Hexamethylene (meth) acrylate composition, active energy ray-curable resin composition, and cured product

Abstract

The purpose of the present invention is to provide: a hexamethylene (meth) acrylate composition which is capable of providing a cured product having excellent physical properties; an active energy ray-curable resin composition which uses the hexamethylene (meth) acrylate composition; and a cured product. The present invention relates to a hexamethylene (meth) acrylate composition containing a hexamethylene (meth) acrylate, the total content of a compound (A1) having two or more secondary hydroxyl groups in one molecule and a (meth) acrylate compound (A2) of the compound (A1) being 100 ppm by mass or less, the total content of the 6-hydroxyhexanal and the derivative (B1) thereof and the (meth) acrylate compound (B2) of the compound (B1) is 1500 mass ppm or less.

Description

Technical Field

[0001] The present invention relates to a hexamethylene (meth)acrylate composition, an active energy ray-curable resin composition, and a cured product. Background Art

[0002] Hexamethylene (meth)acrylate is synthesized by esterifying hexanediol (HD) (meth)acrylate as a raw material. Hexamethylene diacrylate (HDA), one of the hexamethylene (meth)acrylates, is synthesized by esterifying HD diacrylate as a raw material.

[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 a hexamethylene acrylate composition are affected by the purity and impurities of the HD composition used as a raw material. 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] If compounds containing hydroxyl groups, such as compound (A1) having two or more secondary hydroxyl groups per molecule, 6-hydroxyhexanal, and its derivatives (B1), are present in the HD composition, all or part of the hydroxyl groups of compounds (A1) and (B1) containing hydroxyl groups may also be (meth)acrylated during the (meth)acrylation reaction of hexanediol, remaining as impurities in the hexamethylene acrylate composition. Furthermore, unreacted compounds (A1) and (B1) may also remain as impurities in the hexamethylene acrylate composition. Research by the present inventors has shown that these impurities adversely affect the performance of the hexamethylene acrylate composition.

[0014] An object of the present invention is to solve the above-mentioned problems and to provide a hexamethylene (meth)acrylate composition capable of providing a cured product having excellent physical properties, and an active energy ray-curable resin composition and a cured product using the same.

[0015] Means for solving problems

[0016] As a result of intensive research, the present inventors have discovered that by reducing the contents of the compound (A1) and the (meth)acrylate of the compound (A1), and the compound (B1) and the (meth)acrylate 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 hexamethylene acrylate composition containing hexamethylene acrylate, wherein the total content of a compound (A1) having two or more secondary hydroxyl groups in one molecule and a (meth)acrylate compound (A2) of the compound (A1) is 100 mass ppm or less, and the total content of 6-hydroxyhexanal and its derivative (B1) and the (meth)acrylate compound (B2) of the compound (B1) is 1500 mass ppm or less.

[0018] The present invention (2) relates to the hexamethylene acrylate composition described in the present invention (1), wherein the compound (A2) is at least one compound selected from the group consisting of a (meth)acrylate of glucose (a compound represented by the following formula (A2-1)), a (meth)acrylate of 1,4-cyclohexanediol (a compound represented by the following formula (A2-2)), a (meth)acrylate of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3)), and a (meth)acrylate 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 (meth)acryloyl group. However, at least one of R is a (meth)acryloyl group.)

[0022] The present invention (3) relates to the hexamethylene acrylate composition according to 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 (meth)acryloyl group. However, at least one of R is a (meth)acryloyl group.)

[0026] The present invention (4) relates to the hexamethylene acrylate composition according to any one of the present inventions (1) to (3), which contains a (meth)acrylate 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 (meth)acryloyl group. At least one of R's is a (meth)acryloyl group.)

[0030] The present invention (5) relates to the hexamethylene acrylate composition according to any one of the present inventions (1) to (4), which is prepared from a 1,6-hexanediol composition derived from biomass resources.

[0031] Furthermore, the present invention (6) relates to an active energy ray-curable resin composition comprising the hexamethylene acrylate composition according to any one of the present inventions (1) to (5).

[0032] The present invention (7) relates to the active energy ray-curable resin composition described in the present invention (6), which contains a compound having a trifunctional or higher-functional (meth)acryloyl group.

[0033] The present invention (8) relates to the active energy ray-curable resin composition described in the present invention (7), wherein the above-mentioned compound having a trifunctional or higher (meth)acryloyl group is at least one compound selected from dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloyloxyethyl)isocyanurate, trimethylolpropane triacrylate and di-trimethylolpropane tetraacrylate.

[0034] The present invention (9) relates to the active energy ray-curable resin composition according to any one of the present inventions (6) to (8), which contains an epoxy (meth)acrylate resin.

[0035] The present invention (10) relates to the active energy ray-curable resin composition according to any one of the present inventions (6) to (9), which contains a urethane (meth)acrylate resin.

[0036] The present invention (11) relates to the active energy ray-curable resin composition according to any one of the present inventions (6) to (10), which contains a diallyl phthalate resin.

[0037] The present invention (12) relates to the active energy ray-curable resin composition according to any one of the present inventions (6) to (11), which is used for at least one application selected from inks, coatings, paints, and adhesives.

[0038] The present invention (13) relates to a cured product, characterized in that it is obtained by curing the active energy ray-curable resin composition described in any one of the present inventions (6) to (12).

[0039] Effects of the Invention

[0040] The hexamethylene acrylate composition contains hexamethylene acrylate, a compound (A1) having two or more secondary hydroxyl groups in one molecule, and a (meth)acrylate compound (A2) of the compound (A1), and a total content of 100 ppm by mass or less, and 6-hydroxyhexanal and its derivative (B1), and a (meth)acrylate compound (B2) of the compound (B1) of 1500 ppm by mass or less. Thus, a cured product having excellent physical properties can be provided. DETAILED DESCRIPTION

[0041] <Hexamethylene (meth)acrylate composition>

[0042] The total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the (meth)acrylate 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 (meth)acrylate compound (B2) of the compound (B1) is 1500 ppm by mass or less. Thus, the hexamethylene acrylate composition of the present invention can be preferably used as a polymerizable diluent, and can provide a cured product having excellent physical properties, particularly transparency, abrasion resistance, elastic modulus, and tensile strength.

[0043] The reason why such an action effect is exerted is unclear, but is presumed as follows.

[0044] The above-mentioned compound (A1) and / or the above-mentioned compound (B1) do not have a (meth)acrylate group, so when they are contained, the transparency, abrasion resistance, elastic modulus, and tensile strength of the cured product thereof are reduced. The above-mentioned compound (A2) has a rigid structure, which leads to a reduction in the reactivity of the (meth)acrylate group and a reduction in the physical properties of the cured product. Since the above-mentioned compound (A1) originally has a secondary hydroxyl group, it is difficult to undergo (meth)acrylate esterification and contains a large amount of monofunctional (meth)acrylate bodies, which become reaction terminators during curing and thus cause a reduction in physical properties. The above-mentioned compounds (B2-1) to (B2-4) are also monofunctional (meth)acrylate bodies and similarly lead to a reduction in the physical properties of the cured product. The above-mentioned compounds (B2-5) to (B2-6) increase the viscosity of the active energy ray-curable resin composition, leading to a reduction in reactivity and a reduction in the physical properties of the cured product.

[0045] The hexamethylene (meth)acrylate composition of the present invention contains hexamethylene (meth)acrylate, wherein the total content of a compound (A1) having two or more secondary hydroxyl groups in one molecule and a (meth)acrylate 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 (meth)acrylate compound (B2) of the compound (B1) is 1500 ppm by mass or less.

[0046] In this specification, (meth)acrylate means one or both of acrylate and methacrylate, and (meth)acryloyl means one or both of acryloyl and methacryloyl.

[0047] 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.

[0048] In this specification, the (meth)acrylate compound of a compound means a (meth)acrylate form of a compound.

[0049] Examples of the hexamethylene (meth)acrylate include hexamethylene mono(meth)acrylate and hexamethylene di(meth)acrylate. These may be used alone or in combination of two or more. Hexamethylene di(meth)acrylate is preferred because it provides a more suitable cured product with superior physical properties.

[0050] The positions of the hydroxyl groups and / or (meth)acryloyl groups in the hexamethylene (meth)acrylate 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. Of these, the 1,6 positions are preferred because they are more suitable for producing a cured product with superior physical properties. Therefore, 1,6-hexamethylene di(meth)acrylate is particularly preferred as the hexamethylene acrylate.

[0051] In the hexamethylene (meth)acrylate composition of the present invention, the content of the hexamethylene (meth)acrylate is preferably 96.00 to 99.99 mass%, more preferably 98.00 to 99.99 mass%, and even more preferably 99.50 to 99.99 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 hexamethylene acrylate composition within the above ranges, the effects of the present invention tend to be more preferably achieved.

[0052] In this specification, the content of hexamethylene acrylate is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0053] 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, 1,3-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.

[0054] The (meth)acrylate compound (A2) of the compound (A1) is not particularly limited as long as it is a (meth)acrylate of the compound (A1). Examples thereof include (meth)acrylates of aliphatic polyols represented by 2,3-butanediol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and heptyl alcohol; (meth)acrylates of alicyclic polyols represented by 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercetin; and (meth)acrylates 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 esterified with (meth)acrylate.

[0055] Among them, from the viewpoint of having a great influence on the physical properties of the cured product, at least one compound selected from the group consisting of (meth)acrylates of glucose (compounds represented by the following formula (A2-1)), (meth)acrylates of 1,4-cyclohexanediol (compounds represented by the following formula (A2-2)), (meth)acrylates of 1,2-cyclohexanediol (compounds represented by the following formula (A2-3)), and (meth)acrylates of 1,3-cyclohexanediol (compounds represented by the following formula (A2-4)) may be used. Alternatively, the compound may be selected from the group consisting of (meth)acrylates of glucose (compounds represented by the following formula (A2-5)). At least one compound selected from the group consisting of a (meth)acrylate of 1,4-cyclohexanediol (a compound represented by the following formula (A2-2) wherein all R are (meth)acrylates), a (meth)acrylate of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3) wherein all R are (meth)acrylates), and a (meth)acrylate of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4) wherein all R are (meth)acrylates).

[0056] [Chemical Formula 4]

[0057]

[0058] (In the above formulas (A2-1) to (A2-4), R is the same or different and represents a hydrogen atom or a (meth)acryloyl group. However, at least one of R is a (meth)acryloyl group.)

[0059] In the hexamethylene acrylate composition of the present invention, the total content of the compound (A1) having two or more secondary hydroxyl groups per molecule and the (meth)acrylate 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 (no secondary hydroxyl groups). This tends to produce a cured product having excellent physical properties.

[0060] In this specification, the total content of the compound (A1) having two or more secondary hydroxyl groups and the (meth)acrylate compound (A2) of the compound (A1) in one molecule is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0061] The hexamethylene acrylate composition of the present invention contains 6-hydroxyhexanal and its derivative (B1), and the (meth)acrylate compound (B2) of the compound (B1) in a total amount of 1500 ppm by mass or less.

[0062] The compound (B1) is 6-hydroxyhexanal or a derivative thereof.

[0063] 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.

[0064] [Chemical Formula 5]

[0065]

[0066] 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.

[0067] The (meth)acrylate compound (B2) of the compound (B1) is not particularly limited as long as it is a (meth)acrylate of the compound (B1). Examples thereof include a (meth)acrylate of 6-hydroxyhexanal, a (meth)acrylate of a cyclized product of 6-hydroxyhexanal, a (meth)acrylate of an aldol condensate of 6-hydroxyhexanal, a (meth)acrylate of a glycerol reaction product of 6-hydroxyhexanal, and a (meth)acrylate of a hexanediol (HDO) reaction product of 6-hydroxyhexanal. These compounds 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 (meth)acrylated.

[0068] Among them, from the perspective of having a greater influence 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 (meth)acryloyl groups), or it can be a compound represented by the following formula (B2-1).

[0069] [Chemical Formula 6]

[0070]

[0071] (In the above formulas (B2-1) to (B2-7), R is the same or different and represents a hydrogen atom or a (meth)acryloyl group. However, at least one of R is a (meth)acryloyl group.)

[0072] In the hexamethylene acrylate composition of the present invention, the total content of 6-hydroxyhexanal and its derivative (B1), and the (meth)acrylate compound (B2) of the compound (B1) (preferably the content of 6-hydroxyhexanal and the (meth)acrylate 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 content). This tends to produce a cured product having excellent physical properties.

[0073] In this specification, the total content of 6-hydroxyhexanal and its derivative (B1), and the (meth)acrylate compound (B2) of the compound (B1) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0074] The hexamethylene (meth)acrylate composition of the present invention preferably contains a glycerol (meth)acrylate compound (a compound represented by the following formula (C)). This tends to result in a cured product with superior physical properties (particularly abrasion resistance, elastic modulus, flexibility, and tensile strength). This is presumably due to the good compatibility of glycerol (meth)acrylate and hexamethylene (meth)acrylate, allowing the high crosslink density structure of the glycerol (meth)acrylate 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.

[0075] [Chemical Formula 7]

[0076]

[0077] (In the above formula (C), R's are the same or different and represent a hydrogen atom or a (meth)acryloyl group. At least one of R's is a (meth)acryloyl group.)

[0078] In the above formula (C), at least one of R is a (meth)acryloyl group, preferably at least two of R are (meth)acryloyl groups, and more preferably all of R are (meth)acryloyl groups.

[0079] In the hexamethylene acrylate composition of the present invention, the content of glycerol (meth)acrylate (preferably glycerol tri(meth)acrylate) 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 (meth)acrylate is 0.1 ppm or greater, the resulting cured product tends to have an increased crosslinking density and excellent abrasion resistance, elastic modulus, and tensile strength. When the content of glycerol (meth)acrylate is 50,000 ppm or less, the resulting cured product tends to have excellent transparency, adhesion, and flexibility.

[0080] In this specification, the content of the (meth)acrylate of glycerol is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0081] The hexamethylene acrylate 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 (meth)acrylic acid according to a known method.

[0082] The hexamethylene acrylate 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 hexamethylene acrylate 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) are within the above-mentioned range, for example, a hexamethylene glycol 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 used as a raw material and reacted with (meth)acrylic acid according to a known method. Of course, the hexamethylene acrylate composition of the present invention can also be manufactured by manufacturing a hexamethylene acrylate composition with a large amount of impurities and purifying the impurities from the composition.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] Due to global warming and the occurrence of abnormal weather events associated with rising carbon dioxide concentrations, corporate activities that prioritize sustainability are becoming increasingly important. The hexamethylene acrylate composition of the present invention, prepared from a 1,6-hexanediol composition derived from biomass resources, can be obtained by an environmentally friendly production method.

[0087] <Method for producing 1,6-hexanediol composition suitable for the present invention>

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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).

[0093] 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.

[0094] 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.

[0095] 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.

[0096] In this specification, the total content of 6-hydroxyhexanal and its derivative (B1) is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0097] 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 abrasion resistance, elastic modulus, and tensile strength. When the glycerol content is 50,000 ppm or less, the resulting cured product tends to have excellent transparency, adhesion, and flexibility.

[0098] In this specification, the glycerol content is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0099] 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 hexamethylene acrylate composition of the present invention tends to be more preferably obtained.

[0100] In this specification, the content of 1,6-hexanediol is a value measured by gas chromatography-mass spectrometry (GC / MS).

[0101] 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.

[0102] 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.

[0103] Next, a method for producing a 1,6-hexanediol composition suitable for the present invention will be described.

[0104] 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.

[0105] <<Step (1)>>

[0106] 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.

[0107] 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.

[0108] In this specification, CoA means coenzyme A.

[0109] 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.

[0110] The above-mentioned step (1) is preferably a step of producing the 1,6-hexanediol composition at 70°C or lower, and more preferably a step of producing the 1,6-hexanediol composition at 50°C or lower. The lower limit of the temperature is not particularly limited, but is preferably 20°C or higher. Production at a relatively low temperature can reduce carbon dioxide emissions during production, and can also reduce side reactions such as cyclization associated with dehydration, thereby suppressing the formation of by-products such as cyclic oligomers, and improving the performance of the cured product of hexamethylene (meth)acrylate.

[0111] 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 Laid-Open Gazette 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 gazettes.

[0112] 3-oxopropionate and 3-hydroxypropionaldehyde are produced through metabolic pathways within microorganisms.

[0113] 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) in a microorganism through metabolic pathways of glycolysis systems such as the pentose phosphate pathway (PP pathway). Similarly, 3-phosphoglyceraldehyde is produced from glycerol in a microorganism through metabolic pathways. 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.

[0114] An example of production in a microorganism of 3-oxopropionate is described. As described in FIG. 1 of Japanese Patent No. 6680671, 3-phosphoglyceric acid and 2-phosphoglyceric acid are produced in a microorganism by the metabolic pathway of the glycolytic system such as the Embden-Meyerhof pathway (EM pathway) from sugars (pentoses, hexoses). Glyceric acid is produced from 3-phosphoglyceric acid and 2-phosphoglyceric acid by the reverse reaction of the enzymes described in Table 1 of Japanese Patent No. 6680671 or 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 passing through the TCA cycle.

[0115] 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 FIG. 2 to FIG. 5 of Japanese Patent No. 6680671.

[0116] 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.

[0117] 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 (2C in the figure of Japanese Patent No. 6680671), and 1,6-dihydroxy-2-oxohexanoic acid 3-reductase. 6680671), 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).

[0118] 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.

[0119] 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.

[0120] Furthermore, the above-mentioned microorganism preferably has a gene encoding a diol dehydratase and / or a glycerol dehydratase.

[0121] Here, gene introduction can be performed by known methods.

[0122] Examples of prokaryotes include bacteria.

[0123] Examples of eukaryotic organisms include yeast and filamentous fungi.

[0124] Examples of the bacteria include bacteria belonging to the family Enterobacteriaceae, coryneform bacteria, Bacillus bacteria, acetic acid bacteria, actinomycetes, and lactic acid bacteria.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] Examples of the coryneform bacteria include bacteria belonging to the genus Corynebacterium, the genus Brevibacterium, and the genus Microbacterium.

[0129] Specific examples of coryneform bacteria include the following.

[0130] Corynebacterium acetoacidophilum

[0131] Corynebacterium acetoglutamicum

[0132] Corynebacterium alkanolyticum

[0133] Corynebacterium callunae

[0134] Corynebacterium crenatum

[0135] Corynebacterium glutamicum

[0136] Corynebacterium lilium

[0137] Corynebacterium melassecola

[0138] Corynebacterium thermoaminogenes (Corynebacterium efficiens)

[0139] Corynebacterium herculis

[0140] Brevibacterium divaricatum (Corynebacterium glutamicum)

[0141] Brevibacterium flavum (Corynebacterium glutamicum)

[0142] Brevibacterium immariophilum

[0143] Brevibacterium lactofermentum (Corynebacterium glutamicum)

[0144] Brevibacterium roseum

[0145] Brevibacterium saccharolyticum

[0146] Brevibacterium thiogenitalis

[0147] Corynebacterium ammoniagenes (Corynebacterium stationis)

[0148] Brevibacterium album

[0149] Brevibacterium cerinum

[0150] Microbacterium ammoniaphilum

[0151] Specifically, the following strains are exemplified as coryneform bacteria.

[0152] Corynebacterium acetoaceticum ATCC 13870

[0153] Corynebacterium acetoglutamicum ATCC 15806

[0154] Corynebacterium ATCC 21511

[0155] Corynebacterium heatherum ATCC 15991

[0156] Corynebacterium scutellariae AS1.542

[0157] Corynebacterium glutamicum ATCC 13020, ATCC 13032, ATCC 13060, ATCC 13869, FERM BP-734

[0158] Corynebacterium liliiflorum ATCC 15990

[0159] Corynebacterium molasses ATCC 17965

[0160] Effective Corynebacterium (Corynebacterium thermoammoniagenes) AJ12340 (FERM BP-1539)

[0161] Corynebacterium ligusticum ATCC 13868

[0162] Brevibacterium formicum (Corynebacterium glutamicum) ATCC 14020

[0163] Brevibacterium flavum (Corynebacterium glutamicum) ATCC 13826, ATCC 14067, AJ12418 (FERM BP-2205)

[0164] Immature Brevibacterium ATCC 14068

[0165] Brevibacterium lactofermentum (Corynebacterium glutamicum) ATCC 13869

[0166] Brevibacterium roseum ATCC 13825

[0167] Brevibacterium saccharolyticum ATCC 14066

[0168] Brevibacterium thiogenes ATCC 19240

[0169] Corynebacterium ammoniagenes (Corynebacterium stagnantum) ATCC 6871, ATCC 6872

[0170] Brevibacterium albus ATCC 15111

[0171] Brevibacterium cereus ATCC 15112

[0172] Microbacterium ammoniaphilum ATCC 15354

[0173] 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)).

[0174] 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).

[0175] 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.

[0176] 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.

[0177] Examples of actinomycetes include bacteria belonging to the genera Actinomyces, Mycobacterium, Nocardia, Streptomyces, Actinoplanes, and Rhodococcus.

[0178] Specific examples of actinomycetes include Streptomyces coelicolor, Streptomyces griseus, Streptomyces avermitilis, and Rhodococcus zopfii.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] Examples of yeast include yeast belonging to the genera Saccharomyces, Candida, Phichia, Schizosaccharomyces, Kluyveromyces, Rhodotorula, Crytpococcus, Torulopsis, Hansenula, Issatchenkia, Kluyveromyces, and Yarrowia.

[0183] Specific examples of yeast include Saccharomyces cerevisiae, Candida utilis, Pichia pastoris, Hansenula polymorpha, and Schizosaccharomyces pombe.

[0184] Examples of the filamentous fungi (molds) include bacteria belonging to the genera Aspergillus, Paecilomyces, Penicillium, Neurospora, Trichoderma, Fusarium, and Chrysosporium.

[0185] Specific examples of filamentous fungi (molds) include Aspergillus oryzae, Paecilomyces saturatus, Paecilomyces divaricatus, and Penicillium camemberti.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] Alternatively, the C3 aldehyde is obtained via a series of enzymatic steps, which preferably include dehydration of the diol.

[0192] More specifically, using the above-mentioned 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 enzyme reactions of the pathway up to 2G, followed by the enzyme reaction of 4F3 to produce 6-hydroxyhexanoic acid, followed by the enzyme reaction of 5R to produce 6-hydroxyhexanal, and then by the enzyme reaction of 5S to produce 1,6-hexanediol.

[0193] 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.

[0194] 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.

[0195] As the monosaccharide, hexose is more preferred, and glucose is particularly preferred.

[0196] As the alcohol, glycerol is more preferred.

[0197] Therefore, as raw materials derived from biomass resources, glucose and glycerol are most preferred.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] <<Step (2)>>

[0207] 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.

[0208] 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.

[0209] An example of step (2) is described below in detail.

[0210] [Ion exchange step]

[0211] In the ion exchange step, a 1,6-hexanediol composition is obtained through the following steps (a) and (b) in sequence.

[0212] 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.

[0213] 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.

[0214] Examples of the components removed by contact with the cation exchange resin in step (a) include metal cations and ammonium ions.

[0215] 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.

[0216] The treatment with the ion exchange resin is not particularly limited, but is preferably performed by a batch method or a column method.

[0217] <Step (a): Step of Removing Cations Contained in 1,6-Hexanediol Composition>

[0218] In step (a), cations are removed by contacting the 1,6-hexanediol composition with a cation exchange resin.

[0219] 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.

[0220] <Step (b): Step of Removing Anions Contained in 1,6-Hexanediol Composition>

[0221] In step (b), anions are removed by contacting the 1,6-hexanediol composition with an anion exchange resin.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] [Distillation steps]

[0226] 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).

[0227] 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.

[0228] 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.

[0229] 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.

[0230] Step (f): distilling the 1,6-hexanediol composition E obtained in step (e) to obtain 1,6-hexanediol with higher purity.

[0231] 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).

[0232] 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).

[0233] The distillation method is not particularly limited, but removal by continuous or batch distillation is preferred.

[0234] <Step (c): Step of Removing Water Contained in 1,6-Hexanediol Composition>

[0235] 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.

[0236] 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.

[0237] <Step (d): Step of Removing Components Having a Boiling Point Lower than 1,6-Hexanediol>

[0238] In step (d), components having a boiling point lower than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition C.

[0239] 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.

[0240] 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.

[0241] <Step (e): Step of Removing Components Having a Boiling Point Higher Than 1,6-Hexanediol>

[0242] 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).

[0243] 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.

[0244] 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.

[0245] <Step (f): Step of Obtaining a Higher-Purity 1,6-Hexanediol Composition>

[0246] 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.

[0247] 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.

[0248] 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.

[0249] 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.

[0250] 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.

[0251] 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).

[0252] 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.

[0253] <Active energy ray-curable resin composition>

[0254] The active energy ray-curable resin composition of the present invention contains the hexamethylene (meth)acrylate composition of the present invention.

[0255] The content of the hexamethylene (meth)acrylate composition of the present invention in 100% by mass of the active ingredient of the active energy ray-curable resin composition is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 40% by mass. This tends to more suitably produce a cured product with superior physical properties.

[0256] The active energy ray-curable resin composition of the present invention preferably contains, in addition to the hexamethylene (meth)acrylate composition of the present invention, a compound having a trifunctional or higher-functional (meth)acryloyl group. Since the hexamethylene (meth)acrylate composition of the present invention is monofunctional or difunctional, it forms a relatively soft cured product upon curing. In contrast, a compound having a trifunctional or higher-functional (meth)acryloyl group forms a relatively hard and tough cured product upon curing. Furthermore, the combined use of both as a polymerizable diluent tends to yield a cured product with superior physical properties.

[0257] The compound having trifunctional or higher (meth)acryloyl groups is not particularly limited as long as it is a compound having three or more (meth)acryloyl groups, and examples thereof include dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, tris-(2-(meth)acryloyloxyethyl)isocyanurate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and trimethylolpropane propylene oxide-modified tri(meth)acrylate. These may be used alone or in combination of two or more. Among them, at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, ethylene oxide-modified glycerol tri(meth)acrylate, and propylene oxide-modified glycerol tri(meth)acrylate is preferred, and at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloyloxyethyl) isocyanurate, trimethylolpropane triacrylate, and di-trimethylolpropane tetraacrylate is more preferred, because a cured product with better physical properties can be more preferably obtained.

[0258] The content of the compound having trifunctional or higher-functional (meth)acryloyl groups in 100% by mass of the active ingredients of the active energy ray-curable resin composition is preferably 5 to 85% by mass, more preferably 8 to 60% by mass, and even more preferably 10 to 50% by mass. This tends to more suitably produce a cured product having superior physical properties.

[0259] The active energy ray-curable resin composition of the present invention may also contain a polymerizable diluent other than the hexamethylene (meth)acrylate composition of the present invention and a compound having a trifunctional or higher (meth)acryloyl group. Examples of the polymerizable diluent include: aliphatic mono(meth)acrylate compounds such as N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, N,N-dimethyl(meth)acrylamide, acrylamide, acryloylmorpholine, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and octyl(meth)acrylate; alicyclic mono(meth)acrylate compounds such as cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, and adamantyl mono(meth)acrylate; and heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate.Aromatic mono(meth)acrylate compounds such as benzyl(meth)acrylate, phenyl(meth)acrylate, phenylbenzyl(meth)acrylate, phenoxy(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, phenoxybenzyl(meth)acrylate, phenylphenoxyethyl(meth)acrylate, and the like, compounds having one unsaturated group, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Ester, ethylene oxide modified 1,6-hexanediol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethylene oxide modified di(meth)acrylate of bisphenol A, propylene oxide modified di(meth)acrylate of bisphenol A, ethylene oxide modified di(meth)acrylate of bisphenol F, tricyclodecane dimethanol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epoxy resin of glycerol Propane-modified tri(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, ethylene oxide-modified di(meth)acrylate of bisphenoxyethanolfluorene, polytetramethylene glycol di(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, phenoxyethylene glycol (meth)acrylate, stearyl(meth)acrylate, 2-(meth)acryloyloxyethyl succinate, trifluoroethyl(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,3-[(meth)acryloyloxymethyl]norbornane, 2,5-[(meth)acryloyloxymethyl]norbornane, 2,6-[(meth)acryloyloxymethyl] Compounds having two unsaturated groups, such as [(meth)acryloyloxymethyl] norbornane, 1,3-adamantyl di(meth)acrylate, 1,3-bis[(meth)acryloyloxymethyl]adamantane, tris(hydroxyethyl)isocyanuric acid di(meth)acrylate, 3,9-bis[1,1-dimethyl-2-(meth)acryloyloxyethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, di-trimethylolpropane di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and glycerol di(meth)acrylate.

[0260] The active energy ray-curable resin composition of the present invention preferably contains a resin in addition to the hexamethylene (meth)acrylate composition of the present invention. More preferably, it contains a compound having trifunctional or higher-functional (meth)acryloyl groups and a resin in addition to the hexamethylene (meth)acrylate composition of the present invention. This tends to more suitably produce a cured product with superior physical properties.

[0261] The resin is not particularly limited as long as it has a functional group capable of reacting with a (meth)acryloyl group. Examples thereof include epoxy (meth)acrylate resins, urethane (meth)acrylate resins, polyester (meth)acrylate resins, and diallyl phthalate resins. These resins may be used alone or in combination of two or more. Preferably, at least one resin selected from epoxy (meth)acrylate resins, urethane (meth)acrylate resins, and diallyl phthalate resins is used because it is more suitable for obtaining a cured product with superior physical properties.

[0262] Examples of the epoxy (meth)acrylate resin include epoxy vinyl esters obtained by reacting an epoxy resin with an unsaturated monobasic acid using a known method. The epoxy resin may be a bisphenol-type epoxy resin alone or a mixture of a bisphenol-type epoxy resin and a novolac-type epoxy resin. These epoxy (meth)acrylate resins are generally used to improve the mechanical strength and chemical resistance of coating films.

[0263] Here, examples of the bisphenol-type epoxy resin include glycidyl ether-type epoxy resins having substantially two or more epoxy groups per molecule obtained by the reaction of epichlorohydrin with bisphenol A or bisphenol F, dimethyl glycidyl ether-type epoxy resins obtained by the reaction of methylepichlorohydrin with bisphenol A or bisphenol F, and epoxy resins obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or methylepichlorohydrin. Examples of the novolac-type epoxy resin include epoxy resins obtained by the reaction of phenol novolac or cresol novolac with epichlorohydrin or methylepichlorohydrin.

[0264] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutyl maleate, sorbic acid, and mono(2-ethylhexyl)maleate. It should be noted that these unsaturated monobasic acids may be used alone or in combination. The reaction of the epoxy resin with (meth)acrylic acid is preferably carried out at a temperature of 60°C to 140°C, particularly preferably 80°C to 120°C, using an esterification catalyst.

[0265] Examples of the esterification catalyst include known catalysts such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, and tertiary amines such as diazabicyclooctane, triphenylphosphine, and diethylamine hydrochloride.

[0266] As a combination of the epoxy resin and the unsaturated monobasic acid, a resin obtained by reacting an epoxy resin having an average epoxy equivalent of preferably 150 to 450 with (meth)acrylic acid is preferably used. Examples include resins obtained by reacting a bisphenol-A (BPA) epoxy resin with methacrylic acid and resins obtained by reacting a bisphenol-F (BPF) epoxy resin with methacrylic acid. BPA-type epoxy methacrylate resins are excellent in mechanical strength and chemical resistance of the coating film. However, from the perspective of environmental issues such as endocrine problems, BPF-type epoxy methacrylate resins are preferably used due to their low viscosity and excellent workability.

[0267] Examples of the urethane (meth)acrylate resin include those having two or more (meth)acryloyl groups in one molecule obtained by reacting a polyisocyanate with a (meth)acrylate having one or more hydroxyl groups in one molecule. Preferred examples include those having two or more (meth)acryloyl groups in one molecule obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group under the condition of NCO / OH=1.0 to 0.5.

[0268] In addition, examples of the above-mentioned urethane (meth)acrylate resin include those having two or more (meth)acryloyl groups in one molecule obtained by reacting a polyol, a polyisocyanate, and a (meth)acrylate having one or more hydroxyl groups in one molecule. Preferred examples include resins obtained by the following methods: a method in which a (meth)acrylate preferably having one or more hydroxyl groups in one molecule is reacted with a terminal isocyanate compound obtained by reacting a polyisocyanate and a polyol at NCO / OH=1.3 to 2 in a manner such that the hydroxyl group is approximately equivalent to the isocyanate group; and a method in which a polyol is reacted with a single-terminal isocyanate compound obtained by reacting a polyisocyanate and a (meth)acrylate having one or more hydroxyl groups in one molecule at NCO / OH=2 or more.

[0269] Examples of the polyol include polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, p-xylene glycol, dicyclohexyl-4,4'-diol, 2,6-decalinanediol, and 2,7-decalinanediol; polyester polyols, polyether polyols, polycarbonate polyols, and polybutadiene polyols. Polyether polyols are preferably used.

[0270] Examples of the polyether polyol include polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polyols obtained by adding the above-mentioned alkylene oxides to bisphenol A and bisphenol F.

[0271] Examples of the polyester polyol include saturated dibasic acids or their anhydrides, condensation polymers of polyols, and ring-opening polymers of cyclic ester compounds such as polycaprolactone. Examples of the dibasic acids include phthalic acid, phthalic anhydride, halogenated phthalic anhydrides, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof.

[0272] Examples of the polyols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, 1,6-hexanediol, an adduct of bisphenol A with propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanedimethanol, p-xylene glycol, dicyclohexyl-4,4'-diol, 2,6-decalin, and 2,7-decalin. Among these, diols are preferred.

[0273] Examples of the polyisocyanate include 2,4-toluene diisocyanate (hereinafter referred to as 2,4-TDI (2,4-toluene diisocyanate)), isomers thereof or mixtures of isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, uretdione-type polyisocyanate compounds which are polymers of the polyisocyanates, isocyanurate-type polyisocyanate compounds which are polymers of the polyisocyanates, adduct-type polyisocyanate compounds obtained from the polyisocyanates and polyols, allophanate-type polyisocyanates obtained from the adduct-type polyisocyanates and the polyisocyanates, and biuret-type polyisocyanates obtained from the polyisocyanates and water and / or amines. They can be used alone or in combination of two or more. Among them, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-TDI, its isomers or mixtures of isomers, urate ester polyisocyanates obtained from these four types, urea diol polyisocyanates, adduct polyisocyanates, allophanate polyisocyanates, and biuret polyisocyanates are particularly preferred.

[0274] Examples of the (meth)acrylate having one or more hydroxyl groups in one molecule include mono(meth)acrylates such as 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; and poly(meth)acrylates such as tris(hydroxyethyl)isocyanurate di(meth)acrylate and pentaerythritol tri(meth)acrylate.

[0275] Examples of the polyester (meth)acrylate resin include those obtained by reacting a (meth)acrylic compound with the terminal of a saturated polyester or unsaturated polyester having two or more (meth)acryloyl groups per molecule. The number average molecular weight of the resin is preferably 500 to 5000, more preferably 1000 to 5000.

[0276] Examples of the saturated polyester resins include those obtained by the condensation reaction of saturated dibasic acids and polyols. Examples of the unsaturated polyester resins include those obtained by the condensation reaction of dibasic acids including α,β-unsaturated dibasic acids and polyols, and having a functional group for introducing a (meth)acrylic compound at the terminal.

[0277] Examples of the α,β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, and halogenated maleic anhydride. Examples of the saturated dibasic acid include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and dialkyl esters thereof.

[0278] Examples of the polyols to be subjected to a condensation reaction with the saturated dibasic acid or the dibasic acid including the α,β-unsaturated dibasic acid include the same polyols as those mentioned above.

[0279] Examples of the (meth)acrylic acid-based compound used in the polyester (meth)acrylate resin include glycidyl esters of acrylic acid or methacrylic acid, among which glycidyl (meth)acrylate is preferred.

[0280] The diallyl phthalate resin is a prepolymer synthesized from diallyl phthalate monomers or diallyl isophthalate monomers. Several commercially available products exist, depending on the monomer type and molecular weight of the phthalic acid and isophthalic acid. Specific examples include Daiso DAP A, Daiso DAP S, Daiso DAPK, and Daiso Iso DAP sold by Daiso.

[0281] The active ingredient content of the resin in 100% by mass of the active ingredient in the active energy ray-curable resin composition is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 60% by mass. This tends to more suitably produce a cured product with better physical properties.

[0282] The preferred ratio of the content of the hexamethylene (meth)acrylate composition of the present invention, the effective ingredient content of the resin, and the content of the compound having a trifunctional or higher-function (meth)acryloyl group in 100% by mass of the active ingredient of the active energy ray-curable resin composition includes a mass ratio of the content of the hexamethylene (meth)acrylate composition of the present invention / the effective ingredient content of the resin / the content of the compound having a trifunctional or higher-function (meth)acryloyl group of preferably 1 to 60 / 10 to 90 / 5 to 85, more preferably 3 to 50 / 15 to 70 / 8 to 60, and even more preferably 5 to 40 / 20 to 60 / 10 to 50.

[0283] The above-mentioned active ingredient is a compound having an unsaturated bond and participating in curing.

[0284] The active energy ray-curable resin composition of the present invention preferably contains a polymerization initiator. This tends to more suitably produce a cured product having better physical properties.

[0285] As the polymerization initiator, a photopolymerization initiator is preferable, and examples thereof include intramolecular cleavage-type photopolymerization initiators and hydrogen abstraction-type photopolymerization initiators, etc. These may be used alone or in combination of two or more.

[0286] Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl- Acetophenone compounds such as 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) and 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)]; oxime compounds such as 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) compounds, carbazole compounds such as 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-butylcarbazole, benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin compounds; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)butan-1-one, 2-methyl-2-morpholinyl ((4-methylthio) )phenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone and other aminoalkylphenone compounds; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; benzyl, methylphenyl glyoxylate, etc.

[0287] Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenone compounds such as 4,4'-bisdimethylaminobenzophenone and 4,4'-bisdiethylaminobenzophenone; and other examples include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0288] The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the nonvolatile component in the active energy ray-curable resin composition.

[0289] When ultraviolet rays are irradiated as active energy rays to form a cured product, curability can be further improved by using a photosensitizer in addition to the above-mentioned polymerization initiator. Examples of photosensitizers include amine compounds such as aliphatic amines, ureas such as o-toluenethiourea, sulfur compounds such as sodium diethyldithiophosphate and isobenzylisothiouronium-p-toluenesulfonate. These can be used alone or in combination of two or more. From the perspective of improving the curability, the amount of the photosensitizer used is preferably in the range of 1 to 20 parts by mass relative to 100 parts by mass of the non-volatile components in the active energy ray-curable resin composition.

[0290] In addition to the above-mentioned components, the active energy ray-curable resin composition of the present invention may further contain various additives, such as 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, moisture absorbents, fillers, and anti-fogging agents, within a range that does not impair the effects of the present invention. These additives may be used alone or in combination of two or more.

[0291] The active energy ray-curable resin composition of the present invention is useful in applications such as inks, coatings, paints, adhesives, pressure-sensitive adhesives, sheets, and films. It is preferably used in at least one application selected from inks, coatings, paints, and adhesives. The ink is preferably an ink for three-dimensional (3D) printers.

[0292] The ink of the present invention comprises the active energy ray-curable resin composition of the present invention. Furthermore, the coating of the present invention comprises the active energy ray-curable resin composition of the present invention. Furthermore, the coating of the present invention comprises the active energy ray-curable resin composition of the present invention. Furthermore, the adhesive of the present invention comprises the active energy ray-curable resin composition of the present invention.

[0293] When using the active energy ray-curable resin composition of the present invention as an ink, for example, the above components can be mixed all at once, or a polymerizable diluent can be pre-added to the resin to form a resin solution composition and used to prepare the ink. Methods for producing the ink include combining the above components and stirring and mixing them using a blender, etc., followed by grinding using a disperser such as a three-roll mill or bead mill. The resulting ink can then be printed on various substrates and irradiated with active energy rays to form a cured coating film.

[0294] Examples of the ink printing method include offset lithography, relief printing, gravure printing, gravure offset printing, flexographic printing, and screen printing.

[0295] When the active energy ray-curable resin composition of the present invention is used as a coating or paint, for example, a resin composition (paste) is prepared by thoroughly mixing and uniformly dispersing the above-mentioned components using a mixer, ball mill, or other device. A polymerization initiator is then added to the mixture to achieve uniformity, and the mixture is adjusted to the desired viscosity using an organic solvent or the like. 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 irradiating the substrate with active energy rays.

[0296] 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.

[0297] When the active energy ray-curable resin composition of the present invention is used as an adhesive, for example, a resin composition (paste) is prepared in advance in which the above-mentioned components are fully mixed and uniformly dispersed using a mixer, ball mill, or the like, a polymerization initiator is further added thereto to make it uniform, and the desired viscosity is prepared using an organic solvent or the like. The resulting resin composition is then applied to various substrates and then irradiated with active energy rays to bond the substrates. The coating method is the same as that used for coatings and paints.

[0298] Examples of active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α-rays, β-rays, and γ-rays. Ultraviolet rays are preferred. Specific energy sources or curing devices include germicidal lamps, ultraviolet fluorescent lamps, ultraviolet-light emitting diodes (UV-LEDs), carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultrahigh-pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, and electron beams using scanning or curtain-type electron beam accelerators.

[0299] The cured product of the present invention is formed by curing the active energy ray-curable resin composition of the present invention. For example, the active energy ray-curable resin 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 irradiated with active energy rays to cure the resin composition layer, thereby forming a cured layer serving as the cured product. The resin compositions prepared for the various applications described above can be applied using coating and curing methods appropriate to the intended application.

[0300] 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.

[0301] [Example]

[0302] 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.

[0303] (Production Example 1) (Production of genetically modified Escherichia coli)

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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.

[0308] 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.

[0309] 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 (2C in the figure of Japanese Patent No. 6680671), and 1,6-dihydroxy-2-oxohexanoic acid 2-reductase (2D in the figure of Japanese Patent No. 6680671). enzyme (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).

[0310] (Production Example 2: Preparation of 1,6-Hexanediol Composition 1 (1,6-HD Composition 1))

[0311] 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.

[0312] [Purification of 1,6-hexanediol composition]

[0313] <Step (a): Ion exchange to remove cations>

[0314] 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.

[0315] <Step (b): Ion exchange to remove anions>

[0316] 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.

[0317] <Step (c): Step of Removing Water>

[0318] 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).

[0319] <Step (d): Distillation Separation of Low-Boiling Point Components>

[0320] 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.

[0321] <Step (e): Distillation Separation of High-Boiling Point Components>

[0322] 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.

[0323] 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.

[0324] Glycerol: 800 mass ppm

[0325] Glucose: below the detection limit

[0326] 1,3-Cyclohexanediol: below the detection limit

[0327] 1,4-Cyclohexanediol: below the detection limit

[0328] 6-Hydroxyhexanal: 500 ppm by mass

[0329] (Production Example 3: Preparation of 1,6-Hexanediol Composition 2 (1,6-HD Composition 2))

[0330] 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.

[0331] The analysis results of the obtained 1,6-HD composition 2 are shown below.

[0332] Glycerol: 150 ppm by mass

[0333] Glucose: below the detection limit

[0334] 1,3-Cyclohexanediol: below the detection limit

[0335] 1,4-Cyclohexanediol: below the detection limit

[0336] 6-Hydroxyhexanal: 100 ppm by mass

[0337] (Production Example 4: Preparation of 1,6-Hexanediol Composition 3 (1,6-HD Composition 3))

[0338] 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.

[0339] The analysis results of the obtained 1,6-HD composition 3 are shown below.

[0340] Glycerin: 5 ppm by mass

[0341] Glucose: below the detection limit

[0342] 1,3-Cyclohexanediol: below the detection limit

[0343] 1,4-Cyclohexanediol: below the detection limit

[0344] 6-Hydroxyhexanal: 10 ppm by mass

[0345] (Production Example 5: Preparation of 1,6-Hexanediol Composition 4 (1,6-HD Composition 4))

[0346] A 1,6-hexanediol composition 4 (1,6-HD composition 4) was prepared by adding 150 ppm by mass of glycerin and 100 ppm of 1,3-cyclohexanediol to the 1,6-HD composition 3 obtained in Production Example 4.

[0347] (Production Example 6: Preparation of 1,6-Hexanediol Composition 5 (1,6-HD Composition 5))

[0348] A 1,6-hexanediol composition 5 (1,6-HD composition 5) was prepared by adding glycerin to the 1,6-HD composition 3 obtained in Production Example 4 so that the glycerin content became 10,000 ppm by mass.

[0349] (Production Example 7: Preparation of 1,6-Hexanediol Composition 6 (1,6-HD Composition 6))

[0350] 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.

[0351] (Production Example 8: Preparation of 1,6-Hexanediol Composition 7 (1,6-HD Composition 7))

[0352] 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.

[0353] (Example 1: Preparation of Hexamethylene Diacrylate Composition (HDA Composition 1))

[0354] In a reaction vessel equipped with a stirrer, temperature sensor, decanter, and cooling tube, 1,580.2 g (4.91 mol) of the 1,6-hexanediol composition obtained in Preparation Example 2, 848.9 g (11.78 mol) of acrylic acid, 769.5 g of toluene, 3.6 g of hydroquinone (HQ), and 21.4 g of 70% sulfuric acid were added. The mixture was stirred at room temperature until uniform, then the pressure was reduced to 53 kPa and the temperature was raised to 100°C. A dehydration esterification reaction was carried out under these conditions for 10 hours. After returning to normal pressure, the temperature was lowered to 40°C, and 1100.0 g of toluene and 320.0 g of ion-exchanged water were added. The mixture was stirred for 1 hour, allowed to stand, and the aqueous phase (lower layer) was removed. Subsequently, 470.4 g of a 20% aqueous sodium hydroxide solution was added, the mixture was stirred at room temperature for 1 hour, allowed to stand, and the aqueous phase (lower layer) was removed. 240.0 g of ion-exchanged water was further added, and the mixture was stirred and allowed to stand in the same manner. The aqueous phase (lower layer) was removed, 20.0 g of magnesium sulfate was added, dehydration was carried out, and filtration was performed. Then, 0.5 g of hydroquinone monomethyl ether was added, and toluene was distilled off under reduced pressure at 50° C. to obtain 1000.0 g of a hexamethylene diacrylate composition (HDA composition 1).

[0355] The analysis results of the obtained HDA composition 1 are shown below. In the analysis of the HDA composition, the detection limits for glycerol triacrylate (GTA), glucose pentaacrylate (GPA), 1,3-cyclohexanediol diacrylate (1,3-CDA), 1,4-cyclohexanediol diacrylate (1,4-CDA), and 6-acryloyloxyhexanal (AHL) were 5.0 mass ppm, 5.0 mass ppm, 5.0 mass ppm, 5.0 mass ppm, and 10.0 mass ppm, respectively.

[0356] Glyceryl triacrylate: 800 ppm by mass

[0357] Glucose pentaacrylate: below the detection limit

[0358] 1,3-Cyclohexanediol diacrylate: below the detection limit

[0359] 1,4-Cyclohexanediol diacrylate: below the detection limit

[0360] 6-Acryloyloxyhexanal: 500 ppm by mass

[0361] (Examples 2 to 7: Preparation of Hexamethylene Diacrylate Compositions 2 to 7 (HDA Compositions 2 to 7))

[0362] HDA compositions 2 to 7 were prepared by the same operation as in Example 1 except that 1,6-HD compositions 2 to 1,6-HD compositions 7 were used instead of 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 1.

[0363] [Table 1]

[0364]

[0365] (Manufacturing Example 9: Manufacturing and Evaluation of Cured Film 1)

[0366] A photocurable resin solution was prepared by mixing 5.0 g of the hexamethylene diacrylate composition (HDA composition 1) obtained in Example 1, 20.0 g of Miramer M600 (dipentaerythritol hexaacrylate) manufactured by Miwon Co., Ltd., 55.0 g of Luxydir 17-806R (UV-curable urethane acrylate resin) manufactured by DIC Corporation, 20.0 g of Luxydir V-4221 (UV-curable urethane acrylate resin) manufactured by DIC Corporation, and 3.0 g of Omnirad 184 (1-hydroxycyclohexyl phenyl ketone) manufactured by iGM Resins Co., Ltd. as a photoinitiator. The prepared resin solution was applied to an adhesion-treated PET film using a bar coater to a cured film thickness of 10 μm. After drying at 80°C for 1 minute, the film was irradiated with a high-pressure mercury lamp using an ultraviolet irradiation device manufactured by Nippon Battery Co., Ltd. at a dose of 500 mJ / cm 2 The cured film 1 was obtained by irradiating the film with ultraviolet rays in a manner of .

[0367] The cured film for tensile test was prepared by placing the cured film 1 substrate on glass, with a film thickness of 100 μm and an irradiation dose of 1000 mJ / cm 2 Made under the conditions of.

[0368] The following evaluation was performed using Cured Film 1. The results are shown in Table 2.

[0369] Surface hardness: Evaluated according to the pencil hardness test JIS K 5600-5-4.

[0370] Adhesion: Evaluated in accordance with JIS K 5600-5-6.

[0371] Transparency: Transparency was evaluated by total light transmittance using a haze meter (NDH5000) manufactured by Nippon Coloring Industry Co., Ltd.

[0372] Steel wool (SW) abrasion resistance: Using a friction tester, steel wool #0000, with a 500 g load, was passed back and forth 10 times on the cured film. The haze value difference before and after the test was evaluated using the haze meter described above. The smaller the difference in haze value, the better the abrasion resistance.

[0373] Elastic modulus: The cured film was subjected to a tensile test and the elastic modulus was determined.

[0374] Flexibility (elongation %): A tensile test was performed until the cured film broke, and the elongated length was evaluated as a percentage (%) of the test film length.

[0375] Tensile strength: A tensile test was performed until the cured film broke, and the maximum stress at that time was defined as the tensile strength.

[0376] The tensile test was performed at 23° C. and 50% RH using an AUTOGRAPH AGS-X 1 kN manufactured by Shimadzu Corporation.

[0377] (Manufacturing Examples 10 to 15: Manufacturing and Evaluation of Cured Films 2 to 7)

[0378] Instead of the formulation of Production Example 9, a photocurable composition was prepared in the same manner as in Production Example 9 using the formulation shown in Table 2. A cured film was formed and evaluated in the same manner.

[0379] [Table 2]

[0380]

[0381] The components in Table 2 are as follows.

[0382] M600: Miramer M600 (dipentaerythritol hexaacrylate) manufactured by Miwon

[0383] 17-806R: DIC Corporation's LUXYDIR 17-806R (UV-curable urethane acrylate resin (active ingredient content: 80%))

[0384] V-4221: Luxydir V-4221 manufactured by DIC Corporation (UV-curable urethane acrylate resin (active ingredient content 100%))

[0385] M370: Miramer M370 (tris-(2-acryloyloxyethyl) isocyanurate) manufactured by Miwon

[0386] M420: Miramer M420 (pentaerythritol tetraacrylate) manufactured by Miwon

[0387] M410: Miramer M410 (di-trimethylolpropane tetraacrylate) manufactured by Miwon

[0388] M300: Miramer M300 (trimethylolpropane triacrylate) manufactured by Miwon

[0389] DAP: Daiso DAP A (diallyl phthalate resin) manufactured by Osaka SODA Co., Ltd.

[0390] (Comparative Production Example 1: Preparation of 1,6-Hexanediol Composition 8 (1,6-HD Composition 8))

[0391] A 1,6-hexanediol composition 8 (1,6-HD composition 8) was prepared by adding glucose to the 1,6-HD composition 3 obtained in Production Example 4 so that the glucose content became 150 ppm by mass.

[0392] (Comparative Production Example 2: Preparation of 1,6-Hexanediol Composition 9 (1,6-HD Composition 9))

[0393] A 1,6-hexanediol composition 9 (1,6-HD composition 9) was prepared by adding 1,4-cyclohexanediol to the 1,6-HD composition 3 obtained in Production Example 4 so that the content of 1,4-cyclohexanediol became 150 ppm by mass.

[0394] (Comparative Examples 1 and 2: Preparation of Hexamethylene Diacrylate Compositions 8 to 9 (HDA Compositions 8 and 9))

[0395] HDA compositions 8 to 9 were prepared by the same operation as in Example 1 except that 1,6-HD compositions 8 to 1,6-HD compositions 9 were used instead of 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 3.

[0396] [Table 3]

[0397]

[0398] (Comparative Manufacturing Examples 3 to 6: Manufacturing and Evaluation of Cured Films 8 to 11)

[0399] Instead of the formulation of Production Example 9, a curable composition was prepared in the same manner as in Production Example 9 using the formulation shown in Table 4. A cured film was formed and evaluated in the same manner.

[0400] [Table 4]

[0401]

[0402] As can be seen from the above examples and comparative examples, the hexamethylene (meth)acrylate composition of the present invention, which contains hexamethylene (meth)acrylate, wherein the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the (meth)acrylate compound (A2) of the compound (A1) is 100 mass ppm or less, and the total content of 6-hydroxyhexanal and its derivative (B1) and the (meth)acrylate compound (B2) of the compound (B1) is 1500 mass ppm or less, can provide a cured product having excellent physical properties (particularly transparency, abrasion resistance, elastic modulus, and tensile strength).

Claims

1. A hexamethylene (meth)acrylate composition comprising hexamethylene (meth)acrylate, wherein: The total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the (meth)acrylate 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 (meth)acrylate compound (B2) of the compound (B1) is 1500 ppm by mass or less.

2. The hexamethylene (meth)acrylate composition according to claim 1, wherein The compound (A2) is at least one compound selected from the group consisting of a (meth)acrylate of glucose, i.e., a compound represented by the following formula (A2-1); a (meth)acrylate of 1,4-cyclohexanediol, i.e., a compound represented by the following formula (A2-2); a (meth)acrylate of 1,2-cyclohexanediol, i.e., a compound represented by the following formula (A2-3); and a (meth)acrylate 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 (meth)acryloyl group, wherein at least one of R's is a (meth)acryloyl group.

3. The hexamethylene (meth)acrylate 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 (meth)acryloyl group, wherein at least one of R's is a (meth)acryloyl group.

4. The hexamethylene (meth)acrylate composition according to claim 1, comprising a (meth)acrylate of glycerol, namely, 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 (meth)acryloyl group, wherein, At least one of R is a (meth)acryloyl group. The hexamethylene (meth)acrylate composition according to claim 1 , which is prepared from a 1,6-hexanediol composition derived from biomass resources. 6 . An active energy ray-curable resin composition comprising the hexamethylene (meth)acrylate composition according to claim 1 . 7 . The active energy ray-curable resin composition according to claim 6 , comprising a compound having a trifunctional or higher functional (meth)acryloyl group.

8. The active energy ray-curable resin composition according to claim 7, wherein The compound having trifunctional or higher (meth)acryloyl groups is at least one compound selected from dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloyloxyethyl)isocyanurate, trimethylolpropane triacrylate, and di-trimethylolpropane tetraacrylate. 9 . The active energy ray-curable resin composition according to claim 6 , comprising an epoxy (meth)acrylate resin. 10 . The active energy ray-curable resin composition according to claim 6 , comprising a urethane (meth)acrylate resin. 11 . The active energy ray-curable resin composition according to claim 6 , comprising a diallyl phthalate resin. 12 . The active energy ray-curable resin composition according to claim 6 , which is used for at least one application selected from the group consisting of ink, coating, paint, and adhesive.

13. A solidified product, characterized in that: The active energy ray-curable resin composition according to claim 6 is cured.

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