Hexanediol glycidyl ether and / or oligomer composition thereof, curable composition, and cured product

Abstract

The purpose of the present invention is to provide a hexanediol glycidyl ether and / or an oligomer composition thereof which can provide a cured product having excellent physical properties, and a curable composition and a cured product using the same. The present invention relates to a composition containing a hexanediol glycidyl ether and / or an oligomer thereof, in which the total content of a compound (A1) having two or more secondary hydroxyl groups in each molecule and a glycidyl ether compound (A2) of the compound (A1) is 100 ppm by mass or less, and the total content of the compound (A1) and the glycidyl ether compound (A2) of the compound (A1) is 100 ppm by mass or less. The total content of 6-hydroxyhexanal and a derivative (B1) thereof and a glycidyl ether compound (B2) of the compound (B1) is 1500 ppm by mass or less.

Description

Technical Field

[0001] The present invention relates to a composition, a curable composition, and a cured product of hexanediol glycidyl ether and / or its oligomer. Background Art

[0002] Hexanediol glycidyl ether and / or its oligomers (HDG) are synthesized by glycidyl etherification of hexanediol (HD) as a raw material. Hexanediol diglycidyl ether, a type of HDG, is synthesized by diglycidyl etherification of HD as a raw material. Furthermore, during the synthesis of HDG, a reaction between HDG and HD occurs, resulting in the formation of HDG oligomers such as dimers and trimers as by-products.

[0003] HD, the raw material, is converted into an HD composition containing impurities. 1,6-hexanediol (1,6-HD), one type of HD composition, is conventionally produced by esterifying a mixture of carboxylic acids such as adipic acid, 6-hydroxycaproic acid, and glutaric acid, generated by oxidizing cyclohexane, a petrochemical, followed by hydrogenation and purification by distillation.

[0004] Meanwhile, with increasing environmental awareness in recent years, there is a desire for raw materials derived from biomass resources, rather than petroleum, which contributes to global warming. While attempts have been made to produce biomass-derived 1,6-hexanediol compositions from biomass-derived raw materials using microorganisms, no commercially available products have been developed. For example, Patent Documents 1 and 2 disclose methods for producing 1,6-hexanediol compositions using enzymes, describing methods involving the use of enzyme genetic information, metabolic pathways, and purification.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-114227

[0008] Patent Document 2: Japanese Patent No. 6680671 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] The purity and performance of hexanediol glycidyl ether and / or oligomer compositions are affected by the purity and impurities of the raw material HD composition. However, while Patent Documents 1 and 2 disclose environmentally friendly methods for producing 1,6-hexanediol compositions derived from biomass resources, they do not disclose the impurities contained in these 1,6-hexanediol compositions.

[0011] The present inventors have confirmed that the 1,6-hexanediol composition obtained by the production methods described in Patent Documents 1 and 2 contains a large amount of alicyclic diol, 6-hydroxyhexanal, and derivatives thereof as impurities.

[0012] Furthermore, the present inventors have confirmed that, also in a production method in which a carboxylic acid mixture such as adipic acid, 6-hydroxyhexanoic acid, and glutaric acid produced by oxidation of cyclohexane, a petrochemical product, is esterified and then hydrogenated and purified by distillation through organic synthesis, the resulting 1,6-hexanediol composition contains a large amount of alicyclic diols, 6-hydroxyhexanal, and derivatives thereof as impurities.

[0013] When compounds having two or more secondary hydroxyl groups per molecule, such as compound (A1), 6-hydroxyhexanal, and its derivatives (B1), are present in the HD composition, all or part of the hydroxyl groups of compounds (A1) and (B1) are also glycidyl-etherified during the glycidyl-etherification reaction of hexanediol, remaining as impurities in the hexanediol glycidyl ether and / or oligomer composition. Furthermore, unreacted compounds (A1) and (B1) also remain as impurities in the hexanediol glycidyl ether and / or oligomer composition. Furthermore, the present inventors' research has shown that these impurities adversely affect the performance of the hexanediol glycidyl ether and / or oligomer composition.

[0014] An object of the present invention is to solve the above-mentioned problems and provide a hexanediol glycidyl ether and / or oligomer composition thereof that can provide a cured product having excellent physical properties, and a curable composition and a cured product using the same.

[0015] Means used to solve problems

[0016] As a result of intensive research, the present inventors have discovered that by reducing the contents of the compound (A1) and the glycidyl ether product of the compound (A1), and the compound (B1) and the glycidyl ether product of the compound (B1), respectively, to a specific amount or less, a cured product having excellent physical properties can be provided, thereby completing the present invention.

[0017] That is, the present invention (1) relates to a hexanediol glycidyl ether and / or oligomer composition containing hexanediol glycidyl ether and / or oligomer thereof, wherein the total content of a compound (A1) having two or more secondary hydroxyl groups in one molecule and a glycidyl ether compound (A2) of the above compound (A1) is 100 mass ppm or less, and the total content of 6-hydroxyhexanal and its derivative (B1) and the glycidyl ether compound (B2) of the above compound (B1) is 1500 mass ppm or less.

[0018] The present invention (2) relates to the hexanediol glycidyl ether and / or its oligomer composition described in the present invention (1), wherein the above-mentioned compound (A2) is at least one compound selected from the following: a glycidyl ether of glucose (a compound represented by the following formula (A2-1)), a glycidyl ether of 1,4-cyclohexanediol (a compound represented by the following formula (A2-2)), a glycidyl ether of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3)) and a glycidyl ether of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4)).

[0019] [Chemical Formula 1]

[0020]

[0021] (In the above formulas (A2-1) to (A2-4), R is the same or different and represents a hydrogen atom or a glycidyl group. However, at least one of R is a glycidyl group.)

[0022] The present invention (3) relates to the hexanediol glycidyl ether and / or oligomer composition thereof described in the present invention (1) or (2), wherein the compound (B2) is at least one compound selected from the group consisting of compounds represented by the following formulae (B2-1) to (B2-7).

[0023] [Chemical Formula 2]

[0024]

[0025] (In the above formulas (B2-1) to (B2-7), R is the same or different and represents a hydrogen atom or a glycidyl group. However, at least one of R is a glycidyl group.)

[0026] The present invention (4) relates to the hexanediol glycidyl ether and / or oligomer composition thereof according to any one of the present inventions (1) to (3), which contains a glycidyl ether of glycerol (a compound represented by the following formula (C)).

[0027] [Chemical Formula 3]

[0028]

[0029] (In the above formula (C), R's are the same or different and represent a hydrogen atom or a glycidyl group. At least one of R's is a glycidyl group.)

[0030] The present invention (5) relates to the hexanediol glycidyl ether and / or oligomer composition described in any one of the present inventions (1) to (4), which is produced from a 1,6-hexanediol composition derived from biomass resources.

[0031] Furthermore, the present invention (6) relates to a curable composition comprising the hexanediol glycidyl ether and / or oligomer composition thereof according to any one of the present inventions (1) to (5).

[0032] The present invention (7) relates to the curable composition according to the present invention (6), which contains an epoxy resin other than the above-mentioned hexanediol glycidyl ether and / or its oligomer composition.

[0033] The present invention (8) relates to the curable composition described in the present invention (7), wherein the epoxy resin other than the above-mentioned hexanediol glycidyl ether and / or its oligomer composition is a bisphenol F-type epoxy resin.

[0034] The present invention (9) relates to the curable composition described in the present invention (7) or (8), wherein the epoxy resin other than the above-mentioned hexanediol glycidyl ether and / or its oligomer composition is a bisphenol A type epoxy resin.

[0035] The present invention (10) relates to the curable composition according to any one of the present inventions (6) to (9), which contains a polyamine compound.

[0036] The present invention (11) relates to the curable composition according to any one of the present inventions (6) to (10), which contains an acid anhydride.

[0037] The present invention (12) relates to the curable composition according to any one of the present inventions (6) to (11), which contains a phenolic hydroxyl group-containing resin.

[0038] The present invention (13) relates to the curable composition according to any one of the present inventions (6) to (12), which is used for at least one application selected from the group consisting of ink, coating, paint, adhesive and crack repair agent.

[0039] Furthermore, the present invention (14) relates to a cured product characterized in that it is obtained by curing the curable composition according to any one of the present inventions (6) to (13).

[0040] Effects of the Invention

[0041] The hexanediol glycidyl ether and / or oligomer composition of the present invention contains hexanediol glycidyl ether and / or oligomer thereof, a compound (A1) having two or more secondary hydroxyl groups in one molecule, and a glycidyl ether compound (A2) of the compound (A1) in a total content of 100 mass ppm or less, and a total content of 6-hydroxyhexanal and its derivative (B1), and a glycidyl ether compound (B2) of the compound (B1) in a total content of 1500 mass ppm or less. Therefore, a cured product having excellent physical properties can be provided. DETAILED DESCRIPTION

[0042] <Hexanediol glycidyl ether and / or its oligomer composition>

[0043] The hexanediol glycidyl ether and / or oligomer composition of the present invention contains hexanediol glycidyl ether and / or oligomer thereof, wherein the total content of a compound (A1) having two or more secondary hydroxyl groups per molecule and a glycidyl ether compound (A2) of the compound (A1) is 100 ppm by mass or less, and the total content of 6-hydroxyhexanal and its derivative (B1), and the glycidyl ether compound (B2) of the compound (B1) is 1500 ppm by mass or less. Therefore, the hexanediol glycidyl ether and / or oligomer composition of the present invention can be preferably used as an epoxy resin (polymerizable diluent), and can provide a cured product having excellent physical properties, particularly tensile strength, hardness, compressive strength, and flexural strength.

[0044] The reason why such an action effect is exerted is unclear, but is presumed as follows.

[0045] Since compounds (A1) and / or (B1) do not have glycidyl groups, they do not contribute to the curing reaction. When they are contained, the transparency, tensile strength, hardness, compressive strength, and flexural strength of the cured product are reduced. Compound (A2) has a rigid structure and steric hindrance, which reduces the reactivity of the glycidyl groups and reduces the physical properties of the cured product. (A1) originally has secondary hydroxyl groups, so it is difficult to glycidylate. It contains a large number of monofunctional glycidyl groups, which become reaction terminators during curing and cause the reduction of physical properties. (B2-1) to (B2-4) are also monofunctional glycidyl groups and will similarly lead to a reduction in the physical properties of the cured product. (B2-5) to (B2-6) have large molecular weights, which increase the viscosity of the curable composition, leading to a reduction in reactivity and a reduction in the physical properties of the cured product.

[0046] The hexanediol glycidyl ether and / or oligomer composition of the present invention contains hexanediol glycidyl ether and / or oligomers thereof, wherein the total content of a compound (A1) having two or more secondary hydroxyl groups in one molecule and a glycidyl ether compound (A2) of the compound (A1) is 100 ppm by mass or less, and the total content of 6-hydroxyhexanal and its derivative (B1) and the glycidyl ether compound (B2) of the compound (B1) is 1500 ppm by mass or less.

[0047] Hexanediol glycidyl ether and / or its oligomer (HDG) is a compound represented by the following formula (HDG).

[0048] [Chemical Formula 4]

[0049]

[0050] (In the formula, R is the same or different and represents a hydrogen atom or a glycidyl group. n represents an integer greater than or equal to 0. At least one of R is a glycidyl group.)

[0051] In the above formula (HDG), n represents an integer of 0 or greater, and the upper limit is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less.

[0052] In this specification, a secondary hydroxyl group means a hydroxyl group in which the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.

[0053] In this specification, the glycidyl ether compound of a compound means the glycidyl ether form of the compound.

[0054] As the above-mentioned hexanediol glycidyl ether, hexanediol monoglycidyl ether and hexanediol diglycidyl ether are enumerated. They can be used alone or in combination with two or more kinds. Among them, hexanediol diglycidyl ether is preferred because it is more suitable to obtain a cured product having more excellent physical properties.

[0055] As the oligomer of hexanediol glycidyl ether, the monoglycidyl group of hexanediol glycidyl ether, the diglycidyl group of hexanediol glycidyl ether, etc. are listed. These can be used alone or in combination of two or more. Among them, the diglycidyl group of hexanediol diglycidyl ether is preferred because it is more suitable to obtain a cured product with better physical properties.

[0056] Hexanediol glycidyl ether and / or its oligomers (HDG) generally contain a large amount of hexanediol glycidyl ether, and a small amount of hexanediol glycidyl ether oligomers as by-products. The content of hexanediol glycidyl ether in 100% by mass of hexanediol glycidyl ether and its oligomers (HDG) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and may be 100% by mass.

[0057] The positions of the hydroxyl groups and / or glycidyl ether groups in the hexanediol glycidyl ether and / or its oligomers are not particularly limited, and examples thereof include the 1,2, 1,3, 1,4, 1,5, 1,6, 2,5, 2,4, 2,3, and 3,4 positions of the hexanediol structural unit. Among them, the 1,6 positions are preferred because they are more suitable for obtaining a cured product with superior physical properties. Therefore, as hexanediol glycidyl ether and / or its oligomers, 1,6-hexanediol diglycidyl ether and / or its oligomers are particularly preferred.

[0058] In the hexanediol glycidyl ether and / or oligomer composition of the present invention, the content of the hexanediol glycidyl ether and / or oligomer thereof (the total content of the hexanediol glycidyl ether and oligomers thereof) is preferably 70.00 to 99.99% by mass, more preferably 80.00 to 99.99% by mass, and still more preferably 90.00 to 99.99% by mass. By setting the total content of the compound (A1) and the compound (A2), and the total content of the compound (B1) and the compound (B2) within the above ranges, and by setting the purity of the hexanediol glycidyl ether and / or oligomer composition within the above ranges, the effects of the present invention tend to be more preferably achieved.

[0059] In this specification, the content of hexanediol glycidyl ether and / or its oligomers is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0060] The compound (A1) having two or more secondary hydroxyl groups in one molecule is not particularly limited as long as it is a compound having two or more secondary hydroxyl groups in one molecule. Examples thereof include aliphatic polyols represented by 2,3-butanediol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and heptyl alcohol; alicyclic polyols represented by 1,2-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercetin; and oligomers formed by dehydration condensation of any combination of these compounds. These may be used alone or in combination of two or more. Among them, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and glucose are preferred because they have a greater impact on the physical properties of the cured product.

[0061] The glycidyl ether compound (A2) of the compound (A1) is not particularly limited as long as it is a glycidyl ether of the compound (A1). Examples thereof include glycidyl ethers of aliphatic polyols represented by 2,3-butanediol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and heptyl alcohol; glycidyl ethers of alicyclic polyols represented by 1,2-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercetin; and glycidyl ethers of oligomers formed by dehydration condensation of any combination of the above-mentioned aliphatic polyols and the above-mentioned alicyclic polyols. These may be used alone or in combination of two or more. In addition, in the compound (A2), all or part of the hydroxyl groups of the compound (A1) are glycidyl etherified.

[0062] Among them, from the viewpoint of having a great influence on the physical properties of the solidified product, it may be at least one compound selected from the group consisting of a glycidyl ether of glucose (a compound represented by the following formula (A2-1)), a glycidyl ether of 1,4-cyclohexanediol (a compound represented by the following formula (A2-2)), a glycidyl ether of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3)), and a glycidyl ether of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4)). It may also be a glycidyl ether selected from the group consisting of a glycidyl ether of glucose. At least one compound selected from the group consisting of a glycidyl ether of 1,4-cyclohexanediol (a compound represented by the following formula (A2-1) in which all R groups are glycidyl groups), a glycidyl ether of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3) in which all R groups are glycidyl groups), and a glycidyl ether of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4) in which all R groups are glycidyl groups).

[0063] [Chemical Formula 5]

[0064]

[0065] (In the above formulas (A2-1) to (A2-4), R is the same or different and represents a hydrogen atom or a glycidyl group. However, at least one of R is a glycidyl group.)

[0066] In the hexanediol glycidyl ether and / or oligomer composition of the present invention, the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the glycidyl ether compound (A2) of the compound (A1) (preferably the total content of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glucose, and the compounds represented by the above formulae (A2-1) to (A2-4)) is 100 mass ppm or less, preferably 50 mass ppm or less, more preferably 10 mass ppm or less, further preferably 5 mass ppm or less, and particularly preferably 0 mass ppm (not containing any). This tends to produce a cured product having excellent physical properties.

[0067] In this specification, the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the glycidyl ether compound (A2) of the compound (A1) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0068] The hexanediol glycidyl ether and / or oligomer composition of the present invention contains 6-hydroxyhexanal and its derivative (B1), and the glycidyl ether compound (B2) of the compound (B1) in a total amount of 1500 ppm by mass or less.

[0069] The compound (B1) is 6-hydroxyhexanal or a derivative thereof.

[0070] The derivatives of 6-hydroxyhexanal are not particularly limited as long as they are derivatives of 6-hydroxyhexanal (the compound represented by the following formula (B1-1)). Examples thereof include cyclized products, aldol condensation products, glycerol reaction products, and hexanediol (HDO) reaction products. Specific examples include compounds represented by the following formulas (B1-2) to (B1-7). These may be used alone or in combination of two or more.

[0071] [Chemical Formula 6]

[0072]

[0073] As 6-hydroxyhexanal or its derivative (B1), 6-hydroxyhexanal may be used because it has a great influence on the physical properties of the cured product.

[0074] The glycidyl ether compound (B2) of the compound (B1) is not particularly limited as long as it is a glycidyl ether of the compound (B1). Examples thereof include glycidyl ethers of 6-hydroxyhexanal, glycidyl ethers of cyclized products of 6-hydroxyhexanal, glycidyl ethers of aldol condensates of 6-hydroxyhexanal, glycidyl ethers of glycerol reaction products of 6-hydroxyhexanal, and glycidyl ethers of hexanediol (HDO) reaction products of 6-hydroxyhexanal. These glycidyl ethers may be used singly or in combination. Furthermore, the compound (B2) may be a compound wherein all or part of the hydroxyl groups of the compound (B1) are glycidyl-etherified.

[0075] Among them, from the perspective of having a greater impact on the physical properties of the cured product, it can be at least one compound selected from the compounds represented by the following formulas (B2-1) to (B2-7), it can be at least one compound selected from the compounds represented by the following formulas (B2-1) to (B2-7) (compounds in which all R are glycidyl groups), or it can be a compound represented by the following formula (B2-1).

[0076] [Chemical Formula 7]

[0077]

[0078] (In the above formulas (B2-1) to (B2-7), R is the same or different and represents a hydrogen atom or a glycidyl group. However, at least one of R is a glycidyl group.)

[0079] In the hexanediol glycidyl ether and / or oligomer composition of the present invention, the total content of 6-hydroxyhexanal and its derivative (B1), and the glycidyl ether compound (B2) of the compound (B1) (preferably the content of 6-hydroxyhexanal and the glycidyl ether form of 6-hydroxyhexanal) is 1500 mass ppm or less, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 200 mass ppm or less, and particularly preferably 0 mass ppm (no glycidyl ether). This tends to produce a cured product having excellent physical properties.

[0080] In this specification, the total content of 6-hydroxyhexanal and its derivative (B1), and the glycidyl ether compound (B2) of the compound (B1) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0081] The hexanediol glycidyl ether and / or its oligomer composition of the present invention preferably contains a glycidyl ether of glycerol (a compound represented by the following formula (C)). This tends to result in a cured product having superior physical properties (particularly tensile strength, hardness, compressive strength, and flexural strength). This is presumably due to the good compatibility of glycerol glycidyl ether with hexanediol glycidyl ether and / or its oligomers, allowing the high crosslink density structure of glycerol glycidyl ether to be ideally incorporated into the cured product. The compound represented by the following formula (C) can be used alone or in combination of two or more.

[0082] [Chemical Formula 8]

[0083]

[0084] (In the above formula (C), R's are the same or different and represent a hydrogen atom or a glycidyl group. At least one of R's is a glycidyl group.)

[0085] In the above formula (C), at least one of R is a glycidyl group, preferably at least two of R are glycidyl groups, and more preferably all of R are glycidyl groups.

[0086] In the hexanediol glycidyl ether and / or oligomer composition of the present invention, the content of glycerol glycidyl ether (preferably glycerol triglycidyl ether) is preferably 0.1 to 50,000 ppm, more preferably 1 to 10,000 ppm, and even more preferably 5 to 10,000 ppm. When the content of glycerol glycidyl ether is 0.1 ppm or more, the resulting cured product tends to have an increased crosslinking density and excellent flexural strength, elastic modulus, and tensile strength. When the content of glycerol glycidyl ether is 50,000 ppm or less, the resulting cured product tends to have excellent hardness, elastic modulus, and tensile strength.

[0087] In this specification, the content of glycidyl ether of glycerol is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0088] The hexanediol glycidyl ether and / or oligomer composition of the present invention can be produced by, for example, modifying one or both of the two hydroxyl groups of 1,6-hexanediol contained in the 1,6-hexanediol composition with an epihalohydrin such as epichlorohydrin according to a known method.

[0089] The hexanediol glycidyl ether and / or its oligomer composition of the present invention can be manufactured so that the total content of the above-mentioned compound (A1) and the above-mentioned compound (A2), and the total content of the above-mentioned compound (B1) and the above-mentioned compound (B2) are within the above-mentioned range. In order to manufacture the hexanediol glycidyl ether and / or its oligomer composition so that the total content of the above-mentioned compound (A1) and the above-mentioned compound (A2), and the total content of the above-mentioned compound (B1) and the above-mentioned compound (B2) contained in the hexanediol glycidyl ether and / or its oligomer composition are within the above-mentioned range, for example, a hexanediol composition (preferably a 1,6-hexanediol composition) having a total content of the above-mentioned compound (A1) of 100 mass ppm or less and a total content of the above-mentioned compound (B1) of 1500 mass ppm or less can be reacted with epihalohydrin according to a known method. Of course, the hexanediol glycidyl ether and / or its oligomer composition of the present invention can also be manufactured by manufacturing a hexanediol glycidyl ether and / or its oligomer composition having a large amount of impurities and purifying the impurities from the composition.

[0090] A 1,6-hexanediol composition containing a total content of the above-mentioned compounds (A1) of 100 mass ppm or less and a total content of the above-mentioned compounds (B1) of 1500 mass ppm or less can be obtained by the following production method via organic synthesis: esterifying a carboxylic acid mixture such as adipic acid, 6-hydroxyhexanoic acid, and glutaric acid produced by oxidation of cyclohexane, a petrochemical product, followed by hydrogenation and distillation purification. The above-mentioned 1,6-hexanediol composition can also be obtained from raw materials derived from biomass resources by a production method using microorganisms. The production method is not limited. In order to remove the above-mentioned compounds (A1) and (B1) contained in the 1,6-hexanediol composition obtained by any production method, for example, by performing step (2) described below, a 1,6-hexanediol composition containing a total content of the above-mentioned compounds (A1) of 100 mass ppm or less and a total content of the above-mentioned compounds (B1) of 1500 mass ppm or less can be produced.

[0091] As the 1,6-hexanediol composition having a total content of the above-mentioned compounds (A1) of 100 mass ppm or less and a total content of the above-mentioned compounds (B1) of 1500 mass ppm or less, specifically, a 1,6-hexanediol composition (a 1,6-hexanediol composition derived from biomass resources) obtained by the following environmentally friendly production method (a production method suitable for the 1,6-hexanediol composition of the present invention) can be preferably used.

[0092] The method for producing a 1,6-hexanediol composition suitable for the present invention is an environmentally friendly method that can reduce carbon dioxide emissions, since the 1,6-hexanediol composition is produced from a raw material derived from biomass resources.

[0093] Due to global warming and the occurrence of abnormal weather events worldwide caused by increasing carbon dioxide concentrations, corporate activities that prioritize sustainability are becoming increasingly important. The hexanediol glycidyl ether and / or oligomer composition of the present invention can be produced using an environmentally friendly production method by preparing the hexanediol glycidyl ether and / or oligomer composition from a 1,6-hexanediol composition derived from biomass resources.

[0094] <Method for producing 1,6-hexanediol composition suitable for the present invention>

[0095] First, a 1,6-hexanediol composition obtained by the method for producing a 1,6-hexanediol composition suitable for the present invention (also referred to as a 1,6-hexanediol composition suitable for the present invention) will be described.

[0096] In the 1,6-hexanediol composition suitable for the present invention, the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule is 100 ppm by mass or less.

[0097] The compound (A1) having two or more secondary hydroxyl groups in one molecule may be 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, or glucose, since these compounds have a significant influence on the physical properties of the cured product.

[0098] In the 1,6-hexanediol composition suitable for the present invention, the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule (preferably the total content of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and glucose) is 100 mass ppm or less, preferably 50 mass ppm or less, more preferably 10 mass ppm or less, further preferably 5 mass ppm or less, and particularly preferably 0 mass ppm (not containing any). This tends to produce a cured product having excellent physical properties.

[0099] In this specification, the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0100] The total content of 6-hydroxyhexanal and its derivative (B1) suitable for the 1,6-hexanediol composition of the present invention is 1500 ppm by mass or less.

[0101] As the 6-hydroxyhexanal and / or its derivative (B1), 6-hydroxyhexanal may be used because it has a great influence on the physical properties of the cured product.

[0102] In the 1,6-hexanediol composition suitable for the present invention, the total content of 6-hydroxyhexanal and its derivative (B1) (preferably the content of 6-hydroxyhexanal) is 1500 mass ppm or less, preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, further preferably 200 mass ppm or less, and particularly preferably 0 mass ppm (no 6-hydroxyhexanal). This tends to produce a cured product having excellent physical properties.

[0103] In this specification, the total content of 6-hydroxyhexanal and its derivative (B1) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0104] In the 1,6-hexanediol composition suitable for the present invention, the glycerol content is preferably 0.1 to 50,000 ppm, more preferably 1 to 10,000 ppm, and even more preferably 5 to 10,000 ppm. When the glycerol content is 0.1 ppm or greater, the resulting cured product tends to have an increased crosslinking density and excellent flexural strength, elastic modulus, and tensile strength. When the glycerol glycidyl ether content is 50,000 ppm or less, the resulting cured product tends to have excellent hardness, elastic modulus, and tensile strength.

[0105] In this specification, the glycerol content is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0106] In the 1,6-hexanediol composition suitable for the present invention, the 1,6-hexanediol content is preferably 96.00 to 99.99% by mass, more preferably 98.00 to 99.99% by mass, and even more preferably 99.50 to 99.99% by mass. By setting the total content of the compound (A1) and the total content of the compound (B1) within the above ranges and simultaneously setting the purity of the 1,6-hexanediol composition within the above ranges, the hexanediol glycidyl ether and / or oligomer composition of the present invention tends to be more preferably obtained.

[0107] In this specification, the content of 1,6-hexanediol is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0108] The 1,6-hexanediol composition suitable for the present invention may be produced so that the total content of the compound (A1) and the total content of the compound (B1) fall within the above-mentioned ranges.

[0109] Specifically, a 1,6-hexanediol composition suitable for the present invention (a 1,6-hexanediol composition derived from a biomass resource) obtained by the following environmentally friendly production method (production method suitable for the present invention) can be preferably used.

[0110] Next, a method for producing a 1,6-hexanediol composition suitable for the present invention will be described.

[0111] The method for producing a 1,6-hexanediol composition suitable for the present invention comprises: a step (1) of producing the 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from biomass resources; and a step (2) of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and / or distillation.

[0112] <<Step (1)>>

[0113] Step (1) is a step of producing a 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource. Here, producing a 1,6-hexanediol composition from 6-hydroxyhexanoic acid and / or its derivatives obtained from a raw material derived from a biomass resource means producing a 1,6-hexanediol composition from a raw material derived from a biomass resource via 6-hydroxyhexanoic acid and / or its derivatives. Via 6-hydroxyhexanoic acid and / or its derivatives can be any process, and for example, it may be a step of converting a raw material derived from a biomass resource via 6-hydroxyhexanoic acid and / or its derivatives into a 1,6-hexanediol composition within the cells of a microorganism. It may also be a step of producing 6-hydroxyhexanoic acid and / or its derivatives from a raw material derived from a biomass resource by a microorganism, directly applying a culture solution containing the compound, and converting the compound into a 1,6-hexanediol composition by the microorganism. It may also be a step of purifying the culture solution and converting the compound into a 1,6-hexanediol composition by the microorganism in a different reaction tank.

[0114] The derivative of 6-hydroxyhexanoic acid is not particularly limited as long as it is a derivative of 6-hydroxyhexanoic acid. Examples thereof include ester compounds such as 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxyhexanoic acid, cyclized products of 6-hydroxyhexanoic acid, condensates of 6-hydroxyhexanoic acids, and condensates of 6-hydroxyhexanoic acid and 1,6-hexanediol. These may be used alone or in combination of two or more. Among them, 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxyhexanoic acid, is preferred.

[0115] In this specification, CoA means coenzyme A.

[0116] As the 6-hydroxyhexanoic acid and / or its derivative, 6-hydroxyhexanoic acid and 6-hydroxy-hexanoyl-CoA are preferred, and 6-hydroxyhexanoic acid is more preferred.

[0117] The above-mentioned step (1) is preferably a step of producing a 1,6-hexanediol composition under conditions of 70°C or less, and more preferably a step of producing a 1,6-hexanediol composition under conditions of 50°C or less. The lower limit of the temperature is not particularly limited, but is preferably 20°C or above. By carrying out production at a relatively low temperature, the amount of carbon dioxide emitted during production can be reduced, and side reactions such as cyclization associated with dehydration can be reduced, and the generation of by-products such as cyclic oligomers can be suppressed. As a result, fogging, which is a problem in automotive interior materials, can also be suppressed. In addition, the stacking inhibition factor of the polymer chain is reduced, which can improve the physical properties of the film.

[0118] The above step (1) can be performed, for example, using a microorganism that can produce (biosynthesize) 1,6-hexanediol. As microorganisms that can produce 1,6-hexanediol, for example, microorganisms described in Japanese Patent Publication No. 2020-114227 and Japanese Patent No. 6680671 are listed. They can be used alone or in combination of two or more. Those skilled in the art can easily manufacture and obtain microorganisms that can produce 1,6-hexanediol based on known technologies such as the above-mentioned publications.

[0119] 3-oxopropionate and 3-hydroxypropionaldehyde are produced through metabolic pathways within microorganisms.

[0120] An example of the production of 3-hydroxypropionaldehyde in a microorganism is described. As described in FIG. 1 of Japanese Patent Gazette No. 6680671, 3-phosphoglyceraldehyde is produced from sugars (five-carbon sugars, six-carbon sugars) through metabolic pathways of glycolysis systems such as the pentose phosphate pathway (PP pathway) in a microorganism. Similarly, 3-phosphoglyceraldehyde is produced from glycerol through metabolic pathways in a microorganism. Then, 3-hydroxypropionaldehyde is produced from 3-phosphoglyceraldehyde through reactions catalyzed by multiple enzymes possessed by the microorganism. In addition, 3-hydroxypropionaldehyde is produced from glycerol in one reaction by diol dehydratase and / or glycerol dehydratase.

[0121] An example of the production of 3-oxopropionate in a microorganism is described. As described in FIG. 1 of Japanese Patent No. 6680671, 3-phosphoglyceric acid and 2-phosphoglyceric acid are produced from sugars (five-carbon sugars and six-carbon sugars) in a microorganism through metabolic pathways of the glycolytic system such as the Embden-Meyerhof pathway (EM pathway). Glyceric acid is produced from 3-phosphoglyceric acid and 2-phosphoglyceric acid using the enzymes described in Table 1 of Japanese Patent No. 6680671 or the reverse reaction of glycerate kinase. 3-oxopropionate is produced from glyceric acid by diol dehydratase and / or glycerol dehydratase. Further, oxaloacetic acid can also be produced in one reaction from oxaloacetic acid, a metabolic intermediate of the TCA cycle, by ketoacid decarboxylase. Oxaloacetic acid can also be produced from sugars by phosphoenolpyruvate carboxylase and pyruvate carboxylase without going through the TCA cycle.

[0122] For example, 1,6-hexanediol is produced from 3-oxopropionic acid ester and 3-hydroxypropionaldehyde produced by metabolic pathways in microorganisms using various pathways shown in Figures 2 to 5 of Japanese Patent No. 6680671.

[0123] As a suitable example of a microorganism capable of producing 1,6-hexanediol from 3-oxopropionic acid ester and 3-hydroxypropionaldehyde, that is, a microorganism capable of producing 1,6-hexanediol, the following microorganisms are mentioned.

[0124] A microorganism having genes encoding 10 enzymes of the 1,6-hexanediol pathway, wherein the 10 enzymes include 4,6-dihydroxy-2-oxo-hexanoic acid aldolase (2A in the figure of Japanese Patent No. 6680671), 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydratase (2B in the figure of Japanese Patent No. 6680671), 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase (2C in the figure of Japanese Patent No. 6680671), 6-hydroxy-2-oxohexanoic acid 2-reductase (2D in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoic acid CoA-transferase ( 680671), 2,6-dihydroxy-hexanoyl-CoA2-dehydratase (2F in the figure of Japanese Patent No. 6680671), 6-hydroxy-2,3-dehydro-hexanoyl-CoA2,3-reductase (2G in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoyl-CoA-transferase (4F3 in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoate 1-reductase (5R in the figure of Japanese Patent No. 6680671), and 6-hydroxyhexanal 1-reductase (5S in the figure of Japanese Patent No. 6680671).

[0125] The microorganism having genes encoding the 10 enzymes in the 1,6-hexanediol pathway is not particularly limited as long as it has genes encoding the 10 enzymes in the 1,6-hexanediol pathway, and examples thereof include prokaryotes and eukaryotes.

[0126] Furthermore, the microorganisms containing genes encoding the ten enzymes of the 1,6-hexanediol pathway may be genetically modified microorganisms into which all and / or a portion of the ten genes (enzymes) encoding the ten enzymes of the 1,6-hexanediol pathway have been introduced. For example, if the microorganism to be used only possesses eight of the ten enzymes, genes encoding the remaining two enzymes can be introduced into the microorganism. Furthermore, if the microorganism to be used only possesses a portion of the ten enzymes, a single or multiple microorganisms containing genes encoding the remaining enzymes may be used in combination.

[0127] Furthermore, the above-mentioned microorganism preferably has a gene encoding a diol dehydratase and / or a glycerol dehydratase.

[0128] Here, gene introduction can be performed by known methods.

[0129] Examples of prokaryotes include bacteria.

[0130] Examples of eukaryotic organisms include yeast and filamentous fungi.

[0131] Examples of the bacteria include bacteria belonging to the family Enterobacteriaceae, coryneform bacteria, Bacillus bacteria, acetic acid bacteria, actinomycetes, and lactic acid bacteria.

[0132] Examples of bacteria belonging to the Enterobacteriaceae family include bacteria belonging to the genera Escherichia, Enterobacter, Pantoea, Klebsiella, Serratia, Erwinia, Photorhabdus, Providencia, Salmonella, and Morganella. Specifically, bacteria classified as Enterobacteriaceae according to the classification system used in the NCBI (National Center for Biotechnology Information) database (http: / / www.ncbi.nlm.nih.gov / Taxonomy / Browser / wwwtax.cgi?id=91347) can be used.

[0133] As Escherichia bacteria, there is no particular limitation, and examples include bacteria classified as Escherichia by classification known to microbiologists. Examples of Escherichia bacteria include those described in Neidhardt et al.'s work (Backmann, BJ 1996. Derivations and Genotypes of some mutant derivatives of Escherichia coli K-12, p. 2460-2488. Table 1. In FD Neidhardt (ed.), Escherichia coli and Salmonella Cellular and Molecular Biology / Second Edition, American Society for Microbiology Press, Washington, DC). Examples of Escherichia bacteria include Escherichia coli. Examples of Escherichia coli include Escherichia coli K-12 strains such as W3110 strain (ATCC 27325) and MG1655 strain (ATCC 47076); Escherichia coli K5 strain (ATCC 23506); Escherichia coli B strains such as BL21 (DE3) strain; and derivative strains thereof.

[0134] Examples of Enterobacter bacteria include Enterobacter agglomerans and Enterobacter aerogenes. Examples of Pantoea bacteria include Pantoea ananatis, Pantoea stewartii, Pantoea agglomerans, and Pantoea citrea. Examples of Erwinia bacteria include Erwinia amylovora and Erwinia carotovora. Examples of Klebsiella bacteria include Klebsiella planticola.

[0135] Examples of the coryneform bacteria include bacteria belonging to the genus Corynebacterium, the genus Brevibacterium, and the genus Microbacterium.

[0136] Specific examples of coryneform bacteria include the following.

[0137] Corynebacterium acetoacidophilum

[0138] Corynebacterium acetoglutamicum

[0139] Corynebacterium alkanolyticum

[0140] Corynebacterium callunae

[0141] Corynebacterium crenatum

[0142] Corynebacterium glutamicum

[0143] Corynebacterium lilium

[0144] Corynebacterium melassecola

[0145] Corynebacterium thermoaminogenes (Corynebacterium efficiens)

[0146] Corynebacterium herculis

[0147] Brevibacterium divaricatum (Corynebacterium glutamicum)

[0148] Brevibacterium flavum (Corynebacterium glutamicum)

[0149] Brevibacterium immariophilum

[0150] Brevibacterium lactofermentum (Corynebacterium glutamicum)

[0151] Brevibacterium roseum

[0152] Brevibacterium saccharolyticum

[0153] Brevibacterium thiogenitalis

[0154] Corynebacterium ammoniagenes (Corynebacterium stationis)

[0155] Brevibacterium album

[0156] Brevibacterium cerinum

[0157] Microbacterium ammoniaphilum

[0158] Specifically, the following strains are exemplified as coryneform bacteria.

[0159] Corynebacterium acetoaceticum ATCC 13870

[0160] Corynebacterium acetoglutamicum ATCC 15806

[0161] Corynebacterium ATCC 21511

[0162] Corynebacterium heatherum ATCC 15991

[0163] Corynebacterium scutellariae AS1.542

[0164] Corynebacterium glutamicum ATCC 13020, ATCC 13032, ATCC 13060, ATCC 13869, FERM BP-734

[0165] Corynebacterium liliiflorum ATCC 15990

[0166] Corynebacterium molasses ATCC 17965

[0167] Effective Corynebacterium (Corynebacterium thermoammoniagenes) AJ12340 (FERM BP-1539)

[0168] Corynebacterium ligusticum ATCC 13868

[0169] Brevibacterium formicum (Corynebacterium glutamicum) ATCC 14020

[0170] Brevibacterium flavum (Corynebacterium glutamicum) ATCC 13826, ATCC 14067, AJ12418 (FERM BP-2205)

[0171] Immature Brevibacterium ATCC 14068

[0172] Brevibacterium lactofermentum (Corynebacterium glutamicum) ATCC 13869

[0173] Brevibacterium roseum ATCC 13825

[0174] Brevibacterium saccharolyticum ATCC 14066

[0175] Brevibacterium thiogenes ATCC 19240

[0176] Corynebacterium ammoniagenes (Corynebacterium stagnantum) ATCC 6871, ATCC 6872

[0177] Brevibacterium albus ATCC 15111

[0178] Brevibacterium cereus ATCC 15112

[0179] Microbacterium ammoniaphilum ATCC 15354

[0180] It should be noted that, with respect to the genus Corynebacterium, it also includes bacteria that were previously classified as Brevibacterium but are now collectively classified as Corynebacterium (Int. J. Syst. Bacteriol., 41, 255 (1991)). In addition, with respect to Corynebacterium stagnantum, it also includes bacteria that were previously classified as Corynebacterium ammoniagenes but were reclassified as Corynebacterium stagnantum by base sequence analysis of 16S rRNA (Int. J. Syst. Evol. Microbiol., 60, 874-879 (2010)).

[0181] Examples of Bacillus bacteria include Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, Bacillus licheniformis, Bacillus megaterium, Bacillus brevis, Bacillus polymixa, and Bacillus stearothermophilus. Specific examples of Bacillus subtilis include Bacillus subtilis 168 Marburg strain (ATCC 6051) and Bacillus subtilis PY79 strain (Plasmid, 1984, 12, 1-9). Specific examples of Bacillus amyloliquefaciens include Bacillus amyloliquefaciens T strain (ATCC 23842) and Bacillus amyloliquefaciens N strain (ATCC 23845).

[0182] Examples of acetic acid bacteria include those belonging to the genera Gluconobacter, Acetobacter, Gluconacetobacter, Acidicaldus, Acidiphilium, Acidisphaera, Acidocella, Acidomonas, Asaia, Belnapia, Craurococcus, Granulibacter, and Kozakia. bacteria of the genus Pseudomonas, Leahibacter, Muricoccus, Neoasaia, Oleomonas, Paracraurococcus, Rhodopila, Roseococcus, Rubritepida, Saccharibacter, Stella, Swaminathania, Teichococcus, and Zavarzinia.

[0183] Specific examples of acetic acid bacteria include Gluconobacter oxydans, Acetobacter xylinum, Asidomonas methanolicus, Asaia bogorensis, Asaia krungthepensis, Belnapia moabensis, Gluconacetobacter xylinus, Granulibacter bethesdensis, Kozakia baliensis, and Oleomonas sagaranensis.

[0184] Examples of actinomycetes include bacteria belonging to the genera Actinomyces, Mycobacterium, Nocardia, Streptomyces, Actinoplanes, and Rhodococcus.

[0185] Specific examples of actinomycetes include Streptomyces coelicolor, Streptomyces griseus, Streptomyces avermitilis, and Rhodococcus zopfii.

[0186] Examples of lactic acid bacteria include bacteria belonging to the genus Lacticaseibacillus, the genus Lactobacillus, the genus Ligilactobacillus, the genus Limosilactobacillus, the genus Liquorilactobacillus, the genus Lactiplantibacillus, the genus Streptococcus, the genus Lactococcus, and the genus Enterococcus.

[0187] Specific examples of lactic acid bacteria include Lactobacillus casei, Lactobacillus gasseri, Lactobacillus acidophilus, Lactobacillus helveticus, Lactobacillus delbrueckii subsp. bulgaricus, Lactobacillus delbrueckii subsp. delbrueckii, Lactobacillus johnsonii, Ligilactobacillus salivarius, Limosilactobacillus fermentum, Liquorilactobacillus mali, Lactiplantibacillus plantarum, Streptococcus thermophilus, Lactococcus lactis subsp. lactis), Lactococcus lactis subsp. cremoris, Lactococcus plantarum, Lactococcus raffinolactis, Lactococcus cremoris, Enterococcus faecalis, Enterococcus faecium, etc.

[0188] Examples of bacteria other than the above bacteria include bacteria belonging to the genus Pseudomonas, the genus Agrobacterium, the genus Alicyclobacillus, the genus Arthrobacter, the genus Azotobacter, the genus Chromatium, the genus Methylobacterium, the genus Rhodobacter, the genus Rhodopseudomonas, the genus Rhodospirillum, the genus Zymomonas, the genus Achromobacter, and the genus Achr Bacteria such as the genus Aerobacter, Alcaligenes, Arthrobacter, Erwinia, Microbacterium, Micrococcus, Protaminobacter, Proteus, Sartina, Xanthomonas, Aeromonas, Flavobacterium, and Rhizobium.

[0189] Examples of yeast include yeast belonging to the genera Saccharomyces, Candida, Phichia, Schizosaccharomyces, Kluyveromyces, Rhodotorula, Crytpococcus, Torulopsis, Hansenula, Issatchenkia, Kluyveromyces, and Yarrowia.

[0190] Specific examples of yeast include Saccharomyces cerevisiae, Candida utilis, Pichia pastoris, Hansenula polymorpha, and Schizosaccharomyces pombe.

[0191] Examples of the filamentous fungi (molds) include bacteria belonging to the genera Aspergillus, Paecilomyces, Penicillium, Neurospora, Trichoderma, Fusarium, and Chrysosporium.

[0192] Specific examples of filamentous fungi (molds) include Aspergillus oryzae, Paecilomyces saturatus, Paecilomyces divaricatus, and Penicillium camemberti.

[0193] These strains can be obtained, for example, from the American Type Culture Collection (12301 Parklawn Drive, Rockville, Maryland 20852, PO Box 1549, Manassas, VA 20108, United States of America). Specifically, each strain is assigned an accession number, and the accession number can be used to distribute the strain (see http: / / www.atcc.org / ). The accession number corresponding to each strain is listed in the catalog of the American Type Culture Collection. Alternatively, these strains can be obtained, for example, from the depository where the strain is stored.

[0194] The above-mentioned microorganisms may be used alone or in combination of two or more. Among them, prokaryotes are preferred, bacteria are more preferred, microorganisms belonging to the Enterobacteriaceae family are even more preferred, microorganisms belonging to the genus Escherichia are particularly preferred, and Escherichia coli is most preferred. Specifically, prokaryotes having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are preferred, bacteria having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are more preferred, microorganisms belonging to the Enterobacteriaceae family having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are even more preferred, microorganisms belonging to the genus Escherichia having genes encoding the 10 enzymes of the 1,6-hexanediol pathway are particularly preferred, and Escherichia coli having genes encoding the 10 enzymes of the 1,6-hexanediol pathway is most preferred.

[0195] When the above genes (enzymes) are exogenously introduced into a microorganism and expressed, preferably, the above 4,6-dihydroxy-2-oxo-hexanoic acid aldolase is 2,4-dihydroxyhept-2-ene-1,7-dioic acid aldolase encoded by the HpaI gene of Escherichia coli, the above 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydratase is 2-oxo-hept-4-ene-1,7-dioic acid hydratase encoded by the HpcG / HpaH gene of Escherichia coli, and the above 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase is Arabidopsis thaliana with the NADP-dependent enal reductase P1 of GenBank accession number CAC01710.1, the above-mentioned 6-hydroxy-2-oxohexanoic acid 2-reductase is a D-2-hydroxy acid dehydrogenase encoded by the panE gene of Lactococcus lactis, the above-mentioned 2,6-dihydroxy-hexanoic acid CoA-transferase and the above-mentioned 6-hydroxyhexanoyl-CoA-transferase are glutaconate-CoA-transferases encoded by the HadA gene of Clostridium difficile, and the above-mentioned 2,6-dihydroxy-hexanoyl-CoA2-dehydratase is a 2-hydroxyhexanoic acid dehydrogenase expressed by Clostridium difficile. Isohexanoyl-CoA dehydratase, the above-mentioned 6-hydroxy-2,3-dehydrohexanoyl-CoA2,3-reductase is the trans-2-enoyl-CoA reductase of GenBank Accession No. AE017248 of Treponema denticola, the above-mentioned 6-hydroxyhexanoate 1-reductase is the ATP / NADPH-CAR of GenBank Accession No. AAR91681.1 of Nocardia iovanni, and / or the above-mentioned 6-hydroxyhexanal 1-reductase is the 6-hydroxyhexanoate dehydrogenase of GenBank Accession No. AAN37489.1 of Rhodococcus.

[0196] By using the above-mentioned microorganism, it is possible to perform the steps of (a) converting a C3 aldehyde and pyruvate into a C6 β-hydroxyketone intermediate via aldol addition, and then (b) converting the C6 β-hydroxyketone intermediate into 1,6-hexanediol or a solvate thereof via an enzymatic step. Preferably, the conversion comprises reduction of an enoyl group or an enolate, reduction of a ketone, reduction of an aldehyde, dehydration, formation of a thioester, reduction of a thioester, or a combination thereof.

[0197] In addition, it is preferred to further include a step of producing C3 aldehyde and pyruvate from a supply source selected from glycerol, pentose, hexose, phosphoglyceride, other carbon sources, intermediates in the glycolysis pathway, intermediates in propionate metabolism, or a combination thereof.

[0198] Alternatively, the C3 aldehyde is obtained via a series of enzymatic steps, which preferably include dehydration of the diol.

[0199] More specifically, using the aforementioned microorganism, 1,6-hexanediol is produced from 3-oxopropionate and 3-hydroxypropionaldehyde produced through a metabolic pathway within the microorganism, and through the pathways 2A, 2B, 2C, 2D, 2E, 2F, 2G, 4F3, 5R, and 5S shown in Figures 2 and 5 of Japanese Patent No. 6680671. In this biosynthetic pathway, 6-hydroxyhexanoyl-CoA is produced by the enzymatic reactions of the pathway up to 2G, followed by the enzymatic reaction of 4F3 to produce 6-hydroxyhexanoic acid, followed by the enzymatic reaction of 5R to produce 6-hydroxyhexanal, and finally, 1,6-hexanediol is produced by the enzymatic reaction of 5S.

[0200] Therefore, the above-mentioned step (1) can be carried out by culturing the above-mentioned microorganism in a culture medium containing a raw material derived from a biomass resource. That is, by culturing the above-mentioned microorganism in a culture medium containing a raw material derived from a biomass resource, a 1,6-hexanediol composition can be produced from 6-hydroxyhexanoic acid and / or its derivatives obtained from the raw material derived from a biomass resource.

[0201] The raw materials derived from biomass resources are not particularly limited, and examples include pentoses such as xylose, xylulose, ribulose, arabinose, lyxose, and ribose; monosaccharides such as hexoses such as allose, altrose, glucose, mannose, gulose, idose, talose, galactose, fructose, psicose, sorbose, or tagatose; disaccharides such as lactose, cellobiose, sucrose, and maltose; polysaccharides such as starch, cellulose, agarose, and dextran; alcohols such as sorbitol, ethanol, and glycerol; carbon sources used in culture medium components such as peptone, tryptone, and casamino acids; and nitrogen sources used in culture medium components such as organic nitrogen compounds such as peptone, tryptone, casamino acids, yeast extract, meat extract, and corn steep liquor. These can be used alone or in combination of two or more. Among these, carbon sources used in culture medium components are preferred, and monosaccharides and alcohols are more preferred.

[0202] As the monosaccharide, hexose is more preferred, and glucose is particularly preferred.

[0203] As the alcohol, glycerol is more preferred.

[0204] Therefore, as raw materials derived from biomass resources, glucose and glycerol are most preferred.

[0205] The culture medium is not particularly limited as long as it contains the raw materials derived from biomass resources. It can be a conventional culture medium containing a carbon source, a nitrogen source, an inorganic ion, and, if necessary, an organic nutrient source, and can be appropriately prepared according to the microorganisms used. Among them, the raw materials derived from biomass resources preferably contain the carbon source.

[0206] Carbon sources other than the above components are not particularly limited as long as they can be utilized by microorganisms, and examples include organic acids such as fumaric acid, citric acid, acetic acid, and propionic acid, and their salts, carbohydrates such as paraffin, etc. These may be used alone or in combination of two or more.

[0207] Examples of nitrogen sources other than the above components include ammonium salts of inorganic salts such as ammonium sulfate and ammonium chloride, ammonium salts of organic acids such as ammonium fumarate and ammonium citrate, and nitrates such as sodium nitrate and potassium nitrate. These may be used alone or in combination of two or more.

[0208] The above-mentioned culture medium can use the nutrient source used in common culture medium such as trace metal salts, vitamins, hormones. These can be used alone or in combination of two or more. Wherein, as trace metal salts, preferably sodium and / or potassium are included.

[0209] The culture conditions are also not particularly limited. For example, the culture can be carried out for about 4 to 140 hours while appropriately controlling the pH and temperature within the range of pH 3 to 11 and the temperature of 20 to 70°C (more preferably 20 to 50°C). The culture can be carried out under either aerobic or anaerobic conditions, which can be appropriately selected depending on the microorganisms used, but aerobic conditions are preferred.

[0210] As described above, a 1,6-hexanediol composition can be produced by culturing the aforementioned microorganisms in a culture medium containing raw materials derived from biomass resources. Since the 1,6-hexanediol composition exists in the culture medium along with the microorganisms, the microorganisms can be removed from the culture medium as needed. The method for removing the microorganisms is not particularly limited, and for example, centrifugation and / or membrane separation can be used.

[0211] The centrifugal separation is not particularly limited, and for example, continuous centrifugal separation using a continuous centrifuge can be used. Examples of continuous centrifugal separators include cage centrifuges, disc centrifuges, and nozzle centrifuges. These can be used alone or in combination of two or more.

[0212] The membrane used in membrane separation is not particularly limited, for example, a membrane with a pore size of less than 10.0 μm is enumerated, specifically, for example, a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane, etc. are enumerated. These can be used alone or in combination with two or more. In addition, the shape of the membrane is not particularly limited, and can be any shape such as a flat membrane, a hollow fiber membrane, a spiral membrane, a tubular membrane, a pleated membrane. The form of filtration is also not particularly limited, and any of the terminal mode and the tangential flow mode can be used, preferably the tangential flow mode.

[0213] <<Step (2)>>

[0214] Step (2) is a step of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and / or distillation. Step (2) is not particularly limited as long as it is a step of appropriately removing impurities contained in the 1,6-hexanediol composition obtained in step (1), for example, in a culture medium containing the 1,6-hexanediol composition after removal of microorganisms, by ion exchange and / or distillation. However, step (2) is preferably a step of purifying the 1,6-hexanediol composition obtained in step (1) by ion exchange and distillation. Furthermore, the ion exchange is preferably cation exchange and anion exchange, and more preferably cation exchange and anion exchange are performed in this order. Furthermore, the distillation is preferably performed to remove water, components with a boiling point lower than 1,6-hexanediol, and components with a boiling point higher than 1,6-hexanediol, and more preferably water, components with a boiling point lower than 1,6-hexanediol, and components with a boiling point higher than 1,6-hexanediol are removed in this order.

[0215] The 1,6-hexanediol composition obtained in step (1) to be used in step (2) is not particularly limited as long as it is the 1,6-hexanediol composition obtained in step (1). However, it is preferably a liquid obtained by removing microorganisms from a culture medium containing the 1,6-hexanediol composition obtained in step (1). More preferably, it is a liquid obtained by removing microorganisms from the culture medium containing the 1,6-hexanediol composition obtained in step (1) by subjecting the culture medium containing the 1,6-hexanediol composition obtained in step (1) to centrifugation and membrane separation.

[0216] An example of step (2) is described below in detail.

[0217] [Ion exchange step]

[0218] In the ion exchange step, a 1,6-hexanediol composition is obtained through the following steps (a) and (b) in sequence.

[0219] Step (a): a step of contacting the 1,6-hexanediol composition obtained in step (1) with a cation exchange resin to obtain a 1,6-hexanediol composition A.

[0220] Step (b): a step of contacting the 1,6-hexanediol composition A obtained in step (a) with an anion exchange resin to obtain a 1,6-hexanediol composition B.

[0221] Examples of the components removed by contact with the cation exchange resin in step (a) include metal cations and ammonium ions.

[0222] Examples of components removed by contact with the anion exchange resin in step (b) include chloride ions, sulfate ions, phosphate ions, organic acids, etc. The organic acids listed here include compounds (A1) having an acid group and two or more secondary hydroxyl groups in one molecule.

[0223] The treatment with the ion exchange resin is not particularly limited, but is preferably performed by a batch method or a column method.

[0224] <Step (a): Step of Removing Cations Contained in 1,6-Hexanediol Composition>

[0225] In step (a), cations are removed by contacting the 1,6-hexanediol composition with a cation exchange resin.

[0226] Examples of the cation exchange resins used include strongly acidic and weakly acidic resins, without particular limitation. Examples include styrene-based, acrylic-based, and hydrogel-based resins, without particular limitation. Examples include gel-based, porous, and highly porous resins, without particular limitation. Examples of the resin form include powdery, spherical, fibrous, and film-like resins, without particular limitation.

[0227] <Step (b): Step of Removing Anions Contained in 1,6-Hexanediol Composition>

[0228] In step (b), anions are removed by contacting the 1,6-hexanediol composition with an anion exchange resin.

[0229] Examples of the anion exchange resins used include strongly basic and weakly basic resins, without particular limitation. Examples include styrene-based, acrylic-based, and hydrogel-based resins, without particular limitation. Examples include gel-based, porous, and highly porous resins, without particular limitation. Examples of the resin form include powdery, spherical, fibrous, and film-like resins, without particular limitation.

[0230] It should be noted that, while the above description describes a method in which steps (a) and (b) are performed sequentially, steps (b) and (a) may also be performed sequentially. Specifically, the 1,6-hexanediol composition obtained in step (1) may be contacted with an anion exchange resin and then with a cation exchange resin.

[0231] Alternatively, the above step (a) and the above step (b) may be performed simultaneously. That is, the 1,6-hexanediol composition obtained in step (1) may be brought into contact with a cation exchange resin and an anion exchange resin simultaneously.

[0232] [Distillation steps]

[0233] Regarding distillation, the following steps (c), (d), and (e) are sequentially performed to obtain a 1,6-hexanediol composition E. When it is desired to further increase the purity, purification may be performed in step (f).

[0234] Step (c): A step of removing water contained in the 1,6-hexanediol composition-containing liquid from the 1,6-hexanediol composition (eg, 1,6-hexanediol composition B) obtained in the above ion exchange step to obtain 1,6-hexanediol composition C.

[0235] Step (d): a step of removing components having a boiling point lower than that of 1,6-hexanediol from the 1,6-hexanediol composition C obtained in step (c) to obtain a 1,6-hexanediol composition D.

[0236] Step (e): a step of removing components having a boiling point higher than that of 1,6-hexanediol from the 1,6-hexanediol composition D obtained in step (d) to obtain a 1,6-hexanediol composition E.

[0237] Step (f): distilling the 1,6-hexanediol composition E obtained in step (e) to obtain 1,6-hexanediol with higher purity.

[0238] Examples of the component having a boiling point lower than that of 1,6-hexanediol in step (d) include 1,3-propylene glycol, a compound (A1) having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and / or its derivative (B1).

[0239] Examples of the component having a boiling point higher than 1,6-hexanediol in step (e) include glycerol, a compound (A1) having two or more secondary hydroxyl groups in one molecule, 6-hydroxyhexanal and / or its derivative (B1).

[0240] The distillation method is not particularly limited, but removal by continuous or batch distillation is preferred.

[0241] <Step (c): Step of Removing Water Contained in 1,6-Hexanediol Composition>

[0242] In step (c), the 1,6-hexanediol composition obtained in the above ion exchange step (eg, 1,6-hexanediol composition B) is heated to a temperature at which water evaporates, and the pressure is reduced as needed to remove water from the 1,6-hexanediol composition B.

[0243] Examples of the apparatus used include a continuous distillation column, a multi-effect tank, a thin-film evaporator, an evaporator, a batch still, and an atomizing separation device, but are not particularly limited.

[0244] <Step (d): Step of Removing Components Having a Boiling Point Lower than 1,6-Hexanediol>

[0245] In step (d), components having a boiling point lower than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition C.

[0246] Step (d) is performed for the dual purpose of sufficiently removing low-boiling-point components and removing trace amounts of coloring components to obtain high-purity 1,6-hexanediol. In this operation, components with boiling points lower than 1,6-hexanediol, such as the coloring components themselves and their hydrides, are particularly removed or reduced.

[0247] The distillation in step (d) can be performed using known methods and apparatuses, such as atmospheric distillation, reduced pressure distillation, and pressurized distillation. Examples of the apparatus for removal include, but are not particularly limited to, continuous distillation columns, multi-effect tanks, thin-film evaporators, evaporators, batch stills, and atomizing separation devices. The operating conditions used in step (d) can be appropriately set, taking into account the composition of the 1,6-hexanediol composition C, the desired final purity, and the like, and are not particularly limited.

[0248] <Step (e): Step of Removing Components Having a Boiling Point Higher Than 1,6-Hexanediol>

[0249] In step (e), components having a boiling point higher than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition D obtained in step (d).

[0250] In the above step (e), nitrogen-containing components derived from amino acids and proteins, sugars and their decomposition products, and components having a boiling point higher than 1,6-hexanediol, which are specific to fermentation methods, are removed.

[0251] Examples of the apparatus for removal include, but are not limited to, continuous distillation columns, multi-effect tanks, thin-film evaporators, evaporators, batch stills, and atomizing separation devices. The operating conditions used in step (e) can be appropriately set in consideration of the composition of the 1,6-hexanediol composition D, the final purity to be achieved, and the like, and are not particularly limited.

[0252] <Step (f): Step of Obtaining a Higher-Purity 1,6-Hexanediol Composition>

[0253] In step (f), the 1,6-hexanediol composition E obtained through steps (c), (d), and (e) is purified to obtain a 1,6-hexanediol composition with higher purity.

[0254] Examples of the apparatus for obtaining a higher-purity 1,6-hexanediol composition include, but are not particularly limited to, a continuous distillation column, a multi-effect tank, a thin-film evaporator, an evaporator, a batch still, and an atomizing separator.

[0255] The operating conditions used in the above step (f) may be appropriately set in consideration of the composition of the liquid to be purified, the purity to be finally obtained, etc., and are not particularly limited.

[0256] By carrying out the above step (e) and, if necessary, the above step (f), a 1,6-hexanediol composition suitable for the present invention can be obtained.

[0257] It should be noted that, in the above description, a method of performing the above steps (c), (d), and (e) in sequence has been described, but they may be performed in a different order.

[0258] The method for producing a 1,6-hexanediol composition suitable for the present invention only needs to include step (1) and step (2). In addition to step (1) and step (2), the method may also include other steps besides step (1) and step (2).

[0259] By performing the above step (2), the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and its derivative (B1) are within the above ranges. Step (2) may be repeated so that the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and its derivative (B1) are more preferably within the above ranges. By repeating step (2), the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the total content of 6-hydroxyhexanal and its derivative (B1) can be further reduced.

[0260] <Curable composition>

[0261] The curable composition of the present invention comprises the hexanediol glycidyl ether and / or oligomer composition thereof of the present invention.

[0262] The content of the hexanediol glycidyl ether and / or its oligomer composition of the present invention in 100% by mass of the total of the epoxy resin and the curing agent in the curable composition is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass. This tends to more suitably produce a cured product with superior physical properties.

[0263] The curable composition of the present invention preferably contains, in addition to the hexanediol glycidyl ether of the present invention and / or its oligomer composition, an epoxy resin other than the hexanediol glycidyl ether of the present invention and / or its oligomer composition (also referred to as "other epoxy resins"). By using both together, there is a tendency to more suitably obtain a cured product with better physical properties. The other epoxy resins may be used alone or in combination of two or more.

[0264] The other epoxy resins are not particularly limited as long as they are compounds having an epoxy group in the molecule. Examples include bisphenol- or diphenol-type epoxy resins such as bisphenol F epoxy resin, bisphenol A epoxy resin, and tetramethyldiphenol epoxy resin; aliphatic polyol polyglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and glycerol triglycidyl ether; polyglycidyl compounds containing a ring structure such as diglycidyl aniline, resorcinol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether; monofunctional glycidyl compounds containing a ring structure such as alkylphenol monoglycidyl ether; and polyglycidyl ester compounds such as neodecanoic acid glycidyl ester. Among these, bisphenol- or diphenol-type epoxy resins are preferred, bisphenol-type epoxy resins are more preferred, and bisphenol F epoxy resins and bisphenol A epoxy resins are even more preferred because they are more suitable for obtaining cured products with superior physical properties.

[0265] The epoxy equivalent of the other epoxy resin is preferably 150 to 250 g / eq, more preferably 160 to 200 g / eq. This tends to more suitably produce a cured product having better physical properties.

[0266] In this specification, the epoxy equivalent of an epoxy resin is a value measured according to JIS K7236:2001.

[0267] The content of the other epoxy resin in the curable composition, based on 100% by mass of the total of the epoxy resin and the curing agent, is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass. This tends to more suitably produce a cured product with superior physical properties.

[0268] The total content of the hexanediol glycidyl ether and / or its oligomer composition of the present invention and the other epoxy resins described above, i.e., the epoxy resin content, in 100% by mass of the total of the epoxy resin and the curing agent in the curable composition is preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 80% by mass. This tends to more suitably produce a cured product having even better physical properties.

[0269] The content of the hexanediol glycidyl ether and / or its oligomer composition in 100% by mass of the epoxy resin is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, and even more preferably 10 to 30% by mass. This tends to more suitably produce a cured product with better physical properties.

[0270] The curable composition of the present invention preferably contains a curing agent in addition to the hexanediol glycidyl ether and / or its oligomer composition of the present invention. More preferably, it contains the aforementioned other epoxy resin and curing agent in addition to the hexanediol glycidyl ether and / or its oligomer composition of the present invention. This tends to more preferably produce a cured product with superior physical properties.

[0271] As the curing agent, there is no particular limitation as long as it can cure epoxy resin. For example, polyamine compounds, amide compounds, acid anhydrides, phenolic hydroxyl group-containing resins, phosphorus compounds, imidazole compounds, imidazoline compounds, urea-based compounds, organic acid metal salts, Lewis acids, amine complex salts, etc. can be cited. They can be used alone or in combination of two or more. Among them, from the reason that it is more suitable to obtain a cured product with more excellent physical properties, at least one curing agent selected from polyamine compounds, acid anhydrides and phenolic hydroxyl group-containing resins is preferred, and polyamine compounds are more preferred.

[0272] As the above polyamine compounds, for example, trimethylenediamine, ethylenediamine, N,N,N’,N’-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N’,N’-tetramethylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N’,N’-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol and other aliphatic amine compounds; piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N’,N”-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N’-dimethylpiperazine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU) and other alicyclic and heterocyclic amine compounds; o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, α-methylbenzylmethylamine and other aromatic amine compounds; epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-blocked polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex and other modified amine compounds, etc.

[0273] As the above amide compounds, for example, dicyandiamide, polyamideamine, etc. can be cited. As the above polyamideamine, for example, those obtained by reacting aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fatty acids, carboxylic acid compounds such as dimer acid with aliphatic polyamines, polyamines having a polyoxyalkylene chain, etc. can be cited.

[0274] Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0275] Examples of the phenolic hydroxyl group-containing resin include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins (Xylok resins), naphthol aralkyl resins, trimethylolmethane resins, tetraphenylethane resins, naphthol novolac resins, naphthol-phenol co-condensed novolac resins, naphthol-cresol co-condensed novolac resins, biphenyl-modified phenolic resins (polyhydric phenol compounds in which a phenol nucleus is linked with a dimethylene group), biphenyl-modified naphthol resins (polyhydric naphthol compounds in which a phenol nucleus is linked with a dimethylene group), aminotriazine-modified phenolic resins (polyhydric phenol compounds in which a phenol nucleus is linked with melamine, benzoguanamine, or the like), alkoxy-containing aromatic ring-modified novolac resins (a phenol nucleus and a polyhydric phenol compound containing an alkoxy aromatic ring are linked with formaldehyde), and other polyvalent phenol compounds.

[0276] Examples of the phosphorus compound include alkyl phosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkyl phosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine and triphenylphosphine.

[0277] Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2 1-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis(2-cyanoethoxy)methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, and the like.

[0278] Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

[0279] Examples of the urea compound include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, and N-(3-chloro-4-methylphenyl)-N′,N′-dimethylurea.

[0280] The curing agent is preferably incorporated in a ratio such that the active hydrogen groups in the curing agent are in the range of 0.1 to 3.0 mol, more preferably 0.5 to 2.0 mol, and even more preferably 0.7 to 1.2 mol, per 1 mol of epoxy groups in the epoxy resin contained in the curable composition. By adjusting the curing agent amount to this range, a cured product with superior physical properties tends to be more preferably obtained.

[0281] In addition to the above-mentioned components, various additives may be used in the curable composition of the present invention within a range that does not impair the effects of the present invention, such as curing accelerators, fillers, ultraviolet absorbers, pigments, dyes, tackifiers, shrinkage inhibitors, anti-aging agents, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcements, organic solvents, antistatic agents, defoamers, viscosity modifiers, antioxidants, leveling agents, dispersants, waxes, etc. These may be used alone or in combination of two or more.

[0282] The curable composition of the present invention is used in applications such as inks, coatings, paints, adhesives, and crack repair agents. Among them, it is preferably used in at least one application selected from inks, coatings, paints, adhesives, and crack repair agents, and more preferably used in at least one application selected from coatings, adhesives, and crack repair agents. When the curable composition of the present invention is used as a coating or paint, it can be suitably used as a coating or paint for floors or roads due to its good workability at low temperatures and good compressive strength. The crack repair agent is preferably a repair agent for repairing cracks in concrete or mortar.

[0283] The ink of the present invention comprises the curable composition of the present invention. Furthermore, the coating of the present invention comprises the curable composition of the present invention. Furthermore, the coating of the present invention comprises the curable composition of the present invention. Furthermore, the adhesive of the present invention comprises the curable composition of the present invention. Furthermore, the crack repair agent of the present invention comprises the curable composition of the present invention.

[0284] When using the curable composition of the present invention as an ink, for example, the following method is used: the above-mentioned components are blended and stirred and mixed using a stirrer, etc., and then ground using a disperser such as a three-roll mill or a bead mill. The resulting ink is then printed on various substrates and then appropriately heated to form a cured coating film.

[0285] Examples of the ink printing method include offset lithography, relief printing, gravure printing, gravure offset printing, flexographic printing, and screen printing.

[0286] When the curable composition of the present invention is used as a coating or paint, for example, the above-mentioned components are thoroughly mixed and uniformly dispersed using a mixer, ball mill, or other device to prepare a resin composition (paste), which is then adjusted to the desired viscosity using an organic solvent. The resulting resin composition can be applied to various substrates using various coating methods. After the resulting resin composition is applied to various substrates, a cured coating film can be formed by appropriately heating.

[0287] Examples of the coating method include gravure coater, knife coater, roll coater, comma coater, spin coater, bar coater, brush coating, dip coating, and spray coating.

[0288] When the curable composition of the present invention is used as an adhesive, for example, the above-mentioned components are thoroughly mixed and uniformly dispersed using a mixer, ball mill, or other device to prepare a resin composition (paste), and then adjusted to the desired viscosity using an organic solvent or the like. The resulting resin composition is then applied to various substrates and then appropriately heated to bond the substrates. The coating method is the same as that used for coatings or paints.

[0289] The cured product of the present invention is formed by curing the curable composition of the present invention. For example, the curable composition of the present invention is applied to a substrate to form a layer of the resin composition on the substrate. The layer of the resin composition is then appropriately heated to cure the layer of the resin composition, thereby forming a cured layer serving as the cured product. The resin compositions prepared for the various applications described above can be applied and cured using coating and curing methods appropriate to the intended application.

[0290] In addition, the expression of "~" in this specification means more than the value before the description of "~" and less than the value after the description of "~". In addition, in this specification, with respect to a certain characteristic, when multiple numerical ranges are disclosed by the expression of "~", the upper limit and lower limit of each numerical range can be applied in any combination. For example, with respect to the content of a certain compound, when two numerical ranges of 0.001 to 500 mass ppm and 0.05 to 250 mass ppm are disclosed, it means that in addition to 0.001 to 500 mass ppm and 0.05 to 250 mass ppm, the numerical ranges of 0.001 to 250 mass ppm and 0.05 to 500 mass ppm are also disclosed.

[0291] Example

[0292] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

[0293] (Production Example 1) (Production of genetically modified Escherichia coli)

[0294] Plasmid A was prepared by introducing the glycerol dehydrogenase α, β, and γ subunit genes and the dehydrogenase reactivation factor gene derived from Citrobacter freundii into pACYC184 (Nippon Gene Co.) between the BamHI and HindIII restriction enzyme cleavage sites.

[0295] The Escherichia coli -derived HpaI gene for 4,6-dihydroxy-2-oxohexanoic acid aldolase, the Escherichia coli -derived HpcG gene for 4,6-dihydroxy-2-oxohexanoic acid 4-dehydrogenase, the Arabidopsis thaliana -derived NADPH-dependent oxidoreductase 2-alkenal reductase (GenBank: CAC01710.1) gene for 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase, the Lactococcus lactis -derived PanE gene for 6-hydroxy-2-oxohexanoic acid 2-reductase, and the Clostridium difficile -derived HadA gene for 2,6-dihydroxyhexanoic acid CoA-transferase and 6-hydroxyhexanoyl-CoA-transferase were introduced into the multiple cloning site (MCS) of pUC19 (Nippon Gene Co., Ltd.) between the BamHI and EcoRI restriction enzyme cleavage sites to prepare plasmid B.

[0296] The HadB and HadC genes of Clostridium difficile as the α and β subunit genes of 2-hydroxyisocaproyl-CoA dehydrogenase, the HadI gene of Clostridium difficile as the 2-hydroxyisocaproyl-CoA dehydrogenase activating enzyme, the trans-2-enoyl-CoA reductase gene of Treponema denticola (GenBank: AE017248) as the 6-hydroxy-2,3-dehydrohexanoyl-CoA2,3-reductase, and the trans-2-enoyl-CoA reductase gene of 6-hydroxyhexanoic acid 1-reductase were cloned. The carboxylic acid reductase gene (GenBank: AAR91681.1) derived from Nocardia iocardii as an enzyme and the 6-hydroxyhexanal 1-reductase gene (GenBank: AAN37489.1) derived from Rhodococcus as a 6-hydroxyhexanal 1-reductase were introduced into pCOLADuet-1 (Novagen), the HadB, HadC, and HadI genes were introduced into MCS1, and the other genes were introduced into MCS2 to prepare plasmid C.

[0297] The genes in this section refer to open reading frames containing stop codons encoding the respective enzymes. Each gene is introduced into a plasmid with a sequence containing a T7 promoter and ribosome binding site upstream and a sequence containing a T7 terminator downstream. Each gene can be expressed in large quantities in a host strain such as Escherichia coli, where T7 RNA polymerase is expressed through appropriate induction.

[0298] Plasmids A, B, and C were sequentially transformed into chemically competent BL21 Star (DE3) (Invitrogen) cells by heat shock and screened on LB plates containing appropriate antibiotics. As a result, BL21 Star (DE3) strains containing all plasmids A, B, and C were obtained.

[0299] Thus, Escherichia coli was prepared that has genes encoding 10 enzymes of the 1,6-hexanediol pathway, the 10 enzymes being 4,6-dihydroxy-2-oxo-hexanoic acid aldolase (2A in the figure of Japanese Patent No. 6680671), 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydrogenase (2B in the figure of Japanese Patent No. 6680671), 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase (2C in the figure of Japanese Patent No. 6680671), 6-hydroxy-2-oxohexanoic acid 2-reductase (2D in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoic acid CoA-transferase (2A in the figure of Japanese Patent No. 6680671), and 6-hydroxy-2-oxohexanoic acid CoA-transferase (2B in the figure of Japanese Patent No. 6680671). Transferase (2E in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexanoyl-CoA2-dehydrogenase (2F in the figure of Japanese Patent No. 6680671), 6-hydroxy-2,3-dehydro-hexanoyl-CoA2,3-reductase (2G in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoyl-CoA-transferase (4F3 in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoate 1-reductase (5R in the figure of Japanese Patent No. 6680671) and 6-hydroxyhexanal 1-reductase (5S in the figure of Japanese Patent No. 6680671).

[0300] (Production Example 2: Preparation of 1,6-Hexanediol Composition 1 (1,6-HD Composition 1))

[0301] The above-mentioned E. coli is inoculated into an autoclaved culture medium (carbon source: glucose, glycerol, nitrogen source: enzyme extract, inorganic salts: potassium phosphate, potassium hydroxide, vitamin B12, antibiotics: carbenicillin, kanamycin, chloramphenicol, pH: 7.0, glucose and glycerol are raw materials derived from biomass resources) and cultured at 30°C under aerobic conditions for 2 to 3 hours. Then, when the optical density of the E. coli at 600 nm reaches 0.3 to 0.6, isopropyl-β-thiogalactoside is added to a final concentration of 0.5 mM and iron (II) sulfate is added to a final concentration of 10 μM. The culture is further cultured at 30°C for 3 hours to express the enzymes of the 1,6-HD pathway. After expression, an appropriate amount of carbon source (glucose, glycerol) is added, and the culture vessel is placed under a nitrogen atmosphere to establish anaerobic conditions. Under these conditions, culture is continued at 30°C for 48 hours to produce 1,6-hexanediol (step (1)). The culture solution was centrifuged at 4°C for 20 minutes, and the supernatant was recovered and filtered using an appropriate membrane filter with a pore size of 0.2 to 0.4 μm to obtain a 1,6-hexanediol composition as a filtrate.

[0302] [Purification of 1,6-hexanediol composition]

[0303] <Step (a): Ion exchange to remove cations>

[0304] Cations contained in the 1,6-hexanediol composition were removed. In step (a), cation exchange was performed batchwise. The contact temperature with the cation exchange resin was set at 40°C. DIAION SK1BH, manufactured by Mitsubishi Chemical Co., Ltd., was added to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, the mixture was filtered to obtain a 1,6-hexanediol composition A as a filtrate.

[0305] <Step (b): Ion exchange to remove anions>

[0306] Anions contained in 1,6-hexanediol composition A were removed. In step (b), anion exchange was performed batchwise. The temperature for contact with the anion exchange resin was set at 40°C. DIAION SA10AOH (manufactured by Mitsubishi Chemical Co.) was added to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, the mixture was filtered to obtain 1,6-hexanediol composition B as a filtrate.

[0307] <Step (c): Step of Removing Water>

[0308] Water contained in the 1,6-hexanediol composition was removed. A thin-film distiller was used as the apparatus for step (c). The jacket temperature was set at 70°C, and the 1,6-hexanediol-containing composition was continuously introduced, allowing water to be distilled from the top. Simultaneously with the water distillation, the dehydrated 1,6-hexanediol composition C was continuously withdrawn from the bottom as a bottoms liquid. The water concentration in this 1,6-hexanediol composition C was 0.020% by mass (200 ppm by mass).

[0309] <Step (d): Distillation Separation of Low-Boiling Point Components>

[0310] Components with a boiling point lower than 1,6-hexanediol contained in the 1,6-hexanediol composition C were removed using a continuous distillation column. An Oldershaw distillation column was used as the distillation column in step (d). The 1,6-hexanediol composition C obtained in step (c) was continuously supplied to the distillation column, and the column top temperature was controlled to a constant temperature of 240°C. Continuous distillation was performed from the column top and continuous extraction was performed from the column bottom to remove low-boiling-point components from the 1,6-hexanediol composition C. A 1,6-hexanediol composition D, from which components with a boiling point lower than 1,6-hexanediol were removed, was withdrawn from the column bottom.

[0311] <Step (e): Distillation Separation of High-Boiling Point Components>

[0312] Components with a boiling point higher than 1,6-hexanediol contained in the 1,6-hexanediol composition D were removed using a continuous distillation column. An Oldershaw distillation column was used as the distillation column in step (e). The 1,6-hexanediol composition D obtained in step (d) was continuously supplied to the distillation column, and the column bottom temperature was controlled to maintain a constant temperature of 260°C. High-boiling-point components in the 1,6-hexanediol composition D were removed by continuous extraction from the column bottom. From the column top, a 1,6-hexanediol composition E (1,6-HD composition 1) (overhead distillate) from which components with a boiling point higher than 1,6-hexanediol were removed was obtained.

[0313] The analysis results of the obtained 1,6-HD composition 1 are shown below. In the analysis of the 1,6-HD composition, the detection limits of glycerol, glucose, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 6-hydroxyhexanal were 5.0 mass ppm, 5.0 mass ppm, 5.0 mass ppm, 5.0 mass ppm, and 10.0 mass ppm, respectively.

[0314] Glycerol: 800 mass ppm

[0315] Glucose: below the detection limit

[0316] 1,3-Cyclohexanediol: below the detection limit

[0317] 1,4-Cyclohexanediol: below the detection limit

[0318] 6-Hydroxyhexanal: 500 ppm by mass

[0319] (Production Example 3: Preparation of 1,6-Hexanediol Composition 2 (1,6-HD Composition 2))

[0320] In Production Example 2, purification of the 1,6-hexanediol composition obtained by the biological method was repeated to obtain a 1,6-hexanediol composition 2 having a glycerol content of 150 mass ppm and a 6-hydroxyhexanal content of 100 mass ppm.

[0321] The analysis results of the obtained 1,6-HD composition 2 are shown below.

[0322] Glycerol: 150 ppm by mass

[0323] Glucose: below the detection limit

[0324] 1,3-Cyclohexanediol: below the detection limit

[0325] 1,4-Cyclohexanediol: below the detection limit

[0326] 6-Hydroxyhexanal: 100 ppm by mass

[0327] (Production Example 4: Preparation of 1,6-Hexanediol Composition 3 (1,6-HD Composition 3))

[0328] In Production Example 2, purification of the 1,6-hexanediol composition obtained by the biological method was repeated to obtain a 1,6-hexanediol composition 3 having a glycerol content of 5 mass ppm and a 6-hydroxyhexanal content of 10 mass ppm.

[0329] The analysis results of the obtained 1,6-HD composition 3 are shown below.

[0330] Glycerin: 5 ppm by mass

[0331] Glucose: below the detection limit

[0332] 1,3-Cyclohexanediol: below the detection limit

[0333] 1,4-Cyclohexanediol: below the detection limit

[0334] 6-Hydroxyhexanal: 10 ppm by mass

[0335] (Production Example 5: Preparation of 1,6-Hexanediol Composition 4 (1,6-HD Composition 4))

[0336] A 1,6-hexanediol composition 4 (1,6-HD composition 4) was prepared by adding glycerin to the 1,6-HD composition 3 obtained in Production Example 4 so that the glycerin content became 150 ppm by mass.

[0337] (Production Example 6: Preparation of 1,6-Hexanediol Composition 5 (1,6-HD Composition 5))

[0338] A 1,6-hexanediol composition 5 (1,6-HD composition 5) was prepared by adding 1,3-cyclohexanediol to the 1,6-HD composition 3 obtained in Production Example 4 so that the 1,3-cyclohexanediol content became 100 ppm by mass.

[0339] (Production Example 7: Preparation of 1,6-Hexanediol Composition 6 (1,6-HD Composition 6))

[0340] A 1,6-hexanediol composition 6 (1,6-HD composition 6) was prepared by adding 1,4-cyclohexanediol to the 1,6-HD composition 3 obtained in Production Example 4 so that the 1,4-cyclohexanediol content became 100 ppm by mass.

[0341] (Production Example 8: Preparation of 1,6-Hexanediol Composition 7 (1,6-HD Composition 7))

[0342] A 1,6-hexanediol composition 7 (1,6-HD composition 7) was prepared by adding 6-hydroxyhexanal to the 1,6-HD composition 3 obtained in Production Example 4 so that the 6-hydroxyhexanal content became 1500 mass ppm.

[0343] (Production Example 9: Preparation of 1,6-Hexanediol Composition 8 (1,6-HD Composition 8))

[0344] A 1,6-hexanediol composition 8 (1,6-HD composition 8) was prepared by adding glycerin to the 1,6-HD composition 3 obtained in Production Example 4 so that the glycerin content became 1%.

[0345] (Example 1: Preparation of 1,6-hexanediol diglycidyl ether composition (HDG composition 1))

[0346] In a reaction vessel equipped with a stirrer, temperature sensor, decanter, nitrogen inlet tube, and cooling tube, under a nitrogen atmosphere, 547.2 g (4.63 mol) of the 1,6-hexanediol composition obtained in Preparation Example 2 and 1.0 g of a boron trifluoride diethyl ether complex as a catalyst were added. The temperature was raised to 70°C while stirring, and 856.6 g (9.26 mol) of epichlorohydrin was added dropwise at this temperature over 3 hours. The addition reaction was then continued at this temperature for 1 hour. 2800.0 g of toluene was then added, and the temperature was lowered to 30°C while stirring. 810.3 g of a 48% aqueous sodium hydroxide solution was then added dropwise at this temperature over 1 hour. A ring-closure reaction was then carried out at this temperature for 1 hour. 1400.0 g of ion-exchanged water was added, stirred for 1 hour, and the aqueous phase was removed after standing. 700.0 g of ion-exchanged water was then added, stirred for 1 hour, and the mixture was allowed to stand for 1 hour. Another 700.0 g of ion-exchanged water was added, stirred for 30 minutes, and sodium hypophosphite was added until the pH reached 7 or below. After confirming that the pH is below 7, the mixture was allowed to stand and the aqueous phase was removed. A decanter was set up and the temperature was raised to 120°C with stirring for dehydration until no water was discharged. After the precipitation of water was completed, the temperature was lowered to 60°C and filtered and purified using diatomaceous earth at this temperature. The obtained HDG toluene solution was distilled off at 120°C under reduced pressure to obtain 1000.0 g of 1,6-hexanediol diglycidyl ether composition (HDG composition 1). HDG composition 1 also contains oligomer components of HDG, and the content of 1,6-hexanediol diglycidyl ether (HDG) in 100% by mass of HDG composition 1 is 75% by mass.

[0347] The analysis results of the obtained HDG composition 1 are shown below. In the analysis of the HDG composition, the detection limits for glycerol triglycidyl ether (GTG), glucose pentaglycidyl ether (GPG), 1,3-cyclohexanediol diglycidyl ether (1,3CDG), 1,4-cyclohexanediol diglycidyl ether (1,4CDG), and 6-(oxiran-2-ylmethoxy)hexanal (OHL) were 5.0 mass ppm, 5.0 mass ppm, 5.0 mass ppm, and 10.0 mass ppm, respectively.

[0348] Glyceryl triglycidyl ether (GTG): 800 ppm by mass

[0349] Glucose pentaglycidyl ether (GPG): below the detection limit

[0350] 1,3-cyclohexanediol diglycidyl ether (1,3CDG): below the detection limit

[0351] 1,4-cyclohexanediol diglycidyl ether (1,4CDG): below the detection limit

[0352] 6-(Oxiran-2-ylmethoxy)hexanal (OHL): 500 ppm by mass

[0353] (Examples 2 to 8: Preparation of 1,6-hexanediol diglycidyl ether compositions 2 to 8 (HDG compositions 2 to 8))

[0354] HDG compositions 2 to 8 were prepared by the same operation as in Example 1, except that 1,6-HD compositions 2 to 8 were used instead of 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 1.

[0355]

[0356] (Manufacturing Example 9: Manufacture and Evaluation of Curable Composition 1)

[0357] 20.0 g of the 1,6-hexanediol diglycidyl ether composition (HDG composition 1) obtained in Example 1, 80.0 g of EPICLON 850 (bisphenol A type liquid epoxy resin) manufactured by DIC Corporation, and 48.7 g of LUCKAMIDE WN-215 (Mannich type polyamine resin curing agent) manufactured by DIC Corporation were mixed to obtain a curable composition 1.

[0358] Using the curable composition 1, test pieces of cured products were prepared and evaluated as follows.

[0359] Shore D hardness

[0360] The curable composition was poured onto an aluminum petri dish to give a cured film thickness of 7 mm and cured at 23° C. for 7 days to obtain a cured product. The Shore D hardness of the cured product was measured and evaluated using a Durometer Type D in accordance with JIS J7215-1986.

[0361] Tensile test

[0362] The curable composition was poured into a glass container to a thickness of 3 mm and cured at 23°C for 7 days to obtain a cured product. The resulting cured product was cut into dumbbell-shaped No. 1 test pieces and subjected to tensile testing in accordance with JIS-K6911. The maximum stress, elongation, and elastic modulus determined during the test were used as indicators of tensile strength, flexibility, and hardness, respectively.

[0363] Compression test

[0364] The curable composition was poured into a container capable of forming a 20 mm cube and cured at 23°C for 7 days to prepare a cubic test piece. The test piece was subjected to a compression test according to JIS-K6911. The compressive strength was evaluated using the maximum point stress and elastic modulus.

[0365] <Bending test>

[0366] The curable composition was poured into a container capable of forming a 10 mm x 100 mm rectangular parallelepiped and cured at 23°C for 7 days to prepare a rectangular parallelepiped test piece. The test piece was subjected to a bending test according to JIS-K7171. The maximum point stress and elastic modulus were used to evaluate the flexural strength.

[0367] (Manufacturing Examples 10-16; Manufacturing and Evaluation of Cured Compositions 2-8)

[0368] Instead of the formulation of Production Example 9, the formulation shown in Table 2 was used to prepare a curable composition in the same manner as in Production Example 9, and the composition was evaluated in the same manner.

[0369]

[0370] The components in Table 2 are as follows.

[0371] 850: EPICLON 850 manufactured by DIC Corporation (bisphenol A type liquid epoxy resin, epoxy equivalent = 190 g / eq)

[0372] 830: EPICLON 830 manufactured by DIC Corporation (bisphenol F type liquid epoxy resin, epoxy equivalent = 180 g / eq)

[0373] WN215: LUCKAMIDE WN-215 manufactured by DIC Corporation (Mannich-type polyamine resin curing agent, active hydrogen equivalent = 88 g / eq)

[0374] WN505: LUCKAMIDE WN-505 manufactured by DIC Corporation (amine adduct type polyamine resin curing agent active hydrogen equivalent = 58 g / eq)

[0375] WH610: LUCKAMIDE WH-610 manufactured by DIC Corporation (modified amine-type polyamine resin curing agent, active hydrogen equivalent = 91 g / eq)

[0376] EA330: DIC Corporation's LUCKAMIDE EA-330 (polyamide-type polyamine resin curing agent, active hydrogen equivalent = 77 g / eq)

[0377] (Comparative Production Example 1: Preparation of 1,6-Hexanediol Composition 9 (1,6-HD Composition 9))

[0378] A 1,6-hexanediol composition 9 (1,6-HD composition 9) was prepared by adding 1,6-hexanediol to the 1,6-HD composition 3 obtained in Example 4 so that the glucose content became 150 ppm by mass.

[0379] (Comparative Production Example 2: Preparation of 1,6-Hexanediol Composition 10 (1,6-HD Composition 10))

[0380] A 1,6-hexanediol composition 10 (1,6-HD composition 10) was prepared by adding 1,3-cyclohexanediol to the 1,6-HD composition 3 obtained in Example 3 so that the content of 1,3-cyclohexanediol was 150 ppm by mass.

[0381] (Comparative Production Example 3: Preparation of 1,6-Hexanediol Composition 11 (1,6-HD Composition 11))

[0382] A 1,6-hexanediol composition 11 (1,6-HD composition 11) was prepared by adding 1,4-cyclohexanediol to the 1,6-HD composition 3 obtained in Example 3 so that the content of 1,4-cyclohexanediol was 150 ppm by mass.

[0383] (Comparative Examples 1 to 3: Preparation of 1,6-hexanediol diglycidyl ether compositions 9 to 11 (HDG compositions 9 to 11)

[0384] HDG compositions 9 to 11 were prepared by the same operation as in Example 1, except that 1,6-HD compositions 9 to 11 were used instead of 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 3.

[0385]

[0386] (Comparative Production Examples 4-8; Production and Evaluation of Cured Compositions 9-13)

[0387] Instead of the formulation of Production Example 9, the formulation shown in Table 4 was used to prepare a curable composition in the same manner as in Production Example 9, and the composition was evaluated in the same manner.

[0388]

[0389] The above examples and comparative examples show that the hexanediol glycidyl ether and / or oligomer thereof composition of the present invention, which contains hexanediol glycidyl ether and / or oligomer thereof, a compound (A1) having two or more secondary hydroxyl groups in one molecule, and a glycidyl ether compound (A2) of the compound (A1), and a total content of 100 mass ppm or less, and 6-hydroxyhexanal and its derivative (B1), and a glycidyl ether compound (B2) of the compound (B1) of 1500 mass ppm or less, can provide a cured product having excellent physical properties (particularly tensile strength, hardness, compressive strength, and flexural strength).

Claims

1. A composition of hexanediol glycidyl ether and / or its oligomers, comprising hexanediol glycidyl ether and / or its oligomers, wherein: The total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the glycidyl ether compound (A2) of the compound (A1) is 100 ppm by mass or less, The total content of 6-hydroxyhexanal and its derivative (B1) and the glycidyl ether compound (B2) of the compound (B1) is 1500 ppm by mass or less.

2. The hexanediol glycidyl ether and / or oligomer composition according to claim 1, wherein The compound (A2) is at least one compound selected from the group consisting of a glycidyl ether of glucose, i.e., a compound represented by the following formula (A2-1); a glycidyl ether of 1,4-cyclohexanediol, i.e., a compound represented by the following formula (A2-2); a glycidyl ether of 1,2-cyclohexanediol, i.e., a compound represented by the following formula (A2-3); and a glycidyl ether of 1,3-cyclohexanediol, i.e., a compound represented by the following formula (A2-4). In the formulae (A2-1) to (A2-4), R's are the same or different and represent a hydrogen atom or a glycidyl group, wherein at least one of R's is a glycidyl group.

3. The hexanediol glycidyl ether and / or oligomer composition according to claim 1, wherein The compound (B2) is at least one compound selected from the group consisting of compounds represented by the following formulae (B2-1) to (B2-7): In the formulae (B2-1) to (B2-7), R's are the same or different and represent a hydrogen atom or a glycidyl group, wherein at least one of R's is a glycidyl group.

4. The hexanediol glycidyl ether and / or oligomer composition according to claim 1, which contains a glycidyl ether of glycerol, i.e., a compound represented by the following formula (C): In the formula (C), R is the same or different and represents a hydrogen atom or a glycidyl group, wherein, At least one of R is a glycidyl group. 5 . The hexanediol glycidyl ether and / or oligomer composition according to claim 1 , which is prepared from a 1,6-hexanediol composition derived from biomass resources. 6 . A curable composition comprising the hexanediol glycidyl ether and / or oligomer composition according to claim 1 . 7 . The curable composition according to claim 6 , comprising an epoxy resin other than the hexanediol glycidyl ether and / or its oligomer composition.

8. The curable composition according to claim 7, wherein The epoxy resin other than the hexanediol glycidyl ether and / or its oligomer composition is a bisphenol F type epoxy resin.

9. The curable composition according to claim 7, wherein The epoxy resin other than the hexanediol glycidyl ether and / or its oligomer composition is a bisphenol A type epoxy resin.

10. The curable composition according to claim 6, comprising a polyamine compound.

11. The curable composition according to claim 6, comprising an acid anhydride.

12. The curable composition according to claim 6, comprising a phenolic hydroxyl group-containing resin.

13. The curable composition according to claim 6, which is used for at least one application selected from the group consisting of ink, coating, paint, adhesive and crack repair agent.

14. A cured product, characterized in that The curable composition according to claim 6 is cured.

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