respect to the dicarboxylic acid, and 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. When the content of nitrogen atoms contained in the dicarboxylic acid is too large, there is a tendency that the polymerization reaction is delayed, the number of carboxyl terminals in the produced polymer is increased, coloring, partial gelation, and stability is lowered. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.

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

  Further, the sulfur atom content contained in the dicarboxylic acid derived from biomass resources by the above-mentioned method is a mass ratio with respect to the dicarboxylic acid, and the upper limit is usually 100 ppm or less, preferably 20 ppm or less, more preferably the upper limit. Is 10 ppm or less, particularly preferably the upper limit is 5 ppm or less, and 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. If the dicarboxylic acid contains too much sulfur atom, it tends to cause a delay in the polymerization reaction, partial gelation of the produced polymer, an increase in the number of carboxyl ends of the produced polymer, and a decrease in stability. . 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.

  In order to store the raw material by controlling the oxygen concentration, a tank is usually used. 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 or resin, or a glass or resin container is used. From the viewpoint of strength, etc., those made of metal or those subjected to lining 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 usually 16% or less, preferably 14% or less, 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, the color of the produced polyester 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, more preferably 50 ° C. or lower. However, a method of storing at room temperature is most preferable because temperature control is not necessary. If the temperature is too low, the storage cost tends to increase, and if it is too high, the dehydration reaction of dicarboxylic 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, more preferably 0.01% or more. The upper limit is usually 80% or less, preferably 60% or less, more preferably 40% or less. When the humidity is too low, the management process tends to be complicated and economically disadvantageous. When it is too high, the dicarboxylic acid adheres to the storage tank and piping, the dicarboxylic acid is blocked, and the storage tank. When the metal is made of metal, tank corrosion tends to be a problem.

  The pressure in the dicarboxylic acid storage tank is usually atmospheric pressure (normal pressure).

  It is preferable that the dicarboxylic acid used in the present invention is usually 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 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 high YI values has a significant disadvantage in the coloration of the produced polyester. On the other hand, a dicarboxylic acid exhibiting a low YI value is a more preferable form, but it is economically disadvantageous in that it requires a very large capital investment for its production and requires a large production time. In the present invention, the YI value is a value measured by a method based on JIS K7105.

<Diol 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, a diol having an even number of carbon atoms or a mixture thereof is preferable because a polyester 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 addition, a mixture containing 1,4-butanediol as a main component or 1,4-butanediol is particularly preferable. The main component here refers to a component that occupies 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. Examples of both-terminal hydroxy polyethers include those having a lower limit of carbon number of usually 4 or more, preferably 10 or more, and an upper limit of 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 usually an amount calculated as 90% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less as the content of both terminal hydroxy polyether units in the polyester. It is.

  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, 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, Cu / Cr / Zn. 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 treatment, and neutralization step with acid. In this case, specifically, nitrogen atoms derived from amino acids, proteins, ammonia, urea, and fermenting bacteria are included.

  The nitrogen atom content contained in the diol produced by the fermentation method is a mass ratio with respect to the diol, and the upper limit is usually 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less. The lower limit is not particularly limited, but is usually 0.01 ppm or more, preferably 0.05 ppm or more, more preferably 0.1 ppm or more, still more preferably 1 ppm or more, particularly preferably 10 ppm or more for reasons of economic efficiency of the purification step. When the content of nitrogen atoms contained in the diol is too large, there is a tendency that the polymerization reaction is delayed, the number of carboxyl terminals in the produced polymer is increased, coloring, partial gelation, and stability is lowered. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.

  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 produced by the fermentation method is a mass ratio to the diol, and 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, and most 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. If the content of sulfur atoms in the diol is too high, the polymerization reaction may be delayed, the resulting polymer may partially gel, and the number of carboxyl terminals in the resulting polymer may increase or the stability may decrease. . 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, a diol oxidation product such as 2- (4-hydroxybutyloxy) tetrahydrofuran is generated. It is possible to prevent the polyester from being colored by an object.

  In order to store the raw material by controlling the oxygen concentration, a tank is usually used. 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 or resin, or a glass or resin container is used. From the viewpoint of strength, etc., those made of metal or those subjected to lining 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 storage tank of the diol 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% or more. 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 polyester by the oxidation reaction product of the diol tends to increase.

  The lower limit of the storage temperature of the diol in the storage tank is usually 15 ° C or higher, preferably 30 ° C or higher, more preferably 50 ° C or higher, most preferably 100 ° C or higher, and the upper limit is 230 ° C or lower, preferably 200 ° C. ° 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, in order to produce a polyester having good hue, the upper limit of the content of the oxidation product in the diol is usually 10,000 ppm or less, preferably 5000 ppm or less, more preferably 3000 ppm or less, and most preferably 2000 ppm or less. 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 economy of the purification step.

  In the present invention, the diol is usually used as a polyester raw material through a purification process by distillation.

<Combination of dicarboxylic acid unit and diol unit>
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 are all included in the polyester of the present invention. Can be illustrated.

  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 polyesters of oxalic acid and 1,4-butanediol, polyesters 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, polyester of adipic acid 1,4-cyclohexanedimethanol, and the like.

  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 polyesters of 4-butanediol and polyesters of terephthalic acid, succinic acid, and 1,4-butanediol.

<Other copolymer components>
The polyester of the present invention may be a copolymer polyester obtained by adding a copolymer component 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 tri- or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced with 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-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, and 2-hydroxyiso Examples include caproic acid and caprolactone, and these may be oxycarboxylic acid esters or lactones, or derivatives such as 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, or 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. As an acquisition form, an aqueous solution of 30 to 95% by weight is preferable because it 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 amount of use that exhibits the effect is usually 0.02 mol% or more, preferably 0.5 mol% or more as a lower limit with respect to 100 mol% of all monomer units constituting the polyester. More preferably, it is 1.0 mol% or more. 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, relative to the raw material monomer.

  Specific examples of the polyester include those using lactic acid as the bifunctional oxycarboxylic acid, such as a copolymer polyester of succinic acid-1,4-butanediol-lactic acid, or succinic acid-adipic acid. Examples include -1,4-butanediol-lactic acid copolymer polyester. Examples of those using glycolic acid include succinic acid-1,4-butanediol-glycolic acid copolyester.

  Specific examples of the trifunctional or higher functional polyhydric alcohol include glycerin, trimethylolpropane, pentaerythritol, and the like. These may be used alone or as a mixture of two or more.

  Examples of those using pentaerythritol as the trifunctional or higher polyhydric alcohol of the copolymer component include, for example, succinic acid-1,4-butanediol-pentaerythritol copolymerized polyester, and succinic acid-adipic acid-1,4. -Butanediol-pentaerythritol copolyester. These trifunctional or higher polyhydric alcohols can be arbitrarily changed to produce a desired copolyester.

  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 trifunctional or higher polyvalent carboxylic acid or anhydride thereof include propanetricarboxylic acid, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, cyclopentatetracarboxylic anhydride, and the like. It can be used alone or as a mixture of two or more.

  Specific examples of the trifunctional 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 seeds or more. In particular, malic acid, tartaric acid, citric acid and a mixture thereof are preferable because of easy availability.

As what uses malic acid as a trifunctional oxycarboxylic acid of a copolymerization component, for example, copolymer polyester of succinic acid-1,4-butanediol-malic acid, succinic acid-adipic acid-1,4-butane Diol-malic acid copolyester, succinic acid-1,4-butanediol-malic acid-tartaric acid copolyester, succinic acid-adipic acid-1,4-butanediol-malic acid-tartaric acid copolyester, Examples thereof include a copolymer polyester of succinic acid-1,4-butanediol-malic acid-citric acid and a copolymer polyester of succinic acid-adipic acid-1,4-butanediol-malic acid-citric acid.
These trifunctional oxycarboxylic acids can be arbitrarily changed to produce a desired copolyester.

  Further, as a combination of bifunctional oxycarboxylic acids, for example, succinic acid-1,4-butanediol-malic acid-lactic acid copolymer polyester, 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 polyester of succinic acid-adipic acid-1,4-butanediol-malic acid-tartaric acid-lactic acid 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 are also included in the present invention. As a polyester.

  The amount of the above-mentioned trifunctional or higher polyfunctional compound unit causes the generation of gel, and therefore the upper limit is usually 5 mol% or less, preferably 1 with respect to 100 mol% of all monomer units constituting the polyester. The mol% or less, more preferably 0.50 mol% or less, 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 of use at which the effect is manifested is the total monomer units constituting the polyester. It is 0.0001 mol% or more normally with respect to 100 mol%, Preferably it is 0.001 mol% or more, More preferably, it is 0.005 mol% or more, Most preferably, it is 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 be used, but the amount thereof is usually such that a carbonate bond and a urethane bond are based on 100 mol% of all monomer units constituting the polyester. Usually, 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 0, based on 100 mol% of the body unit. 0.01 mol% or less, more preferably 0.001 mol% or less.
The carbonate bond amount and the urethane bond amount are calculated by NMR measurement such as ¹³ C NMR.

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

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

High molecular weight polyesters using these chain extenders (coupling agents) can be produced 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 terminal group obtained by catalyzing diol and dicarboxylic acid (or its anhydride) has substantially a hydroxyl group, and the weight average molecular weight (Mw) is 20,000 or more, preferably Can be obtained by reacting the chain extender with a polyester prepolymer of 40,000 or more to obtain a higher molecular weight polyester resin. If the prepolymer has a weight average molecular weight of 20,000 or more, the use of a small amount of a coupling agent does not affect the remaining catalyst even under severe conditions such as a molten state, so that no gel is formed during the reaction. High molecular weight polyester can be produced.

  Therefore, for example, in the case of further increasing the molecular weight using the above-mentioned diisocyanate as a chain extender, a prepolymer having a weight average molecular weight composed of a diol and a dicarboxylic acid of 20,000 or more, preferably 40,000 or more is used. A polyester having a linear structure linked through a urethane bond derived from diisocyanate is produced.

  The pressure during chain extension of the polyester prepolymer 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. Is most preferred.

  The reaction temperature during chain extension of the polyester prepolymer is usually at least 100 ° C, preferably at least 150 ° C, more preferably at least 190 ° C, most preferably at least 200 ° C, and the upper limit is usually at most 250 ° C, preferably It is 240 degrees C or less, 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.

  The lower limit of chain extension time 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. Minutes or less, 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, the amount used is preferably 0.1 mol% or less, more preferably 10 ⁻⁵ mol% or less, based on 100 mol of all monomer units constituting the polyester.

  Thus, the polyesters of the present invention include polyesters, copolymerized polyesters, chain extended (coupled) high molecular weight polyesters, and modified polyesters.

  In the present invention, the polyester terminal group may be sealed with carbodiimide, an epoxy compound, a monofunctional alcohol or carboxylic acid to modify the polyester.

  The modifier is added for the purpose of adjusting the amount of terminal carboxyl groups of polyester, improving foaming properties, etc., and is effective as an end-capping agent or thickener, and therefore preferably has a carbodiimide group. As such a modifier, examples of the carbodiimide compound include compounds having one or more carbodiimide groups in the molecule (including polycarbodiimide compounds). Specifically, the monocarbodiimide compound includes dicyclohexylcarbodiimide. , Diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide, di-β-naphthylcarbodiimide, N, N′-di-2,6-dii Such as propyl phenyl carbodiimide and the like. As the polycarbodiimide compound, those having a degree of polymerization of usually 2 or more, preferably 4 or more and an upper limit of usually 40 or less, preferably 30 or less are used. US Pat. No. 2,941,956, JP 47-33279, J. Pat. Org. Chem. 28, p2069-2075 (1963), and Chemical Review 1981, 81, No. 4, p. And those produced by the method described in 619-621 and the like.

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

Specific examples of industrially available polycarbodiimides include Carbodilite HMV-8CA (Nisshinbo), Carbodilite LA-1 (Nisshinbo), Starbazole P (Rhein Chemie), Starbazole P100 (Rhein Chemie) and the like. Is done.
The carbodiimide compound can be used alone, but a plurality of compounds can also be mixed and used.
Other modifiers include epoxy and oxazoline compounds that are reactive with the terminal groups of the polyester.

(Epoxy compound)
Further, as the epoxide compound, o-phenol phenyl glycidyl ether, butyl phenyl glycidyl ether, resorching glycidyl ether, hydroquinone glycidyl ether, 1,6-hexanediol glycidyl ether, hydrogenated bisphenol A diglycidyl ether, N-glycidyl phthalimide, terephthale Examples thereof include acid diglycidyl ester, bisphenol A type epoxy resin and / or novolak type epoxy resin, and ethylene-glycidyl methacrylate-vinyl acetate copolymer. In addition, epoxy compounds such as a glycidyl ester compound, a glycidyl amine compound, a glycidyl imide compound, and an alicyclic epoxy compound may be used as the modifier.

(Oxazoline compound)
Examples of the oxazoline compound include 2,2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline).

  In addition, the said modifier may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the modifier used is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, particularly preferably 0.2 parts by weight, based on 100 parts by weight of the polyester. Part or more, usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less. Below the lower limit of this range, the water resistance, the uniformity of predetermined bubbles of the foam, the size of the bubbles and the like cannot be stably maintained. Also, if the upper limit is exceeded, the manufacturing cost becomes too high, and the effects of the modifier such as predetermined foaming characteristics, mechanical strength and water resistance are wasted, and the influence of excess modifier such as carbodiimide However, there is a case where it reacts with the active hydrogen of the terminal hydroxyl group or carboxyl group of the aliphatic polyester to accelerate the gelation and hinder the processing. In particular, when a bifunctional, trifunctional polyhydric alcohol or polyvalent carboxylic acid is used as a polyester reaction monomer, it requires a delicate adjustment in the action as a chain extender or coupling agent as a modifier. Become.

  In addition, within the above range of use amount, the modifier may be added in an amount that quantitatively seals the terminal of the polyester acid, but long-term stability and hydrolysis suppression in the foaming agent impregnation step during foam production In order to express the effect and the effect of improving the melt tension, it is desirable that the modifier is present in excess relative to the polyester terminal. Here, the presence of the modifier in excess means that the modifier is more than the amount capable of quantitatively sealing the terminal carboxyl amount of the base resin (that is, the present polyester and other resins used as appropriate). To add.

(Processing method of modifier)
Although there is no limitation on the specific method of incorporating the modifier into the foam of the present invention, it may be usually during the production of the polyester or during the foam production process, and the polyester and the modifier are mixed. Thus, a modifier is included in the foam. For example, the modifier may be kneaded at the same time when the polyester is melt-kneaded with a biaxial kneader or the like, or the modifier may be mixed with a molten biodegradable resin system. In addition, the resin particle here is produced when producing the foam of the present invention, and the foam of the present invention can be obtained by foam molding of the resin particles.

  When the modifier is kneaded during melt kneading, the kneading temperature is preferably 120 to 250 ° C. This is because if the temperature is too high, a material such as a resin may be thermally deteriorated. In order to remove low-molecular volatile components, it is preferable that vacuum kneading (vent suction) can be performed in the middle of the kneader cylinder during kneading. In addition, the rotation direction of the two screws in the biaxial kneader may be the same direction or different directions.

  Moreover, it is preferable to use a masterbatch containing a high content of the modifier. It is because it can be mixed and diluted so that the content becomes the target concentration.

  Although there is no restriction | limiting in content of the modifier in a masterbatch, Usually, 1 weight% or more, Usually, 45 weight% or less, Preferably it is 40 weight% or less, More preferably, it is 35 weight% or less. If the content of the modifying agent is too small, it is not suitable for use as a masterbatch, and if the content is too large, gelation tends to proceed.

  Resin employ | adopted as a masterbatch is not specifically limited, Although the commercially available masterbatch containing carbodiimide may be sufficient, the masterbatch manufactured using this polyester to be used is more preferable.

<Nitrogen atom content and sulfur atom content in polyester raw material>
In the present invention, the nitrogen atom content contained in the above-mentioned dicarboxylic acid raw material and diol raw material is generally 500 ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less, Preferably it is 50 ppm or less. On the other hand, the lower limit of the nitrogen atom content is not particularly limited, but is usually 0.01 ppm or more, preferably 0.05 ppm or more and 0.1 ppm or more. If the nitrogen atom content in the polyester is too high, the polymerization reaction tends to be delayed, the number of carboxyl ends of the polymer produced increases, coloring, partial gelation, and a decrease in stability. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.

  In the present invention, the sulfur atom content contained in the dicarboxylic acid raw material and the diol raw material is generally 100 ppm or less, preferably 20 ppm or less, more preferably 10 ppm in terms of mass ratio with respect to the total polyester raw material. Hereinafter, the upper limit is particularly preferably 5 ppm or less, and most preferably 0.5 ppm or less. On the other hand, the lower limit of the sulfur atom content 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 content of sulfur atoms in the polyester raw material is too large, there is a tendency that the polymerization reaction is delayed, the number of carboxyl terminals in the produced polymer is increased, coloring, partial gelation, and stability is lowered. On the other hand, an excessively small system is a preferred form, but the purification process becomes complicated and economically disadvantageous.

<Production method of polyester>
The production of the polyester of the present invention mainly comprising a diol unit and a dicarboxylic acid unit can be carried out by a known technique for producing a polyester. 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.

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

  The polyester 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. This is defined as the time until the pressure is restored.

The lower limit of the oxygen concentration in the reaction tank during the polyester production reaction is not particularly limited with respect to the total volume of the reaction tank, but is usually 1.0 × 10 ⁻⁹ % or more, preferably 1.0 × 10 ⁻⁷ % or more. 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 (final stirring speed) before stopping the polymerization reaction under reduced pressure may be controlled. Good. 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 or less. More preferably, it is 5 rpm or less, and most preferably 3 rpm or less. If 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 if 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. 50 rpm or less. If the stirring rate is too slow, the polymerization rate tends to be slow or the viscosity of the product polymer tends to be uneven, and if it is too fast, it may occur during the production of polymers derived from biomass resources that have many impurities due to shearing heat generation. Tends to degrade the polymer in particular.

  Here, the stirring speed during 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 usually 1000 rpm or less, preferably 500 rpm or less. When the stirring speed is too slow, the evaporating efficiency is poor and the esterification reaction tends to be slow. For example, the diol dehydration reaction or dehydration cyclization tends to be caused. As a result, the ratio of the diol / dicarboxylic acid collapses to lower the polymerization rate, and it is necessary to charge more diol, and if it is too fast, it consumes extra power and is economical. 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 subjected to lining 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, 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, 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 dehydration reaction of dicarboxylic acid tends to occur simultaneously.

  The pressure in the transfer pipe is usually 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 the diol used in producing 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 reaction and / or the condensation polymerization reaction. Is used in excess of 0.1 to 20 mol%.
On the other hand, when the aromatic polyester is produced, the number of carboxyl group terminals tends to increase, so that the diol is used in an excess of 10 to 60 mol% with respect to 100 mol of dicarboxylic acid or a derivative thereof.

  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, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.

  Examples of the polymerization catalyst include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium, and potassium. And compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. These catalyst components may be contained in a polyester raw material derived from biomass resources for the reasons described above. In that case, the raw material may be used as it is as a raw material containing a metal without being purified. 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 group 1 metal elements such as sodium and potassium contained in the polyester raw material is smaller. In such a case, the raw material refine | purified to the grade which does not contain a group 1 metal element substantially is used preferably.

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

  The titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof. In addition, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, titanium bis (ethylacetoacetate) diisopropoxide, titanium (triethanolaminate) ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate, butyl titanate dimer and the like are also preferably used. Further, titanium oxide or a composite oxide containing titanium and silicon (for example, titania / silica composite oxide (product name: C-94) manufactured by Acordis Industrial Fibers) is also 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 a composite oxide 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, sulphate 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 amount of catalyst used here is a preferred embodiment because the amount of terminal carboxyl groups of the polyester produced is reduced as the amount used is reduced.

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 reactor 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.

As a production method when producing an aliphatic polyester, the conventional esterification reaction and / or transesterification reaction between the dicarboxylic acid component containing the aliphatic dicarboxylic acid and the aliphatic diol component is carried out under reduced pressure. A method of increasing the degree of polymerization of polyester while distilling off a diol produced by transesterification of the alcohol end of the polyester, or an aliphatic dicarboxylic acid and / or an acid anhydride ring thereof from the end of the aliphatic carboxylic acid of the polyester A method of increasing the degree of polymerization of the polyester while distilling off 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 at the latter stage in the melt polymerization step. However, since aliphatic dicarboxylic acids are easily converted into acid anhydride cyclics under polycondensation reaction conditions, they are often heated and distilled in the form of acid anhydride cyclics. . 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.
On the other hand, when producing an aromatic polyester, a method of increasing the degree of polymerization of the polyester while distilling off the former diol using an excess of diol as described above is a preferred production method.

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 this 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, and if it is too high, the thermal decomposition of the polyester will tend to be noticeable. is there.

  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 tank.

  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.

  In addition, the lower limit of the temperature of the aqueous medium for cooling 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. The temperature is preferably 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, which tends to be economically disadvantageous. If the temperature is too high, the thermal decomposition of the polyester tends to become noticeable when the strand is pulled out. is there.

  The lower limit of the time for cooling the polyester is usually 0.1 seconds 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 2 Min or less, more preferably 1 min or less, and most preferably 30 sec 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.

  The method for cooling is not particularly limited, and examples thereof include a method in which polyester is extracted from the polymerization reaction tank in the form of a strand and submerged in the cooling medium, and a method in which the cooling medium is applied to the strand in a shower form, for example. .

<Polyester pellets>
After 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 reaction tank, the strand drawing speed, the take-up speed, the cutting speed, and the like. Specifically, for example, the pressure is adjusted by adjusting the pressure in the reaction tank when the polyester is extracted or by 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 (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 pellet diameter is too small, deterioration due to hydrolysis during pellet storage tends to be significant, and if the pellet diameter is too large, the bite during molding tends to be poor and the product tends to become uneven. .

  In the polyester pellets of the present invention, the ratio of the powdery body having a maximum diameter of less than 1 mm is preferably 2.0% by weight or less, and the ratio of the powdery body having a maximum diameter of less than 1 mm is 1.0% by weight or less. More preferably. If the ratio of powdery material with a maximum diameter of less than 1 mm is large, the powdery material has poor bite into the molding machine screw at the time of melt molding, and the residence time in the molding machine is long, and the surface area is large. Therefore, it is easy to cause thermal deterioration, and it is mixed as foreign matter such as burns and blisters in the molded body, leading to problems such as a decrease in mechanical strength of the molded body and poor appearance.

  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 water content is not particularly limited with respect to the polyester in terms of mass ratio, 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, The upper limit is usually 3000 ppm or less, preferably 2000 ppm or less, more preferably 1000 ppm or less, particularly preferably 800 ppm or less, and most preferably 500 ppm or less. If the water content is too low, not only will the equipment and management process be complicated and economically disadvantageous, but it will take a long time to dry, so deterioration of the coloring of the polyester and the formation of crumbs will occur. There is a tendency to be caused. On the other hand, when the amount is too large, the polyester tends to deteriorate significantly 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. The method of determining is mentioned.

  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 laminated films 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 packaging bags by means such as 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 in the normal space is usually 300 lux or less, preferably 70 lux or less, more preferably 1 lux or less, and most preferably 0.001 lux or less, and the lower limit is not particularly limited. 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 temperature when storing the polyester pellets has a lower limit of −50 ° C. or higher, preferably −30 ° C. or higher, more preferably 0 ° C. or higher, and an upper limit of 80 ° C. or lower, preferably 50 ° C. or lower, more preferably. Although it is 30 ° C. or lower, it is most preferable to store at room temperature because a management process 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).
In addition, you may pelletize the polyester composition mentioned later and preserve | save on the above-mentioned conditions.

<Physical properties of polyester>
In addition, it is preferable that the polyester pellet of this invention is polyester which shows the following physical properties, and even when it stores, there is little deterioration of the physical property.

The physical properties of the polyester of the present invention will be explained by taking an example of a polyester of an aliphatic diol and an aliphatic dicarboxylic acid such as polybutylene succinate or polybutylene succinate adipate, and a density of 1.2 to 1.3 g / cm ^3. The melting point is 80 to 120 ° C., the tensile strength is 30 to 80 MPa, the ultimate elongation is 300 to 600%, the tensile modulus is 400 to 700 MPa, the impact test strength is about 5 to ²⁰ kJ / m ² , and the glass transition point is −45 to −25 ° C. Possesses the properties of a versatile polymer. 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 kind of polyester raw material and additives, polymerization conditions, molding conditions and the like according to the purpose of use.

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

(Melting point)
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, 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.

(Number average molecular weight)
The number average molecular weight of the polyester of the present invention is usually 5000 or more, 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 or less. is there.

(Composition ratio)
As for the composition ratio of the polyester, it is necessary that the molar ratio of the diol unit to the dicarboxylic acid unit is substantially equal.

(Nitrogen atom content)
The nitrogen atom content other than the functional group covalently bonded to the polyester of the present invention is usually 50 ppm or less based on the mass of the polyester. The nitrogen atom content contained other than the functional group covalently bonded in the polyester is preferably 20 ppm or less, more preferably 10 ppm or less, and still more preferably 5 ppm or less. The nitrogen atom content contained in the polyester other than the covalently bonded functional group is mainly derived from the nitrogen atom in the raw material, but the nitrogen atom content contained in the polyester other than the covalently bonded functional group When the content is 50 ppm or less, coloration or generation of foreign matters during molding is small, and it is preferable that the product after molding is less susceptible to deterioration such as heat or light and hydrolysis.

  On the other hand, the nitrogen atom content contained in the polyester other than the covalently bonded functional group is preferably 0.01 ppm or more. More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, Most preferably, it is 1 ppm or more. If the nitrogen atom content is less than 0.01 ppm, a burden is imposed upon purification of the raw material, which is disadvantageous in terms of energy, and the influence on the environment cannot be ignored.

Further, when the nitrogen atom content is 1 ppm or more, the aliphatic polyester is preferable because the biodegradation rate in the soil is accelerated. By using a raw material having a nitrogen atom content in the above range, usually, the polymerization rate of the polyester can be reduced in the polymerization reaction, and the biodegradability of the resulting polyester can be promoted.
The nitrogen atom content in the polyester can be measured by a chemiluminescence method which is a conventionally known method as described later. Moreover, ppm in this invention is mass ppm.

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

  The ratio of the above-mentioned nitrogen content contained in the polyester of the present invention to the ammonia content contained in the raw material is preferably more than 0 and 0.9 or less, more preferably more than 0 and 0.6 or less, particularly preferably. Is 0.3 or less.

(Sulfur atom content)
The upper limit of the sulfur atom content in the polyester of the present invention is usually 10 ppm or less, preferably 5 ppm or less, more preferably 3 ppm or less, and most preferably 0.3 ppm or less with respect to the mass of the polyester. 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. is there. If the sulfur atom content is too large, the thermal stability and hydrolysis resistance of the polyester tend to be lowered, and if the amount is too small, the purification cost becomes remarkably high and the polyester tends to be economically disadvantageous.

(Volatile organic component content)
In the case of polyester, particularly polyester using a raw material derived from biomass resources, for example, volatile organic components such as tetothehydrofuran and acetaldehyde tend to be contained in the polyester. The upper limit of the content of these volatile organic components in the polyester of the present invention 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. 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. If the content of volatile organic components 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 polyester, in addition to requiring a very high capital investment and a long production time.

(Reduced viscosity)
The reduced viscosity (ηsp / C) value of the polyester produced in the present invention is 0.5 dL / g or more, and preferably 1.5 dL / g or more, because practically sufficient mechanical properties can be obtained. Is preferably 1.8 dL / g or more, particularly preferably 2.0 g / dL or more. The upper limit of the reduced viscosity (ηsp / C) value is usually 6.0 dL / g or less, preferably 5.0 dL / g, from the viewpoint of operability such as ease of extraction after the polymerization reaction of polyester and ease of molding. Hereinafter, it is more preferably 4.0 dL / g 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

(Solubility)
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.

(Terminal carboxyl group content)
The amount of terminal carboxyl groups of the polyester of the present invention is usually 50 equivalents / ton or less, more preferably the concentration is 35 equivalents / ton or less, more preferably 25 equivalents / ton or less, Equivalent / ton or more, preferably 0.5 equivalent / ton or more, particularly preferably 1 equivalent / ton or more. When this amount is increased, the thermal stability, hydrolyzability during the production of polyester foam, and the hydrolysis resistance during relatively long-term use / storage of the product tend to be reduced. Polyesters with too few carboxyl groups Although it is a more preferable form, it is economically disadvantageous to produce such a polyester, such as requiring a very high capital investment and requiring a great amount of production time.

  If a large amount of nitrogen-containing compounds and / or sulfur-containing compounds contained in the dicarboxylic acid and / or diol are present, these impurities become the crosslinking points of the polymer, or the thermal decomposition reaction of the polymer by these nitrogen-containing compounds and sulfur-containing compounds. Is promoted, the amount of terminal carboxyl groups in the polymer tends to increase. For that reason, in order to control the terminal carboxyl group amount within the above range, the nitrogen atom content and the sulfur atom content are controlled within the above range, and the amount of catalyst used is reduced. Alternatively, a method of carrying out polyester production at a lower polymerization temperature is preferably used.

The amount of the terminal carboxyl group of the polyester is usually calculated by a known titration method. In the present invention, the obtained polyester is dissolved in benzyl alcohol and titrated with 0.1N NaOH, and 1 × 10 ⁶ It is the carboxyl group equivalent per g.

(YI value)
It is preferable that the polyester of the present invention is usually 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, and particularly preferably 10 or less. 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 of limiting the use of foamed molded products. On the other hand, polyesters exhibiting a low YI value are a more preferred form, but there are economical disadvantages such as the production process being complicated and requiring extremely high capital investment to produce such polyesters.
In the present invention, the YI value is a value measured by a method based on JIS K7105.

[Polyester composition]
The polyester of the present invention can be subjected to foaming as a polyester composition by blending (kneading) with various conventionally known resins. 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.

  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 blend amount of these biodegradable polymers is merely 99.9 to 0.1% by weight of the biomass-derived polyester of the present invention when both are biodegradable resins for the purpose of biodegradation. On the other hand, even when the biodegradable polymer is blended in an amount of about 0.1 to 99.9% by weight, the biodegradable characteristics are appropriately expressed, so that the composition can exhibit the most appropriate characteristics. 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 and polysaccharide has the property of decaying in the presence of water and air in the natural state and returning to the soil or becoming a fertilizer, and the biomass-derived polyester 99.9 of the present invention. About 0.1 to 9% by weight, natural resin and polysaccharide can be blended by about 0.1 to 99.9% by weight. 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 foam consisting of the composition of the biomass-derived polyester and natural resin of the present invention will be a natural resin, polysaccharide even if there is no early biodegradation disappearance if the used material is discarded. May rot and may be effective as a soil conditioner and compost. This type of polyester composition may be encouraged to be actively and naturally dumped, especially in the soil, which will increase its significance as a green plastic product. Although the specific composition of each resin is disclosed below, it is not specifically limited.

  Examples of the aliphatic polyester-based resin include aliphatic polyester-based resins, aliphatic oxycarboxylic acid-based resins, etc., which have aliphatic and / or alicyclic diol units and aliphatic and / or alicyclic dicarboxylic acid units as essential components. Can be mentioned.

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

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

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

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

  The aliphatic polyester resin may be copolymerized with a tri- or higher functional alcohol or carboxylic acid. Specifically, trifunctional or more polyhydric alcohols such as trimethylolpropane, glycerin, pentaerythritol, propanetricarboxylic acid, malic acid, citric acid, tartaric acid, hydroxyglutaric acid, hydroxymethylglutaric acid, hydroxyisophthalic acid, hydroxyterephthalic acid, etc. , Polyvalent carboxylic acid and polyvalent oxycarboxylic acid may be copolymerized. The amount of the above-mentioned trifunctional or higher polyfunctional compound unit is a cause of gel generation, so the upper limit is usually 5 mol% or less, preferably 1 with respect to 100 mol% of all monomer units that usually constitute polyester. The 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 Is 0.001 mol% or more, more preferably 0.005 mol% or more, and particularly preferably 0.01 mol% or more. In addition, aliphatic oxycarboxylic acid-based resins include aliphatic and / or alicyclic diol units such as 1,4-butanediol units, succinic acid units, and adipic acid units, and aliphatic and / or alicyclic dicarboxylic acids. Units, trimethylolpropane units, glycerin units, pentaerythritol units, propanetricarboxylic acid units, malic acid units, citric acid units, tartaric acid units and other trifunctional or higher aliphatic polyhydric alcohol units, aliphatic polycarboxylic acid units, Aliphatic polyvalent oxycarboxylic acid units may be copolymerized. The upper limit of the amount of the units described above is usually 90 mol% or less, preferably 70 mol% or less, more preferably 50 mol% or less, based on 100 mol% of all monomer units constituting the polyester.

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

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

Examples of the polysaccharide include modified cellulose such as cellulose and 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 copolymer, 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-described resin to the polyester of the present invention in the polyester composition is described in detail above. If the general blending amount common to various resins is clearly shown as a generic 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 or more and 2 or less. / 98 or less.

Moreover, a conventionally well-known various additive can be mix | blended and it can be set as a composition and can also be made into a foam.
Examples of additives include crystal nucleating agents, antioxidants, anti-blocking agents, ultraviolet absorbers, light-resistant agents, plasticizers, heat stabilizers, colorants, flame retardants, mold release agents, antistatic agents, and antifogging agents. And additives for resins such as surface wetting improvers, incinerators, pigments, lubricants, dispersants and various surfactants. These addition amounts are usually 0.01 to 5% by weight with respect to the total composition weight. These can also be used as one kind or a mixture of two or more kinds.

  Moreover, a conventionally well-known various filler and functional additive can be mix | blended and it can be set as a composition, and can also be made into a foam. As functional additives, chemical fertilizers, soil conditioners, plant activators, and the like can be added. Fillers are roughly classified into inorganic fillers and organic fillers. These can also be used as one kind or a mixture of two or more kinds.

  Examples of 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. , Calcinated 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 to 80 weight% normally with respect to the total composition weight, Preferably it is 3 to 70 weight%, More preferably, it is 5 to 60 weight%. Some inorganic fillers, such as calcium carbonate and limestone, have properties of soil improvers. If a polyester composition derived from biomass 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 important to use polyester with added chemical fertilizers, soil conditioners, and plant activators as foam molded products. It will increase the usefulness of the polyesters of the invention.

  Examples of the organic filler include raw starch, processed starch, pulp, chitin / chitosan, coconut powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These can also 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 with respect to the total composition weight. 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 oil or the like can be used for the purpose of uniformly dispersing the various additives.

[Biomass resource-derived polyester foam]
The biomass resource-derived polyester foam of the present invention is obtained by foaming the above-described polyester or polyester composition of the present invention.

The process of obtaining a molded body using the biomass resource-derived polyester of the present invention may be a conventional method, and is not particularly limited. For example, a strand obtained by extruding a resin composition in which a desired additive such as a modifier or a nucleating agent is blended with the above-described polyester or polyester composition of the present invention using a normal melt extruder is used, using a pelletizer, Pellet or particles are molded (polyester resin particle production step), and the polyester resin particles are put into an autoclave and put into a gas phase or a liquid phase such as water or pure water. A resin particle dispersion is prepared using any conventional additive such as an anti-fusing agent or an anti-tack agent, and foamed particles are obtained by foaming using a volatile foaming agent (foaming step). The particles are exposed to the atmosphere, air is permeated into the particle bubbles, and moisture attached to the particles is removed as necessary (aging process). Subsequently, the foamed particles are filled in a closed mold having small holes and slits, and heated and foamed to form a molded body in which the individual particles are fused and integrated.
Each step will be described below.

<Polyester resin particle production process>
In this step, the above-mentioned polyester or a resin composition in which a desired additive such as a modifier or a nucleating agent is blended with the polyester is extruded using a normal melt extruder to form a strand, and a pelletizer is used for the expanded particles. The resin particles are manufactured. In addition to this, resin particles having a predetermined size such as beads, powder, and fine powder can be arbitrarily produced by a conventional molding method. The size of the resin particles is usually in the range of about 0.01 to 8 mm, preferably about 0.1 to 5 mm. However, in consideration of immersion of an inert volatile foaming agent in the subsequent foaming step, a pellet having a maximum major axis and a minimum minor axis within a range of about 1 to 3 mm is ideal. If the size of the resin particles is too small as 0.01 mm, the degree of foaming cannot be accurately determined, and if it is too large as 8 mm or more, it becomes difficult to immerse the foaming agent, making it difficult to form a uniform foam.

  In this step, it is preferable to produce resin particles of an arbitrary size by using the polyester, the modifier, the nucleating agent as the air-conditioning agent, other additives, and other resins. In addition, it is preferable that various additives such as a modifier are produced in advance in a high concentration master batch to produce resin particles.

  A known method can be adopted as the melt-kneading method. Usually, it is preferable to use a general-purpose twin-screw kneading extruder. The kneading temperature is preferably 120 to 250 ° C. This is because if the temperature is too high, a material such as a resin may be thermally deteriorated. In order to remove low-molecular volatile components, it is preferable that vacuum kneading (vent suction) can be performed in the middle of the kneader cylinder during kneading. In addition, the rotation direction of the two screws in the biaxial kneader may be the same direction or different directions.

  The obtained resin particles are preferably adjusted for moisture content and dried with reference to the above-mentioned polyester pellets.

  The foam of the present invention may contain a nucleating agent as a bubble adjusting agent in order to obtain uniform and fine bubble cells. This nucleating agent serves as a core when foaming the resin particles during the production of the foam of the present invention, and is used for the purpose of adjusting the number of bubbles and the diameter of the bubbles, and does not significantly impair the effects of the present invention. Any inorganic nucleating agent and organic nucleating agent can be used. For example, specific examples of inorganic nucleating agents include talc, kaolin, montmorillonite, synthetic adsorbent, synthetic mica, clay, zeolite, silica, graphite, carbon black, hydrotalcites, zinc oxide, magnesium oxide, titanium oxide, sulfide. Examples thereof include calcium, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide, and metal salts of phenylphosphonate. In addition, these inorganic nucleating agents may be modified with an organic substance in order to enhance dispersibility in the composition.

  In addition, these nucleating agents may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  The amount of the nucleating agent used is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, more preferably from the viewpoint of obtaining foamed particles having a high foaming ratio with respect to 100 parts by weight of the biodegradable resin. Is 0.1 parts by weight or more. In addition, when molding the foamed particles of the present invention, from the viewpoint of expressing excellent fusibility and obtaining a foamed molded article having excellent mechanical strength and flexibility from the foamed particles, usually 10 parts by weight or less, The amount is preferably 2 parts by weight or less. If the upper limit of this range is exceeded, the expansion ratio tends to decrease.

    Furthermore, the average particle diameter of the nucleating agent is arbitrary as long as the effects of the present invention are not significantly impaired. However, it is possible to obtain foamed particles having uniform foam and high foaming ratio, and from the point that a foamed molded article having excellent mechanical strength and flexibility can be obtained from the foamed particles, usually 50 μm or less, The thickness is preferably 10 μm or less. Further, from the viewpoint of secondary aggregation and handling workability, it is usually 0.1 μm or more, preferably 0.5 μm or more. When the average particle size exceeds the upper limit of the above range, the particle size of the nucleating agent is larger than the film thickness of the cell walls in the expanded particles, and the cell membrane is easily broken, which is not preferable. Further, when the average particle size of the nucleating agent is less than the lower limit of the above range, it is difficult to become a foaming core point and the foamability tends to be lowered.

  In addition, when the above-mentioned nucleating agent is already contained in the polyester composition used for the preparation of the resin particles, it is not necessary to further mix these, but it may be added for the purpose of arbitrarily adjusting foamability. Good.

<Foaming process>
The polyester resin particles obtained as described above are charged into an autoclave and in the gas phase or liquid phase, any conventional additive such as a dispersant, an anti-fusing agent, or an anti-tacking agent is added. Use to prepare a resin particle dispersion. Since the capacity of the autoclave is carried out using a conventional apparatus at the laboratory level, the internal volume is about 500 mL, but industrially, considering the productivity, the capacity is arbitrarily large with about 500 mL to 5000 L. Can be used.

  The dispersion medium for dispersing the resin particles at the time of foaming is arbitrary as long as it does not dissolve the resin particles. Examples thereof include water, ethylene glycol, methanol, ethanol, and the like, and usually water (for example, pure water). ) Is used. In addition, a dispersion medium may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The dispersion medium such as water or pure water is preferably charged in an amount of about 100 to 500 parts by weight with respect to 100 parts by weight of the resin particles. The amount of each additive is arbitrarily determined in consideration of the resin particles and the amount of the dispersion medium.

When the resin particles are dispersed in a dispersion medium and heated, an anti-fusing agent can be used to prevent the resin particles from fusing together. Any anti-fusing agent can be used regardless of whether it is inorganic or organic as long as it does not dissolve in the dispersion medium and does not melt by heating. In general, an inorganic one is preferred. Specific examples thereof include powders such as tricalcium phosphate, kaolin, talc, mica, aluminum oxide, titanium oxide, and aluminum hydroxide. In addition, an anti-fusing agent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The average particle diameter of the anti-fusing agent is arbitrary, but is usually 0.001 μm or more, and usually 100 μm or less, preferably 30 μm or less.
Further, the amount of the anti-fusing agent used is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin particles.

  Moreover, it is preferable to make a dispersing agent coexist in a dispersion solvent. Although there is no restriction | limiting in a dispersing agent, For example, anionic surfactants, such as sodium dodecylbenzenesulfonate and sodium oleate, etc. are mentioned. In addition, a dispersing agent may be used individually by 1 type and 2 or more types may be used. You may use together in arbitrary combinations and ratios.

  Furthermore, the amount of the dispersant used is arbitrary as long as the effects of the present invention are not significantly impaired, but it is usually preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the resin particles.

  The step of the foaming method comprises a press-in step for press-fitting a volatile foaming agent into the prepared resin particle dispersion and a pressure-release step for bringing it into a pressure-release state.

  In the press-fitting process, after the gas such as air existing in the resin particle dispersion is replaced with nitrogen gas in advance, the temperature is raised to a certain foaming temperature while injecting the volatile foaming agent under high pressure while stirring. Let stand for a certain time as the pressurization time.

  As the volatile foaming agent, it is recommended not to promote the combustion of polyester, but to be friendly to the environment and is relatively safe and easy to handle. For example, an inert gas such as carbon dioxide, nitrogen, helium, and argon, and compressed air are preferable, carbon dioxide, nitrogen, and the like are particularly preferable, and carbon dioxide is more preferable. This is because the solubility in the resin is high. Although air with a high nitrogen content can be used, it is selected in consideration of the effect of about 20% oxygen. These gases may be used alone, or two or more gases may be used at an arbitrary ratio. For example, there is a combination of carbon dioxide and compressed air.

The degree of high-pressure injection varies slightly depending on the type of foaming agent used and the type of resin particles, but usually only about 30 to 60 kgf / cm ² G (2.9 to 5.9 MPa).
Although there are some differences in the foaming temperature depending on the type of resin particles, it is usually about 80 to 120 ° C, preferably about 100 to 110 ° C.
The pressurization time is determined in consideration of the resin particles, temperature, and stirring conditions, but it is sufficient to mature for about 30 to 180 minutes, preferably about 30 to 60 minutes.

  In the pressure release step after the press-fitting step, the temperature is lowered to 100 ° C. or less, preferably about 90 to 98 ° C., in consideration of preventing sudden scattering of the contents and excessive boiling of water. Then, one end of the autoclave is released, and the resin particles are left at normal temperature (about 25 ° C.) and normal pressure (about 1 atmosphere).

The bulk density of the foamed particles thus obtained is usually 0.01 g / cm ³ or more and 0.6 g / cm ³ or less, particularly preferably 0.02 g / cm ³ or more and 0.3 g / cm ³ or less. Such expanded particles can also be referred to as pre-expanded particles. In this specification, the bulk density of expanded particles is indicated by the scale of the graduated cylinder when an empty graduated cylinder is prepared, and the expanded particle left in the graduated cylinder at a relative humidity of 50% and at 23 ° C. atmospheric pressure for more than one day. It is determined by dividing the weight of the foamed particles contained by the volume.

  By adjusting the temperature condition and the pressure release rate by setting the pressure release temperature and pressure release environment temperature in the pressure release step higher or lower than normal temperature, the expansion ratio of the obtained expanded particles is 2.0 to 120 times, Preferably, it can be controlled to about 4 to 60 times. Note that the expansion ratio also affects the quality of the foamed material such as the strength of the foamed molded product and the uniformity of the bubbles. The expansion ratio in the present specification can be quantified according to a number of conventional means, but as a familiar example, unfoamed particles and expanded particles or expanded molded articles, for example, are each put into water in a graduated cylinder, It can be easily quantified by measuring the volume change before and after foaming and calculating the volume ratio.

(About cross-linking)
The polyester resin particles can be gelled so as to be suitable as a thermoforming material that is finally filled in a mold and thermoformed. The method for gelation is optional as long as the effects of the present invention are not significantly impaired. Usually, however, the components in the polyester resin particles are crosslinked using a crosslinking agent and a crosslinking aid.

  The crosslinking agent to be used is arbitrary as long as the polyester resin particles can be crosslinked, but an organic peroxide is usually used. Specific examples of the organic peroxide that can be used as a crosslinking agent include diacyl peroxides such as lauroyl peroxide, stearoyl peroxide, and benzoyl peroxide; bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydi Examples include peroxydicarbonates such as carbonates; peroxyesters such as t-butyl peroxyisobutyrate. In addition, a crosslinking agent may be used individually by 1 type, and may be used 2 or more types by arbitrary combinations and a ratio.

  Moreover, it is preferable to use a crosslinking aid together with the crosslinking agent. Any crosslinking aid can be used as long as it has polymerizability. Among these, it is preferable to use a compound having at least one unsaturated bond in the molecule.

The unsaturated bond of the crosslinking aid includes a triple bond as well as a double bond. Examples of such a crosslinking aid include divinyl compounds such as divinylbenzene; acrylic acid; acrylic acid esters such as methyl acrylate and ethyl acrylate; methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; styrene; acetic acid Vinyl: Ethylene glycol diacrylate, polyethylene glycol diacrylate, trimethylol propane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, ethylene glycol dimethacrylate, trimethylol propane trimethacrylate, allyl methacrylate and other acrylates or methacrylates A compound of cyanuric acid such as triallyl cyanurate or triallyl isocyanurate or allyl ester of isocyanuric acid Allyl esters of carboxylic acids such as trimellitic acid triallyl ester, trimesic acid triallyl ester, pyromellitic acid triallyl ester, benzophenone tetracarboxylic acid triallyl ester, diallyl oxalate, diallyl succinate, diallyl adipate; N -Maleimide compounds such as phenylmaleimide and N, Nm-phenylenebismaleimide; Polymers having a double bond such as 1,2-polybutadiene; Diprovagyl phthalate, Diprobagil isophthalate, Triprovagyl trimesate, Diprobagil itaconate, Malein Examples thereof include compounds having two or more triple bonds such as acid diprobagil. In addition, polyester having an unsaturated bond can also be used.
In addition, a crosslinking adjuvant may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Especially, as a combination of a crosslinking agent and a crosslinking aid, a combination of an organic peroxide as a crosslinking agent and a divinyl compound, acrylic acid, acrylic acid ester or methacrylic acid ester as a crosslinking aid is preferable. In particular, a combination of benzoyl peroxide as a crosslinking agent and divinylbenzene or methyl methacrylate as a crosslinking aid is more preferable.

  There is no limitation on the amount of the crosslinking agent used, as long as the effects of the present invention are not significantly impaired. However, the amount is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more per 100 parts by weight of the polyester resin particles. The amount is usually 10 parts by weight or less, preferably 5 parts by weight or less. If the lower limit of this range is not reached, the crosslinking effect may not be obtained, and if the upper limit is exceeded, unreacted substances and residues of the crosslinking agent may remain on the foamed particles and the molded body thereof.

  Further, the amount of the crosslinking aid used is not limited and is arbitrary as long as the effects of the present invention are not significantly impaired. Usually, 0.001 part by weight or more, preferably 0.01 part by weight per 100 parts by weight of the polyester resin particles. Part or more, and usually 10 parts by weight or less, preferably 2 parts by weight or less. If the lower limit of this range is not reached, the crosslinking effect may not be obtained. If the upper limit is exceeded, unreacted substances and residues of the crosslinking aid may remain in the foamed particles and the molded body thereof.

  The cross-linking agent and the cross-linking aid may coexist in the polyester resin particles at any stage before foaming. For example, it may be included in the polyester in the production process of the polyester, and when mixing each component of the polyester resin particles using a melt extruder, a crosslinking agent and a crosslinking aid may be mixed. The polyester resin particles may be mixed with the crosslinking agent and the crosslinking aid after the production of the polyester resin particles. Alternatively, the polyester resin particles may be mixed and impregnated in the step before impregnating the foaming agent to produce a heated crosslinked body. .

When the polyester resin particles are gelated by crosslinking, the polyester resin particles are usually heated in a dispersion medium in the presence of a crosslinking agent and a crosslinking aid used as appropriate.
There is no restriction | limiting in a dispersion medium, Arbitrary things can be used as long as bridge | crosslinking is possible. For example, water, ethylene glycol, methanol, ethanol and the like can be mentioned. In addition, a dispersion medium may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Further, when water is used as the dispersion medium, in the hot water heat treatment step, the crosslinking agent and the crosslinking aid may be allowed to coexist in the water during heating, and crosslinking may be performed simultaneously.

  Moreover, the temperature conditions at the time of crosslinking are arbitrary as long as crosslinking is possible. The specific temperature condition varies depending on the type of resin of the polyester resin particles, and it is difficult to determine uniquely. Usually, the melting point of the polyester resin is Tm (° C), and [Tm-25 (° C)] to [Tm-25 (° C)] to [ Tm + 10 (° C.)] is preferable. In addition, it is desirable to use a crosslinking agent having a half-life of 1 hour in the above temperature range as a crosslinking agent. If an organic peroxide (crosslinking agent) having a too high decomposition temperature is used, when the resin particles are heated in water, the heating temperature becomes high and the heating time becomes long, so that the polyester resin may be hydrolyzed. This is not preferable.

  Furthermore, the time for heating for crosslinking is arbitrary as long as the effects of the present invention are not significantly impaired. However, holding for a long time under heating conditions may cause the hydrolysis of the polyester to progress, and the gelation efficiency and resin properties may deteriorate, so the reaction time may be less than 3 hours. preferable.

Further, in order to ensure that the polyester resin particles are gelled, an impregnation step of impregnating the polyester resin particles with a crosslinking agent or a crosslinking aid at a temperature lower than the above heating temperature is performed before the above crosslinking. It is preferable to do so.
The impregnation temperature during impregnation is not limited and is arbitrary. A suitable impregnation temperature differs depending on the type of polyester and is difficult to determine uniquely, but is preferably in a range from a temperature at which the crosslinking agent gives a half-life of 20 hours to a temperature at which a half-life of 5 hours is given. .

  Further, the impregnation time of the crosslinking agent or the like is not limited and is arbitrary. A suitable impregnation time varies depending on the weight of the polyester resin particles, but is usually 10 minutes or more, and usually 120 minutes or less, preferably 60 minutes or less. If the impregnation time is too long, the impregnation property is improved, but the polyester resin may be hydrolyzed. On the other hand, if the impregnation time is too short, the gel fraction inside the obtained expanded particles may be lowered.

  Specific examples of the above impregnation temperature and impregnation time include, for example, when benzoyl peroxide is used as a crosslinking agent, the impregnation temperature is usually 65 ° C. or higher, preferably 70 ° C. or higher, and usually 85 ° C. or lower. The temperature is preferably 80 ° C. or lower, and the impregnation time is usually 10 minutes or longer, and usually 120 minutes or shorter, preferably 60 minutes or shorter.

  In addition, when crosslinking is performed by reacting the polyester resin particles with a crosslinking agent and a crosslinking aid used as appropriate in a sealed container, it is preferable to reduce the oxygen concentration in the upper gas phase space in the sealed container. A preferable oxygen concentration is 5% by volume or less, and more preferably 0.5% by volume or less. Thereby, the advantage that the oxidative degradation of a crosslinking agent can be suppressed can be acquired.

Examples of the method for reducing the oxygen concentration include a method of purging with an inorganic gas such as nitrogen gas, carbon dioxide, argon gas, water vapor, etc., but any other method can be adopted.
In this connection, it is desirable that the dispersion medium to be used has a dissolved oxygen concentration of usually 9.5 mg / L or less, preferably 8.5 mg / L or less.
The gel fraction of the expanded particles can be adjusted by the gelation conditions when the polyester resin particles are gelated in the presence of a crosslinking agent in the dispersion medium.

(Foam molding process)
In order to form a desired foamed molded product, a predetermined amount of foamed particles are put into a molding die (mold) having a shape intended for molding of a predetermined size as a foam molding process, and steam is added. It is preferable to perform foam molding by heating to about 100 to 140 ° C., preferably 110 to 125 ° C. with steam as a heating means such as conduction heat, radiant heat, and microwave. The amount of the foam particles to be charged into the mold varies depending on the degree of foaming of the foam particles in advance, but the amount of the foam particles is about 30 to 90% by volume with respect to the mold capacity in consideration of the expansion ratio. Is enough. A foamed molded product having a predetermined shape is molded by heating and foaming it in a molding die (mold).

  On the other hand, the foaming ratio is very high, for example, a predetermined foamed molded product can be produced by compressing foamed particles with a foaming ratio of about 10 to 80 times. In the case of expanded particles that have reached the saturation level, such as about 50 times, a slightly larger amount of expanded particles of about 110 to 180% by volume are put into the mold and reduced in size. It is also possible to harden. Particles with a high expansion ratio are heat-fused, which leads to reduction of bubbles, requires advanced handling techniques, and is not a conventional technique. This foam molding process is usually a design item determined in consideration of various circumstances such as the mold, size, strength, and application of a specific foam molded product. Usually, the foamed particles with relatively low foaming, which can be referred to as pre-foamed particles, are further foamed in the mold and can be called secondary foaming, and the expansion ratio is 10 to 80 times with respect to the unfoamed particles. It is recommended to form a foam molded article having a desired use with an expansion ratio of 20 to 50 times.

  The foamed molded product of the present invention depends on the expansion ratio of the foamed particles and the molding conditions of the molding die (mold), but the molding die with a relatively low temperature during molding of the foamed molded product. If molding is performed with (mold), a foamed molded article with a skin can be molded. When foamed to a high degree in the mold, the foam structure in which the bubbles are arranged in an elliptical shape in the foam direction is often adopted, but the expanded particles in the part corresponding to the surface layer part pressed against the mold surface are In some cases, it is easily crushed and the skin has a low foaming ratio, or the air bubbles in the surface layer portion become air bubbles flattened in equilibrium on the surface layer surface. The surface structure of this foam molded product will affect the occurrence of shrinkage, breathability, water permeability, heat insulation, and strength of the foam molded product. Should be. For foam molded products that require partial strength, mechanical materials and structural devices are beneficial by providing skins or ribs.

(Secondary processing process)
The foamed molded product thus obtained has surface functions such as chemical function, electrical function, magnetic function, mechanical function, friction / abrasion / lubricating function, optical function, thermal function, biocompatibility, etc. Various purposeful secondary processing can be performed for the purpose of providing the above. 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.).

  There are no particular restrictions on the shape of the foamed molded article thus obtained, and examples include various shapes such as a container shape, a plate shape, a cylindrical shape, a column shape, a sheet shape, a board shape, and a block shape. As its use, it is expected to be used for daily sundries, toys, industrial materials, industrial materials, heat insulating materials and buffer materials for cold storage boxes. Moreover, it is good also as a laminated body with the non-foamed body of the same or other resin.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples, unless the summary is exceeded. The characteristic values in the following examples were measured by the following method. Moreover, ppm in this invention is mass ppm.

Dilute solution viscosity (reduced viscosity): Polyester is dissolved in phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) to a concentration of 0.5 g / dL, and the solution is a viscosity tube in a thermostatic bath at 30 ° C. The time t (sec) for dropping was measured. Further, the time t ₀ (sec) during which only the solvent falls was measured, and the reduced viscosity ηsp / C (= (t−t ₀ ) / t ₀ · C) at 30 ° C. was calculated (C is the concentration of the solution).

  Nitrogen atom content: A sample of 10 mg was taken into a quartz boat, the sample was burned using a total nitrogen analyzer (TN-10 manufactured by Mitsubishi Chemical Corporation), and determined by a chemiluminescence method.

  Sulfur atom 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), and 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).

  Water content (water content): A water vaporizer (VA-100 model manufactured by Mitsubishi Chemical Corporation) was used to heat and melt a 0.5 g sample at 200 ° C. to vaporize water in the sample, and then vaporized. The water content in the sample was determined by quantifying the total water content by a coulometric titration method based on the principle of the Karl Fischer reaction using a trace moisture measuring device (CA-100 model manufactured by Mitsubishi Chemical Corporation).

Terminal carboxyl group amount: The value obtained by dissolving the obtained polyester in benzyl alcohol and titrating with 0.1 N NaOH, which is the carboxyl group equivalent per 1 × 10 ⁶ g.

  YI value: Measured based on the method of JIS K7105.

[Reference Example 1]
<Construction of vector for gene disruption>
(A) Extraction of Bacillus subtilis genomic DNA In 10 mL of LB medium [composition: tryptone 10 g, yeast extract 5 g, NaCl 5 g dissolved in 1 L of distilled water], 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 solution (pH 8.0) / 1 mM EDTA · 2Na solution containing lysozyme at a concentration of 10 mg / mL.

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

  (B) Amplification and cloning of SacB gene by PCR 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. PCR was performed using the synthetic DNAs (SEQ ID NO: 1 and SEQ ID NO: 2) designed in the above.

Composition of reaction solution: Template DNA 1 μL, PfxDNA polymerase (manufactured by Invitrogen) 0.2 μL, 1 × concentration attached buffer, 0.3 μM each primer, 1 mM MgSO ₄ , 0.25 μM dNTPs were mixed to make a total volume of 20 μL.
Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds and 68 ° C. for 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 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. .

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

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

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

(D) Acquisition of kanamycin resistance gene The kanamycin resistance gene is obtained by PCR using the DNA of E. coli plasmid vector pHSG299 (Takara Shuzo: Kanamycin resistance marker) as a template and the synthetic DNAs shown in SEQ ID NO: 3 and SEQ ID NO: 4 as primers. Went by.
Composition of reaction solution: Template DNA 1 ng, Pyrobest DNA polymerase (Takara Shuzo) 0.1 μL, 1-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 condition: 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 FMCBioProducts) gel electrophoresis and then visualized by ethidium bromide staining to detect a fragment of about 1.1 kb. 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).

(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 strain 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, distilled water 1 L] 10 mL In addition, Brevibacterium flavum MJ-233 strain was cultured until the late logarithmic growth phase, and genomic DNA was prepared from the obtained cells by the method shown in (A) of Reference Example 1 above.

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

Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds, 55 ° C. for 20 seconds, and 72 ° C. for 1 minute was repeated 30 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute 20 seconds, and the heat retention at 72 ° C. in the final cycle was 5 minutes.
Confirmation of the amplification product was carried out by separating by 0.75% agarose (SeaKem GTG agarose: manufactured by FMCBioProducts) gel electrophoresis and then visualized by ethidium bromide staining to detect a fragment of about 0.95 kb. 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 SacI and SphI, an inserted fragment of about 1.0 kb was recognized, and this was named pGEMT / CgLDH.

(C) Construction of a plasmid for disrupting the lactate dehydrogenase gene 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) was cyclized to transform 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, so that an insert fragment of about 0.75 kb was selected and named pKMB1 / ΔLDH (FIG. 2).

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

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

  Since the strain grown on this medium is a plasmid in which pKMB1 / ΔLDH cannot be replicated in Brevibacterium flavum MJ233-ES, the lactate dehydrogenase gene of the plasmid and Brevibacterium flavum MJ-233 strain As a result of homologous recombination with the same gene on the genome, the kanamycin resistance gene and SacB gene derived from the plasmid should be inserted on the 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 a mutant type or a wild type is 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 was analyzed using primers (SEQ ID NO: 7 and SEQ ID NO: 8) for PCR amplification, a DNA fragment of 720 bp should be observed in the wild type and a 471 bp DNA fragment in the mutant type having the deletion region.

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

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

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

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

[Reference Example 3]
<Construction of Coryneform Bacterial Expression Vector>
(A) Preparation of Promoter Fragment for Coryneform Bacteria A DNA fragment (hereinafter referred to as TZ4 promoter) described in SEQ ID NO: 4 of JP-A-7-95891 reported to have 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 a synthetic DNA designed based on the sequence described in SEQ ID NO: 4 of JP-A-7-95891 ( It was performed by PCR using 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: Using DNA thermal cycler PTC-200 (manufactured by MJ Research), 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 kit ver. 2 (Takara Shuzo) was used to bind to the SmaI site of E. coli vector pUC19 (Takara Shuzo), and Escherichia coli (DH5α strain) was transformed with the resulting plasmid DNA. The recombinant Escherichia coli thus obtained was smeared on an LB agar medium containing 50 μg / mL ampicillin and 50 μg / mL X-Gal.

  Six clones that formed white colonies on this medium were subjected to liquid culture by a conventional method, and then the plasmid DNA was purified and the nucleotide sequence was determined. Among them, a clone in which the TZ4 promoter was inserted so as to have a transcriptional activity in the reverse direction to the lac promoter of pUC19 was selected and named pUC / TZ4.

  Next, a DNA fragment prepared by cleaving pUC / TZ4 with restriction enzymes BamHI and PstI is composed of synthetic DNA (SEQ ID NO: 11 and SEQ ID NO: 12) phosphorylated at the 5 ′ end, and BamHI and A DNA linker having a sticky end against PstI was mixed, and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (DH5α strain) was transformed with the obtained plasmid DNA. This DNA linker contains a ribosome binding sequence (AGGAGG) and a cloning site (PacI, NotI, ApaI in this order from the upstream).

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

(B) Construction of Coryneform Bacterial Expression Vector pHSG298par-rep described in JP-A-12-93183 is used as a plasmid that can stably replicate independently in coryneform bacteria. This plasmid comprises a replication region of the natural plasmid pBY503 possessed by Brevibacterium stachynis IFO12144 strain and a region having a stabilizing function, 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 on the basis of the gene sequence (GenBank Database Accession No. AP005276) of the ATCC13032 strain.

Composition of reaction solution: Template DNA 1 μL, PfxDNA polymerase (manufactured by Invitrogen) 0.2 μL, 1 × concentration attached buffer, 0.3 μM each primer, 1 mM MgSO ₄ , 0.25 μM dNTPs were mixed to make a total volume of 20 μL.
Reaction temperature conditions: DNA thermal cycler PTC-200 (manufactured by MJ Research) was used, and a cycle consisting of 94 ° C. for 20 seconds and 68 ° C. for 4 minutes was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute and 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 FMCBioProducts) 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 is 0.75 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, so that an insert 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 SONIFIER350 (manufactured by BRANSON), and the centrifuged supernatant was used as a cell-free extract. The pyruvate carboxylase activity was measured using the obtained cell-free extract. The enzyme activity was measured using 100 mM Tris / HCl buffer (pH 7.5), 0.1 mg / 10 ml biotin, 5 mM magnesium chloride, 50 mM sodium bicarbonate, 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 a medium of 100 mL is placed in a 500 mL Erlenmeyer flask at 120 ° C. for 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 medium is 5 L The mixture was placed in a 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. Glucose was almost consumed after 12 hours.

  Magnesium sulfate heptahydrate: 1.5 g, ferrous sulfate heptahydrate: 60 mg, manganese sulfate hydrate: 60 mg, D-biotin: 600 μg, thiamine hydrochloride: 600 μg, defoamer (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 carried out with aeration at 500 mL / min and stirring at 300 rpm. In 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.

[Reference Example 6]
<Purification of succinic acid from succinic acid fermentation broth>
103 L (succinic acid content: 5.87 kg) of the succinic acid fermentation broth obtained as described above was concentrated in a stirred tank with a jacket while reducing the pressure. The concentration of succinic acid was 32.9% and ammonia 11.9% concentrate: 17.8 kg (calculated value) was obtained. To this, 8.58 kg of acetic acid (manufactured by Daicel Chemical Industries) was added and cooled to 30 ° C., 4.0 kg of methanol (manufactured by Kishida Chemical Co., Ltd.) was added, cooled to 15 ° C. and stirred for 1 hour, and then at 20 ° C. Stirring was continued for 4 hours.

Crystals were precipitated and filtered with a centrifugal filter to obtain 4.95 kg of crystals containing 74.6% succinic 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 87.9% succinic acid, 8.4% acetic acid, and 0.6% ammonia. 2.44 kg was obtained.

The obtained crystals were washed with 3.5 L of demineralized water cooled to 5 ° C., and filtered with a centrifugal filter. 90% succinic acid, 1.7% acetic acid, 0.05% ammonia (approximately 500 ppm) ) Containing 2.08 kg of crystals was obtained.
This crude succinic 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. While continuously feeding this to a rotary evaporator under reduced pressure, the solution was concentrated to approximately 5.2 L. 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% succinic acid. When this was dried with a vacuum dryer, 1.68 kg of succinic acid could be obtained.

[Reference Example 7]
<Production of 1,4-butanediol>
1,4-butanediol was obtained by a known method using the biomass resource-derived succinic acid obtained by the above method. Such 1,4-butanediol was obtained, for example, by the following method.
A mixed solution of 100 parts by weight of biomass resource-derived succinic acid, 317 parts by weight of methanol and 2 parts by weight of concentrated sulfuric acid (97%) was stirred for 2 hours under reflux. After cooling the reaction solution, 3.6 parts by weight of sodium bicarbonate was added, and the reaction solution was stirred at 60 ° C. for 30 minutes. Distillation under normal pressure and the distillation residue were filtered and then distilled under reduced pressure to obtain dimethyl succinate (yield 93%). In the presence of 15 parts by weight of CuO-ZnO catalyst (T-8402, manufactured by Zude Chemie), 100 parts by weight of the obtained dimethyl succinate was subjected to an autoclave (Hastelloy C) having a volume capacity about 4 times that of the charged dimethyl succinate. The temperature was raised to 230 ° C. over 1 hour while stirring under pressure of 5 MPa using hydrogen. Thereafter, the reaction solution was stirred for 9 hours at 230 ° C. under a hydrogen pressure of 15 MPa. After the reaction solution was cooled, degassing was performed. The catalyst was removed from the reaction solution by filtration. The filtrate was distilled under reduced pressure to obtain purified 1,4-butanediol (yield 81%). The purified 1,4-butanediol produced contained 0.7 ppm of nitrogen atoms, but did not contain sulfur atoms. Further, 1,4-butanediol contained 1000 ppm of 2- (4-hydroxybutyloxy) tetrahydrofuran as an oxidation product.

[Production Example 1]
<Production of polyester and biomass pellets using biomass resource-derived succinic acid having a nitrogen atom content of 5 ppm and a sulfur atom content of 0.2 ppm>
In a reaction vessel equipped with a stirrer, a nitrogen inlet, a heating device, a thermometer, and a vacuum outlet, 100 parts by weight of biomass resource-derived succinic acid having a nitrogen atom content of 5 ppm and a sulfur atom content of 0.2 ppm (YI = 2 5), 88.5 parts by weight of industrial grade 1,4-butanediol manufactured by Mitsubishi Chemical Corporation, 0.37 parts by weight of malic acid, and 88% lactic acid aqueous solution 5 in which 0.98% by weight of germanium dioxide was previously dissolved as a catalyst. .4 parts by weight were charged, and after reducing pressure (attainment pressure reduction degree 0.2 kPa), the system was put under nitrogen atmosphere by repeating the operation of returning to atmospheric pressure with nitrogen gas three times.
Next, the system was heated to 220 ° C. while stirring at 150 rpm, and reacted 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, and the reaction was performed at the same degree of pressure for 1.8 hours. Here, the stirring rotation speed of the stirring apparatus after depressurization was decreased stepwise to 150 rpm, 60 rpm, and 40 rpm, and the rotation speed for 30 minutes before the completion of polymerization was set to 6 rpm. The obtained polyester was extracted as a strand from the bottom of the reaction vessel at 220 ° C., submerged in 10 ° C. water, and then cut with a cutter to obtain white pellets (yellowness YI of 11). The white polyester pellet obtained had a minimum diameter of 2 mm and a maximum diameter of 3.5 mm. The pellet was heat-dried at 80 ° C. for 8 hours under vacuum to obtain a pellet having a water content of 358 ppm. The nitrogen atom content and sulfur atom content in the polyester after drying are 2 ppm and 0.1 ppm, respectively, the reduced viscosity (ηsp / C) of the polyester is 2.5 dL / g, and the terminal carboxyl group content is 26 equivalents / ton. Met. 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 dried pellets were stored for half a year in a polyester / aluminum / polyethylene composite film bag in the absence of light, and no significant deterioration in the tensile elongation properties of the pellets was observed.
On the other hand, for the purpose of further reducing the water content of the pellets, it was found that when heated and dried under vacuum at 100 ° C. for 72 hours, coloring of the polymer was observed, and long-term drying was not preferable.

[Production Example 2]
<Production of polyester using biomass resource-derived succinic acid having a nitrogen atom content of 12 ppm and a sulfur atom content of 5 ppm>
Derived from biomass resources containing 12 ppm nitrogen atoms and 5 ppm sulfur atom content instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm nitrogen atoms and 0.2 ppm sulfur atom content of Production Example 1 as raw materials The same white polyester pellets as in Production Example 1 were produced under the same conditions as in Production Example 1 except that 100 parts by weight of succinic acid (yellowness YI was 7) was used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2 hours.
The obtained polyester (yellowness YI is 22) has a nitrogen atom content of 3.6 ppm, a sulfur atom content of 2.6 ppm, a reduced viscosity (ηsp / C) of the polyester of 2.3 dL / g, and a terminal carboxyl group. The amount 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.

[Production Example 3]
<Production of polyester using biomass resource-derived succinic acid having a nitrogen atom content of 115 ppm and a sulfur atom content of 0.3 ppm>
As a raw material, instead of 100 parts by weight of succinic acid derived from a biomass resource containing 5 ppm of nitrogen atom and 0.2 ppm of sulfur atom of Production Example 1, biomass resource containing 115 ppm of nitrogen atom and 0.3 ppm of sulfur atom content Polyester pellets similar to Production Example 1 were produced under the same conditions as Production Example 1 except that 100 parts by weight of succinic acid derived from was used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.9 hours.
The obtained polyester (yellowness YI is 23) has a nitrogen atom content of 19 ppm, a sulfur atom content of 0.2 ppm, and the polyester has a reduced viscosity (ηsp / C) of 2.5 dL / g and a terminal carboxyl group content of 19 Equivalent / 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.

[Production Example 4]
<Production of polyester and pellets using biomass resource-derived succinic acid having a nitrogen atom content of 230 ppm and a sulfur atom content of 1 ppm>
Derived from biomass resources containing 230 ppm nitrogen atoms and 1 ppm sulfur atom content instead of 100 parts by weight of succinic acid derived from biomass resources containing 5 ppm nitrogen atoms and 0.2 ppm sulfur atom content of Production Example 1 as raw materials The same polyester pellets as in Production Example 1 were produced under the same conditions as in Production Example 1 except that 100 parts by weight of succinic acid (yellowness YI was 11) was used. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 2.6 hours.
The obtained polyester (yellowness YI is 39) has a nitrogen atom content of 27 ppm, a sulfur atom content of 0.6 ppm. The polyester has a reduced viscosity (ηsp / C) of 2.4 dL / g and a terminal carboxyl group content of 19 equivalents. / Ton. The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

[Production Example 5]
<Production of polyester and pellets thereof using petroleum-derived succinic acid containing no nitrogen atom and sulfur atom and biomass resource-derived 1,4-butanediol containing 0.7 ppm of nitrogen atom>
As a raw material, instead of the succinic acid of Production Example 1, petroleum-derived succinic acid containing no nitrogen and sulfur atoms (Kawasaki Chemical Co., Ltd., industrial grade (Yellowness YI is 2) 100 parts by weight) Polyester pellets similar to Production Example 1 under the same conditions as Production Example 1 except that 88.5 parts by weight of 1,4-butanediol derived from biomass resources were used instead of petroleum-derived 1,4-butanediol. The polymerization reaction time under reduced pressure of 0.07 × 10 ³ Pa was 3.4 hours.
The obtained polyester (yellowness YI was 7) had a nitrogen atom content of 0.5 ppm, a reduced viscosity (ηsp / C) of the polyester of 2.5 dL / g, and a terminal carboxyl group content of 28 equivalents / ton. . The obtained polyester (0.5 g) was uniformly dissolved in 1 dL of phenol / tetrachloroethane (1/1 (mass ratio) mixed solution) at room temperature.

[Production Example 6]
<Production of polyester using biomass resource-derived succinic acid having a nitrogen atom content of 660 ppm and a sulfur atom content of 330 ppm and its pellets>
Production Example 1 except that 100 parts by weight of succinic acid (yellowness YI is 8) derived from biomass resources containing 660 ppm nitrogen atom and 330 ppm sulfur atom instead of succinic acid of Production Example 1 was used as a raw material. A polyester was produced under the same polycondensation reaction conditions. The polymerization reaction was carried out under a reduced pressure of 0.07 × 10 ³ Pa for 2.5 hours, but the obtained polyester was colored dark brown (yellow degree YI was 60 or more).
The polyester of the obtained brown tea had a nitrogen atom content of 54 ppm, a sulfur atom content of 16 ppm, a reduced viscosity (ηsp / C) of the polyester of 0.7 dL / g, and a terminal carboxyl group content of 139 equivalents / ton. It was.

[Production Example 7]
<Production of polyester and biomass pellets using biomass resource-derived succinic acid having a nitrogen atom content of 850 ppm and a sulfur atom content of 290 ppm>
Production Example 1 except that 100 parts by weight of succinic acid (yellowness YI is 8) derived from a biomass resource containing nitrogen atom content 850 ppm and sulfur atom 290 ppm instead of succinic acid of Production Example 1 was used as a raw material. Polyester pellets similar to Production Example 1 were produced under the same conditions. The polymerization reaction was carried out for 2.5 hours under a reduced pressure of 0.07 × 10 ³ Pa, but the resulting polyester was colored dark brown (yellowness YI was 60 or more).
The polyester of the obtained brown tea had a nitrogen atom content of 51 ppm, a sulfur atom content of 16 ppm, a reduced viscosity (ηsp / C) of the polyester of 1.1 dL / g, and a terminal carboxyl group content of 69 equivalents / ton. .

  From this production example, it can be seen that as the content of nitrogen atoms and sulfur atoms in the polyester increases, the coloration and polymerization inhibition of the polyester tend to become remarkable. In particular, the greater the nitrogen atom content, the more prominent the coloration of the polymer.On the other hand, if the sulfur atom is contained in more than a certain amount, or if the production at high temperature is attempted, the amount of carboxyl group carboxyl groups increases, There is a tendency for insoluble matter in organic solvents, which are thought to be partially formed by gelation, to increase. It is known that when these insoluble materials are mixed into a product, the product landscape is impaired and physical properties are deteriorated.

[Example 1]
100 parts by weight of the aliphatic polyester obtained in Production Example 1 and 0.2 parts by weight of talc (manufactured by Matsumura Sangyo Co., Ltd., High Filler # 12; average particle size 3 to 4 μm) as a nucleating agent (bubble adjusting agent) After melt-kneading at 190 ° C. with a twin-screw extruder (KZW15) manufactured by Technobel, it was extruded into a strand shape, and then this strand was cut to have a diameter of about 1.7 mm, a length of about 1.9 mm, and about 1 per piece. 3 mg of aliphatic polyester resin particles were obtained (aliphatic polyester resin particle production step).
Table 1 shows the terminal carboxyl group content, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles.
100 parts by weight of the obtained aliphatic polyester resin particles, 300 parts by weight of pure water, 0.02 part by weight of tricalcium phosphate (average particle size μm) as an anti-fusing agent, sodium dodecylbenzenesulfonate as a dispersant 0.0006 part by weight was put into an autoclave having an internal volume of 500 mL, and nitrogen gas was introduced to remove oxygen in the autoclave. While stirring, the temperature was raised to the foaming temperature (105 ° C.), carbon dioxide was injected until the autoclave pressure reached 45 kgf / cm ² G (3.9 MPa), and the temperature was maintained for 60 minutes. Thereafter, the contents are cooled to 95 ° C. and held at the same temperature for 5 minutes, then one end of the autoclave is opened, and expanded particles (bulk density 0.028 g / cm ³ ) with an expansion ratio of 30 times under atmospheric pressure. Obtained (foaming step).
The expansion ratio, terminal carboxyl group amount, and reduced viscosity of the obtained expanded particles were measured.
The obtained expanded particles are allowed to stand for 1 day or more under the conditions of a temperature of 25 ° C. and a relative humidity of 50%, and a mold of 40 mm × 40 mm × 25 mm is filled with 90% of the volume, and the molding temperature is 120 ° C. with steam. When molding was performed by heating, the moldability was satisfactory (◯) with no problems in the evaluation of moldability.
The obtained in-mold foam molded article was cured at 40 ° C. under atmospheric pressure for 48 hours (in-mold molding process).

[Example 2]
Polyester resin particles, expanded particles, and in-mold molded articles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 2 was used as the base resin. The obtained expanded particles were expanded particles having an expansion ratio of 30 times. Further, the molded body in the mold could be molded without any problem as in the case of Example 1, and the moldability was good (◯).
The amount of terminal carboxyl groups, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles and the expansion ratio, terminal carboxyl group amount and reduced viscosity of the obtained expanded particles were measured, and in-mold moldability is shown in Table 1. It was.

[Example 3]
Polyester resin particles, expanded particles, and in-mold molded articles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 3 was used as the base resin. The obtained expanded particles were expanded particles having an expansion ratio of 33 times. Further, the molded body in the mold could be molded without any problem as in the case of Example 1, and the moldability was good (◯).
The amount of terminal carboxyl groups, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles and the expansion ratio, terminal carboxyl group amount and reduced viscosity of the obtained expanded particles were measured, and in-mold moldability is shown in Table 1. It was.

[Example 4]
Polyester resin particles, foamed particles, and in-mold molded articles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 4 was used as the base resin. The obtained expanded particles were expanded particles having an expansion ratio of 32 times. Further, the molded body in the mold could be molded without any problem as in the case of Example 1, and the moldability was good (◯).
The amount of terminal carboxyl groups, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles and the expansion ratio, terminal carboxyl group amount and reduced viscosity of the obtained expanded particles were measured, and in-mold moldability is shown in Table 1. It was.

[Example 5]
Polyester resin particles, expanded particles, and in-mold molded articles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 5 was used as the base resin. The obtained expanded particles were expanded particles having an expansion ratio of 35 times. Further, the molded body in the mold could be molded without any problem as in the case of Example 1, and the moldability was good (◯).
The amount of terminal carboxyl groups, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles and the expansion ratio, terminal carboxyl group amount and reduced viscosity of the obtained expanded particles were measured, and in-mold moldability is shown in Table 1. It was.

[Example 6]
In the resin particle production process of Example 1, resin particles were obtained except that 0.5 part by weight of a carbodiimide compound (Nisshinbo Carbodilite LA-1) was added. In the expanded particle production process, polyester expanded particles and in-mold molded bodies were produced under the same conditions as in Example 1. The obtained expanded particles were expanded particles having an expansion ratio of 34 times. Further, the molded body in the mold could be molded without any problem as in the case of Example 1, and the moldability was good (◯).
The amount of terminal carboxyl groups, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles and the expansion ratio, terminal carboxyl group amount and reduced viscosity of the obtained expanded particles were measured, and in-mold moldability is shown in Table 1. It was.

[Comparative Example 1]
Polyester resin particles and expanded particles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 6 was used as the base resin.
However, the coalescence of the bubbles and the deformation of the particles were remarkable, and satisfactory foamed particles could not be obtained.
Moreover, although the obtained foamed particles were subjected to in-mold molding, a foam molded article was not obtained.
Table 1 shows the terminal carboxyl group content, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles, and the expansion ratio, terminal carboxyl group content and reduced viscosity of the obtained expanded particles.
In this comparative example, since the amount of impurities (nitrogen, sulfur) mixed from the raw material derived from biomass resources is large, a satisfactory molecular weight cannot be obtained, and it can be seen that this is unsuitable for the production of foamed molded products. Furthermore, it was found that impurities contained in the polyester promote hydrolysis during the foaming process, resulting in a reduction in reduced viscosity and an increase in the amount of terminal carboxyl groups.

[Comparative Example 2]
Polyester resin particles and expanded particles were produced under the same conditions as in Example 1 except that the aliphatic polyester obtained in Production Example 7 was used as the base resin.
However, the coalescence of the bubbles and the deformation of the particles were remarkable, and satisfactory foamed particles could not be obtained.
Moreover, although the obtained foamed particles were subjected to in-mold molding, a foam molded article was not obtained.
Table 1 shows the terminal carboxyl group content, reduced viscosity, nitrogen atom and sulfur atom content of the aliphatic polyester resin particles, and the expansion ratio, terminal carboxyl group content and reduced viscosity of the obtained expanded particles.
In this comparative example, since the amount of impurities (nitrogen, sulfur) mixed from the raw material derived from biomass resources is large, a satisfactory molecular weight cannot be obtained, and it can be seen that this is unsuitable for the production of foamed molded products. Furthermore, it was found that impurities contained in the polyester promote hydrolysis during the foaming process, resulting in a reduction in reduced viscosity and an increase in the amount of terminal carboxyl groups.

The birth of the polyester of the present invention and its background will be described in detail. In a large cycle on the ground, in the atmosphere, the birth of the polyester of the present invention is the preservation of the global environment, resource saving, pollution prevention, aesthetic environment protection, new The presence of the polyester can be evaluated from many viewpoints such as the direction of technical development.
The characteristics of the polyester of the present invention are completely different from conventional recognition in terms of its presence in the global environment, compared to conventional underground fossil fuel dependent type, for example, petroleum resource dependent polyester. To do.
In particular, since a so-called diol unit or dicarboxylic acid unit obtained from a natural material vegetated under the global environment of the present atmospheric environment by a method such as fermentation is used as a polyester monomer, the raw material can be obtained at a very low cost. 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 used waste, which is the acquisition of monomers, synthesis of polyester, and biodegradation, is based exclusively on the natural process of the global environment in the atmosphere. The polyester of the invention provides a cycle that gives reliability and a sense of security. It is clear that this is an important background that cannot be ignored in the technological development of polyester, industrial development and expansion of consumer society.

  However, it can be said that the main reason contributing to the birth of the polyester of the present invention is the background that can be said to be a request of an era based on technological progress. Countermeasures against the deterioration of the global environment, including the so-called greenhouse effect caused by carbon dioxide, countermeasures against the danger of oil resources being wasted and depleted, and the extremely important developments in recent years, such as the remarkable development of biotechnology such as fermentation technology Advances in technology have made it possible. First, a method that depends on vegetation in the atmosphere is to absorb a large amount of carbon dioxide in the production of a plant as a raw material, and this absorption amount is set to Abs. Although some carbon dioxide and thermal 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, the mass balance of absorption and release of carbon dioxide is not only balanced, but is also considered 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 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 further expansion, development and consumption of typical polyesters for plastic materials. It is.

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 (22)

  In a foam obtained from a polyester whose main repeating unit is a dicarboxylic acid unit and a diol unit, at least one of a dicarboxylic acid and a diol as a raw material of the polyester is obtained from a biomass resource, A biomass resource-derived polyester foam characterized in that the amount of terminal carboxyl groups is 50 equivalents / ton or less.   2. The biomass resource-derived polyester foam according to claim 1, wherein the polyester has a reduced viscosity (ηsp / C) of 1.5 dL / g or more.   The nitrogen atom content in the polyester excluding nitrogen atoms contained in the functional group covalently bonded in the molecule of the polyester is 0.01 ppm to 50 ppm by mass with respect to the polyester. The biomass resource-derived polyester foam according to claim 1 or 2.   4. The biomass-resource-derived polyester foam according to claim 1, wherein a sulfur atom content in the polyester is 0.0001 ppm to 10 ppm by mass with respect to the polyester. .   The biomass resource-derived polyester according to any one of claims 1 to 4, wherein the dicarboxylic acid unit constituting the main repeating unit of the polyester is an aliphatic dicarboxylic acid unit derived from biomass resources. Foam.   6. The biomass resource-derived polyester foam according to claim 5, wherein the dicarboxylic acid unit constituting the main repeating unit of the polyester is a succinic acid unit derived from biomass resources.   7. The polyester according to any one of claims 1 to 6, wherein the polyester is modified with a modifier of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyester. Polyester foam derived from biomass resources.   The biomass-derived polyester foam according to claim 7, wherein the modifier has a carbodiimide group.   In a method for producing a foam using a polyester obtained by reacting a raw material containing at least a dicarboxylic acid and a diol, at least one of a dicarboxylic acid raw material and a diol raw material used for a polyester production reaction is derived from a biomass resource. And the nitrogen atom content in the dicarboxylic acid raw material and the diol raw material is 0.01 ppm or more and 500 ppm or less in a mass ratio with respect to the total of the raw materials, and the terminal carboxyl group amount in the polyester is 50 equivalents / ton or less. A method for producing a foam made of a biomass resource-derived polyester, characterized by using the following.   In a method for producing a foam using a polyester obtained by reacting a raw material containing at least a dicarboxylic acid and a diol, at least one of a dicarboxylic acid raw material and a diol raw material used for a polyester production reaction A method for producing a biomass resource-derived polyester foam, characterized in that a sulfur atom content in the raw material is 0.01 ppm or more and 100 ppm or less by mass ratio with respect to the total of the raw materials.   11. The biomass resource-derived polyester according to claim 10, wherein a nitrogen atom content in the dicarboxylic acid raw material and / or diol raw material is 0.01 ppm or more and 500 ppm or less in a mass ratio with respect to the total of the raw materials. A method for producing a foam.   Presence of at least one trifunctional or higher polyfunctional compound selected from the group consisting of the dicarboxylic acid and the diol, a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid, and a trifunctional or higher oxycarboxylic acid The method for producing a biomass resource-derived polyester foam according to any one of claims 9 to 11, wherein the reaction is performed under the following conditions.   0.1-99.9 wt% of at least one selected from the group consisting of thermoplastic resins, biodegradable resins, natural resins, and polysaccharides is blended with 99.9-0.1 wt% of the polyester. The method for producing a biomass resource-derived polyester foam according to any one of claims 9 to 12, wherein the polyester composition is used.   The method for producing a biomass resource-derived polyester foam according to claim 13, wherein the biodegradable resin is an aliphatic polyester.   The method for producing a biomass resource-derived polyester foam according to claim 13 or 14, wherein the biodegradable resin is an aliphatic oxycarboxylic acid resin.   The method for producing a biomass resource-derived polyester foam according to any one of claims 13 to 15, wherein the biodegradable resin is an aromatic / aliphatic copolyester resin.   The method for producing a biomass resource-derived polyester foam according to claim 15 or 16, wherein the biodegradable resin is an aromatic / aliphatic copolyester resin.   The method for producing a biomass resource-derived polyester foam according to any one of claims 9 to 17, wherein a chain extender is allowed to act on the polyester.   The method for producing a biomass resource-derived polyester foam according to any one of claims 9 to 18, wherein a polyester containing 0.01 to 10 parts by weight of a carbodiimide compound is used per 100 parts by weight of the polyester. .   The method for producing a biomass resource-derived polyester foam according to claim 19, wherein the carbodiimide compound is a polycarbodiimide compound having a polymerization degree of 2 to 40.   A biomass resource-derived polyester foam obtained by the production method according to any one of claims 9 to 20. A cushioning material comprising the biomass resource-derived polyester foam according to any one of claims 1 to 8 and claim 21.

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