JP6048159B2 - Method for producing polyurethane - Google Patents

Description

The present invention relates to a method for producing a polyurethane, and more specifically, by reacting a polyester polyol and an isocyanate compound in the presence of sugar and / or a derivative thereof, the reaction rate during the production of the polyurethane is improved, and the polyurethane obtained The present invention relates to a method for producing polyurethane that improves tensile strength, elastic recovery rate, and the like.
The polyurethane produced by the present invention is useful for a wide range of applications such as synthetic / artificial leather, foam resin for shoe soles, skin resin for shoes, thermoplastic resin, thermosetting resin, paint, laminate adhesive and elastic fiber. is there.
The present invention also relates to a polyester polyol suitably used in the method for producing a polyurethane of the present invention.

  Conventionally, the main soft segment part of a polyurethane resin produced on an industrial scale, that is, polyol is a polyether type typified by polypropylene glycol and polytetramethylene glycol, a polyester polyol type typified by dicarboxylic acid polyester, a poly It is classified into a polylactone type typified by caprolactone and a polycarbonate type obtained by reacting a carbonate source with a diol (Non-patent Document 1).

  Among these, the polyester type, that is, polyurethane obtained by reacting a polyester polyol and an isocyanate compound has a feature excellent in heat resistance, weather resistance and the like, and is applied to a wide range of applications.

  Further, in recent years, various technologies using raw materials derived from biomass resources have been proposed as polyester polyurethane production techniques. For example, Patent Document 1 uses a material derived from biomass resources as a dicarboxylic acid of a polyester polyol raw material. The production method of polyurethane characterized by the above is described, and it is described that the diol of the polyester polyol raw material is also derived from biomass resources. Patent Document 2 describes that a polyurethane is produced using a polyester polyol produced from a diol derived from biomass resources. Moreover, although patent document 3 describes manufacturing a polyurethane using the polyester polyol manufactured using the diol derived from biomass resources, all of these patent documents 1-3 are polyester polyol manufacturing raw materials. There is no description that the diol or the polyester polyol of the polyurethane production raw material contains sugar and / or a derivative thereof.

  That is, the diol derived from biomass resources described in Patent Documents 1 to 3 is obtained by, for example, fermenting sugar, but the fermentation liquid obtained by fermentation removes polymers and other impurities. Therefore, as a result of undergoing a multi-step purification process such as extraction, crystallization, distillation, etc., high-boiling sugars and the like are separated and removed and generally do not contain them.

  Patent Document 4 describes that a polyurethane prepolymer is produced by reacting a polyhydric alcohol containing molasses or a sugar compound with a polyisocyanate. The polyurethane prepolymer is excellent in biodegradability and physically durable. However, there is no description on the production of polyester polyol and the production of polyurethane using the produced polyester polyol, and in that case, if the polyurethane raw material contains sugar Is not described.

In Patent Document 5, as a method for producing a flexible polyurethane foam, not a thermoplastic polyurethane, it is obtained by subjecting a sugar alcohol having 5 or more OH groups to addition reaction of one or both of propylene oxide and ethylene oxide. It is described that a flexible polyurethane foam having high water resistance can be obtained by reacting a polyol mixture containing 0.5% or more of a low molecular polyol with a polyisocyanate having an average number of NCO groups of 2.1 to 2.5. ing.
Since the method described in Patent Document 5 is a method for producing a flexible polyurethane foam, the reaction conditions are different from the method for producing a thermoplastic polyurethane, and the reaction is different from the reaction for producing a thermoplastic polyurethane. For this reason, in the production of the flexible polyurethane foam of Patent Document 5, it is necessary to greatly increase the degree of crosslinking to ensure strength, so that the amount of polyfunctional sugar alcohol derivative used as a low molecular polyol is also large. 5% (5000 ppm by weight) or more is essential.

International Publication WO2011-125720 Pamphlet JP 2012-97189 A JP 2011-225863 A JP 2000-1646 A JP 2009-191223 A

"Polyurethane Basics and Applications", page 96-supervised by Katsuharu Matsunaga, CMC Publishing, November 2006

  In the production of polyester polyurethane, improving the reaction rate between polyester polyols and isocyanate compounds is an industrially extremely important improvement in terms of improving productivity and reducing the amount of relatively expensive isocyanate compounds used in raw materials. It is an item. Further, in the use of polyurethane, increasing mechanical properties such as tensile strength and elastic recovery rate is also an important item in terms of improving product durability and expanding applications.

  The present invention improves the reaction rate when a polyurethane is produced by reacting a polyester polyol and an isocyanate compound, and also improves the tensile strength and elastic recovery rate of the resulting polyurethane. It aims at providing the polyester polyol used suitably for a manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have increased the reaction rate by reacting a polyester polyol and an isocyanate compound in the presence of a predetermined amount of sugar and / or a derivative thereof, Moreover, it discovered that the polyurethane excellent in tensile strength, an elastic recovery rate, etc. can be manufactured.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] A process for producing a polyurethane comprising a step of reacting a polyester polyol and an isocyanate compound in the presence of a sugar and / or a derivative thereof, wherein the abundance of the sugar and / or the derivative is within the reaction system. A method for producing a polyurethane, characterized by being 0.1 to 80 ppm by weight based on the total amount of a polyhydroxy compound other than sugar and / or its derivative and sugar and / or its derivative.

[2] The method for producing a polyurethane according to [1], comprising a step of producing the polyester polyol by esterifying and / or transesterifying a dicarboxylic acid and / or a derivative thereof and a dihydroxy compound.

[3] The method for producing a polyurethane according to [2], wherein the sugar and / or derivative thereof is contained in the polyester polyol obtained by the dihydroxy compound containing the sugar and / or derivative thereof. .

[4] The method for producing a polyurethane according to [2] or [3], wherein at least one component of the dihydroxy compound is 1,4-butanediol.

[5] The method for producing a polyurethane according to any one of [1] to [4], wherein the polyester polyol has a number average molecular weight of 500 or more and 5000 or less.

[6] The method for producing a polyurethane according to any one of [1] to [5], wherein a chain extender is further reacted with the polyester polyol and the isocyanate compound.

[7] The method for producing a polyurethane according to [6], wherein the chain extender contains the sugar and / or a derivative thereof.

[8] The method for producing a polyurethane according to [6] or [7], wherein at least one component of the chain extender is 1,4-butanediol.

[9] The method for producing a polyurethane according to any one of [1] to [8], wherein the sugar and / or derivative thereof is a carbonyl compound containing two or more oxygen atoms.

[10] The method for producing a polyurethane according to any one of [1] to [9], wherein the polyurethane is a thermoplastic polyurethane.

[11] A polyester polyol having a number average molecular weight of 500 or more and 5000 or less, obtained by esterifying and / or transesterifying a dicarboxylic acid and / or derivative thereof with a dihydroxy compound, wherein the sugar and / or derivative thereof is A polyester polyol characterized by containing.

[12] A polyurethane produced by the polyurethane production method according to any one of [1] to [10].

[13] The polyurethane according to [12], which is a polyurethane for shoes.

  According to the present invention, the reaction rate between the polyester polyol and the isocyanate compound can be improved, and polyurethane can be produced efficiently. Moreover, since the obtained polyurethane is excellent in tensile strength, elastic recovery rate, etc., it is useful for various applications.

  Hereinafter, although the form of this invention is demonstrated in detail, this invention is not limited to the following embodiment, Various deformation | transformation can be implemented within the range of the summary.

The method for producing a polyurethane of the present invention is a method for producing a polyurethane having a step of reacting a polyester polyol and an isocyanate compound in the presence of sugar and / or a derivative thereof, and the amount of the sugar and / or the derivative thereof. Is 0.1 to 80 ppm by weight with respect to the total of the polyhydroxy compound other than sugar and / or its derivative in the reaction system and sugar and / or its derivative.
In the reaction between the polyester polyol and the isocyanate compound, a chain extender may be further present.
Moreover, the manufacturing method of the polyurethane of this invention has the process of manufacturing the polyester polyol used as a polyurethane raw material by esterifying and / or transesterifying the dicarboxylic acid and / or its derivative (s), and a dihydroxy compound normally.

  In the present invention, the polyurethane refers to a thermoplastic polyurethane or polyurethane urea unless otherwise specified, and it has been conventionally known that these two types of resins have substantially the same physical properties. On the other hand, as structural differences, polyurethane is manufactured using a short-chain polyol as a chain extender, and polyurethane urea is manufactured using a polyamine compound as a chain extender. Is.

[Sugar and / or its derivatives]
In the present invention, sugars present in the reaction system of polyurethane include, for example, hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose, pentoses such as arabinose, xylose, ribose, xylulose, ribulose, sucrose, raffinose, starch And the like. Among these, glucose, sucrose, and xylose are preferable. One reason why these saccharides are preferable is that they react efficiently with isocyanate compounds and become the core of crosslinking.

  In addition, the sugar derivative is not particularly limited as long as it is a component derived from sugar. , Sugar dehydrogenated products such as gluconolactone, single molecule dehydrated products such as levoglucosan and 4-deoxy-3-hexosulose, trimolecular dehydrated products such as hydroxymethylfurfural and furfural, 2-hydroxy-3-oxobutanal, Examples thereof include retroaldol products of glucose such as erythrose, acetol, glycoaldehyde and the like, hydrogenated products of the above specific examples, and dehydrates thereof. Here, the “dehydrated body” may be either a dehydrated body by heating or a dehydrated body by bacteria during fermentation.

  Among these, glucose and xylose 1 to 4 molecular dehydrates having an appropriate number of functional groups are preferable from the viewpoint of easily controlling the reaction rate, and among these, carbonyl compounds containing two or more oxygen atoms are particularly preferable. These sugar derivatives can be derived from sugar by methods such as chemical conversion, thermal decomposition, and fermentation.

  In the present invention, one or more of the above sugars may be present in the reaction system, one or more of the sugar derivatives may be present in the reaction system, and one or two sugars are present. One or two or more sugar derivatives may be present in the reaction system.

In the present invention, the sugar and / or derivative thereof may be separately added to the raw material for producing the polyurethane containing the polyester polyol and the isocyanate compound, and are contained in these raw materials and exist in the reaction system. You may do.
That is, for example, a polyester polyol, an isocyanate compound, a chain extender used as necessary, preferably a polyester polyol and / or a chain extender containing sugar and / or a derivative thereof is used in the reaction system. Also good.

  As a polyester polyol containing a sugar and / or a derivative thereof, for example, when a polyester polyol is produced by esterifying and / or ester-converting a dicarboxylic acid component and a dihydroxy compound by a method described later, the raw material dicarboxylic acid is used. Examples of the component and / or dihydroxy compound, preferably a dihydroxy compound, include those in which sugar and / or a derivative thereof are contained in the polyester polyol obtained by using a dihydroxy compound containing a sugar and / or a derivative thereof.

In the present invention, the amount of sugar and / or its derivative present in the reaction system during polyurethane production is 0 with respect to the total of the polyhydroxy compound and sugar and / or its derivative other than the sugar and / or its derivative in the reaction system. .1 to 80 ppm by weight. If the amount of the sugar and / or its derivative is less than 0.1 ppm by weight, the effect of improving the reaction rate due to the presence of the sugar and / or its derivative, and the effect of improving the physical properties such as tensile strength and elastic recovery rate of the resulting polyurethane are obtained. However, when the amount exceeds 80 ppm by weight, the polymerization is inhibited and the reaction rate tends to decrease. This decrease in reaction rate is presumed to be due to deterioration of the catalyst used in the production of polyurethane by sugar and / or its derivatives.
The preferred amount of sugar and / or its derivative is 0.2 to 40 ppm by weight, particularly preferably based on the total of the polyhydroxy compound other than sugar and / or its derivative in the reaction system and sugar and / or its derivative. Is 0.5 to 10 ppm by weight.

  In addition, as a polyhydroxy compound in a reaction system here, the polyester polyol used for polyurethane manufacture normally, and the below-mentioned chain extender and crosslinking agent used as needed are mentioned.

  In the present invention, the details of the action mechanism of the effect of improving the reaction rate due to the presence of sugar and / or its derivative in the reaction system and the effect of improving the tensile strength and elastic recovery rate of the obtained polyurethane are not clear. Since sugar and / or derivatives thereof have a large number of hydroxyl groups in the molecule, the degree of crosslinking of the resulting polyurethane can be increased by the reaction. As a result, the polymerization reaction of polyurethane formation is promoted and the resulting polyurethane is This is considered to be due to the introduction of a crosslinked structure to improve physical properties such as tensile strength and elastic recovery rate. The improvement of the reaction rate mentioned here indicates that a higher molecular weight polyurethane can be obtained within the same time.

[Production of polyester polyol]
Next, a method for producing a polyester polyol (hereinafter sometimes referred to as “polyester polyol of the present invention”) that is suitably used as a raw material for producing the polyurethane of the present invention will be described.

  This polyester polyol is produced by esterifying and / or transesterifying a dicarboxylic acid and / or a derivative thereof (hereinafter sometimes referred to as “dicarboxylic acid component”) with a dihydroxy compound.

(1) Dicarboxylic acid component Examples of the dicarboxylic acid component used in the present invention include aliphatic dicarboxylic acids, aliphatic dicarboxylic acid derivatives, aromatic dicarboxylic acids, and aromatic dicarboxylic acid derivatives. You may use, and 2 or more types may be mixed and used for it. Among these, for applications that require weather resistance such as synthetic / artificial leather and paint, those containing aliphatic dicarboxylic acid and / or a derivative thereof as a main component are preferable in that yellowing due to light is small. On the other hand, for applications that require strength, such as elastic fibers, those containing aromatic dicarboxylic acids and / or derivatives thereof having high cohesive strength as a main component are preferable.

  The term “main component” as used herein means that the content relative to the total dicarboxylic acid component is usually preferably 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more. Is more preferably 90 mol% or more.

  Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid. Examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of the aromatic dicarboxylic acid. Specific examples of the lower alkyl ester of aromatic dicarboxylic acid include methyl ester, ethyl ester, propyl ester, and butyl ester.

  Among these, terephthalic acid and isophthalic acid are preferable as the aromatic dicarboxylic acid. As the aromatic dicarboxylic acid derivative, dimethyl terephthalate and dimethyl isophthalate are preferable. For example, a desired aromatic polyester polyol polyurethane can be produced by using any aromatic dicarboxylic acid such as polyester of dimethyl terephthalate and 1,4-butanediol.

  As the aliphatic dicarboxylic acid, a chain or alicyclic dicarboxylic acid having 2 to 40 carbon atoms is usually preferable.

  Specific examples of the chain or alicyclic dicarboxylic acid having 2 to 40 carbon atoms include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexane. And dicarboxylic acid. Among these, as the aliphatic dicarboxylic acid, adipic acid, succinic acid, sebacic acid or a mixture thereof is preferable from the viewpoint of the physical properties of the obtained polyurethane, and those having succinic acid as the main component are particularly preferable.

  Examples of the derivative of the aliphatic dicarboxylic acid include, for example, lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of the aliphatic dicarboxylic acid, and cyclic acids of the aliphatic dicarboxylic acid such as succinic anhydride. An anhydride etc. are mentioned. Of these, the derivatives of aliphatic dicarboxylic acids are preferably methyl esters of adipic acid and succinic acid, or mixtures thereof.

  The dicarboxylic acid component used in the present invention may contain a component derived from biomass resources. Preferable components derived from biomass resources contained in the dicarboxylic acid component include, for example, adipic acid, succinic acid, and sebacic acid, and among these, succinic acid is particularly preferable.

  In the present invention, the term “dicarboxylic acid component includes a component derived from biomass resources” means that when the dicarboxylic acid component is one kind, a mixture of petroleum-derived raw materials such as succinic acid and biomass resources derived from succinic acid, for example. Well, in the case of a mixture of two or more kinds of dicarboxylic acids, it is sufficient that at least one dicarboxylic acid component is derived from biomass resources, and a mixture of dicarboxylic acid components derived from biomass resources and dicarboxylic acid components of petroleum-derived raw materials. There may be. In the case of a mixture of a dicarboxylic acid component derived from a biomass resource and a dicarboxylic acid component of a petroleum-derived raw material, the dicarboxylic acid component derived from a biomass resource is preferably 20 mol% or more, more preferably 40% mol or more, and even more preferably 60%. More than mol, and particularly preferably 90 to 100 mol%.

  Biomass resources as used in the present invention are those in which solar light energy is converted and stored in the form of starch, sugar, cellulose, etc., by the photosynthetic action of plants, animal bodies that grow by eating plants, and plants Products made by processing the body or animal body are included.

  Among these, a more preferable biomass resource is a plant resource. Plant resources include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapioca cass, bagasse, vegetable oil dregs, straw, buckwheat, soybeans, fats, waste paper, paper residue , Marine product residues, livestock excrement, sewage sludge and food waste.

  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, straw, buckwheat, soybeans, fats, waste paper and paper residue More preferred are wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, fats and oils, waste paper and papermaking residue, and most preferred are corn, sugar cane, cassava and sago palm. These biomass resources generally contain many alkali metals and alkaline earth metals such as elemental nitrogen, Na, K, Mg and Ca.

  These biomass resources are not particularly limited. For example, the biomass resources are converted into carbon sources through known pretreatment and saccharification processes such as chemical treatment such as acid and alkali, biological treatment using microorganisms, and physical treatment. Be guided.

  The process usually includes, for example, a micronization process by pretreatment such as chipping, scraping and crushing of biomass resources, although not particularly limited. If necessary, a grinding step by a grinder or a mill is further included.

  The biomass resources thus refined are further guided to a carbon source through pretreatment and saccharification steps. Specific methods thereof include, for example, chemical methods such as acid treatment with strong acids such as sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid, alkali treatment, ammonia freeze steaming explosion method, solvent extraction, supercritical fluid treatment and oxidant treatment. , Pulverization, steaming explosion method, microwave treatment, electron beam irradiation and other physical methods, and biological treatment such as hydrolysis by microorganisms or enzyme treatment.

  Examples of the carbon source derived from the biomass resource include hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose, pentoses such as arabinose, xylose, ribose, xylulose and ribulose, pentose, saccharose, starch and cellulose. Disaccharides or polysaccharides such as butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monoctinic acid, arachidic acid, eicosene Fatty acids such as acid, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid and ceracolonic acid, and polyalls such as glycerin, mannitol, xylitol and ribitol It includes fermentable carbohydrates such Lumpur acids. Among these, glucose, maltose, fructose, sucrose, lactose, trehalose and cellulose are preferable.

  Using these carbon sources, fermentation methods by microbial conversion using microorganisms capable of producing dicarboxylic acid or chemical conversion methods including reaction steps such as hydrolysis, dehydration reaction, hydration reaction, oxidation reaction, and the fermentation method A dicarboxylic acid is synthesized by a combination with the chemical conversion method. Among these, the fermentation method by microbial conversion is preferable.

  The microorganism having dicarboxylic acid-producing ability is not particularly limited as long as it is a microorganism having dicarboxylic acid-producing ability, and examples thereof include enteric bacteria such as Escherichia coli, Bacillus bacteria, and coryneform bacteria. Among these, it is preferable to use an aerobic microorganism, a facultative anaerobic microorganism, or a microaerobic microorganism.

  Examples of the aerobic microorganism include Coryneform Bacterium, Bacillus genus bacteria, Rhizobium genus bacteria, Arthrobacter genus bacteria, Mycobacterium genus bacteria, Rhodococcus genus bacteria, and Rhodococcus genus bacteria. Examples include Rhodococcus bacteria, Nocardia bacteria, and Streptomyces bacteria, with coryneform bacteria being more preferred.

  The coryneform bacterium is not particularly limited as long as it is classified as such, and examples thereof include bacteria belonging to the genus Corynebacterium, bacteria belonging to the genus Brevibacterium, and bacteria belonging to the genus Arthrobacter. Of these, those belonging to the genus Corynebacterium or Brevibacterium are preferred, and Corynebacterium glutamicum, Brevibacterium flavum, Brevibacterium ammoniagenes or Brevibacterium ammonage or Brevibacterium ammonage Bacteria classified as Bacterium lactofermentum are further preferred.

  When a succinic acid-producing bacterium is used as a microorganism having dicarboxylic acid-producing ability, it is preferable to use a strain having enhanced pyruvate carboxylase activity and reduced lactate dehydrogenase activity.

  Reaction conditions such as reaction temperature and pressure in microbial conversion will depend on the activity of microorganisms such as selected cells or molds, but suitable conditions for obtaining dicarboxylic acids are selected in each case. do it.

  In general, the dicarboxylic acid component used in the present invention is preferably less colored. The upper limit of the yellowness (YI value) of the dicarboxylic acid component used in the present invention is usually preferably 50 or less, more preferably 20 or less, still more preferably 10 or less, still more preferably 6 or less, Particularly preferably, it is 4 or less. On the other hand, the lower limit is not particularly limited, but it is usually preferably −20 or more, more preferably −10 or more, further preferably −5 or more, and particularly preferably −3 or more. Most preferably, it is −1 or more.

  By using a dicarboxylic acid component having a YI value of 50 or less, coloring of the resulting polyurethane can be suppressed. On the other hand, the use of a dicarboxylic acid component having a YI value of −20 or more is economically advantageous in that it does not require an extremely high capital investment for its production and does not require a great amount of production time. In addition, the YI value in this specification is a value measured by the method based on JIS-K7105.

(2) Dihydroxy compound Examples of the dihydroxy compound used in the present invention include an aromatic dihydroxy compound and an aliphatic dihydroxy compound having two hydroxyl groups. One of these may be used alone, or two or more of them may be used. You may mix and use.
Of these, aliphatic dihydroxy compounds, that is, linear or branched chain or alicyclic dihydroxy compounds are preferred from the viewpoint of easy handling of the resulting polyester polyol and the balance of physical properties among them. The lower limit value of the carbon number is preferably 2 or more, and the upper limit value is preferably 10 or less, more preferably 6 or less.

  Specific examples of the aliphatic dihydroxy compound include, for example, ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1, Examples include 5-pentanediol, 1,2-butanediol, 1,6-hexanediol, decamethylene glycol, 1,9-nonanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.

  Of these, ethylene glycol, 1,4-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol are preferred, and among these, ethylene glycol and 1,4-butanediol and a mixture thereof are preferable, and 1,4-butanediol as a main component or 1,4-butanediol is particularly preferable.

  The term “main component” as used herein is preferably usually 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 90 mol%, based on the total dihydroxy compound. It means that it is more than mol%.

  When a methylene chain between hydroxyl groups and a dihydroxy compound having an even number of carbon atoms are used, the mechanical strength of the polyurethane produced using the resulting polyester polyol is increased, and when a dihydroxy compound having an odd number or a branched structure is used. The handleability of the resulting polyester polyol is improved.

  The aromatic dihydroxy compound is not particularly limited as long as it is an aromatic dihydroxy compound having two hydroxyl groups, but the lower limit of the carbon number is preferably 6 or more, and the upper limit is usually preferably 15 or less. Group dihydroxy compounds.

  Specific examples of the aromatic dihydroxy compound include, for example, hydroquinone, 1,5-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, bis (p-hydroxyphenyl) methane, and bis (p-hydroxyphenyl) -2,2- Examples include propane.

  In the present invention, the content of the aromatic dihydroxy compound in the total dihydroxy compound used for the production of the polyester polyol is usually preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. It is.

  Moreover, as a dihydroxy compound, both terminal hydroxy polyether can also be used. The lower limit of the number of carbon atoms of both terminal hydroxy polyethers is usually preferably 4 or more, more preferably 10 or more, and the upper limit is usually preferably 1000 or less, more preferably 200 or less, still 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 amount of these both terminal hydroxy polyethers used is usually preferably 90% by weight or less, more preferably 50% by weight or less, as the content of structural units derived from both terminal hydroxy polyethers in the resulting polyester polyol. More preferably, it is 30% by weight or less.

  In the present invention, these dihydroxy compounds may be derived from biomass resources. Specifically, the dihydroxy compound may be produced directly from a carbon source such as glucose by a fermentation method, or dihydroxy acid, dicarboxylic acid anhydride or cyclic ether obtained by the fermentation method is chemically reacted with dihydroxy compound. It may be converted into a compound.

  For example, 1,4-butanediol is produced by chemical synthesis from succinic acid, succinic anhydride, succinic acid ester, maleic acid, maleic acid anhydride, maleic acid ester, tetrahydrofuran and γ-butyrolactone obtained by fermentation. Alternatively, 1,4-butanediol may be directly produced by the fermentation method, or 1,4-butanediol may be produced from 1,3-butadiene obtained by the fermentation method. Among them, a method of directly producing 1,4-butanediol by a fermentation method and a method of obtaining 1,4-butanediol by hydrogenating succinic acid with a reduction catalyst are efficient and preferable.

Examples of the reduction catalyst used when 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 / Examples include CrO ₃ , phosphoric acid Ru, Ni / Co, Co / Ru / Mn, Cu / Pd / KOH, and Cu / Cr / Zn. Among these, Ru / Sn or Ru / Pt / Sn is preferable in terms of catalytic activity.

  Furthermore, a method for producing a dihydroxy compound from a biomass resource by a combination of known organic chemical catalytic reactions can also be used. For example, when pentose is used as a biomass resource, it can be easily combined with a known dehydration reaction and catalytic reaction. Dihydroxy compounds such as butanediol can be produced.

  Dihydroxy compounds derived from biomass resources may contain nitrogen atoms as impurities due to biomass resources origin, fermentation treatment, and purification treatment including acid neutralization step. In this case, specifically, nitrogen atoms derived from amino acids, proteins, ammonia, urea or fermenting bacteria are included.

  The nitrogen atom content contained in the dihydroxy compound produced by the fermentation method is a weight concentration with respect to the dihydroxy compound, and the upper limit is preferably usually 2000 ppm or less, more preferably 1000 ppm or less, still more preferably 100 ppm or less, most preferably Preferably it is 50 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually preferably 0.01 ppm or more, more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, and even more preferably 1 ppm, for reasons of economic efficiency of the purification step. As described above, it is particularly preferably 10 ppm or more.

  By setting the nitrogen atom content contained in the dihydroxy compound produced by the fermentation method to the upper limit or less, the polymerization reaction is delayed, the carboxyl terminal quantity of the polyester polyol is increased, coloring, partial gelation, and A decrease in stability can be prevented. On the other hand, by setting it to the lower limit or more, it is possible to prevent the purification process from becoming complicated and economically advantageous. The nitrogen atom content is a value measured by a known elemental analysis method.

  Moreover, as another aspect, the nitrogen atom content contained in the dicarboxylic acid component and the dihydroxy compound is a weight concentration with respect to the total amount of the polyester polyol production raw material, and the upper limit is preferably usually 2000 ppm or less, more preferably 1000 ppm or less. More preferably, it is 100 ppm or less, and most preferably 50 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and further preferably 0.1 ppm or more.

  When using the dihydroxy compound 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 dihydroxy compound produced by the fermentation method is the weight concentration with respect to the dihydroxy compound, and the upper limit is preferably preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 10 ppm or less, particularly preferably Preferably it is 5 ppm or less, and most preferably 0.5 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually preferably 0.001 ppm or more, more preferably 0.01 ppm or more, still more preferably 0.05 ppm or more, and particularly preferably 0.1 ppm or more.

  By setting the sulfur atom content contained in the dihydroxy compound produced by the fermentation method to the upper limit or less, the polymerization reaction is delayed, the carboxyl terminal quantity of the polyester polyol is increased, coloring, partial gelation, and A decrease in stability can be prevented. On the other hand, by setting it to the lower limit or more, it is possible to prevent the purification process from becoming complicated and economically advantageous. The sulfur atom content is a value measured by a known elemental analysis method.

  Further, as another aspect, the sulfur atom content contained in the dicarboxylic acid component and the dihydroxy compound is a weight concentration with respect to the total amount of the polyester polyol production raw material, and the upper limit is preferably preferably 100 ppm or less, more preferably 20 ppm or less. More preferably, it is 10 ppm or less, particularly preferably 5 ppm or less, and most preferably 0.5 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually preferably 0.001 ppm or more, more preferably 0.01 ppm or more, still more preferably 0.05 ppm or more, and particularly preferably 0.1 ppm or more.

  In the present invention, in using a biomass resource-derived dihydroxy compound as a polyester polyol raw material, the oxygen concentration or temperature in the tank for storing the dihydroxy compound connected to the reaction system in order to suppress the coloration of polyurethane due to the impurities. May be controlled.

  By the control, the coloring of the impurity itself and the oxidation reaction of the dihydroxy compound promoted by the impurity are suppressed. For example, when using 1,4-butanediol, a dihydroxy compound such as 2- (4-hydroxybutyloxy) tetrahydrofuran It is possible to prevent the polyurethane from being colored by the oxidation product.

  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 for example, a known metal, or an inner surface of which a lining such as glass or resin is applied, or a glass or resin container is used. From the viewpoint of strength and the like, metal or those with lining on them can be mentioned.

  As the constituent material of the metal tank, known materials are used. Specifically, for example, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic stainless steel such as SUS310, SUS304, and SUS316. Examples include steel, clad steel, cast iron, copper, copper alloy, aluminum, inconel, hastelloy, and titanium.

  The oxygen concentration in the storage tank of the dihydroxy compound is not particularly limited as a volume% with respect to the total volume of the storage tank, but is usually preferably 0.00001% or more, more preferably 0.0001% or more, More preferably, it is 0.001% or more, most preferably 0.01% or more, and the upper limit is usually preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, most preferably 0. .1% or less.

  By setting the oxygen concentration in the storage tank of the dihydroxy compound to 0.00001% or more, the management process is prevented from becoming complicated, which is economically advantageous. Further, by setting the oxygen concentration to 10% or less, it is possible to prevent an increase in the coloration of polyurethane due to the oxidation reaction product of the dihydroxy compound.

  The lower limit of the storage temperature of the dihydroxy compound in the storage tank is usually preferably 15 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 50 ° C. or higher, most preferably 100 ° C. or higher, and the upper limit is It is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower, and most preferably 160 ° C. or lower.

  By setting the storage temperature in the storage tank of the dihydroxy compound to 15 ° C. or higher, it is possible to prevent the temperature increase during the production of the polyester polyol, making the production of the polyester polyol economically advantageous, and the type of the dihydroxy compound. Can prevent this from solidifying. On the other hand, by setting the temperature to 230 ° C. or lower, it is possible to suppress the vaporization of the dihydroxy compound and to prevent the need for a high-pressure storage facility, which is economically advantageous and to prevent the dihydroxy compound from deteriorating.

  The pressure in the dihydroxy compound storage tank is usually preferably a slight pressurization with dry nitrogen gas or dry air. If the pressure is too low or too high, the management facilities become complicated and economically disadvantageous.

  In the present invention, in order to obtain a polyurethane having a good hue, the upper limit of the content of the oxidation product of the dihydroxy compound used in the production of the polyester polyol is usually preferably 10,000 ppm or less as the weight concentration in the dihydroxy compound. More preferably, it is 5000 ppm or less, More preferably, it is 3000 ppm or less, Most preferably, it is 2000 ppm or less. On the other hand, the lower limit is not particularly limited, but is usually preferably 1 ppm or more, more preferably 10 ppm or more, and further preferably 100 ppm or more for reasons of economic efficiency of the purification step.

  The dihydroxy compound derived from biomass resources is usually purified by distillation. In the present invention, a polyester polyol containing sugar and / or its derivative is produced using a dihydroxy compound containing sugar and / or its derivative. When a predetermined amount of sugar and / or its derivative is present in a reaction system for producing polyurethane using a polyester polyol containing sugar and / or its derivative, the sugar and / or its derivative derived from the fermentation broth is contained. It can also be used for the production of polyester polyols in a heated state.

  When a polyester polyol containing a dihydroxy compound is produced using a dihydroxy compound containing a saccharide and / or a derivative thereof, the content of the saccharide and / or the derivative in the raw dihydroxy compound is determined depending on the sugar and / or its The amount of the derivative may be such that it can be present in the above-mentioned abundance. For example, a dihydroxy compound containing 0.1 to 100 ppm by weight of sugar and / or its derivative can be preferably used. Here, the content of the sugar and / or derivative thereof is the content in the dihydroxy compound containing the sugar and / or derivative thereof, that is, the sugar and / or the sum of the sugar and / or derivative thereof and the dihydroxy compound. The content of the derivative.

(3) Manufacture of polyester polyol The polyester polyol in this invention is manufactured by esterifying and / or transesterifying the said dicarboxylic acid component and a dihydroxy compound.

In particular, when using a dicarboxylic acid component and / or dihydroxy compound derived from a biomass resource, the polyester polyol may be produced in a reaction tank in which the oxygen concentration is controlled to a specific value or less during the production reaction of the polyester polyol.
As a result, the polyester polyol is colored by the oxidation reaction of the nitrogen compound as an impurity, or, for example, generated by the oxidation reaction of 1,4-butanediol when 1,4-butanediol is used as the dihydroxy compound. Since the coloring of the polyester polyol due to the oxidation reaction product of a dihydroxy compound such as (4-hydroxybutyloxy) tetrahydrofuran can be suppressed, a polyester polyol having a good hue can be produced.

  The production reaction means that a raw material is charged into a reaction vessel, polyester polyol having a desired viscosity is produced in the reaction vessel under normal pressure or reduced pressure from the time when the temperature rise is started, and the reaction vessel is restored from reduced pressure to normal pressure or higher. It is defined as the time until pressure is applied.

The lower limit of the oxygen concentration in the reaction tank during the production reaction is not particularly limited, but is preferably 1.0 × 10 ⁻⁹ % or more, more preferably 1.0%, as a volume% with respect to the total volume of the reaction tank. × is ^{10 -7%} or more, preferably the upper limit is usually not more than 10%, more preferably 1% or less, more preferably 0.1% or less, and most preferably 0.01% or less. By making the oxygen concentration 1.0 × 10 ⁻⁹ % or more, the management process can be prevented from becoming complicated. Moreover, it can prevent that coloring of a polyester polyol becomes remarkable by setting it as 10% or less.

  When supplying the dicarboxylic acid component derived from biomass resources to the reaction vessel, if the dicarboxylic acid component is solid, it can be supplied to the reaction vessel in a solid state. It is important to operate before the start of the production reaction so that the oxygen concentration in the reaction tank during the supply or after the supply becomes a desired concentration. When adjusting the oxygen concentration, the raw material dicarboxylic acid component may rise to the gas phase, making it difficult to operate. Therefore, the particle size (average particle size) of the raw material dicarboxylic acid component at the time of supply is 0.01 mm to 100 mm, preferably 0. .05 mm to 10 mm is preferably employed.

  In addition, when supplying a dicarboxylic acid component derived from a biomass resource to a reaction vessel as a polyester polyol raw material, the dicarboxylic acid component is supplied in a molten state, or the dicarboxylic acid component is added to the raw material dihydroxy compound or an appropriate solvent in the previous stage of the reaction vessel. It is also possible to provide a dissolution tank that dissolves and supply the raw dicarboxylic acid component solution or suspension to the reaction tank.

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

  Specific examples of the type of the transfer pipe include, for example, a commonly known metal, those having a lining such as glass and resin on the inner surface thereof, and those made of glass or resin. From the viewpoint of strength and the like, those made of metal or those subjected to lining are preferable.

  As a constituent material of the metal transfer pipe, known materials are used. Specifically, for example, carbon steel, ferritic stainless steel, martensitic stainless steel such as SUS410, austenitic series such as SUS310, SUS304, and SUS316. Examples include stainless steel, clad steel, cast iron, copper, copper alloy, aluminum, inconel, hastelloy, and titanium.

  The oxygen concentration in the transfer pipe is volume% with respect to the total volume of the transfer pipe, and the lower limit is not particularly limited, but is usually preferably 0.00001% or more, and more preferably 0.01% or more. On the other hand, the upper limit is usually preferably 16% or less, more preferably 14% or less, and still more preferably 12% or less. By setting the oxygen concentration to 0.00001% or more, it is economically advantageous to prevent complicated capital investment and management processes. On the other hand, when the content is 16% or less, coloring of the produced polyester polyol can be suppressed.

  The lower limit of the humidity in the transfer pipe is not particularly limited, but it is usually preferably 0.0001% or more, more preferably 0.001% or more, still more preferably 0.01% or more, and most preferably 0.00. It is preferably 1% or more, and the upper limit is preferably 80% or less, more preferably 60% or less, and still more preferably 40% or less.

  By making the humidity in the transfer pipe 0.0001% or more, the management process is prevented from becoming complicated, which is economically advantageous. Moreover, corrosion of a storage tank or piping can be prevented by setting it as 80% or less. Furthermore, by setting the humidity in the transfer pipe to 80% or less, problems such as adhesion of the dicarboxylic acid component to the storage tank or piping, blocking of the dicarboxylic acid component, etc. are prevented, and corrosion of the piping due to these adhesion phenomena is suppressed. be able to.

  The lower limit of the temperature in the transfer pipe is preferably usually −50 ° C. or higher, more preferably 0 ° C. or higher. On the other hand, the upper limit is usually preferably 200 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 50 ° C. or lower. By setting the temperature to −50 ° C. or higher, the transfer cost can be suppressed. Moreover, by setting it as 200 degrees C or less, it can suppress that the dehydration reaction of a dicarboxylic acid component, etc. occur together.

  The pressure in the transfer tube is usually preferably from 0.1 kPa to 1 MPa, and more preferably from 0.05 MPa to 0.3 MPa in view of operability.

  The amount of the dihydroxy compound used in producing the polyester polyol is substantially equimolar to the amount of the dihydroxy compound required to become a polyester polyol having a desired molecular weight with respect to the number of moles of the dicarboxylic acid component. In view of distilling of the dihydroxy compound during esterification and / or transesterification, it is preferably used in an excess of 0.1 to 20 mol%.

  The esterification and / or transesterification reaction is preferably performed in the presence of an esterification catalyst. The addition timing of the esterification catalyst is not particularly limited, and may be added at the time of charging the raw material, or after removing water to some extent or at the start of pressure reduction.

  When dicarboxylic acid is used as a raw material, the raw material dicarboxylic acid itself exhibits a catalytic action. Therefore, the reaction is performed without adding a catalyst at the initial stage of the reaction, and the raw material is used when the reaction rate becomes insufficient in accordance with the production rate of generated water. It is common to add an esterification catalyst different from the components. At this time, when the esterification catalyst different from the raw material component is added, the final esterification reaction rate is preferably 1/3 or less, more preferably 1/5 or less, compared to the esterification reaction rate in the initial stage of the non-addition reaction. It is preferable that the reaction is easy to control.

  As an esterification catalyst, the compound containing the periodic table group 1-14 group metal element except a hydrogen atom and a carbon atom is mentioned, for example. Specifically, for example, at least one or more selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium Examples thereof include compounds containing organic groups such as metal-containing carboxylates, metal alkoxides, organic sulfonates, and β-diketonate salts, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof.

  In addition, these catalyst components may be contained in the raw material induced | guided | derived from biomass resources for the above-mentioned reason. In that case, the raw material may be used as it is as a raw material containing a metal without purification.

  Among the above esterification catalysts, 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 during the esterification reaction or that dissolves in the produced polyester polyol because the reaction rate increases when the catalyst is melted or dissolved during the esterification reaction.

As the titanium compound, for example, tetraalkyl titanate is preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate. , Tetrabenzyl titanate and mixed titanates thereof.

Examples of preferable titanium compounds include titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide) acetylacetonate, titanium bis (ammonium lactate) dihydroxide, and titanium bis (ethylacetoacetate) diisopropoxy. And titanium (triethanolaminate) isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolamate and butyl titanate dimer.
Furthermore, as a preferable titanium compound, for example, titanium oxide or a composite oxide containing titanium and silicon (for example, titania / silica composite oxide) can also be used.

  Among these, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titanium bis (ammonium lactate) dihydroxide, polyhydroxytitanium stearate Preferred are rate, titanium lactate, butyl titanate dimer, titanium oxide and titania / silica composite oxide, tetra-n-butyl titanate, titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, polyhydroxy titanium stearate, titanium lactate , Butyl titanate dimer and titania / silica composite oxide are more preferable, in particular, tetra-n-butyl titanate, polyhydroxy titanium stearate, titanium ( Carboxymethyl) acetylacetonate, titanium tetraacetyl acetonate, and titania / silica composite oxide.

Examples of the zirconium compound include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, polyhydroxyzirconium stearate, zirconium ethoxide. Zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide and zirconium tributoxyacetylacetonate and mixtures thereof.
Further, as the zirconium compound, zirconium oxide or a composite oxide containing zirconium and silicon is also preferably used.

  Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate acetate, zirconium ammonium oxalate, potassium zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxide Zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide are preferred, zirconyl diacetate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris (butoxy) stearate, zirconium ammonium oxalate, Zirconium tetra-n-propoxide and zirconium tetra-n-butoxide are more preferred , In particular zirconium tris (butoxy) stearate is preferred.

  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 catalyst used in the case of using a metal compound as these esterification catalysts is preferably such that the lower limit is usually 1 ppm or more, more preferably 3 ppm or more, as the weight concentration in terms of metal with respect to the polyester polyol to be produced. The value is usually preferably 30000 ppm or less, more preferably 1000 ppm or less, still more preferably 250 ppm or less, and particularly preferably 130 ppm or less. When the amount of the catalyst used is 30000 ppm or less, not only is it economically advantageous, but also the thermal stability of the resulting polyester polyol can be improved. Moreover, the polymerization activity at the time of polyester polyol manufacture reaction can be improved by setting it as 1 ppm or more.

  The lower limit of the reaction temperature of the esterification reaction and / or transesterification reaction between the dicarboxylic acid component and the dihydroxy compound is usually preferably 150 ° C or higher, more preferably 180 ° C or higher, and the upper limit is usually 260 ° C or lower. Is preferable, and more preferably 250 ° C. or lower. The reaction atmosphere is usually an inert gas atmosphere such as nitrogen and argon. The reaction pressure is usually preferably from normal pressure to 100 Torr, and more preferably from normal pressure to 10 Torr.

  The lower limit of the reaction time is usually preferably 10 minutes or more, and the upper limit is usually preferably 10 hours or less, more preferably 5 hours or less.

  Further, the esterification reaction and / or transesterification reaction is carried out at normal pressure or reduced pressure, but the reaction rate is matched and the boiling point of the raw material dihydroxy compound, and when the azeotropic solvent is coexisted, the boiling point is matched. It is preferable to adjust the degree of vacuum. In order to perform a more stable operation, the reaction is carried out at normal pressure at the start of the esterification reaction and / or transesterification reaction, and the resulting esterification reaction and / or transesterification reaction rate becomes ½ or less of the initial rate. After that, it is preferable to start depressurization at a preferred time. The decompression start time may be any before or after the catalyst addition time.

  As a reaction apparatus used for producing the polyester polyol, a known vertical or horizontal stirred tank reactor can be used. For example, a method using a stirred tank reactor equipped with a vacuum exhaust pipe connecting a vacuum pump and the reactor can be mentioned. Further, a method in which a condenser is connected between the vacuum exhaust pipe connecting the vacuum pump and the reactor, and a volatile component or unreacted raw material generated during the polycondensation reaction in the condenser is recovered.

  In the industrial production method, the reaction is judged solely by the outflow amount of the distillate component, and the end point of the reaction is determined. The appropriate outflow amount depends on the boiling point (ease of outflow) of the raw material dihydroxy compound. Generally, the reaction end point is determined by the acid value during the reaction. In some cases, a treatment for adjusting the polyester polyol to a desired molecular weight (recondensation or depolymerization by adding a raw material dihydroxy compound) is added. In general, the end point of the reaction is judged based on the outflow amount. After the reaction is completed, the acid value of the product is measured. The reaction is re-executed and the acid value of the resulting polyester polyol is adjusted to the desired acid value.

  The acid value used as the end point of the reaction is preferably 1.0 mgKOH / g or less, more preferably 0.5 mgKOH / g or less, still more preferably 0.2 mgKOH / g or less. In addition, a preferable water content at the end of the reaction is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. In order to adjust an appropriate acid value and water content at the end point, It is also possible to carry out the reaction by adding an azeotropic solvent that forms an azeotrope and forms two phases and does not have active hydrogen. The azeotropic solvent is not particularly limited as long as it has such performance, but inexpensive aromatic compounds such as benzene and toluene are generally used.

  After such polyester polyol production reaction, it can be supplied to the storage or urethanization reaction as it is, or can be supplied to the storage or urethanization reaction after the treatment for deactivating the added catalyst. Although there is no restriction | limiting in particular in the method of deactivating an addition catalyst, It is more preferable to use catalyst deactivation additives, such as a phosphorous acid triester, than the method with a possibility of destroying polyester polyol structures, such as water treatment.

(4) Polyester polyol Specific examples of the polyester polyol used in the production of the polyurethane of the present invention include polyester polyols produced by esterifying or transesterifying a dicarboxylic acid component and a dihydroxy compound in the following combinations. .

  Examples of polyester polyols using succinic acid include polyester polyols of succinic acid and ethylene glycol, polyester polyols of succinic acid and 1,3-propylene glycol, and succinic acid and 2-methyl-1,3-propanediol. Polyester polyol, polyester polyol of succinic acid and 3-methyl-1,5-pentanediol, polyester polyol of succinic acid and neopentyl glycol, polyester polyol of succinic acid and 1,6-hexamethylene glycol, succinic acid And polyester of 1,4-butanediol, and polyester polyol of succinic acid and 1,4-cyclohexanedimethanol.

  Examples of polyester polyols using oxalic acid include polyester polyols of oxalic acid and ethylene glycol, polyester polyols of oxalic acid and 1,3-propylene glycol, and oxalic acid and 2-methyl-1,3-propane. Polyester polyol of diol, polyester polyol of oxalic acid and 3-methyl-1,5-pentanediol, polyester polyol of oxalic acid and neopentyl glycol, polyester polyol of oxalic acid and 1,6-hexamethylene glycol, Examples include polyester polyols of oxalic acid and 1,4-butanediol, and polyester polyols of oxalic acid and 1,4-cyclohexanedimethanol.

  Examples of polyester polyols using adipic acid include polyester polyols of adipic acid and ethylene glycol, polyester polyols of adipic acid and 1,3-propylene glycol, and adipic acid and 2-methyl-1,3-propane. Polyester polyol of diol, polyester polyol of adipic acid and 3-methyl-1,5-pentanediol, polyester polyol of adipic acid and neopentyl glycol, polyester polyol of adipic acid and 1,6-hexamethylene glycol, Examples include polyester polyols of adipic acid and 1,4-butanediol, and polyester polyols of adipic acid and 1,4-cyclohexanedimethanol.

  In addition, a polyester polyol using a combination of two or more of the above dicarboxylic acids is also preferable, a polyester polyol of succinic acid, adipic acid and ethylene glycol, a polyester polyol of succinic acid, adipic acid and 1,4-butanediol, And polyester polyols of terephthalic acid, adipic acid and 1,4-butanediol, and polyester polyols of terephthalic acid, succinic acid and 1,4-butanediol.

  The number average molecular weight (Mn) of these polyester polyols is usually preferably 500 to 5000, more preferably 700 to 4000, and still more preferably 800 to 3000 in terms of hydroxyl value. When the number average molecular weight of the polyester polyol is 500 or more, a material having satisfactory physical properties as a polyurethane can be obtained using this polyester polyol. Moreover, the handleability is favorable without the viscosity of polyester polyol being too high as it is 5000 or less.

  Furthermore, the molecular weight distribution (Mw / Mn) of this polyester polyol as measured by GPC (gel permeation chromatography) is usually preferably from 1.2 to 4.0, more preferably from 1.5 to 3.5, still more preferably. Is 1.8 to 3.0. By making molecular weight distribution 1.2 or more, the economical efficiency of polyester polyol manufacture improves. Moreover, the physical property of the polyurethane obtained using this polyester polyol improves by setting it as 4.0 or less.

  Further, these polyester polyols preferably have a liquid state at 40 ° C., more preferably a viscosity at 40 ° C. of 15000 mPa · s or less when the urethane production reaction is carried out without solvent.

  The polyester polyol of the present invention is not particularly limited whether it is solid at room temperature or liquid (liquid), but it is preferably liquid at room temperature for handling.

  The nitrogen atom content other than the functional group covalently bonded to the polyester polyol of the present invention is preferably 1000 ppm or less as the weight concentration in the polyester polyol. The nitrogen atom content other than the functional group covalently bonded to the polyester polyol is preferably 500 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, of which 40 ppm or less is preferable, and 30 ppm or less is more preferable. 20 ppm or less is most preferable.

  The nitrogen atom content other than the functional group covalently bonded to the polyester polyol is mainly derived from the nitrogen atom in the raw material, but the nitrogen atom included other than the functional group covalently bonded to the polyester polyol. When the content is 20 ppm or less, the resulting polyurethane is less colored.

  The polyester polyol of the present invention is usually preferably a polyester polyol with little coloring. The upper limit of the value represented by the Hazen color number of the polyester polyol of the present invention (APHA value: conforming to JIS-K0101) is preferably preferably 50 or less, more preferably 40 or less, still more preferably 30 or less. Particularly preferably, it is 25 or less. On the other hand, the lower limit is not particularly limited, but it is usually preferably 1 or more, more preferably 2 or more, and further preferably 5 or more.

  The polyester polyol having an APHA value of 50 or less has an advantage that, for example, use applications such as polyurethane films and sheets using the polyester polyol as a raw material are not limited. On the other hand, a polyester polyol having an APHA value of 1 or more is economically advantageous because the production process for producing the polyester polyol is not complicated and an extremely expensive equipment investment is not required.

  In the present invention, when a predetermined amount of sugar and / or its derivative is present in a reaction system for producing polyurethane using a polyester polyol containing sugar and / or its derivative, the sugar and / or its derivative in this polyester polyol. The content of can be any amount that allows the sugar and / or derivative thereof to be present in the reaction system in the aforementioned abundance. For example, the sugar and / or derivative thereof is 0.1 to 80 ppm by weight, particularly A polyester polyol containing 0.2 to 40 ppm by weight, particularly 0.5 to 10 ppm by weight can be preferably used. Here, the content of the sugar and / or the derivative thereof is the content in the polyester polyol containing the sugar and / or the derivative thereof, that is, the sugar and / or the sum of the sugar and / or the derivative thereof and the polyester polyol. The content of the derivative.

  In the present invention, for the production of polyurethane, one of the above-mentioned polyester polyols may be used alone, or two or more of them may be mixed and used. Further, a polyether polyol may be used by mixing with a polycarbonate diol, or may be used as a copolymer polyol by modification.

[Production of polyurethane]
Next, the manufacturing method of the polyurethane by this invention is demonstrated.

  In the present invention, polyurethane is produced by reacting the aforementioned polyester polyol with an isocyanate compound in the presence of a predetermined amount of sugar and / or a derivative thereof. At this time, a chain extender may be used as necessary.

(1) Isocyanate compound Examples of the isocyanate compound used in the present invention include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate, 1 , 5-naphthalene diisocyanate, aromatic diisocyanate such as tolidine diisocyanate, and aliphatic diisocyanate having an aromatic ring such as α, α, α ′, α′-tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, 2, Aliphatic diisocyanates such as 2,4- or 2,4,4-trimethylhexamethylene diisocyanate and 1,6-hexamethylene diisocyanate; Rhohexane diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI), 1-isocyanate-3-isocyanate methyl-3,5,5-trimethylcyclohexane (IPDI), 4,4'-dicyclohexylmethane diisocyanate and isopropylidene dicyclohexyl-4,4 And alicyclic diisocyanates such as' -diisocyanate. These may be used alone or in combination of two or more.

  In the present invention, it is preferable to use an aliphatic diisocyanate and / or an alicyclic diisocyanate from the viewpoint of less yellowing due to light for applications requiring weather resistance such as synthetic / artificial leather and paint. Of these, 1,6-hexamethylene diisocyanate, 1-isocyanate-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, and 4,4'-dicyclohexylmethane diisocyanate are preferably used because of their good physical properties and availability. . On the other hand, it is preferable to use aromatic diisocyanates with high cohesive strength for applications that require strength such as elastic fibers, and in particular, tolylene diisocyanate (TDI) and diphenylmethane diisocyanate from the viewpoint of good physical properties and availability. (Hereinafter sometimes referred to as MDI) is preferably used. Further, a part of the NCO group of the isocyanate compound may be modified to urethane, urea, burette, allophanate, carbodiimide, oxazolidone, amide, imide, etc., and the polynuclear substance contains isomers other than the above. Some are included.

  The amount of these isocyanate compounds used is usually preferably from 0.1 equivalents to 10 equivalents, more preferably from 0.8 equivalents to 1 equivalent of the hydroxyl group of the polyester polyol and 1 equivalent of the hydroxyl group and amino group of the chain extender. 1.5 equivalents, more preferably 0.9 equivalents to 1.05 equivalents.

  By making the usage-amount of an isocyanate compound below the said upper limit, it is prevented that an unreacted isocyanate group raise | generates an unfavorable reaction and a desired physical property is easy to be obtained. Moreover, by making the usage-amount of an isocyanate compound more than the said minimum, the molecular weight of the polyurethane obtained becomes large enough, and desired performance can be expressed.

Since the isocyanate compound reacts with moisture contained in the polyurethane raw material other than the isocyanate compound, such as polyester polyol and chain extender, and partially disappears, the amount to compensate for it may be added to the desired amount of isocyanate compound used. Specifically, before mixing with an isocyanate compound during the reaction, the moisture content of polyester polyol, chain extender, etc. is measured, and an isocyanate compound having an isocyanate group corresponding to twice the moisture content is added. In addition to the predetermined usage amount.
The mechanism by which the isocyanate group disappears by reacting with moisture is that the isocyanate group reacts with water molecules to become an amine compound, and the amine compound further reacts with the isocyanate group to form a urea bond. Two isocyanate groups disappear. Since the disappearance of the isocyanate compound required due to this disappearance may result in failure to obtain the desired physical properties, it is effective to add an isocyanate compound to compensate for the amount of water by the method described above. is there.

(2) Chain extender In this invention, you may use the chain extender which has two or more active hydrogens as needed. Chain extenders are mainly classified into compounds having two or more hydroxyl groups and compounds having two or more amino groups. Among these, short-chain polyols, specifically compounds having two or more hydroxyl groups, are preferred for polyurethane applications, and polyamine compounds, specifically compounds having two or more amino groups, are preferred for polyurethane urea applications.

  In addition, it is more preferable in view of physical properties to use a compound having a molecular weight (number average molecular weight) of 500 or less as the chain extender because the rubber elasticity of the polyurethane elastomer is improved.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3. -Butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2- Propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1, -Hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8-octanediol and Examples include aliphatic glycols such as 1,9-nonanediol and alicyclic glycols such as bishydroxymethylcyclohexane, and glycols having an aromatic ring such as xylylene glycol and bishydroxyethoxybenzene.

  Examples of the compound having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine and 4,4'-diphenylmethanediamine, ethylenediamine, 1,2- Propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or 2, Aliphatic diamines such as 4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine and 1,10-decanediamine; Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethane Amine (hydrogenated MDA), isopropylidene cyclohexyl-4,4'-diamine, alicyclic diamine such as 1,4-diaminocyclohexane and 1,3-bis-aminomethyl cyclohexane.

  Among these, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3 are preferable in the present invention. -Propanediol, isophorone diamine, hexamethylene diamine, ethylene diamine, propylene diamine, 1,3-diaminopentane and 2-methyl-1,5-pentane diamine, particularly with ease of handling and storage and physical properties of the resulting polyurethane 1,4-butanediol is preferred in terms of excellent balance.

  As these chain extenders, those derived from biomass resources can also be used, and the production method in that case is the same as the production method of the dihydroxy compound derived from biomass resources described above.

  Among these chain extenders, those having a hydroxyl group when an aromatic polyisocyanate is used as the isocyanate compound, and those having an amino group when an aliphatic polyisocyanate is used are preferred. Moreover, these chain extenders may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Although the usage-amount of these chain extenders is not specifically limited, It is preferable that they are 0.1 equivalent or more and 10 equivalent or less normally with respect to 1 equivalent of polyester polyols.

  By setting the amount of the chain extender to be not more than the above upper limit, the obtained polyurethane (or polyurethane urea) is prevented from becoming too hard, desired properties are obtained, and it is easily soluble in a solvent and easy to process. Moreover, by setting it as the said minimum or more, sufficient intensity | strength, elastic recovery performance, or elastic retention performance is obtained without the polyurethane (or polyurethane urea) obtained being too soft, and a high temperature characteristic can be improved.

  In the present invention, a chain extender containing a sugar and / or derivative thereof may be used so that a predetermined amount of sugar and / or derivative thereof is present in the reaction system. In that case, the content of the sugar and / or derivative thereof in the chain extender may be an amount that allows the sugar and / or derivative thereof to be present in the reaction system in the above-described amount. And / or a chain extender containing 0.1 to 800 ppm by weight, particularly 0.5 to 100 ppm by weight, more preferably 10 to 100 ppm by weight, of the derivative thereof can be preferably used. Here, the content of the sugar and / or the derivative thereof is the content in the chain extender containing the sugar and / or the derivative thereof, that is, the sugar and the sugar and / or the derivative and the chain extender in total. / Or the content of its derivatives.

  It is also possible to use a polyester polyol containing sugar and / or its derivative as a raw material for producing polyurethane and a chain extender containing sugar and / or its derivative so that sugar and / or its derivative exist in the reaction system. .

(3) Chain terminator In the present invention, a chain terminator having one active hydrogen group may be used as necessary for the purpose of controlling the molecular weight of the resulting polyurethane. These chain terminators include aliphatic monohydroxy compounds such as methanol, ethanol, propanol, butanol and hexanol having a hydroxyl group, and aliphatic monoamines such as morpholine, diethylamine, dibutylamine, monoethanolamine and diethanolamine having an amino group. Is exemplified. These may be used alone or in combination of two or more.

(4) Crosslinking agent In the present invention, a crosslinking agent having three or more active hydrogen groups or isocyanate groups can be used as necessary for the purpose of increasing the heat resistance and strength of the resulting polyurethane. As these cross-linking agents, trimethylolpropane, glycerin, isocyanate-modified products thereof, polymeric MDI, and the like can be used.

(5) Production of polyurethane In the present invention, in the presence of a predetermined amount of sugar and / or a derivative thereof using the above-described polyester polyol and isocyanate compound and, if necessary, the above-mentioned chain extender, chain terminator, etc. To produce polyurethane.

  In the present invention, the polyurethane may be produced by reacting in bulk, that is, without solvent, or may be produced by reacting in a solvent excellent in solubility of polyurethane such as an aprotic polar solvent.

  Although an example of a manufacturing method is shown below, it is not limited to the following methods at all. Examples of the production method include a one-stage method and a two-stage method.

  The one-stage method is a method in which a polyester polyol, an isocyanate compound and a chain extender are reacted simultaneously.

  The two-stage method is a method in which a polyester polyol and an isocyanate compound are first reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer and a chain extender are reacted (hereinafter referred to as two-stage isocyanate group termination). Also called the law). In addition, after preparing a prepolymer having hydroxyl groups at both ends, a method of reacting the prepolymer with an isocyanate compound can also be mentioned.

  Among these, the two-stage method at the end of the isocyanate group comprises a step of preparing an intermediate sealed with isocyanate at both ends corresponding to the soft segment of the polyurethane by reacting the polyester polyol with one or more equivalents of an isocyanate compound in advance. It is going to be.

  By preparing a prepolymer and then reacting with a chain extender, it is easy to adjust the molecular weight of the soft segment part, and the phase separation between the soft segment and the hard segment is easy to achieve, making it easy to achieve performance as an elastomer. .

  In particular, when the chain extender is a diamine, the reaction rate with the isocyanate group is greatly different from that of the hydroxyl group of the polyester polyol. Therefore, it is more preferable to carry out the polyurethane urea formation by the prepolymer method.

<One-step method>
The one-stage method is also called a one-shot method, and is a method in which a reaction is performed by charging together a polyester polyol, an isocyanate compound, and a chain extender. The amount of each compound used may be the amount described above.

  The one-shot method may or may not use a solvent. When a solvent is not used, the isocyanate compound and polyester polyol may be reacted using a low-pressure foaming machine or a high-pressure foaming machine, or may be reacted by stirring and mixing using a high-speed rotary mixer.

  When using a solvent, examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, and aromatics such as toluene and xylene. Hydrocarbons, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, and γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide And aprotic polar solvents such as N, N-dimethylacetamide and mixtures of two or more thereof.

  Among these organic solvents, an aprotic polar solvent is preferable from the viewpoint of solubility. Preferable specific examples of the aprotic polar solvent include methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethyl sulfoxide, more preferably N, N-dimethylformamide and N, N-dimethylacetamide are mentioned.

  In the one-shot method, the lower limit of the reaction equivalent ratio of NCO / active hydrogen group (polyester polyol and chain extender) is usually preferably 0.50, more preferably 0.8, and the upper limit is usually 1. 5 is preferable, and a range of 1.2 is more preferable.

  By setting the reaction equivalent ratio to 1.5 or less, it is possible to prevent excessive isocyanate groups from causing side reactions and undesirably affecting the physical properties of polyurethane. Moreover, by setting it as 0.50 or more, it can prevent that the molecular weight of the polyurethane obtained rises sufficiently and a problem arises in an intensity | strength or heat stability.

  The reaction is preferably carried out at a temperature of 0 to 100 ° C., but this temperature is preferably adjusted according to the amount of the solvent, the reactivity of the raw materials used, the reaction equipment and the like. If the reaction temperature is too low, the progress of the reaction is too slow, and the solubility of the raw materials and the polymer is low, so that the productivity is poor. On the other hand, if the reaction temperature is too high, side reactions and polyurethane decomposition occur. The reaction may be performed while degassing under reduced pressure.

  Moreover, a catalyst, a stabilizer, etc. can also be added to a reaction system as needed.

  Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid.

  Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, and tri (dinonylphenyl) phosphite.

<Two-stage method>
The two-stage method, also called a prepolymer method, produces a prepolymer obtained by reacting an isocyanate compound and a polyester polyol in advance at a reaction equivalent ratio of preferably 0.1 to 10.00. Next, an isocyanate compound and an active hydrogen compound component that is a chain extender are added to the prepolymer and reacted in two stages. In particular, a method of obtaining a polyurethane by reacting a polyester polyol with an equivalent amount or more of an isocyanate compound to obtain an NCO prepolymer at both ends and subsequently reacting with a short chain diol or diamine as a chain extender is useful.

  The two-stage method may or may not use a solvent. When a solvent is used, examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as dioxane and tetrahydrofuran, hydrocarbons such as hexane and cyclohexane, and aromatic carbonization such as toluene and xylene. Hydrogens, esters such as ethyl acetate and butyl acetate, halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide and N , N-dimethylacetamide and other aprotic polar solvents and mixtures of two or more thereof.

  In the present invention, among these organic solvents, an aprotic polar solvent is preferable from the viewpoint of solubility. Preferred specific examples of the aprotic polar solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and more preferably N, N-dimethylformamide. And N, N-dimethylacetamide.

  When synthesizing an isocyanate group-terminated prepolymer, (1) a prepolymer may be synthesized by directly reacting an isocyanate compound and a polyester polyol without using a solvent, and the prepolymer may be used as it is. (2) Method (1) The prepolymer may be synthesized in step 1 and then dissolved in a solvent, and (3) the prepolymer may be synthesized by reacting the isocyanate compound and the polyester polyol using a solvent.

  In the case of (1), when the chain extender is allowed to act on the chain extender, the polyurethane is allowed to coexist with the solvent by dissolving the chain extender in the solvent or simultaneously introducing the prepolymer and the chain extender into the solvent. It is preferable to obtain.

  As for the reaction equivalent ratio of NCO / active hydrogen group (polyester polyol) at the time of prepolymer synthesis, the lower limit is usually preferably 0.6, more preferably 0.8, and the upper limit is usually preferably 10. More preferably, it is in the range of 5, more preferably 3.

  The amount of chain extender used is not particularly limited, but the lower limit is usually preferably 0.8, more preferably 0.9, relative to the equivalent of NCO groups or OH groups contained in the prepolymer. The upper limit is usually preferably 2, and more preferably 1.2. By setting this ratio to 2 or less, it is possible to prevent an excessive chain extender from causing a side reaction and adversely affecting the physical properties of the polyurethane. Moreover, by setting this ratio to 0.8 or more, it is possible to prevent the resulting polyurethane from having a sufficiently increased molecular weight and causing problems in strength and thermal stability.

  Moreover, you may coexist monofunctional organic amine and alcohol at the time of reaction.

  The reaction temperature is preferably 0 to 250 ° C., but this temperature is preferably adjusted by the amount of the solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the reaction temperature is too low, the progress of the reaction is too slow, and the solubility of the raw materials and the polymer is low, so that the productivity is poor. On the other hand, if the reaction temperature is too high, side reactions and polyurethane decomposition occur. The reaction may be performed while degassing under reduced pressure.

  Moreover, a catalyst, a stabilizer, etc. can also be added to a reaction system as needed.

  Examples of the catalyst include triethylamine, tributylamine, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dineodecanate, stannous octylate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid. However, when the chain extender is highly reactive, such as a short-chain aliphatic amine, it is preferable to carry out without adding a catalyst.

  Examples of the stabilizer include 2,6-dibutyl-4-methylphenol, distearylthiodipropionate, di-β-naphthylphenylenediamine, and tri (dinonylphenyl) phosphite.

  When using a commonly used petroleum-derived dicarboxylic acid component during polyurethane production, it is difficult to control the reaction during the urethane reaction, the molecular weight becomes abnormally high due to gelation or the like, and the molecular weight distribution becomes abnormally large. However, when the dicarboxylic acid component in which the content of the organic acid is in a specific range is used as the polyester polyol production raw material, the reaction control during the urethanization reaction is possible, and the above-described problem does not occur. Accordingly, since a linear polyurethane can be produced, the handleability of the obtained polyurethane is improved, and it is possible to use in a wide range of fields by adjusting the formulation depending on the application.

  When using the polyurethane of the present invention, when adding a cross-linking agent in applications that require heat resistance and strength, the amount added is greater than when using a commonly used petroleum-derived dicarboxylic acid component. Is preferred. Also, since the viscosity of the resulting polyurethane is low during the production of the polyurethane of the present invention, it is preferable to lower the temperature a little when using a petroleum-derived succinic acid in the post-treatment and processing of the polyurethane. It is preferable in terms of handleability, safety and economy.

(6) Properties of polyurethane, etc. Polyurethane produced by the method for producing polyurethane of the present invention (hereinafter sometimes referred to as “polyurethane of the present invention”) is an organic acid having a pKa value at 25 ° C. of 3.7 or less. It is preferable that the content of the organic acid unit is more than 0 mol% and not more than 0.09 mol% with respect to the dicarboxylic acid unit.

The lower limit of the content of the organic acid unit is not particularly limited, but is preferably 9 × 10 ⁻⁸ mol% or more, more preferably 9 × 10 ⁻⁷ mol% or more, and still more preferably 4. with respect to the dicarboxylic acid unit. 5 × 10 ⁻⁶ mol% or more, particularly preferably 6.3 × 10 ⁻⁶ mol% or more, most preferably 9 × 10 ⁻⁶ mol% or more, and the upper limit is 9 × 10 ⁻² mol% or less. Preferably, it is 7.2 × 10 ⁻² mol% or less, more preferably 5.4 × 10 ⁻² mol% or less.

  When the content of the organic acid unit exceeds 0.09 mol%, the molecular weight is abnormally high or the molecular weight distribution is abnormally large due to gelation or the like in the polyurethane reaction. It tends to be a polyurethane with poor properties. In addition, when the content of the organic acid unit exceeds 0.09 mol%, the content tends to vary, and the physical properties of the resulting polyurethane are not constant, and the manufacturing process is stable. Tend to be difficult. On the other hand, by setting it to more than 0 mol%, there is a tendency to become polyurethane having high mechanical strength.

  The polyurethane of the present invention preferably exhibits the following physical properties.

  The physical properties of the polyurethane of the present invention will be explained by taking an example of a polyurethane of an aliphatic diol and an aliphatic dicarboxylic acid such as polybutylene succinate or polybutylene succinate adipate. It is preferable to have a very wide range of physical properties such as 100 to 1500%.

  Moreover, when targeting a specific use, it can be set as the polyurethane which has the characteristics of arbitrary wide ranges beyond the range of the above ranges. These characteristics can be arbitrarily adjusted by changing the types of polyurethane raw materials and additives, polymerization conditions, molding conditions, and the like according to the purpose of use.

  The ranges of typical physical property values of the polyurethane of the present invention are disclosed in detail below.

  As for the composition ratio of the polyurethane, it is preferable that the molar ratio of the diol unit (the structural unit derived from the dihydroxy compound) and the dicarboxylic acid unit is substantially equal.

  The upper limit of the sulfur atom content in the polyurethane of the present invention is preferably 50 ppm or less, more preferably 5 ppm or less, still more preferably 3 ppm or less, and most preferably 0. 3 ppm or less. On the other hand, the lower limit is not particularly limited, but is preferably 0.0001 ppm or more, more preferably 0.001 ppm or more, still more preferably 0.01 ppm or more, particularly preferably 0.05 ppm or more, and most preferably. Is 0.1 ppm or more.

  By setting the sulfur content to 50 ppm or less, the thermal stability or hydrolysis resistance of the polyurethane can be improved. Moreover, by setting it as 0.001 ppm or more, it prevents that refining cost becomes high remarkably, and is economically advantageous in manufacture of a polyurethane.

  The polyurethane of the present invention is usually preferably a polyurethane with little coloring. The upper limit of the YI value (based on JIS-K7105) of the polyurethane of the present invention is usually preferably 20 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less. The lower limit is not particularly limited, but it is usually preferably −20 or more, more preferably −5 or more, and further preferably −1 or more.

  Polyurethane having a YI value of 20 or less has an advantage that the usage of films and sheets is not limited. On the other hand, a polyurethane having a YI value of −20 or more is economically advantageous because the production process for producing the polyurethane does not become complicated, and an extremely expensive capital investment is not required.

  The weight average molecular weight of the polyurethane as measured by gel permeation chromatography (GPC) varies depending on the use, but as a polyurethane polymerization solution, it is usually preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, still more preferably. Is 100,000 to 400,000, particularly preferably 100,000 to 300,000. As molecular weight distribution, Mw / Mn is preferably 1.5 to 3.5, more preferably 1.8 to 2.5, and still more preferably 1.9 to 2.3.

  By setting the molecular weight to 1 million or less, the solution viscosity is prevented from becoming too high, and the handleability is improved. Moreover, it can prevent that the physical property of the obtained polyurethane falls too much by setting it as 10,000 or more. By setting the molecular weight distribution to 1.5 or more, it is possible to prevent the economics of polyurethane production from being excessively deteriorated and to improve the elastic modulus of the obtained polyurethane. Moreover, by making it 3.5 or less, it prevents that a solution viscosity becomes high too much, a handleability improves, and prevents the elasticity modulus of the polyurethane obtained too high, and an elastic recovery property improves.

  For example, in applications such as synthetic leather / artificial leather, polyurethane for shoe soles, films, sheets, tubes, and moisture-permeable resins, the weight average molecular weight of polyurethane is usually preferably 10,000 to 1,000,000, more preferably 5 It is 10,000 to 500,000, more preferably 100,000 to 400,000, and particularly preferably 150,000 to 350,000. As the molecular weight distribution, Mw / Mn is preferably 1.5 to 3.5, more preferably 1.8 to 2.5, and still more preferably 1.9 to 2.3.

  By setting the molecular weight to 1 million or less, the melt viscosity is prevented from becoming too high, and the handleability is improved. Moreover, by setting it as 50,000 or more, it can prevent that the physical property of the polyurethane obtained falls too much. When the molecular weight distribution is 1.5 or more, the economical efficiency of polyurethane production is improved, and the elastic modulus of the obtained polyurethane can be improved. Moreover, by making it 3.5 or less, the melt viscosity is prevented from becoming too high, the handleability is improved, the elasticity of the resulting polyurethane is prevented from becoming too high, and the elastic recovery property is improved. Can do.

  A solution in which the polyurethane of the present invention is dissolved in an aprotic solvent (hereinafter, also referred to as “polyurethane solution”) is less prone to gelation, has a good storage stability such as a small change in viscosity with time, and has thixotropy. Since the properties are small, it is convenient for processing into films and yarns.

  The content of polyurethane in the polyurethane solution is usually preferably 1 to 99% by weight, more preferably 5 to 90% by weight, still more preferably 10 to 70% by weight, particularly based on the total weight of the polyurethane solution. Preferably it is 15 to 50% by weight. By setting the content of polyurethane in the polyurethane solution to 1% by weight or more, it is not necessary to remove a large amount of solvent, and productivity can be improved. Moreover, by setting it as 99 weight% or less, the viscosity of a solution can be suppressed and operativity or workability can be improved.

  The polyurethane solution is not particularly specified, but is preferably stored in an atmosphere of an inert gas such as nitrogen or argon when stored over a long period of time.

(7) Additives for polyurethane Various additives may be added to the polyurethane of the present invention as necessary. Examples of these additives include CYANOX 1790 [manufactured by Cyanamid Co., Ltd.], IRGANOX 245, IRGANOX 1010 [manufactured by Ciba Specialty Chemicals Co., Ltd.], Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) and 2 , 6-dibutyl-4-methylphenol (BHT), etc., TINUVIN 622LD, TINUVIN 765 [above, manufactured by Ciba Specialty Chemicals Co., Ltd.], SANOL LS-2626, LS-765 [above, Sankyo Corporation ) UV stabilizers such as TINUVIN 328 and TINUVIN 234 (above, manufactured by Ciba Specialty Chemicals), silicon compounds such as dimethylsiloxane polyoxyalkylene copolymer, red phosphorus, organic phosphorus Compound, phosphorus and halogen-containing organic compounds, bromine or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc. and reactive flame retardants, pigments such as titanium dioxide, colorings such as dyes and carbon black Agent, hydrolysis inhibitor such as carbodiimide compound, short glass fiber, carbon fiber, alumina, talc, graphite, filler such as melamine and clay, lubricant, oil agent, surfactant, other inorganic extender and organic solvent It is done. Moreover, you may add foaming agents, such as water and a substitute Freon. It is particularly useful for polyurethane foam for shoe soles.

(8) Polyurethane molded product / use The polyurethane of the present invention and its polyurethane solution can express various properties, such as foam, elastomer, paint, fiber, adhesive, flooring, sealant, medical material, artificial leather, etc. Can be widely used. Hereinafter, although the use is mentioned, the use of the polyurethane and polyurethane solution of the present invention is not limited to the following.

(1) Use as cast polyurethane elastomer. For example, rolls such as rolling rolls, papermaking rolls, office equipment and pretension rolls, solid tires such as forklifts, automobile vehicles neutrals, trolleys and transporters, casters, conveyor belt idlers, guide rolls, pulleys, steel pipe linings, ores Industrial products such as rubber screens, gears, connection rings, liners, pump impellers, cyclone cones and cyclone liners. Belts for OA equipment, paper feed rolls, squeegees, copying cleaning blades, snow plows, toothed belts, surface rollers, etc.

(2) Use as a thermoplastic elastomer. For example, tubes or hoses, spiral tubes and fire hoses in pneumatic equipment, coating equipment, analytical equipment, physics and chemistry equipment, metering pumps, water treatment equipment and industrial robots used in the food and medical fields. Various belts such as round belts, V-balts and flat belts, various transmission mechanisms, spinning machines, packing equipment and printing machines.

(3) Footwear heel tops, shoe soles, couplings, packing, pole joints, bushes, gears, rolls and other equipment parts, sports equipment, leisure equipment, watch belts, etc.

(4) As automobile parts, oil stoppers, gear boxes, spacers, chassis parts, interior parts and tire chain substitutes, films such as keyboard films and automobile films, curl cords, cable sheaths, bellows, transport belts, flexible containers, Binders, synthetic leather, depinning products and adhesives.

(5) Use as a solvent-based two-component paint. For example, wood products such as musical instruments, Buddhist altars, furniture, decorative plywood and sports equipment. Also used for automobile repair as tar epoxy urethane.

(6) Components such as moisture-curing one-component paints, blocked isocyanate solvent paints, alkyd resin paints, urethane-modified synthetic resin paints, and UV-curing paints.
For example, plastic bumper paints, strippable paints, magnetic tape coatings, floor tiles, flooring, paper, wood-printed film and other overprint varnishes, wood varnishes, high processing coil coats, optical fiber protective coatings, solder resists , Top coat for metal printing, base coat for vapor deposition, white coat for food cans, etc.

(7) Shoes, footwear, magnetic tape binder, decorative paper, wood and structural members, etc. as adhesives. Low temperature adhesive, hot melt component.

(8) Examples of binders include magnetic recording media, inks, castings, fired bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortars, resin mortars, rubber chip binders, recycled foams and glass fiber sizings.

(9) Anti-shrinking, anti-molding, water-repellent finishing, etc.

(10) As sealant caulking, concrete wall, induction joint, sash area, wall-type PC joint, ALC joint, board joint, composite glass sealant, thermal insulation sash sealant, and automotive sealant.

(11) Polyurethane for shoe soles, synthetic leather, artificial leather. In this case, the raw material polyester polyol component may have a skeleton such as adipic acid or sebacic acid. Further, when polyurethane is derived from plants and has biodegradability, it is more suitable for non-durable consumer materials such as resin for shoes.

(9) Artificial leather / synthetic leather Hereinafter, artificial leather or synthetic leather which is an example of typical uses of the polyurethane of the present invention will be described in detail.
Artificial leather or synthetic leather has a base fabric, an adhesive layer, and a skin layer as main components. The skin layer is made of a skin layer compounded liquid obtained by mixing the polyurethane of the present invention with other resins, antioxidants, UV absorbers, etc. to create a polyurethane solution, and mixing this with a colorant and an organic solvent. . In addition, a hydrolysis inhibitor, a pigment, a dye, a flame retardant, a filler, a crosslinking agent, and the like can be added to the polyurethane solution as necessary.

  Examples of other resins include polyurethanes other than the polyurethane of the present invention, poly (meth) acrylic resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl propionate copolymers, polyvinyl butyral resins, fibers Examples thereof include base resins, polyester resins, epoxy resins and phenoxy resins, and polyamide resins.

  Examples of the cross-linking agent include organic polyisocyanates, crude MDI, TDI adduct of trimethylolpropane, and polyisocyanate compounds such as triphenylmethane triisocyanate.

  Examples of the base fabric include tetron / rayon, cotton raised fabric, knitted fabric, nylon tricot, and the like. Moreover, as an adhesive agent, the 2 liquid type polyurethane which consists of a polyurethane, a polyisocyanate compound, and a catalyst is mentioned, for example.

  Moreover, as a polyisocyanate compound, the TDI adduct of a trimethylol propane etc. are mentioned, for example. Examples of the catalyst include amine-based or tin-based catalysts.

Next, a method for producing synthetic leather using the polyurethane of the present invention will be described.
That is, other resins or the like are mixed with the polyurethane of the present invention to prepare a polyurethane solution, and a colorant or the like is mixed therewith to prepare a skin layer compounded solution. Next, this compounded solution is applied onto a release paper and dried, and then an adhesive is further applied to form an adhesive layer. After aging, artificial leather and synthetic leather can be obtained by peeling the release paper.

  The manufactured artificial leather and synthetic leather can be used for clothing, shoes, bags, and the like.

The shoe sole polyurethane of the present invention will be described in detail.
The above-described method for producing a polyurethane foam for a shoe sole using the polyester polyol of the present invention mainly includes (1) when a polyurethane foam is produced by reacting and foaming a polyisocyanate component and a polyol component as a polyol component. , A method using a polyol component containing the polyester polyol (hereinafter referred to as production method A), and (2) reacting and foaming an isocyanate prepolymer obtained by reacting a polyisocyanate component with a polyol component, and the polyol component. Thus, when a polyurethane foam is produced, there is a method of using a polyol component containing the polyester polyol (hereinafter referred to as production method B) as a polyol component used as a raw material for the isocyanate prepolymer.

First, the manufacturing method A is demonstrated.
In the manufacturing method A, the polyol component containing the said polyester polyol is used as a polyol component used when making a polyurethane foam react by making a polyol component and a polyisocyanate component react and foam.

  In addition to the polyester polyol, the polyol component may contain other polyester polyols, polyether polyols such as polypropylene glycol and polyoxytetramethylene glycol, polycaprolactone polyols, and polycarbonate polyols. These may be used alone or in combination of two or more.

  A typical example of the polyisocyanate component used in production method A is an isocyanate prepolymer. The isocyanate prepolymer can be obtained by stirring and reacting a polyisocyanate monomer and a polyol in a conventional manner in the presence of an excess of the polyisocyanate monomer.

  Specific examples of the polyisocyanate monomer include tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, dimethyl-4,4-biphenylene. Examples thereof include polyisocyanate compounds such as diisocyanate, and modified products thereof such as carbodiimide modified products.

  These may be used alone or in combination of two or more. Among these, 4,4-diphenylmethane diisocyanate is used alone or 4,4-diphenylmethane diisocyanate and its carbodiimide modified product are preferably used in combination.

  The NCO% of the isocyanate prepolymer is preferably 15% or more, more preferably 17% or more, from the viewpoint of preventing the molding with a low-pressure foaming machine from becoming difficult due to the increase in viscosity. From the viewpoint of avoiding a decrease in the measurement accuracy of the foaming machine, it is preferably 25% or less, more preferably 23% or less, and even more preferably 22% or less.

  Since the isocyanate prepolymer exhibits a liquid state at a temperature of 15 ° C. or higher and can be discharged even at a low pressure, for example, a polyurethane foam can be easily produced even at a molding temperature of 40 to 50 ° C.

  In the manufacturing method A, when making a polyisocyanate component and a polyol component react, it is preferable to adjust the ratio of both so that an isocyanate index may be set to 95-110.

  In the production method A, a polyurethane foam can be produced by mixing and stirring a polyisocyanate component and a polyol component with a molding machine, injecting the mixture into a mold, and foaming. More specifically, for example, after adjusting the temperature of the polyol component to a temperature of about 40 ° C. using a tank or the like, using a foaming machine such as an automatic mixing injection type foaming machine and an automatic mixing injection type foaming machine. A polyurethane foam can be produced by mixing and reacting a polyol component and a polyisocyanate component.

  Moreover, according to the manufacturing method A, after mixing a polyisocyanate component and a polyol component, a urethane shoe sole can be shape | molded with the foaming machine normally temperature-controlled at about 40-50 degreeC.

Next, the manufacturing method B is demonstrated.
In the production method B, an isocyanate prepolymer obtained by reacting a polyisocyanate component and a polyol component and a polyol component are reacted and foamed to produce a polyurethane foam, and used to prepare an isocyanate prepolymer. As the polyol component to be used, a polyol component containing the polyester polyol is used.

  The polyester polyol of the present invention is used as the polyester polyol contained in the polyol component used when preparing the isocyanate prepolymer. As a polyisocyanate component which is a manufacturing raw material of an isocyanate prepolymer, the polyisocyanate monomer etc. which are used by the manufacturing method A are mentioned, for example.

  As a polyisocyanate monomer, the same thing as the specific example of the polyisocyanate monomer used by the manufacturing method A is illustrated. Among these examples, 4,4-diphenylmethane diisocyanate alone or a combined use of 4,4-diphenylmethane diisocyanate and a modified carbodiimide thereof is preferable.

  In the production method B, by using the polyester polyol, the viscosity of the resulting isocyanate prepolymer can be suitably maintained, so that a polyurethane foam having excellent mechanical strength can be obtained.

  The polyol component can contain other polyester polyols in addition to the polyester polyol. As another polyester polyol component, the same thing as what is used by the manufacturing method A is illustrated, for example.

  The content of the polyester polyol in the polyol component is preferably 10 to 100% by weight, more preferably 50 to 100% by weight, and the content of the other polyester polyol is preferably 0 to 90% by weight, more preferably. Is 0 to 50% by weight.

  The ratio of the polyisocyanate component and the polyol component is preferably adjusted so that the equivalent ratio of NCO groups / OH groups is usually preferably about 5 to 30.

  Next, an isocyanate prepolymer is obtained by mixing a polyisocyanate component, a polyol component and, if necessary, an additive by a conventional method, stirring and reacting.

  The NCO% of the isocyanate prepolymer thus obtained is preferably at least 12%, more preferably at least 14% from the viewpoint of reducing the viscosity and facilitating molding with a low-pressure foaming machine. From the viewpoint of improving the measurement accuracy of the foaming machine, it is preferably 25% or less, more preferably 23% or less, and still more preferably 22% or less.

  Since the isocyanate prepolymer exhibits a liquid state at a temperature of 15 ° C. or higher and can be discharged even at a low pressure, for example, a polyurethane foam can be satisfactorily produced even at a molding temperature of 40 to 50 ° C.

  Next, the polyurethane foam is obtained by reacting and foaming the isocyanate prepolymer and the polyol component.

  As a polyol component used for reaction with an isocyanate prepolymer, the same thing as other polyols other than the polyester polyol used for a polyol component in the manufacturing method A is illustrated.

  In addition, a chain extender, a foaming agent, a urethanization catalyst, a stabilizer, a pigment, and the like may be appropriately added in an appropriate amount to the polyol component used for the reaction with the isocyanate prepolymer.

  In the production method B, when the polyisocyanate component and the polyol component are reacted, it is preferable to adjust the ratio of the two so that the isocyanate index is preferably 95 to 110.

  In the production method B, a polyurethane foam can be produced by mixing and stirring an isocyanate prepolymer, a polyol component and, if necessary, an additive with a molding machine, injecting the mixture into a molding die and foaming. More specifically, for example, after adjusting the polyol component to a temperature of usually about 40 ° C. using a tank or the like, the isocyanate is then used using a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. A polyurethane foam can be produced by mixing and reacting with a prepolymer.

  Moreover, according to the manufacturing method B, after mixing an isocyanate prepolymer and a polyol component, a urethane shoe sole can be shape | molded with the foaming machine normally adjusted to about 40-50 degreeC. When production method B is used for the production of shoe soles, the resulting polyurethane foam can sufficiently improve the mechanical strength such as tensile strength and tear strength, although the amount of resin per unit volume is reduced. it can.

Thus, the density of the molded body of the polyurethane foam obtained by the production method A or the production method B is preferably 0.15 to 1.0 g / cm ³ , more preferably from the viewpoint of having sufficient mechanical strength and reducing the density. Is 0.2 to 0.4 g / cm ³ .

  EXAMPLES Hereinafter, although this invention is demonstrated still in detail based on an Example, this invention is not limited to a following example, unless the summary is exceeded.

  In the following examples and comparative examples, methods for analyzing physical properties and the like of each component are as follows.

<Number average molecular weight of polyester polyol>
The number average molecular weight of the polyester polyol was determined from the hydroxyl value (OH value: mgKOH / g).

<Weight average molecular weight of polyurethane>
Using a Tosoh GPC device (product name HLC-8220, column TSKgelGMH-XL, 2; solvent is lithium bromide-added N, N-dimethylacetamide), the weight average molecular weight of polyurethane in terms of standard polystyrene was measured.

<Moisture content>
Water analysis was performed using the Karl Fischer method. The apparatus used was a moisture analyzer CA-21 manufactured by Mitsubishi Chemical Corporation, and Aquamicron AKX was used as the anolyte and Aquamicron CXU was used as the catholyte.

<Physical properties of film>
The produced polyurethane solution was applied on a fluororesin sheet (fluorine tape nitoflon 900, thickness 0.1 mm, manufactured by Nitto Denko Corporation) with a 9.5 MIL applicator and dried at 80 ° C. for 15 hours. The obtained polyurethane film was formed into a strip shape having a width of 10 mm, a length of 100 mm, and a thickness of 50 to 100 μm, and a tensile tester (Tensilon UTM-III-100 manufactured by Orientec Co., Ltd.) was used. Tensile strength was measured under conditions of 500 mm / min and a temperature of 23 ° C. (relative humidity 40%). 5 to 10 points were measured per sample, and the average value was adopted.

[Example 1]
In a dry box (moisture of 10% or less) in which dry air is circulated, 10 ppm by weight of D-(+)-glucose is added to a reaction vessel (1 L separable flask) equipped with a thermometer, a stirrer and a nitrogen blowing tube. 70.0 g of polybutylene adipate (hydroxyl value 56 KOH mg / g, number average molecular weight 2004) and 6.3 g of 1,4-butanediol (manufactured by Mitsubishi Chemical Corporation) as a chain extender were added, and N, N-dimethylacetamide was added. (Hereinafter referred to as DMAc) (Wako Pure Chemical Industries, Ltd. Special Grade Reagent) Diluted with 240.0 g, and further dioctyltin catalyst (Nitto Kasei Co., Ltd .: Neostan U-830) 0.017 g (50 mol ppm as tin) ) Was added. The reaction vessel was heated and stirred in an oil bath (50 ° C.) for about 1 hour so that the DMAc solution was uniform. The water content of this DMAc solution was measured, and the required amount of diphenylmethane diisocyanate (hereinafter referred to as MDI) (Japan Polyurethane Industry Co., Ltd .: Millionate MT) was calculated. Specifically, the required number of NCO groups was calculated assuming that 1 mol of water inactivates 1 mol of MDI and that the number of OH groups of the glucose was 5. As a result, the equivalent was 26.23 g of MDI.
While the reaction vessel was heated to 70 ° C. and stirred, MDI was gradually added, sampled each time, the weight average molecular weight (Mw) was measured using GPC, and the tensile strength was measured.
As a result, when the MDI addition amount was 0.95 times the equivalent, Mw was 300,000, and the stress at 300% elongation was 21 MPa.

[Example 2]
70.0 g of polybutylene adipate containing no D-(+)-glucose was used in place of polybutylene adipate containing 10 ppm by weight of D-(+)-glucose and 1,4 containing 100 ppm of D-(+)-glucose -Polyurethane was produced in the same manner as in Example 1 except that butanediol was used as the chain extender.
As a result, when the amount of MDI added was 0.95 times the equivalent, Mw was 300,000, and the stress at 300% elongation was 20 MPa.

[Comparative Example 1]
A polyurethane was produced in the same manner as in Example 1 except that 70.0 g of polybutylene adipate containing no D-(+)-glucose was used instead of polybutylene adipate containing 10 ppm of D-(+)-glucose.
As a result, Mw was 120,000 when the amount of MDI added was 0.95 times the equivalent. Finally, 0.97 times MDI was added to the equivalent, Mw was 250,000, and the stress at 300% elongation was 14 MPa.

[Comparative Example 2]
A polyurethane was produced in the same manner as in Example 1 except that 70.0 g of polybutylene adipate containing 100 ppm of D-(+)-glucose was used instead of polybutylene adipate containing 10 ppm of D-(+)-glucose.
As a result, when the amount of MDI added was 0.95 times the equivalent, Mw was 710,000, and gelation was observed. A film could not be made and the tensile strength could not be measured.

[Comparative Example 3]
A polyurethane was produced in the same manner as in Example 1 except that 70.0 g of polybutylene adipate containing 1000 ppm of D-(+)-glucose was used instead of polybutylene adipate containing 10 ppm of D-(+)-glucose.
As a result, Mw was 50,000 when the amount of MDI added was 0.95 times the equivalent. Finally, 0.98 times MDI was added to the equivalent, Mw was 80,000, and the stress at 300% elongation was 10 MPa.

  The above results of Examples 1 and 2 and Comparative Examples 1 to 3 were compared with the amount of D-(+)-glucose in the polyurethane production reaction system (total polyhydroxy compounds in the reaction system (polybutylene adipate and 1,4 -Butanediol) and the weight ratio of D-(+)-glucose to the sum of D-(+)-glucose) and the results are summarized in Table 1 below.

From the results of Examples 1 and 2 and Comparative Examples 1 to 3, the presence of an appropriate amount of glucose in the reaction system increases the reaction rate of polyurethane formation, and a polyurethane having a preferred molecular weight with an MDI equivalent of 0.95 times can be obtained. I understand that I can do it.
The manufactured polyurethane has a high tensile strength and an excellent elastic recovery rate, and is found to be particularly desirable for synthetic / artificial leather, foam resin for shoe soles, and elastic fibers.

Claims (13)

A process for producing a polyurethane comprising a step of reacting a polyester polyol and an isocyanate compound in the presence of sugar and / or a derivative thereof,
The abundance of the sugar and / or derivative thereof is 0.1 to 80 ppm by weight based on the total amount of the polyhydroxy compound other than the sugar and / or derivative thereof and the sugar and / or derivative thereof in the reaction system. A process for producing polyurethane characterized by the above.   The method for producing a polyurethane according to claim 1, further comprising a step of producing the polyester polyol by esterification and / or transesterification of a dicarboxylic acid and / or a derivative thereof and a dihydroxy compound.   The method for producing a polyurethane according to claim 2, wherein the sugar and / or derivative thereof is contained in the polyester polyol obtained by the dihydroxy compound containing the sugar and / or the derivative thereof.   The method for producing a polyurethane according to claim 2 or 3, wherein at least one component of the dihydroxy compound is 1,4-butanediol.   The number average molecular weight of the said polyester polyol is 500-5000, The manufacturing method of the polyurethane of any one of Claim 1 thru | or 4 characterized by the above-mentioned.   The method for producing a polyurethane according to any one of claims 1 to 5, wherein a chain extender is further reacted with the polyester polyol and the isocyanate compound.   The method for producing a polyurethane according to claim 6, wherein the chain extender contains the sugar and / or a derivative thereof.   The method for producing a polyurethane according to claim 6 or 7, wherein at least one component of the chain extender is 1,4-butanediol.   The method for producing a polyurethane according to any one of claims 1 to 8, wherein the sugar and / or derivative thereof is a carbonyl compound containing two or more oxygen atoms.   The method for producing a polyurethane according to claim 1, wherein the polyurethane is a thermoplastic polyurethane.   A polyester polyol having a number average molecular weight of 500 or more and 5000 or less, obtained by esterifying and / or transesterifying a dicarboxylic acid and / or derivative thereof with a dihydroxy compound, and containing a sugar and / or a derivative thereof. A polyester polyol characterized by   The polyurethane manufactured by the manufacturing method of the polyurethane of any one of Claim 1 thru | or 10.   The polyurethane according to claim 12, which is a polyurethane for shoes.