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

Abstract

The present invention aims 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 cured product using the same. The composition of the present invention relates to a hexamethylene (meth)acrylate composition containing hexamethylene (meth)acrylate, in which 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 a (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 technology]

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

[0003] The raw material HD is manufactured as a HD composition containing impurities. 1,6-hexanediol (1,6-HD), one of the HD compositions, is conventionally produced by oxidizing cyclohexane, a petrochemical product, to produce a mixture of carboxylic acids such as adipic acid, 6-hydroxycaproic acid, and glutaric acid, followed by esterification, hydrogenation, and distillation purification.

[0004] On the other hand, with the recent increase in environmental awareness, raw materials derived from biomass resources are desired, rather than petroleum-derived raw materials that have an impact on global warming, and in the case of 1,6-hexanediol, attempts have been made to produce a 1,6-hexanediol composition derived from biomass resources using microorganisms from raw materials derived from biomass resources, but no products have been put on the market. For example, Patent Documents 1 and 2 disclose descriptions of enzyme gene information and metabolic pathways and production methods by purification regarding methods for producing 1,6-hexanediol compositions using enzymes. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2020-114227 A [Patent Document 2] Patent No. 6680671 Summary of the Invention [Problem to be solved by the invention]

[0006] The purity and performance of the hexamethylene (meth)acrylate composition are affected by the purity and impurities of the HD composition, which is the raw material. However, although Patent Documents 1 and 2 disclose an environmentally friendly method for producing a 1,6-hexanediol composition derived from biomass resources, they do not disclose impurities contained in the 1,6-hexanediol composition.

[0007] The present inventors have confirmed that the 1,6-hexanediol compositions obtained by the production methods described in Patent Documents 1 and 2 contain large amounts of alicyclic diols, 6-hydroxyhexanal, and derivatives thereof as impurities.

[0008] Furthermore, the present inventors have confirmed that even in a production process using organic synthesis, such as esterifying a mixture of carboxylic acids, such as adipic acid, 6-hydroxycaproic acid, and glutaric acid, produced by oxidizing cyclohexane, a petrochemical product, followed by hydrogenation and distillation purification, the resulting 1,6-hexanediol composition similarly contains large amounts of alicyclic diols, 6-hydroxyhexanal, and derivatives thereof as impurities.

[0009] When a compound having a hydroxyl group such as a compound (A1) having two or more secondary hydroxyl groups in one molecule or 6-hydroxyhexanal and its derivative (B1) is present in the HD composition, in the reaction of (meth)acrylating hexanediol, all or part of the hydroxyl groups of the compound having a hydroxyl group such as the compound (A1) or the compound (B1) are (meth)acrylated, and remain in the hexamethylene (meth)acrylate composition as impurities. In addition, the unreacted compound (A1) or the compound (B1) also remains in the hexamethylene (meth)acrylate composition as impurities. The present inventors' investigations have revealed that these impurities adversely affect the performance of the hexamethylene (meth)acrylate composition.

[0010] An object of the present invention is to provide a hexamethylene (meth)acrylate composition that can solve the above problems and provide a cured product having excellent physical properties, and an active energy ray-curable resin composition and a cured product using the same. [Means for solving the problem]

[0011] As a result of intensive research, the present inventors have found that a cured product having excellent physical properties can be provided by controlling the contents of the compound (A1), the (meth)acrylate of the compound (A1), and the compound (B1), and the (meth)acrylate of the compound (B1) to be not more than specific amounts, respectively, and have completed the present invention. That is, the present invention (1) relates to a hexamethylene (meth)acrylate composition in which 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 derivatives (B1), and a (meth)acrylate compound (B2) of the compound (B1) is 1,500 ppm by mass or less.

[0012] The present invention (2) relates to the hexamethylene (meth)acrylate composition according to 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)). [ka] (In the formulas (A2-1) to (A2-4), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0013] The present invention (3) relates to the hexamethylene (meth)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 formulas (B2-1) to (B2-7): [ka] (In the formulas (B2-1) to (B2-7), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0014] The present invention (4) relates to the hexamethylene (meth)acrylate composition according to any one of the present inventions (1) to (3), which contains a (meth)acrylate of glycerin (a compound represented by the following formula (C)). [ka] (In the formula (C), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0015] The present invention (5) relates to the hexamethylene (meth)acrylate composition according to any one of the present inventions (1) to (4), which is prepared from a 1,6-hexanediol composition derived from a biomass resource.

[0016] The present invention (6) also relates to an active energy ray-curable resin composition containing the hexamethylene (meth)acrylate composition according to any one of the present inventions (1) to (5).

[0017] The present invention (7) relates to the active energy ray-curable resin composition according to the present invention (6), which contains a compound having a tri- or higher functional (meth)acryloyl group.

[0018] The present invention (8) relates to the active energy ray-curable resin composition according to the present invention (7), wherein the compound having tri- or higher functional (meth)acryloyl groups is at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloxyethyl)isocyanurate, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate.

[0019] 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.

[0020] The present invention (10) relates to an active energy ray-curable resin composition according to any one of the present inventions (6) to (9), which contains a urethane (meth)acrylate resin.

[0021] 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.

[0022] 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 the group consisting of inks, coatings, paints, and adhesives.

[0023] The present invention (13) also relates to a cured product obtained by curing the active energy ray-curable resin composition according to any one of the present inventions (6) to (12). Effect of the Invention

[0024] The hexamethylene (meth)acrylate composition of the present invention contains hexamethylene (meth)acrylate, and has a total content of compound (A1) having two or more secondary hydroxyl groups in one molecule and (meth)acrylate compound (A2) of said compound (A1) of 100 ppm by mass or less, and a total content of 6-hydroxyhexanal and derivatives thereof (B1), and (meth)acrylate compound (B2) of said compound (B1) of 1,500 ppm by mass or less, thereby providing a cured product with excellent physical properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] <Hexamethylene (meth)acrylate composition> The hexamethylene (meth)acrylate composition of the present invention contains hexamethylene (meth)acrylate, and 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. As a result, the hexamethylene (meth)acrylate composition of the present invention can be suitably used as a polymerizable diluent, and can provide a cured product having excellent physical properties, particularly transparency, abrasion resistance, elastic modulus, and tensile strength. The reason why such an effect is exhibited is not clear, but is presumed to be as follows.

[0026] The compound (A1) and / or the compound (B1) does not have a (meth)acrylate group, and therefore, when it contains these, it causes a decrease in the transparency, abrasion resistance, elastic modulus, and tensile strength of the cured product. The compound (A2) has a rigid structure, which reduces the reactivity of the (meth)acrylate group, resulting in a decrease in the physical properties of the cured product. In the first place, the compound (A1) has a secondary hydroxyl group, which makes it difficult to proceed with (meth)acrylation, and contains a large amount of monofunctional (meth)acrylate, which acts as a reaction stopper during curing and causes a decrease in physical properties. The compounds (B2-1) to (B2-4) are also monofunctional (meth)acrylates, which similarly cause a decrease in the physical properties of the cured product. The compounds (B2-5) to (B2-6) thicken the active energy ray-curable resin composition, which reduces the reactivity and leads to a decrease in the physical properties of the cured product.

[0027] The hexamethylene (meth)acrylate composition of the present invention contains hexamethylene (meth)acrylate, and has a 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) of 100 ppm by mass or less, and a total content of 6-hydroxyhexanal and derivatives thereof (B1), and a (meth)acrylate compound (B2) of the compound (B1) of 1500 ppm by mass or less.

[0028] In this specification, the term "(meth)acrylate" refers to either or both of an acrylate and a methacrylate, and the term "(meth)acryloyl group" refers to either or both of an acryloyl group and a methacryloyl group. 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. In this specification, the (meth)acrylate compound of a compound means a (meth)acrylate form of a compound.

[0029] 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. Among them, hexamethylene di(meth)acrylate is preferred because it can more suitably produce a cured product with excellent physical properties.

[0030] The position of the hydroxyl group and / or (meth)acryloyl group of the hexamethylene (meth)acrylate is not particularly limited, and examples thereof include 1,2-position, 1,3-position, 1,4-position, 1,5-position, 1,6-position, 2,5-position, 2,4-position, 2,3-position, and 3,4-position. Among them, 1,6-position is preferred because it is possible to more suitably obtain a cured product having superior physical properties. Therefore, 1,6-hexamethylene di(meth)acrylate is particularly preferred as the hexamethylene (meth)acrylate.

[0031] 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 compounds (A1) and (A2), and the total content of the compounds (B1) and (B2) within the above ranges and setting the purity of the hexamethylene (meth)acrylate composition within the above ranges, the effects of the present invention tend to be more favorably obtained. In this specification, the content of hexamethylene (meth)acrylate is a value measured by gas chromatography mass spectrometry (GC / MS).

[0032] 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, and examples thereof include aliphatic polyols such as 2,3-butylene glycol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and volemitol; alicyclic polyols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercitol; and oligomers obtained by dehydration condensation of these compounds in any combination; and the like. 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 may be used because they have a large effect on the physical properties of the cured product.

[0033] 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), and examples thereof include (meth)acrylates of aliphatic polyols such as 2,3-butylene glycol, erythritol, threitol, arabitol, xylitol, ribitol, iditol, galactitol, sorbitol, mannitol, and volemitol; (meth)acrylates of alicyclic polyols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glucose, fructose, inositol, and quercitol; and (meth)acrylates of oligomers obtained by dehydration condensation of the aliphatic polyols and the alicyclic polyols in any combination; and the like. These may be used alone or in combination of two or more. In the compound (A2), all or a part of the hydroxyl groups in the compound (A1) are (meth)acrylated.

[0034] Among these, since it has a large effect on the physical properties of the cured product, it may be 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)). wherein R is a (meth)acryloyl group), a (meth)acrylate of 1,4-cyclohexanediol (a compound represented by the following formula (A2-2) in which all of the R are (meth)acryloyl groups), a (meth)acrylate of 1,2-cyclohexanediol (a compound represented by the following formula (A2-3) in which all of the R are (meth)acryloyl groups), and a (meth)acrylate of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4) in which all of the R are (meth)acryloyl groups). [ka] (In the formulas (A2-1) to (A2-4), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0035] In the hexamethylene (meth)acrylate composition of the present invention, 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) (preferably the total content of 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glucose, and the compounds represented by the formulas (A2-1) to (A2-4)) is 100 mass ppm or less, preferably 50 mass ppm or less, more preferably 10 mass ppm or less, even more preferably 5 mass ppm or less, and particularly preferably 0 mass ppm (not included). This tends to give a cured product with excellent physical properties. In this specification, 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 a value measured by gas chromatography mass spectrometry (GC / MS).

[0036] The hexamethylene (meth)acrylate composition of the present invention has a total content of 6-hydroxyhexanal and derivatives thereof (B1), and the (meth)acrylate compound (B2) of the compound (B1) of 1500 ppm by mass or less.

[0037] The compound (B1) is 6-hydroxyhexanal or a derivative thereof. The derivative of 6-hydroxyhexanal is not particularly limited as long as it is a derivative of 6-hydroxyhexanal (a compound represented by the following formula (B1-1)), and examples thereof include cyclization products, aldol condensation products, glycerin reaction products, and hexanediol (HDO) reaction products, and specific examples thereof include compounds represented by the following formulae (B1-2) to (B1-7). These may be used alone or in combination of two or more kinds. [ka]

[0038] 6-hydroxyhexanal or a derivative thereof (B1) may be 6-hydroxyhexanal since it has a large effect on the physical properties of the cured product.

[0039] 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), and 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 condensation product of 6-hydroxyhexanal, a (meth)acrylate of a glycerin reaction product of 6-hydroxyhexanal, and a (meth)acrylate of a hexanediol (HDO) reaction product of 6-hydroxyhexanal. These may be used alone or in combination of two or more. In addition, the compound (B2) is a compound in which all or a part of the hydroxyl groups of the compound (B1) are (meth)acrylated.

[0040] Among these, since it has a large effect on the physical properties of the cured product, it may be at least one compound selected from the group consisting of compounds represented by the following formulas (B2-1) to (B2-7), it may be at least one compound selected from the group consisting of compounds represented by the following formulas (B2-1) to (B2-7) (compounds in which all R are (meth)acryloyl groups), or it may be a compound represented by the following formula (B2-1). [ka] (In the formulas (B2-1) to (B2-7), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0041] In the hexamethylene (meth)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, even more preferably 200 mass ppm or less, and particularly preferably 0 mass ppm (not included). This tends to give a cured product with excellent physical properties. In this specification, the total content of 6-hydroxyhexanal and its derivatives (B1) and the (meth)acrylate compound (B2) of the compound (B1) is a value measured by gas chromatography mass spectrometry (GC / MS).

[0042] The hexamethylene (meth)acrylate composition of the present invention preferably contains a (meth)acrylate of glycerin (a compound represented by the following formula (C)). This tends to more suitably obtain a cured product with better physical properties (particularly, abrasion resistance, elastic modulus, flexibility, and tensile strength). This is presumably due to the fact that the high crosslink density structure provided by the (meth)acrylate of glycerin can be ideally introduced into the cured product due to the good compatibility between the (meth)acrylate of glycerin and hexamethylene (meth)acrylate. The compound represented by the following formula (C) may be used alone or in combination of two or more. [ka] (In the formula (C), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

[0043] In the formula (C), at least one of R is a (meth)acryloyl group, but it is preferable that at least two of R are (meth)acryloyl groups, and it is more preferable that all of R are (meth)acryloyl groups.

[0044] In the hexamethylene (meth)acrylate composition of the present invention, the content of the glycerin (meth)acrylate (preferably glycerin 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 the glycerin (meth)acrylate is 0.1 ppm or more, the obtained cured product tends to have an improved crosslink density and excellent abrasion resistance, elastic modulus, and tensile strength, and when the content of the glycerin (meth)acrylate is 50,000 ppm or less, the obtained cured product tends to have excellent transparency, adhesion, and flexibility. In this specification, the content of glycerin (meth)acrylate is a value measured by gas chromatography mass spectrometry (GC / MS).

[0045] The hexamethylene (meth)acrylate composition of the present invention may be produced, for example, by modifying one or both of the two hydroxyl groups contained in 1,6-hexanediol contained in the 1,6-hexanediol composition with (meth)acrylic acid in accordance with a known method.

[0046] The hexamethylene (meth)acrylate composition of the present invention may be produced so that the total content of the compound (A1) and the compound (A2), and the total content of the compound (B1) and the compound (B2) are within the above ranges. In order to produce a hexamethylene (meth)acrylate composition so that the total content of the compound (A1) and the compound (A2), and the total content of the compound (B1) and the compound (B2) contained in the hexamethylene (meth)acrylate composition are within the above ranges, for example, a hexanediol composition (preferably a 1,6-hexanediol composition) having a total content of the compound (A1) of 100 mass ppm or less and a total content of the compound (B1) of 1500 mass ppm or less may be reacted with (meth)acrylic acid according to a known method. Of course, the hexamethylene (meth)acrylate composition of the present invention may be produced by producing a hexamethylene (meth)acrylate composition having a large amount of impurities and purifying the impurities from the composition.

[0047] The 1,6-hexanediol composition having a total content of the compound (A1) of 100 mass ppm or less and a total content of the compound (B1) of 1500 mass ppm or less may be obtained by a production method using organic synthesis, such as esterification of a mixture of carboxylic acids such as adipic acid, 6-hydroxycaproic acid, and glutaric acid produced by oxidizing cyclohexane, a petrochemical product, followed by hydrogenation and distillation purification, or may be obtained by a production method using microorganisms from raw materials derived from biomass resources. The production method is not limited, and in order to remove the compound (A1) and the compound (B1) contained in the 1,6-hexanediol composition obtained by any of the production methods, for example, the step (2) described below can be carried out to produce a 1,6-hexanediol composition having a total content of the compound (A1) of 100 mass ppm or less and a total content of the compound (B1) of 1500 mass ppm or less.

[0048] Specifically, as the 1,6-hexanediol composition having a total content of the compound (A1) of 100 ppm by mass or less and a total content of the compound (B1) of 1,500 ppm by mass or less, a 1,6-hexanediol composition (a 1,6-hexanediol composition derived from a biomass resource) obtained by the following environmentally friendly production method (a production method of a 1,6-hexanediol composition suitable for the present invention) can be suitably used.

[0049] The method for producing a 1,6-hexanediol composition suitable for the present invention produces a 1,6-hexanediol composition from raw materials derived from biomass resources, and is therefore an environmentally friendly production method that makes it possible to reduce carbon dioxide emissions.

[0050] Due to global warming caused by increased carbon dioxide concentrations and the occurrence of abnormal weather worldwide, there is a growing demand for corporate activities that emphasize sustainability. By preparing the hexamethylene (meth)acrylate composition of the present invention from a 1,6-hexanediol composition derived from biomass resources, it is possible to obtain a hexamethylene (meth)acrylate composition obtained by an environmentally friendly production method.

[0051] <Method for producing 1,6-hexanediol composition suitable for the present invention> First, a 1,6-hexanediol composition (also referred to as a 1,6-hexanediol composition suitable for the present invention) obtained by a method for producing a 1,6-hexanediol composition suitable for the present invention will be described.

[0052] A 1,6-hexanediol composition suitable for the present invention has a total content of compounds (A1) having two or more secondary hydroxyl groups in one molecule of 100 ppm by mass or less.

[0053] 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 have a large effect on the physical properties of the cured product.

[0054] 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 (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, even more preferably 5 mass ppm or less, and particularly preferably 0 mass ppm (not included). This tends to give a cured product with excellent physical properties. 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).

[0055] A 1,6-hexanediol composition suitable for the present invention has a total content of 6-hydroxyhexanal and its derivatives (B1) of 1500 ppm by mass or less.

[0056] 6-hydroxyhexanal and / or a derivative thereof (B1) may be 6-hydroxyhexanal since it has a large effect on the physical properties of the cured product.

[0057] 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, even more preferably 200 mass ppm or less, and particularly preferably 0 mass ppm (not included). This tends to give a cured product with excellent physical properties. In this specification, the total content of 6-hydroxyhexanal and its derivatives (B1) is a value measured by gas chromatography mass spectrometry (GC / MS).

[0058] In the 1,6-hexanediol composition suitable for the present invention, the content of glycerin is preferably 0.1 to 50000 ppm, more preferably 1 to 10000 ppm, and even more preferably 5 to 10000 ppm. When the content of glycerin is 0.1 ppm or more, the obtained cured product tends to have an improved crosslink density and excellent abrasion resistance, elastic modulus, and tensile strength, and when the content of glycerin is 50000 ppm or less, the obtained cured product tends to have excellent transparency, adhesion, and flexibility. In this specification, the glycerin content is a value measured by gas chromatography mass spectrometry (GC / MS).

[0059] In the 1,6-hexanediol composition suitable for the present invention, the content of 1,6-hexanediol 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 total content of the compound (B1) within the above ranges and setting the purity of the 1,6-hexanediol composition within the above ranges, the hexamethylene (meth)acrylate composition of the present invention tends to be more suitably obtained. In this specification, the content of 1,6-hexanediol is a value measured by gas chromatography mass spectrometry (GC / MS).

[0060] 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.

[0061] Specifically, as a 1,6-hexanediol composition suitable for the present invention, a 1,6-hexanediol composition (a 1,6-hexanediol composition derived from a biomass resource) obtained by the following environmentally friendly production method (production method of a 1,6-hexanediol composition suitable for the present invention) can be preferably used.

[0062] Next, a method for producing a 1,6-hexanediol composition suitable for the present invention will be described. A method for producing a 1,6-hexanediol composition suitable for the present invention includes a step (1) of producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and / or a derivative thereof obtained from a raw material derived from a biomass resource, and a step (2) of purifying the 1,6-hexanediol composition obtained in the step (1) by ion exchange and / or distillation.

[0063] <<Process (1)>> Step (1) is a step of producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and / or a derivative thereof obtained from a raw material derived from a biomass resource. Here, producing a 1,6-hexanediol composition from 6-hydroxycaproic acid and / or a derivative thereof 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-hydroxycaproic acid and / or a derivative thereof. "Going via 6-hydroxycaproic acid and / or a derivative thereof" may mean going via 6-hydroxycaproic acid and / or a derivative thereof, and may be, for example, a process of converting a raw material derived from a biomass resource into a 1,6-hexanediol composition via 6-hydroxycaproic acid and / or a derivative thereof in the cells of a microorganism; a process of producing 6-hydroxycaproic acid and / or a derivative thereof from a raw material derived from a biomass resource by a microorganism and converting the culture solution containing the compound directly into the 1,6-hexanediol composition by the microorganism; or a process of purifying the culture solution and converting the compound into the 1,6-hexanediol composition by the microorganism in a different reaction tank.

[0064] The derivative of 6-hydroxycaproic acid is not particularly limited as long as it is a derivative of 6-hydroxycaproic acid, and examples thereof include ester compounds such as 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxycaproic acid, a cyclized product of 6-hydroxycaproic acid, a condensation product of 6-hydroxycaproic acid with itself, and a condensation product of 6-hydroxycaproic acid with 1,6-hexanediol. These may be used alone or in combination of two or more. Among these, 6-hydroxy-hexanoyl-CoA, which is a thioester of 6-hydroxycaproic acid, is preferred. As used herein, CoA means coenzyme A.

[0065] As the 6-hydroxycaproic acid and / or a derivative thereof, 6-hydroxycaproic acid and 6-hydroxy-hexanoyl-CoA are preferred, and 6-hydroxycaproic acid is more preferred.

[0066] The step (1) is preferably a step of producing a 1,6-hexanediol composition at 70° C. or less, and more preferably a step of producing a 1,6-hexanediol composition at 50° C. or less. The lower limit of the temperature is not particularly limited, but 20° C. or more is preferable. By carrying out the production at a relatively low temperature, it is possible to reduce the amount of carbon dioxide emitted during the production, and it is also possible to reduce side reactions such as cyclization accompanied by dehydration, suppress the generation of by-products such as cyclic oligomers, and improve the performance of the cured product of hexamethylene (meth)acrylate.

[0067] The step (1) may be carried out, for example, using a microorganism capable of producing (biosynthesizing) 1,6-hexanediol. Examples of microorganisms capable of producing 1,6-hexanediol include those described in JP 2020-114227 A and JP 6680671 A. These may be used alone or in combination of two or more kinds. Those skilled in the art can easily produce or obtain a microorganism capable of producing 1,6-hexanediol based on known techniques such as those described in the publications.

[0068] The metabolic pathway within the microorganism produces 3-oxopropionate and 3-hydroxypropanal.

[0069] An example of the production of 3-hydroxypropanal in a microorganism will be described. As shown in FIG. 1 of Japanese Patent Publication No. 6680671 and the like, in a microorganism, 3-phospho-glyceraldehyde is produced from sugars (pentose, hexose) by a metabolic pathway of glycolysis such as a pentose phosphate pathway (PP pathway). Similarly, in a microorganism, 3-phospho-glyceraldehyde is produced from glycerin by a metabolic pathway. Then, 3-hydroxypropanal is produced from 3-phospho-glyceraldehyde by a reaction catalyzed by multiple enzymes contained in the microorganism. Also, 3-hydroxypropanal is produced from glycerin in one reaction by diol dehydratase and / or glycerol dehydratase.

[0070] An example of the production of 3-oxopropionate in a microorganism will be described. As shown in FIG. 1 of Japanese Patent No. 6680671 and the like, 3-phosphoglyceric acid and 2-phosphoglyceric acid are produced from sugars (pentoses and hexoses) in a microorganism through a metabolic pathway of glycolysis such as the Embden-Meyerhof pathway (EM pathway). Glyceric acid is produced from 3-phosphoglyceric acid and 2-phosphoglyceric acid by using enzymes described in Table 1 of Japanese Patent No. 6680671 and the like, or the reverse reaction of glyceric acid kinase. 3-oxopropionate is produced from glyceric acid by diol dehydratase and / or glycerol dehydratase. Furthermore, oxaloacetate can be produced in one reaction from oxaloacetate, a metabolic intermediate of the TCA cycle, by ketoacid decarboxylase. Oxaloacetate can also be produced from sugars by phosphoenolpyruvate carboxylase and pyruvate carboxylase without going through the TCA cycle.

[0071] From 3-oxopropionate and 3-hydroxypropanal produced by metabolic pathways in microorganisms, 1,6-hexanediol is produced, for example, by utilizing various pathways shown in Figures 2 to 5 of Japanese Patent No. 6680671. Suitable examples of microorganisms capable of producing 1,6-hexanediol from 3-oxopropionate and 3-hydroxypropanal, that is, microorganisms capable of producing 1,6-hexanediol, include the following microorganisms.

[0072] 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 (2E in the figure of Japanese Patent No. 6680671), 2,6-dihydroxy-hexa A microorganism having genes encoding 10 enzymes of the 1,6-hexanediol pathway consisting of 6-hydroxyhexanoyl-CoA 2-dehydratase (2F in the figure of Japanese Patent No. 6680671), 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase (2G in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoyl-CoA-transferase (4F3 in the figure of Japanese Patent No. 6680671), 6-hydroxyhexanoic acid 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).

[0073] As a microorganism having genes encoding the 10 enzymes of the 1,6-hexanediol pathway, it is particularly preferable that the microorganism has genes encoding the 10 enzymes of the 1,6-hexanediol pathway. .Examples include, but are not limited to, prokaryotes and eukaryotes. Furthermore, the microorganism having genes encoding the 10 enzymes of the 1,6-hexanediol pathway may be a genetically modified microorganism into which all and / or a part of the genes (enzymes) have been introduced so as to have genes encoding the 10 enzymes of the 1,6-hexanediol pathway. For example, when a microorganism to be used has only eight of the 10 enzymes, genes encoding the remaining two enzymes may be introduced into the microorganism. When a microorganism to be used has only some of the 10 enzymes, a single / multiple microorganisms having genes encoding the remaining enzymes may be used in combination. Furthermore, the microorganism preferably has a gene encoding diol dehydratase and / or glycerol dehydratase. Here, gene introduction can be carried out by known techniques.

[0074] Prokaryotes include, for example, bacteria. Examples of eukaryotes include yeasts and filamentous fungi.

[0075] Examples of bacteria include bacteria belonging to the family Enterobacteriaceae, coryneform bacteria, Bacillus bacteria, acetic acid bacteria, actinomycetes, and lactic acid bacteria.

[0076] Examples of bacteria belonging to the family Enterobacteriaceae 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 method 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.

[0077] Examples of bacteria belonging to the genus Escherichia include, but are not limited to, bacteria classified into the genus Escherichia according to the classification known to experts in microbiology. Examples of bacteria belonging to the genus Escherichia include those described in the book by Neidhardt et al. (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 bacteria belonging to the genus Escherichia 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 derivatives thereof.

[0078] Examples of bacteria belonging to the genus Enterobacter include Enterobacter agglomerans and Enterobacter aerogenes. Examples of bacteria belonging to the genus Pantoea include Pantoea ananatis, Pantoea stewartii, Pantoea agglomerans, and Pantoea citrea. Examples of bacteria belonging to the genus Erwinia include Erwinia amylovora and Erwinia carotovora. Examples of bacteria belonging to the genus Klebsiella include Klebsiella planticola.

[0079] Examples of coryneform bacteria include bacteria belonging to the genera Corynebacterium, Brevibacterium, and Microbacterium.

[0080] Specific examples of coryneform bacteria include the following species: Corynebacterium acetoacidophilum Corynebacterium acetoglutamicum Corynebacterium alkanolyticum Corynebacterium callunae Corynebacterium crenatum Corynebacterium glutamicum Corynebacterium lilium Corynebacterium melassecola Corynebacterium thermoaminogenes (Corynebacterium efficiens) Corynebacterium herculis Brevibacterium divaricatum (Corynebacterium glutamicum) Brevibacterium flavum (Corynebacterium glutamicum) Brevibacterium immariophilum Brevibacterium lactofermentum (Corynebacterium glutamicum) Brevibacterium roseum Brevibacterium saccharolyticum Brevibacterium thiogenitalis Corynebacterium ammoniagenes (Corynebacterium stationis) Brevibacterium album Brevibacterium cerinum Microbacterium ammoniaphilum

[0081] Specific examples of coryneform bacteria include the following strains: Corynebacterium acetoacidophilum ATCC 13870 Corynebacterium acetoglutamicum ATCC 15806 Corynebacterium alkanolyticum ATCC 21511 Corynebacterium callunae ATCC 15991 Corynebacterium crenatum AS1.542 Corynebacterium glutamicum ATCC 13020, ATCC 13032, ATCC 13060, ATCC 13869, FERM BP-734 Corynebacterium lilium ATCC 15990 Corynebacterium melassecola ATCC 17965 Corynebacterium efficiens (Corynebacterium thermoaminogenes) AJ12340 (FERM BP-1539) Corynebacterium herculis ATCC 13868 Brevibacterium divaricatum (Corynebacterium glutamicum) ATCC 14020 Brevibacterium flavum (Corynebacterium glutamicum) ATCC 13826, ATCC 14067, AJ12418 (FERM BP-2205) Brevibacterium immariophilum ATCC 14068 Brevibacterium lactofermentum (Corynebacterium glutamicum) ATCC 13869 Brevibacterium roseum ATCC 13825 Brevibacterium saccharolyticum ATCC 14066 Brevibacterium thiogenitalis ATCC 19240 Corynebacterium ammoniagenes (Corynebacterium stationis) ATCC 6871, ATCC 6872 Brevibacterium album ATCC 15111 Brevibacterium cerinum ATCC 15112 Microbacterium ammoniaphilum ATCC 15354

[0082] The genus Corynebacterium includes bacteria that were previously classified as Brevibacterium but have now been integrated into the genus Corynebacterium (Int. J. Syst. Bacteriol., 41, 255(1991)). Corynebacterium stathionis also includes bacteria that were previously classified as Corynebacterium ammoniagenes but have been reclassified as Corynebacterium stathionis based on the analysis of 16S rRNA sequences (Int. J. Syst. Evol. Microbiol., 60, 874-879(2010)).

[0083] Examples of the 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).

[0084] Examples of acetic acid bacteria include the genus Gluconobacter, Acetobacter, Gluconacetobacter, Acidicaldus, Acidiphilium, Acidiphyllum, Acidisphaera, Acidocella, Acidomonas, Asaia, Belnapia, Craurococcus, Granulibacter, Kozakia, and the like. Examples of bacteria include those belonging to the genera Kozakia, Leahibacter, Muricoccus, Neoasaia, Oleomonas, Paracraurococcus, Rhodopila, Roseococcus, Rubritepida, Saccharibacter, Stella, Swaminathania, Teicococcus, and Zavarzinia.

[0085] Specific examples of acetic acid bacteria include Gluconobacter oxydans, Acetobacter xylinum, Asidomonas methanolicus, Asaia bogorensis, Asaia kulungsapensis, Bernapia morevensis, Gluconacetobacter xylinus, Granulibacter bethesdensis, Kozakia variensis, and Oleomonas sagaranensis.

[0086] Examples of actinomycetes include bacteria belonging to the genera Actinomyces, Mycobacterium, Nocardia, Streptomyces, Actinoplanes, and Rhodococcus.

[0087] Specific examples of actinomycetes include Streptomyces coelicolor (), Streptomyces griseus, Streptomyces avermitilis, Rhodococcus zopfii, and the like.

[0088] Examples of lactic acid bacteria include bacteria belonging to the genera Lacticaseibacillus, Lactobacillus, Ligilactobacillus, Limosilactobacillus, Liquorilactobacillus, Lactiplantibacillus, Streptococcus, Lactococcus, and Enterococcus.

[0089] Specific examples of lactic acid bacteria include Lacticaseibacillus casei, Lactobacillus gasseri, Lactobacillus acidophilus, Lactobacillus helveticus, Lactobacillus delbrueckii subsp. bulgaricus, Lactobacillus delbrueckii subsp. delbrueckii, Lactobacillus johnsonii, Ligilactobacillus salivarius, and the like. salivarius, Limosilactobacillus fermentum, Liquorilactobacillus mali, Lactiplantibacillus plantarum, Streptococcus thermophilus, Lactococcus lactis subsp. lactis, Lactococcus lactis subsp. cremoris, Lactococcus plantarum, Lactococcus raffinolactis, Lactococcus cremoris Examples of such bacteria include Enterococcus cremoris, Enterococcus faecalis, and Enterococcus faecium.

[0090] Examples of bacteria other than the above-mentioned bacteria include bacteria belonging to the genus Pseudomonas, Agrobacterium, Alicyclobacillus, Arthrobacter, Azotobacter, Chromatium, Methylobacterium, Rhodobacter, Rhodopseudomonas, Rhodospirillum, Zymomonas, Achromobacter, and the like. Examples of bacteria that can be used include bacteria belonging to the genera Bacter, Aerobacter, Alcaligenes, Arthrobacter, Erwinia, Microbacterium, Micrococcus, Protaminobacter, Proteus, Sartina, Xanthomonas, Aeromonas, Flavobacterium, and Rhizobium.

[0091] Examples of yeast include yeasts belonging to the genera Saccharomyces, Candida, Pichia, Schizosaccharomyces, Kluyveromyces, Rhodotorula, Cryptococcus, Torulopsis, Hansenula, Issatchenkia, Kluyveromyces, and Yarrowia.

[0092] Specific examples of yeast include Saccharomyces cerevisiae, Candida utilis, Pichia pastoris, Hansenula polymorpha, Schizosaccharomyces pombe, and the like.

[0093] Examples of filamentous fungi (molds) include fungi belonging to the genera Aspergillus, Paecilomyces, Penicillium, Neurospora, Trichoderma, Fusarium, and Chrysosporium.

[0094] Specific examples of filamentous fungi (molds) include Aspergillus oryzae, Paecilomyces saturatus, Paecilomyces divaricatus, Penicillium camemberti, and the like.

[0095] These strains can be obtained, for example, from the American Type Culture Collection (Address: 12301 Parklawn Drive, Rockville, Maryland 20852 PO Box 1549, Manassas, VA 20108, United States of America). That is, a corresponding accession number is assigned to each strain, and the strains can be obtained using the accession number (see http: / / www.atcc.org / ). The accession numbers corresponding to each strain are listed in the catalog of the American Type Culture Collection. In addition, these strains can be obtained, for example, from the depository institution where each strain was deposited.

[0096] The microorganisms may be used alone or in combination of two or more kinds. 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. That is, 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.

[0097] In the case where the gene (enzyme) is exogenously introduced into a microorganism and expressed, the 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, and the 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 genes of Escherichia coli, The 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase is an NADP-dependent alkenal reductase P1 of Arabidopsis thaliana having GenBank accession number CAC01710.1, the 6-hydroxy-2-oxohexanoic acid 2-reductase is a D-2-hydroxy acid dehydrogenase encoded by the panE gene of Lactococcus lactis, and the 2,6-dihydroxy-hexanoic acid CoA-transferase and the 6 The 2,6-dihydroxy-hexanoyl-CoA 2-dehydratase is a 2-hydroxyisocaproyl-CoA dehydratase expressed in Clostridium difficile, and the 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase is a 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase encoded by the GenA gene of Treponema denticola. Preferably, the 6-hydroxyhexanoate 1-reductase is a trans-2-enoyl-CoA reductase of GenBank Accession No. AE017248, the 6-hydroxyhexanoate 1-reductase is an ATP / NADPH-CAR of Nocardia iowensis of GenBank Accession No. AAR91681.1, and / or the 6-hydroxyhexanal 1-reductase is a 6-hydroxyhexanoate dehydrogenase of Rhodococcus of GenBank Accession No. AAN37489.1.

[0098] The microorganism can be used to (a) convert a C3 aldehyde and pyruvate to a C6 β-hydroxyketone intermediate via aldol addition, and then (b) convert the C6 β-hydroxyketone intermediate to 1,6-hexanediol or a solvate thereof via an enzymatic process, where the conversion preferably includes enoyl or enoate reduction, ketone reduction, aldehyde reduction, dehydration, thioester formation, thioester reduction, or a combination thereof. It is also preferred that the method further comprises the step of preparing a C3 aldehyde and pyruvate from a source selected from glycerin, pentoses, hexoses, phosphoglycerates, other carbon sources, intermediates of the glycolytic pathway, intermediates of propanoic acid metabolism, or combinations thereof. Alternatively, the C3 aldehyde can be obtained via a series of enzymatic steps, which preferably include the dehydration of a diol.

[0099] More specifically, by using the microorganism, 1,6-hexanediol is produced from 3-oxopropionate and 3-hydroxypropanal produced by a metabolic pathway in the microorganism through the pathways 2A, 2B, 2C, 2D, 2E, 2F, 2G, 4F3, 5R, and 5S shown in Figures 2 and 5 of Japanese Patent Publication No. 6680671. In this biosynthetic pathway, the enzyme reaction of the pathway up to 2G proceeds to produce 6-hydroxy-hexanoyl-CoA, then the enzyme reaction of 4F3 proceeds to produce 6-hydroxycaproic acid, then the enzyme reaction of 5R proceeds to produce 6-hydroxyhexanal, and then the enzyme reaction of 5S proceeds to produce 1,6-hexanediol.

[0100] Therefore, the step (1) can be carried out by culturing the microorganism in a medium containing a raw material derived from a biomass resource. That is, by culturing the microorganism in a medium containing a raw material derived from a biomass resource, a 1,6-hexanediol composition can be produced from 6-hydroxycaproic acid and / or a derivative thereof obtained from the raw material derived from a biomass resource.

[0101] The raw material derived from the biomass resource is not particularly limited, and examples thereof include pentoses such as xylose, xylulose, ribulose, arabinose, lyxose, and ribose, hexoses such as allose, altrose, glucose, mannose, gulose, idose, talose, galactose, fructose, psicose, sorbose, and tagatose, and other monosaccharides, disaccharides such as lactose, cellobiose, sucrose, and maltose, polysaccharides such as starch, cellulose, agarose, and dextran, alcohols such as sorbitol, ethanol, and glycerin, carbon sources used in medium components such as peptone, tryptone, and casamino acids, and nitrogen sources used in medium components such as organic nitrogen compounds such as peptone, tryptone, casamino acids, yeast extract, meat extract, and corn steep liquor. These may be used alone or in combination of two or more. Among these, carbon sources used in medium components are preferred, and monosaccharides and alcohols are more preferred. As the monosaccharide, hexose is more preferable, and glucose is particularly preferable. As the alcohol, glycerin is more preferable. Therefore, glucose and glycerin are most preferable as raw materials derived from biomass resources.

[0102] The medium is not particularly limited as long as it contains the raw material derived from the biomass resource, and may be a normal medium containing a carbon source, a nitrogen source, inorganic ions, and further an organic nutrient source as necessary, and can be appropriately prepared depending on the microorganism to be used. Among them, it is preferable that the raw material derived from the biomass resource contains the carbon source.

[0103] The carbon source other than the above components is not particularly limited as long as it can be utilized by the microorganism, and examples thereof include organic acids such as fumaric acid, citric acid, acetic acid, propionic acid, etc., and their salts, carbohydrates such as paraffin, etc. These may be used alone or in combination of two or more kinds.

[0104] Examples of nitrogen sources other than the above-mentioned components include inorganic ammonium salts such as ammonium sulfate and ammonium chloride, organic ammonium salts 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.

[0105] The medium may contain nutrients such as trace metal salts, vitamins, hormones, etc., which are used in ordinary media. These may be used alone or in combination of two or more. Among them, it is preferable to contain sodium and / or potassium as trace metal salts.

[0106] There are no particular limitations on the culture conditions, and the culture may be performed for about 4 to 140 hours while appropriately controlling the pH and temperature within the ranges of pH 3 to 11 and temperature 20 to 70° C. (more preferably 20 to 50° C.). The culture may be performed under aerobic or anaerobic conditions, which may be appropriately selected depending on the microorganism used, but aerobic conditions are preferred.

[0107] As described above, the 1,6-hexanediol composition can be produced by culturing the microorganism in a medium containing a raw material derived from a biomass resource. Since the 1,6-hexanediol composition is present in the medium together with the microorganism, the microorganism may be removed from the medium as necessary. The method for removing the microorganism is not particularly limited, and may be, for example, centrifugation and / or membrane separation.

[0108] The centrifugation is not particularly limited, and for example, continuous centrifugation using a continuous centrifuge can be used. Examples of continuous centrifuges include a cage centrifuge, a disk centrifuge, and a nozzle centrifuge. These may be used alone or in combination of two or more.

[0109] The membrane used for membrane separation is not particularly limited, and examples thereof include membranes with a pore size of 10.0 μm or less, and specific examples thereof include microfiltration membranes, ultrafiltration membranes, nanofiltration membranes, and reverse osmosis membranes. These may be used alone or in combination of two or more. The shape of the membrane is not particularly limited, and may be any shape such as a flat membrane, a hollow fiber membrane, a spiral membrane, a tubular membrane, or a pleated membrane. The type of filtration is also not particularly limited, and either a dead-end type or a tangential flow type can be applied, with the tangential flow type being preferred.

[0110] <<Process (2)>> 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, 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. In addition, ion exchange is preferably cation exchange and anion exchange, and it is more preferable to perform cation exchange and anion exchange in this order. In addition, distillation is preferably performed to remove water, remove components having a boiling point lower than 1,6-hexanediol, and remove components having a boiling point higher than 1,6-hexanediol, and it is more preferable to remove water, remove components having a boiling point lower than 1,6-hexanediol, and remove components having a boiling point higher than 1,6-hexanediol in this order.

[0111] The 1,6-hexanediol composition obtained in step (1) and subjected to step (2) is not particularly limited as long as it is a 1,6-hexanediol composition obtained in step (1). However, it is preferably a liquid obtained by removing microorganisms from a medium containing the 1,6-hexanediol composition obtained in step (1), and more preferably a liquid obtained by removing microorganisms by subjecting the medium containing the 1,6-hexanediol composition obtained in step (1) to centrifugation and membrane separation treatment.

[0112] An example of step (2) will be described in detail below.

[0113] [Ion exchange process] In the ion exchange step, a 1,6-hexanediol composition is obtained through the following steps (a) and (b) in this order. 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. 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.

[0114] Components to be removed by contact with the cation exchange resin in the step (a) include, for example, metal cations and ammonium ions.

[0115] Components to be removed by contact with the anion exchange resin in the step (b) include, for example, chloride ions, sulfate ions, phosphate ions, organic acids, etc. The organic acids listed here include compounds (A1) having two or more secondary hydroxyl groups in one molecule having an acid group.

[0116] The treatment with an ion exchange resin is not particularly limited, but it is preferable to carry out the treatment in a batch or column manner.

[0117] <Step (a): Step of Removing Cations Contained in the 1,6-Hexanediol Composition> In step (a), the 1,6-hexanediol composition is contacted with a cation exchange resin to remove cations.

[0118] The cation exchange resin used may be, for example, strongly acidic or weakly acidic, but is not particularly limited thereto. In addition, styrene-based, acrylic-based, and hydrogel-based resins may be used, but are not particularly limited thereto. In addition, gel-type, porous-type, and highly porous-type resins may be used, but are not particularly limited thereto. The form of the resin may be, for example, powder, sphere, fiber, membrane, etc., but are not particularly limited thereto.

[0119] <Step (b): Step of Removing Anions Contained in the 1,6-Hexanediol Composition> In step (b), the 1,6-hexanediol composition is contacted with an anion exchange resin to remove anions.

[0120] Examples of the anion exchange resin used include, but are not limited to, strong basic and weak basic. Examples of the anion exchange resin include, but are not limited to, styrene-based, acrylic-based, and hydrogel-based resins. Examples of the anion exchange resin include, but are not limited to, gel-type, porous-type, and highly porous-type resins. Examples of the form of the resin include, but are not limited to, powder, sphere, fiber, and membrane.

[0121] In the above description, the step (a) and the step (b) are carried out in this order, but the step (b) and the step (a) may be carried out in this order. That is, the 1,6-hexanediol composition obtained in the step (1) may be contacted with an anion exchange resin, and then with a cation exchange resin. Moreover, the steps (a) and (b) may be carried out simultaneously, that is, the 1,6-hexanediol composition obtained in the step (1) may be contacted with a cation exchange resin and an anion exchange resin simultaneously.

[0122] [Distillation process] The distillation is carried out in the following steps (c), (d), and (e) in order to obtain a 1,6-hexanediol composition E. If it is desired to further increase the purity, the composition can be optionally purified in step (f). Step (c): A step of removing water contained in the 1,6-hexanediol composition-containing liquid from the 1,6-hexanediol composition (for example, 1,6-hexanediol composition B) obtained in the ion exchange step to obtain a 1,6-hexanediol composition C. 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. 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. Step (f): A step of distilling the 1,6-hexanediol composition E obtained in step (e) to obtain 1,6-hexanediol of higher purity.

[0123] Examples of components having a boiling point lower than that of 1,6-hexanediol in the step (d) include 1,3-propanediol, a compound (A1) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and / or a derivative thereof (B1).

[0124] Examples of components having a boiling point higher than that of 1,6-hexanediol in the step (e) include glycerin, a compound (A1) having two or more secondary hydroxyl groups in one molecule, and 6-hydroxyhexanal and / or a derivative thereof (B1).

[0125] The distillation method is not particularly limited, but removal by continuous or batch distillation is preferred.

[0126] <Step (c): Step of Removing Water Contained in the 1,6-Hexanediol Composition> In step (c), the 1,6-hexanediol composition (e.g., 1,6-hexanediol composition B) obtained in the ion exchange step is heated to a temperature at which water evaporates, and if necessary, the pressure is reduced, thereby removing water from the 1,6-hexanediol composition B.

[0127] Examples of the apparatus to be used include a continuous distillation column, a multi-effect canister, a thin film evaporator, an evaporator, a batch still, an atomization separation apparatus, and the like, but are not particularly limited.

[0128] <Step (d): Step of Removing Components with a Boiling Point Lower than that of 1,6-Hexanediol> In step (d), components having a boiling point lower than that of 1,6-hexanediol are removed from the 1,6-hexanediol composition C.

[0129] The step (d) is a step for the purpose of sufficiently removing low boiling point components in order to obtain high purity 1,6-hexanediol and removing trace amounts of color-causing components. In this operation, in particular, components with boiling points lower than that of 1,6-hexanediol, such as the color-causing components themselves and hydrogenated products of the color-causing components, are removed or reduced.

[0130] The distillation in the step (d) can be carried out by known means and devices, such as atmospheric distillation, reduced pressure distillation, and pressurized distillation. Examples of the device for removing the components include a continuous distillation column, a multi-effect can, a thin film evaporator, an evaporator, a batch distiller, and an atomization separation device, but the device is not particularly limited. The operating conditions used in the step (d) can be appropriately set in consideration of the composition of the 1,6-hexanediol composition C, the purity to be finally obtained, and the like, and are not particularly limited.

[0131] <Step (e): Step of Removing Components with a Boiling Point Higher than 1,6-Hexanediol> In the 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 the step (d).

[0132] In the step (e), components with a boiling point higher than that of 1,6-hexanediol, which are specific to the fermentation method, such as nitrogen-containing components derived from amino acids and proteins, sugars and their decomposition products, are removed.

[0133] Examples of the apparatus for removing the hexane include, but are not limited to, a continuous distillation column, a multi-effect can, a thin-film evaporator, an evaporator, a batch distiller, an atomization separation apparatus, etc. The operating conditions used in the step (e) may be appropriately set taking into consideration the composition of the 1,6-hexanediol composition D, the purity to be finally obtained, etc., and are not particularly limited.

[0134] <Step (f): Step of obtaining a 1,6-hexanediol composition with higher purity> In step (f), the 1,6-hexanediol composition E obtained via steps (c), (d) and (e) is purified to obtain a 1,6-hexanediol composition of higher purity.

[0135] Examples of devices for obtaining a 1,6-hexanediol composition of higher purity include, but are not limited to, a continuous distillation column, a multi-effect canister, a thin-film evaporator, an evaporator, a batch still, and an atomization separation device.

[0136] The operating conditions used in the step (f) are not particularly limited and may be appropriately set taking into consideration the composition of the liquid to be purified, the purity to be finally obtained, and the like.

[0137] By carrying out the step (e) and, if necessary, the step (f), a 1,6-hexanediol composition suitable for the present invention can be obtained.

[0138] In the above description, the steps (c), (d) and (e) are carried out in this order, but they may be carried out in a different order.

[0139] The method for producing a 1,6-hexanediol composition suitable for the present invention may include steps (1) and (2), and may also include, in addition to steps (1) and (2), steps other than steps (1) and (2).

[0140] By carrying out the step (2), the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and its derivative (B1) are within the above range, but the step (2) may be repeated so that the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and its derivative (B1) are more preferably within the above range. By repeating the step (2), it is possible to further reduce the total content of the compound (A1) having two or more secondary hydroxyl groups in one molecule and the total content of 6-hydroxyhexanal and its derivative (B1).

[0141] <Active energy ray-curable resin composition> The active energy ray-curable resin composition of the present invention contains the hexamethylene (meth)acrylate composition of the present invention. 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, which tends to more suitably obtain a cured product with more excellent physical properties.

[0142] The active energy ray curable resin composition of the present invention preferably contains a compound having a trifunctional or higher (meth)acryloyl group in addition to the hexamethylene (meth)acrylate composition of the present invention. The hexamethylene (meth)acrylate composition of the present invention is monofunctional or bifunctional, and therefore forms a relatively soft cured product when cured, whereas the compound having a trifunctional or higher (meth)acryloyl group forms a relatively hard and tough cured product when cured. In addition, by using both in combination as a polymerizable diluent, a cured product having better physical properties tends to be more suitably obtained.

[0143] The compound having a trifunctional or higher (meth)acryloyl group 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)acryloxyethyl)isocyanurate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, etc. These may be used alone or in combination of two or more. Among these, at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloxyethyl)isocyanurate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethylene oxide-modified glycerol tri(meth)acrylate, and propylene oxide-modified glycerol tri(meth)acrylate is preferred, because it more suitably gives a cured product with superior physical properties, and at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloxyethyl)isocyanurate, trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate is more preferred.

[0144] The content of the compound having tri- 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, which tends to more suitably obtain a cured product with superior physical properties.

[0145] The active energy ray-curable resin composition of the present invention may contain a polymerizable diluent other than the hexamethylene (meth)acrylate composition of the present invention and the compound having a tri- or higher functional (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; heterocyclic mono(meth)acrylate compounds such as glycidyl(meth)acrylate and tetrahydrofurfuryl acrylate; (meth)acrylate compounds; 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 other aromatic mono (meth)acrylate compounds, such as compounds having one unsaturated group, 1,4-butanediol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified 1,6-Hexanediol di(meth)acrylate, hydroxypivalic acid 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, propylene oxide modified tri(meth)acrylate of glycerin, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, bis Phenoxyethanol fluorene ethylene oxide modified di(meth)acrylate, 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]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,Examples of the compound include compounds having two unsaturated groups, such as 10-tetraoxospiro[5.5]undecane, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and glycerin di(meth)acrylate.

[0146] 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, and more preferably contains a compound having a trifunctional or higher (meth)acryloyl group and a resin in addition to the hexamethylene (meth)acrylate composition of the present invention. This tends to more suitably obtain a cured product with better physical properties.

[0147] The resin is not particularly limited as long as it has a functional group capable of reacting with a (meth)acryloyl group, and examples thereof include epoxy (meth)acrylate resin, urethane (meth)acrylate resin, polyester (meth)acrylate resin, diallyl phthalate resin, etc. These may be used alone or in combination of two or more. Among them, at least one resin selected from the group consisting of epoxy (meth)acrylate resin, urethane (meth)acrylate resin, and diallyl phthalate resin is preferred because it can more suitably obtain a cured product having superior physical properties.

[0148] The epoxy (meth)acrylate resin may be a bisphenol type epoxy resin alone or a mixture of a bisphenol type epoxy resin and a novolac type epoxy resin, and may be an epoxy vinyl ester obtained by reacting the epoxy resin with an unsaturated monobasic acid by a known method. The epoxy (meth)acrylate resin is generally used to improve the mechanical strength, chemical resistance, etc. of the coating film.

[0149] Examples of the bisphenol-type epoxy resin include glycidyl ether-type epoxy resins having substantially two or more epoxy groups in one molecule obtained by reacting epichlorohydrin with bisphenol A or bisphenol F, dimethylglycidyl ether-type epoxy resins obtained by reacting 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 novolak-type epoxy resin include epoxy resins obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methylepichlorohydrin.

[0150] Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, monobutene maleate, sorbic acid, mono(2-ethylhexyl) maleate, etc. These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction of the epoxy resin with (meth)acrylic acid is carried out using an esterification catalyst at a temperature of preferably 60 to 140°C, particularly preferably 80 to 120°C.

[0151] Examples of the esterification catalyst include known catalysts such as tertiary amines such as triethylamine, N,N-dimethylbenzylamine, N,N-dimethylaniline, and diazabicyclooctane, triphenylphosphine, and diethylamine hydrochloride.

[0152] 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, and examples thereof include a resin obtained by reacting a bisphenol A (BPA) type epoxy resin with methacrylic acid, and a resin obtained by reacting a bisphenol F (BPF) type epoxy resin with methacrylic acid. Regarding the BPA type epoxy methacrylate resin, it is a resin excellent in mechanical strength of the coating film, chemical resistance, etc., but from the viewpoint of environmental problems such as endocrine problems, it is preferable to use a BPF type epoxy methacrylate resin, which has low viscosity and excellent workability, etc.

[0153] The urethane (meth)acrylate resin may be one 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, and preferably one having two or more (meth)acryloyl groups in one molecule obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group at NCO / OH=1.0 to 0.5. Examples of the urethane (meth)acrylate resin include those having two or more (meth)acryloyl groups in one molecule obtained by reaction with a polyol, a polyisocyanate, and a (meth)acrylate having one or more hydroxyl groups in one molecule. Preferred examples include a resin obtained by a method in which a terminal isocyanate compound obtained by reacting a polyisocyanate with a polyol at NCO / OH=1.3 to 2 is reacted with a (meth)acrylate having one or more hydroxyl groups in one molecule so that the amount of hydroxyl groups is approximately equivalent to the amount of isocyanate groups; and a method in which a one-terminal isocyanate compound obtained by reacting a polyisocyanate with a (meth)acrylate having one or more hydroxyl groups in one molecule at NCO / OH=2 or more is reacted with a polyol.

[0154] Examples of the polyol include polyhydric alcohols 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-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, and 2,7-decalin glycol, polyester polyols, polyether polyols, polycarbonate polyols, and polybutadiene polyols. Of these, polyether polyols are preferably used.

[0155] The polyether polyol may be, for example, a polyalkylene oxide such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, or may be a polyol obtained by adding the alkylene oxide to bisphenol A or bisphenol F.

[0156] The polyester polyol may be a condensation polymer of a saturated dibasic acid or its acid anhydride with a polyhydric alcohol, or a ring-opening polymer of a cyclic ester compound such as polycaprolactone. The dibasic acids may be, for example, 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-dodecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, or dialkyl esters thereof.

[0157] Examples of the polyhydric alcohols 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-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. Among these, dihydric alcohols are preferred.

[0158] Examples of the polyisocyanate include 2,4-tolylene diisocyanate (hereinafter abbreviated as 2,4-TDI), its isomers or a mixture of isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the above-mentioned polyisocyanates. Examples of the polyisocyanate include a uretdione type polyisocyanate compound which is a polymer, an isocyanurate type polyisocyanate compound which is a polymer of the above-mentioned polyisocyanate, an adduct type polyisocyanate compound obtained from the above-mentioned polyisocyanate and a polyhydric alcohol, an allophanate type polyisocyanate obtained from the above-mentioned adduct type polyisocyanate and the above-mentioned polyisocyanate, and a biuret type polyisocyanate obtained from the above-mentioned polyisocyanate and water and / or an amine. These can be used alone or in combination of two or more. Among them, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-TDI, its isomer or a mixture of isomers, and nurate type polyisocyanate obtained from these four types, uretdione type polyisocyanate, adduct type polyisocyanate, allophanate type polyisocyanate, and biuret type polyisocyanate are particularly preferred.

[0159] 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 polyhydric (meth)acrylates such as tris(hydroxyethyl)isocyanuric acid di(meth)acrylate and pentaerythritol tri(meth)acrylate.

[0160] The polyester (meth)acrylate resin is a saturated polyester resin or an unsaturated polyester resin having two or more (meth)acryloyl groups in one molecule, and includes a resin obtained by reacting a (meth)acrylic compound with the terminal of a saturated polyester or an unsaturated polyester. The number average molecular weight of the resin is preferably 500 to 5,000, more preferably 1,000 to 5,000.

[0161] The saturated polyester resin may be one obtained by a condensation reaction between a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester resin may be one obtained by a condensation reaction between a dibasic acid, including an α,β-unsaturated dibasic acid, and a polyhydric alcohol, and has a functional group at the end for introducing a (meth)acrylic compound.

[0162] Examples of the α,β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, halogenated maleic anhydride, etc. 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-dodecane diacid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, and dialkyl esters thereof.

[0163] Examples of the polyhydric alcohols which undergo a condensation reaction with the saturated dibasic acid or the dibasic acid including the α,β-unsaturated dibasic acid include the same polyhydric alcohols as those mentioned above.

[0164] Examples of the (meth)acrylic compound used in the polyester (meth)acrylate resin include glycidyl esters of acrylic acid or methacrylic acid, etc. Among these, glycidyl (meth)acrylate is preferred.

[0165] The diallyl phthalate resin refers to a prepolymer synthesized from a diallyl phthalate monomer or a diallyl isophthalate monomer, and there are several commercially available products depending on the type and molecular weight of the orthophthalic and isophthalic monomers. Specific examples include Daiso DAP A, Daiso DAP S, Daiso DAP K, and Daiso Isodap, which are sold by Daiso Co., Ltd.

[0166] The content of the active component resin in 100% by mass of the active components of 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, which tends to more suitably obtain a cured product with more excellent physical properties.

[0167] A preferred ratio of the content of the hexamethylene (meth)acrylate composition of the present invention, the content of the active ingredient of the resin, and the content of the compound having tri- or higher functional (meth)acryloyl groups in 100 mass % of the active ingredient of the active energy ray-curable resin composition is preferably a mass ratio of the content of the hexamethylene (meth)acrylate composition of the present invention / the content of the active ingredient of the resin / the content of the compound having tri- or higher functional (meth)acryloyl groups of a preferred range is 1-60 / 10-90 / 5-85, more preferably 3-50 / 15-70 / 8-60, and even more preferably 5-40 / 20-60 / 10-50. The above-mentioned active ingredient refers to a compound having an unsaturated bond and participating in curing.

[0168] The active energy ray-curable resin composition of the present invention preferably contains a polymerization initiator, which tends to more suitably give a cured product having superior physical properties.

[0169] The polymerization initiator is preferably a photopolymerization initiator, and examples thereof include an intramolecular cleavage type photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator, etc. These may be used alone or in combination of two or more kinds.

[0170] Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)phenyl}-ketone, and the like. acetophenone compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one; oxime compounds such as 1-[4-(phenylthio)-,2-(O-benzoyloxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime); carbazole compounds such as 9-butylcarbazole, benzoin, benzoin methyl ether, benzoin isopropyl ether, and other benzoin compounds; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-methyl-2-morpholino((4-methylthio)phenyl)propan-1-one, 2-benzyl-2-dimethylamino ... aminoalkylphenone compounds such as benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; benzyl, methylphenyl glyoxyesters, and the like.

[0171] Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone-based compounds such as benzophenone, o-benzoylmethylbenzoate-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone-based compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; aminobenzophenone-based compounds such as 4,4'-bisdimethylaminobenzophenone and 4,4'-bisdiethylaminobenzophenone; and others such as 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

[0172] The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the non-volatile components in the active energy ray-curable resin composition, which tends to more suitably obtain a cured product with more excellent physical properties.

[0173] When the cured product is formed by irradiating ultraviolet rays as active energy rays, it is possible to further improve the curability by using a photosensitizer in addition to the polymerization initiator. Examples of the photosensitizer include amine compounds such as aliphatic amines, ureas such as o-tolylthiourea, and sulfur compounds such as sodium diethyl dithiophosphate and s-benzylisothiuronium-p-toluenesulfonate. These may be used alone or in combination of two or more. 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 non-volatile components in the active energy ray-curable resin composition in order to improve the curability.

[0174] In addition to the above components, the active energy ray-curable resin composition of the present invention may contain various additives, such as fillers, ultraviolet absorbers, pigments, dyes, thickeners, shrinkage reducing agents, antioxidants, plasticizers, aggregates, flame retardants, stabilizers, fiber reinforcements, organic solvents, antistatic agents, defoamers, viscosity modifiers, antioxidants, leveling agents, dispersants, waxes, moisture absorbents, fillers, antifogging agents, etc., within the range that does not impair the effects of the present invention. These may be used alone or in combination of two or more.

[0175] The active energy ray curable resin composition of the present invention is used for applications such as ink, coating, paint, adhesive, pressure sensitive adhesive, sheet, film, etc. Among them, it is preferable to use it for at least one application selected from the group consisting of ink, coating, paint, and adhesive. In addition, the ink is preferably an ink for 3D printers.

[0176] The ink of the present invention comprises the active energy ray-curable resin composition of the present invention. The coating of the present invention comprises the active energy ray-curable resin composition of the present invention. The paint of the present invention comprises the active energy ray-curable resin composition of the present invention. The adhesive of the present invention comprises the active energy ray-curable resin composition of the present invention.

[0177] When the active energy ray curable resin composition of the present invention is used as an ink, for example, the above-mentioned components may be mixed at once, or a polymerizable diluent may be added to the resin in advance to prepare a resin solution-like composition for use in preparing the ink. Examples of a method for producing the ink include a method in which the above-mentioned components are blended, stirred and mixed in a mixer or the like, and milled using a dispersing machine such as a three-roll mill or a bead mill. The obtained ink can then be printed on various substrates and irradiated with active energy rays to form a cured coating film.

[0178] Examples of the printing method for the ink include lithographic offset printing, letterpress printing, gravure printing, gravure offset printing, flexographic printing, and screen printing.

[0179] When the active energy ray curable resin composition of the present invention is used as a coating or paint, for example, the above-mentioned components are thoroughly kneaded and uniformly dispersed using a device such as a mixing mixer or a ball mill to prepare a resin composition (paste), which is then further mixed with a polymerization initiator to make it uniform, and the desired viscosity is adjusted with an organic solvent or the like. The obtained resin composition can be applied to various substrates by various coating methods. Then, the obtained resin composition can be applied to various substrates and then irradiated with active energy rays to form a cured coating film.

[0180] Examples of the coating method include coating methods using a gravure coater, a knife coater, a roll coater, a comma coater, a spin coater, a bar coater, brush coating, dipping coating, spray coating, and the like.

[0181] When the active energy ray curable resin composition of the present invention is used as an adhesive, for example, the above-mentioned components are thoroughly kneaded and uniformly dispersed using a device such as a mixing mixer or a ball mill to prepare a resin composition (paste), which is then further mixed with a polymerization initiator to make it uniform, and the desired viscosity is adjusted with an organic solvent or the like. The obtained resin composition is then applied to various substrates, and then irradiated with active energy rays to bond the substrates. The application method can be the same as that when the composition is used as a coating or paint.

[0182] Examples of active energy rays include ultraviolet rays, electron beams, ionizing radiation such as α rays, β rays, and γ rays. Of these, ultraviolet rays are preferred. Specific examples of energy sources or curing devices include germicidal lamps, ultraviolet fluorescent lamps, UV-LEDs, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium- or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrodeless lamps, metal halide lamps, ultraviolet rays using natural light as a light source, and electron beams from scanning or curtain-type electron beam accelerators.

[0183] The cured product of the present invention is obtained 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, and then the layer of the resin composition is cured by irradiating the layer of the resin composition with active energy rays to form a cured layer, which is a cured product. Here, the resin composition prepared according to the above-mentioned various applications may be appropriately applied and cured according to the applicable application.

[0184] In this specification, the notation "~" means a value equal to or greater than the value before the notation "~" and equal to or less than the value after the notation "~". In addition, in this specification, when multiple numerical ranges are disclosed for a certain characteristic, etc., the upper and lower limits of each numerical range can be used in any combination. For example, when two numerical ranges, 0.001 to 500 ppm by mass and 0.05 to 250 ppm by mass, are disclosed for the content of a certain compound, this means that in addition to 0.001 to 500 ppm by mass and 0.05 to 250 ppm by mass, the numerical ranges 0.001 to 250 ppm by mass and 0.05 to 500 ppm by mass are also disclosed. EXAMPLES

[0185] EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0186] (Production Example 1) (Creation of genetically modified E. coli) Plasmid A was constructed by inserting the glycerol dehydratase α, β, and γ subunit genes and the dehydratase reactivator gene derived from Citrobacter freundii between the BamHI and HindIII restriction enzyme sites of pACYC184 (Nippon Gene Co., Ltd.). The HpaI gene from Escherichia coli was used as a 4,6-dihydroxy-2-oxo-hexanoic acid aldolase, the HpcG gene from Escherichia coli was used as a 4,6-dihydroxy-2-oxo-hexanoic acid 4-dehydratase, and the NADPH-dependent oxidoreductase 2-alkenal from Arabidopsis thaliana was used as a 6-hydroxy-3,4-dehydro-2-oxohexanoic acid 3-reductase. Plasmid B was constructed by inserting the 6-hydroxy-2-oxohexanoate 2-reductase gene (GenBank: CAC01710.1) from Lactococcus lactis as 6-hydroxy-2-oxohexanoate 2-reductase, the PanE gene from Lactococcus lactis as 2,6-dihydroxyhexanoate CoA-transferase and the HadA gene from Clostridium difficile as 2,6-dihydroxyhexanoate CoA-transferase between the BamHI and EcoRI restriction enzyme cleavage sites of the multiple cloning site (MCS) of pUC19 (Nippon Gene Co., Ltd.). The HadB and HadC genes from Clostridium difficile were used as the α and β subunit genes of 2-hydroxyisocaproyl-CoA dehydratase, the HadI gene from Clostridium difficile was used as the 2-hydroxyisocaproyl-CoA dehydratase activating enzyme, and the trans-2-enoyl-CoA reductase from Treponema denticola was used as the 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-reductase (GenBank: Plasmid C was created by introducing the HadB, HadC, and HadI genes into MCS1 and the other genes into MCS2 of pCOLADuet-1 (Novagen), the AE017248 gene as a 6-hydroxyhexanoate 1-reductase, the Nocardia iowensis-derived carboxylic acid reductase gene (GenBank: AAR91681.1) gene as a 6-hydroxyhexanoate 1-reductase, and the Rhodococcus sp.-derived 6-hydroxyhexanoate dehydrogenase gene (GenBank: AAN37489.1) gene as a 6-hydroxyhexanal 1-reductase, into pCOLADuet-1 (Novagen). In this section, the gene refers to an open reading frame containing a stop codon that codes for each enzyme. Each gene is introduced into a plasmid in such a way that a sequence containing a T7 promoter and a ribosome binding site is located upstream of the gene, and a sequence containing a T7 terminator is located downstream of the gene. Each gene can be expressed in large amounts in a host strain of Escherichia coli that expresses T7 RNA polymerase by appropriate expression induction. Plasmids A, B, and C were successively transformed into chemically competent BL21 Star(DE3) (Invitrogen) cells by the heat shock method, and the transformants were selected on LB plates containing the appropriate antibiotics. As a result, a BL21 Star(DE3) strain containing all of plasmids A, B, and C was obtained. As a result, 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 (2E in the figure of Japanese Patent No. 6680671), and 2,6-dihydroxy-hexanoic acid CoA-transferase were detected. We constructed Escherichia coli strains carrying genes encoding the 10 enzymes of the 1,6-hexanediol pathway, including 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2-dehydratase (2F in the figure of Japanese Patent No. 6680671), 6-hydroxy-2,3-dehydro-hexanoyl-CoA 2,3-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).

[0187] (Production Example 2: Preparation of 1,6-Hexanediol Composition 1 (1,6-HD Composition 1)) The Escherichia coli was inoculated into an autoclave-sterilized medium (carbon source: glucose, glycerin, nitrogen source: enzyme extract, inorganic salts: potassium phosphate, potassium hydroxide, vitamin B12, antibiotics: carbenicillin, kanamycin, chloramphenicol, pH: 7.0, among the above components, glucose and glycerin were raw materials derived from biomass resources) and cultured under aerobic conditions at 30°C for 2 to 3 hours. Thereafter, when the optical density at 600 nm of the Escherichia coli reached 0.3 to 0.6, isopropyl-β-thiogalactopyranoside was added to a final concentration of 0.5 mM and iron(II) sulfate was added to a final concentration of 10 μM, and the culture was continued for another 3 hours at 30°C to express the enzymes of the 1,6-HD pathway. After expression, an appropriate amount of carbon source (glucose, glycerin) was added, and the inside of the culture vessel was placed under a nitrogen atmosphere to create anaerobic conditions. Under these conditions, the culture was carried out 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 collected and then filtered using a membrane filter with an appropriate pore size of 0.2 to 0.4 μm to obtain a 1,6-hexanediol composition as the filtrate.

[0188] [Purification of 1,6-hexanediol composition] <Step (a): Ion exchange to remove cations> The cations contained in the 1,6-hexanediol composition were removed. In step (a), cation exchange was performed in a batch manner. The temperature for contact with the cation exchange resin was set to 40°C, and DIAION SK1BH manufactured by Mitsubishi Chemical Corporation was added as a cation exchange resin to the 1,6-hexanediol composition and stirred for 3 hours. After stirring, filtration was performed to obtain 1,6-hexanediol composition A as the filtrate. <Step (b): Ion exchange to remove anions> The anions contained in the 1,6-hexanediol composition A were removed. In step (b), anion exchange was carried out in a batch manner. The temperature for contact with the anion exchange resin was set to 40°C, and DIAION SA10AOH manufactured by Mitsubishi Chemical Corporation was added as an anion exchange resin to the 1,6-hexanediol composition, followed by stirring for 3 hours. After stirring, filtration was carried out to obtain a 1,6-hexanediol composition B as a filtrate.

[0189] <Step (c): Step of Removing Water> 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 to 70°C, the 1,6-hexanediol-containing composition was continuously introduced, and water was distilled from the top. At the same time as the water was distilled, the dehydrated 1,6-hexanediol composition C was continuously withdrawn from the bottom as a bottom product. The water concentration in this 1,6-hexanediol composition C was 0.020% by mass (200 ppm by mass).

[0190] <Step (d): Distillative separation of low boiling point components> Components having a boiling point lower than that of 1,6-hexanediol contained in the 1,6-hexanediol composition C were removed in 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 fed to the distillation column, and the column top temperature was controlled at a constant temperature of 240°C. Continuous distillation was performed from the top of the column, and continuous withdrawal was performed from the bottom of the column to remove the low boiling point components in the 1,6-hexanediol composition C, and a 1,6-hexanediol composition D from which components having a boiling point lower than that of 1,6-hexanediol had been removed was taken out from the bottom of the column.

[0191] <Step (e): Distillative separation of high boiling point components> Components having a higher boiling point than 1,6-hexanediol contained in 1,6-hexanediol composition D were removed in a continuous distillation column. An Oldershaw distillation column was used as the distillation column in step (e). 1,6-hexanediol composition D obtained in step (d) was continuously fed to the distillation column, and the column bottom temperature was controlled to be constant at 260°C. Continuous extraction was performed from the column bottom to remove high boiling components in 1,6-hexanediol composition D. 1,6-hexanediol composition E (1,6-HD composition 1) from which components having a higher boiling point than 1,6-hexanediol were removed was obtained from the column top (column top distillate).

[0192] The results of the analysis of the obtained 1,6-HD Composition 1 are shown below. In the analysis of the 1,6-HD Composition, the detection limits for glycerin, glucose, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 6-hydroxyhexanal were 5.0 ppm by mass, 5.0 ppm by mass, 5.0 ppm by mass, 5.0 ppm by mass, and 10.0 ppm by mass, respectively. Glycerin: 800 ppm by mass Glucose: Below detection limit 1,3-Cyclohexanediol: Below detection limit 1,4-Cyclohexanediol: Below detection limit 6-Hydroxyhexanal: 500 ppm by mass

[0193] (Production Example 3: Preparation of 1,6-Hexanediol Composition 2 (1,6-HD Composition 2)) In Production Example 2, the 1,6-hexanediol composition obtained by the bio-method was repeatedly purified to obtain 1,6-hexanediol composition 2 having a glycerin content of 150 ppm by mass and a 6-hydroxyhexanal content of 100 ppm by mass.

[0194] The analytical results of the obtained 1,6-HD Composition 2 are shown below. Glycerin: 150 ppm by mass Glucose: Below detection limit 1,3-Cyclohexanediol: Below detection limit 1,4-Cyclohexanediol: Below detection limit 6-Hydroxyhexanal: 100 ppm by mass

[0195] (Production Example 4: Preparation of 1,6-Hexanediol Composition 3 (1,6-HD Composition 3)) In Production Example 2, the 1,6-hexanediol composition obtained by the bio-method was repeatedly purified to obtain 1,6-hexanediol composition 3 having a glycerin content of 5 ppm by mass and a 6-hydroxyhexanal content of 10 ppm by mass.

[0196] The analytical results of the obtained 1,6-HD composition 3 are shown below. Glycerin: 5 ppm by mass Glucose: Below detection limit 1,3-Cyclohexanediol: Below detection limit 1,4-Cyclohexanediol: Below detection limit 6-Hydroxyhexanal: 10 ppm by mass

[0197] (Production Example 5: Preparation of 1,6-Hexanediol Composition 4 (1,6-HD Composition 4)) Glycerin was added to 1,6-HD Composition 3 obtained in Production Example 4 so that the glycerin concentration was 150 ppm by mass, and 1,3-cyclohexanediol was added so that the 1,3-cyclohexanediol concentration was 100 ppm by mass to prepare 1,6-Hexanediol Composition 4 (1,6-HD Composition 4).

[0198] (Production Example 6: Preparation of 1,6-Hexanediol Composition 5 (1,6-HD Composition 5)) Glycerin was added to the 1,6-HD composition 3 obtained in Production Example 4 so that the glycerin concentration was 10,000 ppm by mass, thereby preparing a 1,6-hexanediol composition 5 (1,6-HD composition 5).

[0199] (Production Example 7: Preparation of 1,6-Hexanediol Composition 6 (1,6-HD Composition 6)) 1,6-Hexanediol Composition 6 (1,6-HD Composition 6) was prepared by adding 1,4-cyclohexanediol to 1,6-HD Composition 3 obtained in Production Example 4 so that the 1,4-cyclohexanediol content was 100 ppm by mass.

[0200] (Production Example 8: Preparation of 1,6-Hexanediol Composition 7 (1,6-HD Composition 7)) 1,6-Hexanediol Composition 7 (1,6-HD Composition 7) was prepared by adding 6-hydroxyhexanal to 1,6-HD Composition 3 obtained in Production Example 4 so that the concentration of 6-hydroxyhexanal was 1,500 ppm by mass.

[0201] Example 1: Preparation of hexamethylene diacrylate composition (HDA composition 1) In a reaction vessel equipped with a stirrer, a temperature sensor, a decanter, and a cooling tube, 580.2g (4.91mol) of 1,6-hexanediol composition 1 obtained in Production Example 2, 848.9g (11.78mol), 769.5g toluene, 3.6g hydroquinone (HQ), and 21.4g 70% sulfuric acid were charged and stirred until homogeneous at room temperature, then the pressure was reduced to 53kPa, the temperature was raised to 100°C, and a dehydration esterification reaction was carried out under the above conditions for 10 hours. After returning to normal pressure, the temperature was lowered to 40°C, 1100.0g toluene and 320.0g ion-exchanged water were added, stirred for 1 hour, and allowed to stand, and the aqueous phase (lower layer) was removed. Next, 470.4g of 20% sodium hydroxide aqueous solution was added, stirred for 1 hour at room temperature, and allowed to stand, and the aqueous phase (lower layer) was removed. Further, 240.0 g of ion-exchanged water was added, and the mixture was stirred and allowed to stand in the same manner, after which the aqueous phase (lower layer) was removed. 20.0 g of magnesium sulfate was added, and the mixture was dehydrated and filtered. After that, 0.5 g of hydroquinone monomethyl ether was added, and the toluene was distilled off under reduced pressure at 50° C. to obtain 1000.0 g of hexamethylene diacrylate (HDA composition 1). The analytical results of the obtained HDA composition 1 are shown below. In the analysis of the HDA composition, the detection limits of glycerin triacrylate (GTA), glucose pentaacrylate (GPA), 1,3-cyclohexanediol diacrylate (1,3CDA), 1,4-cyclohexanediol diacrylate (1,4CDA), and 6-acryloyloxyhexanal (AHL) were 5.0 ppm by mass, 5.0 ppm by mass, 5.0 ppm by mass, 5.0 ppm by mass, and 10.0 ppm by mass, respectively. Glycerin triacrylate: 800 ppm by mass Glucose pentaacrylate: Below detection limit 1,3-Cyclohexanediol diacrylate: Below detection limit 1,4-Cyclohexanediol diacrylate: Below detection limit 6-Acryloyloxyhexanal: 500 ppm by mass

[0202] (Examples 2 to 7: Preparation of hexamethylene diacrylate compositions 2 to 7 (HDA compositions 2 to 7)) HDA compositions 2 to 7 were prepared in the same manner as in Example 1, except that 1,6-HD compositions 2 to 7 were used instead of the 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 1.

[0203] [Table 1]

[0204] (Production Example 9: Production and Evaluation of Cured Film 1) 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, 55.0 g of Luxidia 17-806R (ultraviolet light curable acrylic urethane resin) manufactured by DIC Corporation, 20.0 g of Luxidia V-4221 (ultraviolet light curable urethane acrylate resin) manufactured by DIC Corporation, and 3.0 g of Omnirad184 (1-hydroxycyclohexyl-phenyl ketone) manufactured by iGM Resins as a photoinitiator. The prepared resin solution was applied to an easily adhesive treated PET film using a bar coater so that the cured film thickness was 10 μm, and after drying at 80° C. for 1 minute, it was irradiated with a high pressure mercury lamp at a dose of 500 mJ / cm using an ultraviolet irradiation device manufactured by Japan Battery Co., Ltd. 2 The cured film 1 was obtained by irradiating with ultraviolet light so as to obtain a cured film 1. The cured film for tensile testing is a cured film 1 with a glass substrate, a film thickness of 100 μm, and a radiation dose of 1000 mJ / cm. 2 It was created under the following conditions.

[0205] Cured film 1 was used and evaluated as follows. The results are shown in Table 2. Surface hardness: Evaluated by the pencil hardness test JIS K 5600-5-4. Adhesion: Evaluated according to JIS K 5600-5-6. Transparency: Evaluated as total light transmittance using a haze meter (NDH5000) manufactured by Nippon Coloring Industries Co., Ltd. Steel wool (SW) abrasion resistance: A 500g load of steel wool #0000 was rubbed back and forth on the cured film 10 times with a rubbing tester, and 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. Elastic modulus: The cured film was subjected to a tensile test to determine the elastic modulus. Flexibility (elongation %): A tensile test was carried out on a cured film until it broke, and the length that was stretched was evaluated as a percentage (%) of the length of the test film. Tensile strength: A tensile test was carried out on the cured film until it broke, and the maximum stress at that time was taken as the tensile strength. The tensile test was carried out under conditions of 23° C. and 50% RH using an AUTOGRAPH AGS-X 1kN manufactured by Shimadzu Corporation.

[0206] (Production Examples 10-15: Production and Evaluation of Cured Films 2-7) Photocurable compositions were prepared in the same manner as in Production Example 9 except that the formulations shown in Table 2 were used instead of those in Production Example 9, and cured films were prepared and evaluated in the same manner.

[0207] [Table 2]

[0208] The components in Table 2 are as follows. M600: Miramer M600 (dipentaerythritol hexaacrylate) manufactured by Miwon 17-806R: Luxidia 17-806R manufactured by DIC Corporation (UV-curable urethane acrylate resin (active ingredient is 80%)) V-4221: Luxidia V-4221 manufactured by DIC Corporation (UV-curable urethane acrylate resin (active ingredient is 100%)) M370: Miramer M370 (tris-(2-acryloxyethyl) isocyanurate) manufactured by Miwon M420: Miramer M420 (pentaerythritol tetraacrylate) manufactured by Miwon M410: Miramer M410 (ditrimethylolpropane tetraacrylate) manufactured by Miwon M300: Miramer M300 (trimethylolpropane triacrylate) manufactured by Miwon DAP: Daiso DAP A (diallyl phthalate resin) manufactured by Osaka Soda Co., Ltd.

[0209] (Comparative Production Example 1: Preparation of 1,6-Hexanediol Composition 8 (1,6-HD Composition 8)) Glucose was added to the 1,6-HD composition 3 obtained in Production Example 4 so as to have a concentration of 150 ppm by mass to prepare 1,6-hexanediol composition 8 (1,6-HD composition 8).

[0210] (Comparative Production Example 2: Preparation of 1,6-Hexanediol Composition 9 (1,6-HD Composition 9)) 1,6-Hexanediol Composition 9 (1,6-HD Composition 9) was prepared by adding 1,4-cyclohexanediol to 1,6-HD Composition 3 obtained in Production Example 4 so that the 1,4-cyclohexanediol content was 150 ppm by mass.

[0211] (Comparative Examples 1-2: Preparation of Hexamethylene Diacrylate Compositions 8-9 (HDA Compositions 8-9)) HDA compositions 8 to 9 were prepared in the same manner as in Example 1, except that 1,6-HD compositions 8 to 9 were used instead of the 1,6-HD composition 1 used in Example 1. The synthesis results are shown in Table 3.

[0212] [Table 3]

[0213] (Comparative Production Examples 3-6: Production and Evaluation of Cured Films 8-11) Curable compositions were prepared in the same manner as in Production Example 9 except that the formulations shown in Table 4 were used instead of the formulation in Production Example 9, and cured films were prepared and evaluated in the same manner.

[0214] [Table 4]

[0215] From the above examples and comparative examples, it was found that the hexamethylene (meth)acrylate composition of the present invention, which contains hexamethylene (meth)acrylate and has a total content of compound (A1) having two or more secondary hydroxyl groups in one molecule and (meth)acrylate compound (A2) of compound (A1) of 100 ppm by mass or less, and has a total content of 6-hydroxyhexanal and derivatives thereof (B1), and (meth)acrylate compound (B2) of compound (B1) of 1500 ppm by mass or less, can provide a cured product having excellent physical properties (particularly transparency, abrasion resistance, elastic modulus, and tensile strength).

Claims

1. Contains 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) is 100 ppm by mass or less; The total content of 6-hydroxyhexanal (meth)acrylate compounds is 1500 ppm by mass or less, A hexamethylene (meth)acrylate composition, 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)), and a (meth)acrylate of 1,3-cyclohexanediol (a compound represented by the following formula (A2-4)). (In the formulas (A2-1) to (A2-4), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

2. The hexamethylene (meth)acrylate composition according to claim 1, which contains a (meth)acrylate of glycerin (a compound represented by the following formula (C)). 【Chemistry 3】 (In the formula (C), R may be the same or different and represents a hydrogen atom or a (meth)acryloyl group, provided that at least one of R is a (meth)acryloyl group.)

3. The hexamethylene (meth)acrylate composition according to claim 1, which is prepared from a 1,6-hexanediol composition derived from a biomass resource.

4. An active energy ray-curable resin composition comprising the hexamethylene (meth)acrylate composition according to any one of claims 1 to 3.

5. 5. The active energy ray-curable resin composition according to claim 4, which contains a compound having a tri- or higher functional (meth)acryloyl group.

6. The active energy ray curable resin composition according to claim 5, wherein the compound having a trifunctional or higher (meth)acryloyl group is at least one compound selected from the group consisting of dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tris-(2-acryloxyethyl)isocyanurate, trimethylolpropane triacrylate, and ditrimethylolpropane tetraacrylate.

7. 5. The active energy ray-curable resin composition according to claim 4, which contains an epoxy (meth)acrylate resin.

8. 5. The active energy ray-curable resin composition according to claim 4, which contains a urethane (meth)acrylate resin.

9. 5. The active energy ray-curable resin composition according to claim 4, which contains a diallyl phthalate resin.

10. 5. The active energy ray-curable resin composition according to claim 4, which is used for at least one application selected from the group consisting of inks, coatings, paints and adhesives.

11. A cured product obtained by curing the active energy ray-curable resin composition according to claim 4.

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