Tricyclodecane dimethanol composition, ultraviolet curable composition, polymer composition, and method for producing tricyclodecane dimethanol composition

Abstract

A tricyclodecane dimethanol composition, comprising tricyclodecane dimethanols, wherein the tricyclodecane dimethanols comprise a chiral compound A, one of whose mirror image isomers is represented by the following formula (I), a chiral compound B, one of whose mirror image isomers is represented by the following formula (II), and a chiral compound C, one of whose mirror image isomers is represented by the following formula (III). In the composition, the sum of the peak area Xc of the gas chromatogram of the chiral compound C and the peak area Xt of the gas chromatogram of the tricyclodecane dimethanols detected by gas chromatography satisfies Xc / Xt≥0.35.

Description

Technical Field

[0001] The present invention relates to a tricyclodecane dimethanol composition, an ultraviolet curable composition, a polymer composition and a method for producing the tricyclodecane dimethanol composition. Background Art

[0002] In the fields of molding materials, electronic materials, and display device members, materials having an alicyclic molecular structure are used from the viewpoints of transparency, heat resistance, and low water absorption.

[0003] Tricyclodecane dimethanol (hereinafter referred to as "TCDDM") is a diol having an alicyclic structure. TCDDM is produced by subjecting dicyclopentadiene to a hydroformylation reaction in the presence of a catalyst by reacting carbon monoxide with hydrogen to obtain an aldehyde, followed by hydrogen reduction (Patent Documents 1 and 2).

[0004] TCDDM has been used as a synthetic raw material for molding materials such as polyester and polycarbonate. It is known that polymers containing TCDDM as a constituent component have excellent properties in terms of hardness, transparency, heat resistance and low water absorption due to its alicyclic structure, and are therefore used in the fields of molding materials, electronic materials, and display device components.

[0005] Derivatives such as diacrylate derivatives, dimethacrylate derivatives, and urethane acrylate of TCDDM synthesized using TCDDM as a raw material are used as ultraviolet curable compositions.

[0006] The cured product using the ultraviolet curable composition containing TCDDM as a constituent component has the characteristics of high surface hardness, high glass transition temperature, excellent thermal decomposition resistance, excellent development tolerance, etc., and is used in electronic materials such as hard coatings, antifouling coatings, and resists, and components for display devices.

[0007] In the method of obtaining TCDDM by subjecting dicyclopentadiene to hydroformylation reaction, the reactivity of the double bond of the norbornene ring of dicyclopentadiene is higher than that of the double bond of the five-membered ring. Therefore, after the first formyl group is added to the norbornene ring, the second formyl group is added to the double bond of the five-membered ring (Non-Patent Document 1). As a result, it is known that the TCDDM obtained by this reaction is a mixture of TCDDM with three isomers having different bonding positions of the hydroxymethyl group in the five-membered ring as the main component (hereinafter referred to as "TCDDM composition") (Non-Patent Document 2).

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2020-132624

[0011] Patent Document 2: Japanese Patent Application Publication No. 2021-520401

[0012] Non-patent literature

[0013] Non-patent document 1: Hitachi Chemical Technology Report, No. 51 (2008-7), P7-12

[0014] Non-patent document 2: Applied Catalyst, Vol. 19, pp259-273 (1985) Summary of the invention

[0015] Problems to be solved by the invention

[0016] The TCDDM compositions described in Patent Documents 1 and 2 are prone to stringing during handling such as a mixing operation, and therefore have poor handling properties.

[0017] Therefore, in the case of conventional TCDDM compositions, when used as raw materials for producing polymers or ultraviolet curable compositions, it is required to improve handling properties by reducing stringiness so as to prevent the composition from adhering to containers and equipment and thereby reducing productivity.

[0018] In the field of using ultraviolet curable compositions synthesized using TCDDM as a raw material, in applications such as resists, a method of applying the above-mentioned ultraviolet curable compositions on a substrate using screen printing or flexographic printing and curing the compositions is used. From the perspectives of being able to apply the compositions lightly and evenly, or being able to apply the compositions in a thick and accumulated manner, and being able to print fine patterns on the substrate with high precision, the ultraviolet curable compositions are required to have a high viscosity.

[0019] In applications such as inkjet printing of hard coatings and antifouling coatings, a method of applying the above-mentioned ultraviolet curable composition on a substrate by a coater method, a sprayer method, or a dispenser method and curing the composition is used. From the viewpoint of accurately and quantitatively ejecting the ultraviolet curable composition, a high viscosity is required for the ultraviolet curable composition.

[0020] However, conventional ultraviolet curable compositions synthesized using TCDDM as a raw material have a significantly reduced viscosity due to conversion of the alcohol portion of TCDDM into an ester bond, etc. If a viscosity enhancer is added to increase the viscosity, the performance originally required of the ultraviolet curable composition is impaired.

[0021] An object of the present invention is to provide a TCDDM composition having reduced stringiness and excellent handleability.

[0022] Another object of the present invention is to provide a TCDDM composition that can provide a high-viscosity ultraviolet curable composition.

[0023] Methods for solving problems

[0024] The present inventors have found that, in a mixture of TCDDM having three isomers with different bonding positions of the hydroxymethyl group as main components, it is effective to appropriately control the isomer ratio. More specifically, the following insight was obtained: one of the three isomers has a structure with extremely high crystallinity, and by manufacturing in a manner such that the ratio of this component is above a specified value, the crystallinity of the TCDDM composition can be adjusted, thereby obtaining a TCDDM composition that is not prone to stringing and has excellent handling properties. The following insight was further obtained: by using a large amount of TCDDM composition containing a structure with high crystallinity as a raw material, the orientation of the molecular structure can be improved, thereby obtaining a high-viscosity UV-curable composition.

[0025] The gist of the present invention is as follows.

[0026] [1] A tricyclodecane dimethanol composition, which is a composition containing tricyclodecane dimethanols, wherein the tricyclodecane dimethanols include a chiral compound A whose one mirror image isomer is represented by the following formula (I), a chiral compound B whose one mirror image isomer is represented by the following formula (II), and a chiral compound C whose one mirror image isomer is represented by the following formula (III), wherein in the composition, the sum of the peak area Xc of the gas chromatogram of the chiral compound C and the peak area Xt of the gas chromatogram of the tricyclodecane dimethanols detected by gas chromatography satisfies Xc / Xt≥0.35.

[0027] [Chemistry 1]

[0028]

[0029] [2] The tricyclodecane dimethanol composition as described in [1], wherein the peak area Xb of the gas chromatogram of the chiral compound B detected by gas chromatography and the above Xc satisfy Xc / Xb≥1.00.

[0030] [3] The tricyclodecane dimethanol composition as described in [1] or [2], wherein the peak area Xa of the gas chromatogram of the chiral compound A, the peak area Xb of the gas chromatogram of the chiral compound B and the above Xc detected by gas chromatography satisfy Xc / (Xa+Xb)≥0.60.

[0031] [4] The tricyclodecane dimethanol composition according to any one of [1] to [3], wherein the peak area Xa of the gas chromatogram of the chiral compound A detected by gas chromatography and the Xt satisfy Xa / Xt≤0.27.

[0032] [5] The tricyclodecane dimethanol composition according to any one of [1] to [4], wherein the peak area Xb of the gas chromatogram of the chiral compound B detected by gas chromatography and the Xt satisfy Xb / Xt≤0.32.

[0033] [6] An ultraviolet curable composition derived from the tricyclodecane dimethanol composition described in any one of [1] to [5].

[0034] [7] The ultraviolet curable composition according to [6], which is used for any one of a hard coating material, an antifouling coating material, a resist material, an inkjet ink, and a material for a 3D printer.

[0035] [8] A polymer composition derived from the tricyclodecane dimethanol composition described in any one of [1] to [5], or the ultraviolet curable composition described in [6] or [7].

[0036] [9] The polymer composition according to [8], which is at least one selected from the group consisting of polyester resins, epoxy resins, acrylate resins, polycarbonate resins, and polyurethane resins.

[0037]

[10] A method for producing a tricyclodecane dimethanol composition according to any one of [1] to [5], comprising: a step of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarboxaldehyde; a step of reducing the tricyclodecane dicarboxaldehyde to obtain a crude reaction liquid containing tricyclodecane dimethanol; and a step of distilling and purifying the crude reaction liquid to obtain a tricyclodecane dimethanol composition.

[0038] Effects of the Invention

[0039] According to the present invention, a TCDDM composition having high crystallinity and excellent handling properties can be provided. More specifically, the TCDDM composition of the present invention has excellent crystallinity by appropriately selecting the isomer ratio. As a result, the wire drawing when the TCDDM composition is handled can be reduced, thereby improving production efficiency.

[0040] Furthermore, the ultraviolet curable composition synthesized using the TCDDM composition of the present invention as a raw material can be controlled to have a high viscosity without impairing the performance originally required of the ultraviolet curable composition, and therefore has excellent coating stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] [ Figure 1 ] Figure 1 This is a diagram showing a gas chromatogram of the TCDDM composition obtained in Example 3. DETAILED DESCRIPTION

[0042] The present invention will be described in detail below. The present invention is not limited to the following description, and can be implemented in any modified form without departing from the gist of the present invention.

[0043] Unless otherwise specified, the numerical range expressed using "to" in the present specification means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit. "A to B" means A or more and B or less.

[0044] <TCDDM composition>

[0045] The TCDDM composition of the present invention is a composition containing tricyclodecane dimethanols.

[0046] The tricyclodecane dimethanols are a mixture of a chiral compound A in which one mirror image isomer is represented by the following formula (I), a chiral compound B in which one mirror image isomer is represented by the following formula (II), and a chiral compound C in which one mirror image isomer is represented by the following formula (III).

[0047] The chiral compounds A, B and C are represented by the following general formulae (I) to (III), and have one hydroxymethyl group (CH2OH group) in the six-membered ring portion of the norbornane ring and another hydroxymethyl group in the five-membered ring portion.

[0048] [Chemistry 2]

[0049]

[0050] More specifically, the tricyclodecane dimethanols in the present invention include: a chiral compound A, which includes a compound represented by the following formula (I) and a compound represented by the following formula (IA) which is a mirror image isomer of the compound; a chiral compound B, which includes a compound represented by the following formula (II) and a compound represented by the following formula (IIA) which is a mirror image isomer of the compound; and a chiral compound C, which includes a compound represented by the following formula (III) and a compound represented by the following formula (IIIA) which is a mirror image isomer of the compound.

[0051] [Chemistry 3]

[0052]

[0053] Thus, the chiral compound A, the chiral compound B, and the chiral compound C in the present invention exist as mirror image isomers (also called optical isomers) in the form of R and S, but both are included regardless of their differences.

[0054] In addition, regarding the chiral compound A, the chiral compound B and the chiral compound C in the present invention, there are stereoisomers depending on whether the two hydroxymethyl groups are bonded to the same side as the bridgehead position of the norbornane ring or to the opposite side, and as shown in formula (I) to formula (III) or formula (IA) to formula (IIIA), compounds having hydroxymethyl groups bonded to the same side as the bridgehead position of the norbornane ring are shown. Furthermore, there are endo and exo forms in the tricyclodecane skeleton, but the chiral compound A, the chiral compound B and the chiral compound C in the present invention only show the endo form.

[0055] Compounds having a hydroxymethyl group bonded to the side opposite to the bridgehead position and compounds having a tricyclodecane skeleton in an exo form may or may not be included in the tricyclodecane dimethanols as other components, but the "total peak area Xt of the gas chromatogram of tricyclodecane dimethanols" includes the peak areas of these compounds.

[0056] Hereinafter, “chiral compound A”, “chiral compound B”, and “chiral compound C” may be abbreviated as “compound A”, “compound B”, and “compound C”, respectively.

[0057] In the TCDDM composition of the present invention, from the viewpoint of the handleability of the composition, the lower limit of Xc / Xt calculated from the peak area Xc of the gas chromatogram of the chiral compound C detected by gas chromatography and the total peak area Xt of the gas chromatogram of the tricyclodecane dimethanol is Xc / Xt≥0.35. This ratio is preferably Xc / Xt≥0.38, and more preferably Xc / Xt≥0.42. On the other hand, the upper limit of the above-mentioned Xc / Xt is not particularly limited, but from the viewpoint of being able to well maintain the handleability of the composition, it is generally preferably Xc / Xt≤0.55, and more preferably Xc / Xt≤0.50.

[0058] The method for controlling the value of Xc / Xt is not particularly limited, and those skilled in the art can control the value of Xc / Xt by optimizing the manufacturing conditions according to known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is distilled and purified, etc. can be optimized to control the value of Xc / Xt.

[0059] In the TCDDM composition of the present invention, from the viewpoint of the handleability of the composition, the lower limit of Xc / Xb calculated from the peak area Xb of the gas chromatogram of the compound B detected by gas chromatography and the above Xc is preferably Xc / Xb≥1.00, more preferably Xc / Xb≥1.25, and further preferably Xc / Xb≥1.50. On the other hand, the upper limit of the above Xc / Xb is not particularly limited, but from the viewpoint of being able to well maintain the handleability of the composition, it is generally preferably Xc / Xb≤3.0, and more preferably Xc / Xb≤2.0.

[0060] The method for controlling the value of Xc / Xb is not particularly limited, and those skilled in the art can control the value by optimizing the manufacturing conditions according to known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is distilled and purified, etc. can be optimized to control the value of Xc / Xb.

[0061] In the TCDDM composition of the present invention, from the viewpoint of the handleability of the composition, the lower limit of Xc / (Xa+Xb) calculated from the peak area Xa of the gas chromatogram of compound A detected by gas chromatography, the above Xb and the above Xc is preferably Xc / (Xa+Xb)≥0.60, more preferably Xc / (Xa+Xb)≥0.70, and further preferably Xc / (Xa+Xb)≥0.80. On the other hand, the upper limit of the above Xc / (Xa+Xb) is not particularly limited, but from the viewpoint of being able to well maintain the handleability of the composition, it is generally preferably Xc / (Xa+Xb)≤1.10, and more preferably Xc / (Xa+Xb)≤1.00.

[0062] The method for controlling the value of Xc / (Xa+Xb) is not particularly limited, and a person skilled in the art can control the value by appropriately optimizing the production conditions according to a known technique.

[0063] For example, the value of Xc / (Xa+Xb) can be controlled by optimizing the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is purified by distillation, and the like.

[0064] In the TCDDM composition of the present invention, from the viewpoint of the handleability of the composition, the upper limit of Xa / Xt calculated from the above Xa and the above Xt is preferably Xa / Xt≤0.27, and more preferably Xa / Xt≤0.23. On the other hand, the lower limit of the above Xa / Xt is not particularly limited, but from the viewpoint of being able to well maintain the handleability of the composition, it is generally preferably Xa / Xt≥0.18, and more preferably Xa / Xt≥0.20.

[0065] The method for controlling the value of Xa / Xt is not particularly limited, and those skilled in the art can control the value of Xa / Xt by optimizing the manufacturing conditions according to known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is distilled and purified, etc. can be optimized to control the value of Xa / Xt.

[0066] In the TCDDM composition of the present invention, from the viewpoint of the handleability of the composition, the upper limit of Xb / Xt calculated from the above Xb and the above Xt is preferably Xb / Xt≤0.32, more preferably Xb / Xt≤0.30, and further preferably Xb / Xt≤0.28. On the other hand, the lower limit of the above Xb / Xt is not particularly limited, but from the viewpoint of being able to well maintain the handleability of the composition, it is generally preferably Xb / Xt≥0.22, and more preferably Xb / Xt≥0.24.

[0067] The method for controlling the value of Xb / Xt is not particularly limited, and those skilled in the art can control the value of Xb / Xt by optimizing the manufacturing conditions according to known techniques. For example, the reaction conditions of hydroformylation, the distillation conditions when the obtained TCDDM composition is distilled and purified, etc. can be optimized to control the value of Xb / Xt.

[0068] The purity of the TCDDM composition in the present invention is not particularly limited as long as it satisfies the above-mentioned Xc / Xt value, etc., and the purity may be increased by purification, etc., and may contain impurities other than TCDDM.

[0069] In the TCDDM composition of the present invention, the lower limit of the content ratio of tricyclodecane dimethanols is not particularly limited. From the viewpoint of the handleability of the composition, it is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more relative to the total mass 100% by mass of the TCDDM composition. On the other hand, the upper limit of the above-mentioned content ratio is not particularly limited, and the higher the better, and it can be 100% by mass relative to the total mass of the composition.

[0070] In the TCDDM composition of the present invention, the lower limit of the total content ratio of chiral compound A, chiral compound B and chiral compound C is not particularly limited, but from the viewpoint of the handleability of the composition, relative to the total mass 100 mass %, preferably 80 mass % or more, more preferably 90 mass % or more, and further preferably 95 mass % or more. On the other hand, the upper limit of the above-mentioned total content ratio is not particularly limited, the higher the better, and relative to the total mass of the composition, it can be 100 mass %.

[0071] <Method for producing TCDDM composition>

[0072] The method for producing the TCDDM composition is not particularly limited, and as one embodiment, the method for producing the TCDDM composition of the present invention can be used.

[0073] The method for producing the TCDDM composition of the present invention is a method for producing the composition comprising the following steps: a step of hydroformylating dicyclopentadiene to obtain tricyclodecane dicarboxaldehyde; a step of obtaining a crude reaction liquid containing tricyclodecane dimethanol by a reduction reaction of the tricyclodecane dicarboxaldehyde; and a step of distilling and refining the crude reaction liquid to obtain a tricyclodecane dimethanol composition.

[0074] At this time, isomers are generated in the step of introducing a formyl group by hydroformylation, so tricyclodecane dicarboxaldehydes that are precursors of chiral compound A, chiral compound B, and chiral compound C are obtained as a mixture. Then, chiral compound A, chiral compound B, and chiral compound C are obtained by hydrogenation.

[0075] There is no particular limitation on the method for controlling the ratio of chiral compound A, chiral compound B, and chiral compound C of the present invention. The ratio can be controlled by adjusting the reaction conditions of hydroformylation, isomerization can be achieved by heating, etc., or the ratio can be adjusted by distilling and refining the manufactured TCDDM composition.

[0076] <Hydroformylation of dicyclopentadiene>

[0077] The method for hydroformylating dicyclopentadiene is not particularly limited and can be carried out according to a conventional method.

[0078] For example, according to the method described in Japanese Patent Application Laid-Open No. 2001-10999, dicyclopentadiene can be hydroformylated using hydrogen and carbon monoxide in a hydroformylation reaction solvent containing a hydrocarbon compound in the presence of a catalyst containing a rhodium compound and an organic phosphorus compound as shown in the following reaction formula (IV) to produce tricyclodecane dicarboxaldehyde.

[0079] [Chemistry 4]

[0080]

[0081] The rhodium compound used in the hydroformylation step is not limited to the form of its precursor as long as it forms a complex with an organic phosphorus compound and exhibits hydroformylation activity in the presence of hydrogen and carbon monoxide. 12 、Rh6(CO) 16, Rh(NO3)3 and other catalyst precursor substances are introduced into the reaction mixture together with the organic phosphorus compound to form a catalytically active rhodium metal hydrogenated carbonyl phosphorus complex in the reaction vessel. The rhodium metal hydrogenated carbonyl phosphorus complex catalyst can also be prepared in advance and introduced into the reaction vessel.

[0082] In a preferred embodiment of the present invention, Rh(acac)(CO)2 is used as a rhodium precursor material, which is reacted with an organophosphorus compound in the presence of a solvent and then introduced into a reactor together with an excess of free organophosphorus compound to prepare a catalytically active rhodium-organophosphorus complex catalyst.

[0083] Examples of the organic phosphorus compound that forms a catalyst for the hydroformylation reaction with the rhodium compound include phosphites and phosphines.

[0084] Among them, the phosphite is preferably a phosphite of the general formula P(-OR 1 )(-OR 2 )(-OR 3 )(where R 1 , R 2 and R 3 and (where R represents an aryl group or an alkyl group which may be substituted). 1 , R 2 and R 3 Specific examples include: aryl groups such as phenyl and naphthyl which may be substituted with methyl, ethyl, isopropyl, n-butyl, tert-butyl, methoxy, etc.; aliphatic alkyl groups such as methyl, ethyl, isopropyl, n-butyl, tert-butyl, etc.; alicyclic alkyl groups such as cyclopentyl and cyclohexyl which may be substituted with lower alkyl groups such as methyl, ethyl, isopropyl, n-butyl, tert-butyl, etc.

[0085] Specific examples of preferred phosphites include tris(2-tert-butylphenyl)phosphite, tris(3-methyl-6-tert-butylphenyl)phosphite, tris(3-methoxy-6-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, di(2-tert-butylphenyl) (tert-butyl)phosphite, etc., but are not limited thereto. These phosphites may be used alone or in combination of two or more.

[0086] As phosphine, alkyl phosphine with large steric hindrance is particularly effective for the hydroformylation reaction of dicyclopentadiene. Representative examples thereof include tricyclopropyl phosphine, tricyclobutyl phosphine, tricyclopentyl phosphine, tricyclohexyl phosphine, tricycloheptyl phosphine, tricyclooctyl phosphine, etc., but are not limited to these. These phosphines can be used alone or in combination of two or more.

[0087] Regarding the amount of the organic phosphorus compound used, if the organic phosphorus compound is present in the hydroformylation reaction liquid in an amount ranging from 1 to 400 times, preferably 3 to 200 times, the amount of the rhodium metal, tricyclodecane dicarboxaldehyde can be obtained at a sufficient hydroformylation reaction rate.

[0088] The hydroformylation reaction of dicyclopentadiene can be carried out without using a solvent, but can be carried out more preferably by using an inert organic solvent in the reaction.

[0089] As described later, after the hydroformylation reaction is completed, the reaction product liquid containing tricyclodecane dicarboxaldehyde is brought into contact with an alcohol, and the tricyclodecane dicarboxaldehyde is extracted into an extraction solvent layer containing alcohol while the catalyst component remains in the hydroformylation reaction solvent layer, and the layers are separated. Therefore, the hydroformylation reaction solvent is preferably a solvent that undergoes layer separation with the alcohol. Examples of such solvents include aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, and alicyclic hydrocarbon compounds.

[0090] As the aromatic hydrocarbon compound, benzene and methylbenzenes such as toluene, xylene, mesitylene, and pseudocumene; ethylbenzenes such as ethylbenzene, diethylbenzene, and triethylbenzene; propylbenzenes such as isopropylbenzene, 1,3-diisopropylbenzene, and 1,4-diisopropylbenzene; and various alkylbenzenes other than these can also be suitably used.

[0091] Examples of the aliphatic hydrocarbon compound include pentane, hexane, heptane, octane, isooctane, dodecane, and decane, but are not limited to these compounds as long as they are liquid at standard temperature and pressure.

[0092] As the alicyclic hydrocarbon compound, cyclohexane, cyclooctane, cyclododecane, decahydronaphthalene, methylcyclohexane, etc. can be preferably used.

[0093] These solvents may be used alone or in combination of two or more.

[0094] From the viewpoint of reaction efficiency, the solvent is preferably used so that the concentration of dicyclopentadiene in the reaction solution becomes about 10 to 95% by mass, particularly about 30 to 90% by mass.

[0095] The amount of the rhodium catalyst used is usually 10 to 5000 ppm by weight, more preferably 50 to 2000 ppm by weight, based on the dicyclopentadiene as a raw material, in terms of rhodium metal. When rhodium is used in an amount of 50 ppm by weight or more, recovery of the catalyst is required.

[0096] The temperature and pressure of the hydroformylation reaction of dicyclopentadiene are usually 40°C to 160°C, preferably 80°C to 140°C, and usually 1MPa to 15MPa. When the temperature is lower than 40°C, the reaction rate of the hydroformylation is slow. When the temperature is higher than 160°C, the dicyclopentadiene and hydroformylation reaction products in the reaction solution undergo side reactions, and the yield of the aldehyde is reduced. When the pressure is lower than 1MPa, the reaction rate of the hydroformylation is slow. When the pressure is higher than 15MPa, a high-pressure reaction device must be used, and the device cost becomes high.

[0097] The molar ratio of hydrogen to carbon monoxide in the hydrogen / carbon monoxide mixed gas used in the reaction can be selected from the range of 0.2 to 5.0 based on the introduced gas composition (hydrogen / carbon monoxide). If the hydrogen / carbon monoxide mixed gas deviates from this range, the reaction activity or aldehyde selectivity of the hydroformylation reaction decreases.

[0098] As a reaction mode of hydroformylation, a continuous feeding mode can be adopted, wherein the continuous feeding mode is carried out while supplying dicyclopentadiene as a raw material alone or in the form of a mixed solution of dicyclopentadiene and a solvent to a reactor in the presence of a rhodium-organophosphorus complex catalyst, a solvent and a hydrogen / carbon monoxide mixed gas. If this method is used, the situation in which dicyclopentadiene is thermally decomposed in the reactor to generate cyclopentadiene that hinders the hydroformylation reaction can be reduced, and a good reaction rate and yield can be maintained. In order to maintain the fluidity of dicyclopentadiene, it is preferably diluted with the above-mentioned solvent and supplied to the reactor at a temperature at which they do not depolymerize to generate cyclopentadiene.

[0099] <Extraction of tricyclodecane dicarboxaldehyde>

[0100] After the hydroformylation reaction is completed, the reaction product liquid is brought into contact with alcohol as it is or after being diluted with a hydrocarbon compound used as a hydroformylation reaction solvent or other hydrocarbon compound in the reaction, and tricyclodecane dicarboxaldehyde as a product is extracted into the alcohol while leaving the catalyst component in the hydroformylation reaction solvent layer, and the layers are separated.

[0101] Examples of the alcohol include primary alcohols having 1 to 3 carbon atoms and polyols having 2 to 6 carbon atoms.

[0102] Examples of the primary alcohol include methanol, ethanol and propanol.

[0103] As the polyol having 2 to 6 carbon atoms, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, isomers of pentanediol, neopentyl glycol, hexanediol, glycerol, pentaerythritol, trimethylolpropane and the like can be used.

[0104] Among them, methanol, ethylene glycol, propylene glycol, and butylene glycol have relatively low boiling points, are inexpensive, and are easy to handle as liquids, and therefore can be suitably used. These extraction solvents may be used alone or in combination of two or more.

[0105] Extraction can also be performed in the presence of water and alcohol. Adding water makes it easier for aldehydes and catalyst components to be distributed in each layer.

[0106] In order to achieve effective layer separation, the reaction solvent and the extraction solvent used in the hydroformylation reaction preferably have a difference in density. A preferred example of the combination of the hydroformylation reaction solvent containing tricyclodecane dicarboxaldehyde and the extraction solvent is a combination of methylcyclohexane as a reaction solvent and ethylene glycol as an extraction solvent, methylcyclohexane as a reaction solvent and methanol as an extraction solvent, and water.

[0107] The distribution of tricyclodecane dicarboxaldehyde between the hydroformylation reaction solvent and the extraction solvent is balanced. In contrast, the rhodium and the organic phosphorus compound as catalyst components are substantially present only in the hydroformylation reaction solvent and only in an amount below the analytical limit in the extraction solvent.

[0108] The volume ratio of the extraction solvent to the reaction product liquid used is determined by the solubility of tricyclodecane dicarboxaldehyde in the extraction solvent and the amount of tricyclodecane dicarboxaldehyde to be extracted. For example, when the tricyclodecane dicarboxaldehyde to be separated has a high solubility in the extraction solvent and is present in the reaction product liquid at a low concentration, the tricyclodecane dicarboxaldehyde can be practically extracted using an extraction solvent with a low volume ratio (extraction solvent / reaction product liquid).

[0109] The higher the concentration of the product, the higher the volume ratio (extraction solvent / reaction liquid) used to extract tricyclodecane dicarboxaldehyde from the reaction liquid.

[0110] When tricyclodecane dicarboxaldehyde has a low solubility in the extraction solution, the volume ratio (extraction solvent / reaction product liquid) can be varied in the range of 10:1 to 1:10. In addition, in order to increase the extraction amount of tricyclodecane dicarboxaldehyde with a small amount of extraction solvent, it is effective to divide the extraction solvent and perform multiple extraction operations. In addition, in the final stage of the extraction operation, a hydroformylation reaction solvent such as methylcyclohexane can be added in an amount of about 5 to 20% by mass relative to the reaction product liquid. By adding the hydroformylation reaction solvent, the removal rate of the catalyst can be improved.

[0111] The temperature for performing the extraction operation is not particularly limited, but it is practical to perform it below the hydroformylation reaction temperature. The extraction operation can be performed by adding an extraction solvent to the hydroformylation reactor after the reaction, or the hydroformylation reaction product liquid can be extracted from the hydroformylation reactor and the operation can be performed in an extraction tank. The extraction operation can also be performed by directly adding an extraction solvent to the hydroformylation reactor, and the next hydroformylation reaction can be performed while the catalyst component is maintained in the hydroformylation reactor. In the case where the hydroformylation reaction product liquid is extracted and the operation is performed in the extraction tank, the reaction solvent layer of the hydrocarbon compound containing the catalyst is returned to the hydroformylation reactor and used for the reaction again. This process can be performed as a batch process or a continuous process.

[0112] By the extraction operation as described above, a solution containing tricyclodecane dicarboxaldehyde of 10 to 90% by mass and an extraction solvent of 10 to 90% by mass can be obtained. When a reaction solvent is added, a solution containing tricyclodecane dicarboxaldehyde of 5 to 90% by mass, an extraction solvent of 5 to 90% by mass and a reaction solvent of 5 to 90% by mass can be obtained.

[0113] The alcohol in the extraction solvent reacts with a portion of tricyclodecane dicarboxaldehyde, which is a hydroformylation product, to produce an acetal compound in which tricyclodecane dicarboxaldehyde is acetalized.

[0114] The content of the acetal compound in tricyclodecane dicarboxaldehyde is generally about 0.1 to 50% by mass, and further about 1 to 25% by mass.

[0115] <Hydrogen reduction reaction>

[0116] The extract containing tricyclodecane dicarboxaldehyde (tricyclodecane dicarboxaldehyde-containing solution) obtained by the above extraction operation is then subjected to hydrogenation reduction in the presence of a hydrogenation catalyst, preferably a ruthenium (Ru) catalyst, to produce TCDDM as shown in the following reaction formula (V).

[0117] The above-mentioned hydrogenation reduction reaction is carried out in the presence of water and a Ru catalyst, thereby rapidly converting the acetal compound into tricyclodecane dicarboxaldehyde in the hydrogenation reaction of tricyclodecane dicarboxaldehyde. By hydrogenating the tricyclodecane dicarboxaldehyde converted from the acetal compound, TCDDM can be produced in high yield, which is preferred.

[0118] [Chemistry 5]

[0119]

[0120] The water present in the hydrogenation reduction reaction is preferably an amount equal to or greater than the amount of the acetal compound in the hydrogenation reduction reaction solution and the reaction solution does not undergo phase separation. The water content is preferably set to be 2% by mass or more, preferably 2 to 30% by mass, more preferably 5 to 25% by mass, and particularly 10 to 20% by mass relative to the entire reaction solution. When the water content is within the above range, water and the reaction solvent do not undergo phase separation, and the above-mentioned effect brought about by the presence of water in the hydrogenation reaction system can be effectively obtained. The addition of the water can be carried out in the extraction step of separating the catalyst component and tricyclodecane dicarboxaldehyde from the hydroformylation reaction product solution, or water can be added to the reaction system immediately before the hydrogenation reduction reaction.

[0121] As the reaction form, the following methods can be used as appropriate: a method in which the catalyst is charged in the form of slurry in a stirring reactor, the reaction is carried out in an intermittent manner, and the catalyst is filtered and separated from the product liquid after the reaction; a liquid filling type reaction in which the shaped catalyst is charged in a tubular reactor and the product liquid and hydrogen flow onto the catalyst. The amount of the catalyst used is not particularly limited as long as TCDDM can be produced at an industrially advantageous productivity.

[0122] The reaction temperature and pressure of the hydrogenation reduction reaction are usually 40 to 200° C., preferably 70 to 150° C., and the reaction pressure is usually 15 MPa or less. When the temperature is lower than 40° C., the hydrogenation reduction reaction rate is slow. When the temperature is higher than 200° C., a side reaction occurs by TCDDM, which is the target product, and the yield of TCDDM decreases. When the pressure is higher than 15 MPa, a high-pressure reaction device must be used, so the device cost becomes high.

[0123] <Removal of residual metal>

[0124] The crude reaction liquid obtained by the above-mentioned hydrogenation reduction reaction operation contains metal elements derived from the hydrogenation catalyst as eluted components. By removing the metal elements in the crude reaction liquid before distillation purification, thermal decomposition of TCDDM caused by the metal elements in the distillation purification step can be suppressed.

[0125] The method for removing the metal elements in the crude reaction liquid to reduce the content thereof is not particularly limited, and examples thereof include activated carbon treatment, cation exchange resin, silica gel adsorption, etc. Activated carbon treatment is preferred in view of removal efficiency and the ability to reuse the adsorbent.

[0126] The activated carbon treatment method may be an intermittent treatment in which activated carbon is added to the crude reaction liquid and stirred, followed by filtration to separate the activated carbon into a solid and liquid state, or a continuous treatment in which the crude reaction liquid is passed through a tower filled with activated carbon.

[0127] In the case of intermittent treatment, the amount of activated carbon added to the crude reaction solution can be appropriately determined according to the metal element adsorption capacity of the activated carbon, the metal element content ratio in the crude reaction solution, etc. As a general condition, it is preferred to add activated carbon in a concentration of about 0.01 to 10% by mass relative to the crude reaction solution and stir.

[0128] In the case of continuous treatment, the treatment flow rate is not particularly limited, and the treatment may be performed at a space velocity (LHSV) of 1 to 10.

[0129] Such activated carbon treatment may be performed multiple times. That is, the activated carbon-treated liquid obtained by subjecting the crude reaction liquid to the activated carbon treatment may be subjected to activated carbon treatment again. In this case, the type, amount, treatment conditions, etc. of activated carbon used in the first activated carbon treatment and the second activated carbon treatment may be changed.

[0130] From the viewpoint of suppressing the thermal decomposition of TCDDM, the metal element content of the crude reaction liquid subjected to distillation purification in the next step is as low as possible. The metal element content of the crude reaction liquid subjected to distillation purification is preferably set to 10 mass ppm or less, particularly 5 mass ppm or less, and especially 1 mass ppm or less.

[0131] The pH of the crude reaction liquid subjected to distillation purification is preferably in the range of 6 to 8. If the lower limit of the pH is 6 or more, the by-production of low-boiling point compounds believed to be caused by dehydration of TCDDM and the by-production of high-boiling point compounds believed to be caused by dimerization such as etherification can be suppressed, so it is preferred. If the upper limit of the pH is 8 or less, the distillation purification equipment is less susceptible to alkali corrosion, so it is preferred.

[0132] Generally, the pH of the reaction product liquid obtained by the hydrogenation reduction reaction is 6 to 8, and even if it is subjected to a hydrogenation catalyst removal treatment or a metal element removal treatment, the pH hardly changes, but the pH may deviate from the range of 6 to 8 due to acid or alkaline components eluted from the hydrogenation catalyst. In this case, it is preferred to appropriately add a pH adjuster such as an acid or an alkali to adjust the pH to 6 to 8.

[0133] <Distillation>

[0134] The crude reaction liquid with reduced metal element content is then subjected to distillation purification.

[0135] The above-mentioned distillation purification is preferably carried out using a distillation column having 10 to 30 theoretical stages and a bottom temperature of the distillation column within a range of 150 to 250°C.

[0136] If the theoretical number of stages of the distillation column used in the distillation purification is 10 or more, impurities and products can be easily separated. If the theoretical number of stages is 30 or less, the pressure difference between the top and the bottom of the column is small, the temperature of the bottom of the column becomes low, and the heat load of the device becomes small. The more preferred theoretical number of stages is 15 to 30.

[0137] When the column bottom temperature is 150°C or higher, TCDDM can be volatilized, and when it is 250°C or lower, by-production of high boiling point impurities due to dimerization of TCDDM can be suppressed. A more preferred column bottom temperature is 160 to 230°C.

[0138] There are no particular restrictions on other conditions of the distillation tower in the distillation purification, and the distillation is usually carried out at a pressure of 0.1 to 100 kPa and a reflux ratio of about 1 to 30. In particular, by controlling the reflux ratio and the distillate amount, the existence ratio of the chiral compound A, the chiral compound B, and the chiral compound C in the obtained TCDDM composition can be adjusted. The conditions can be arbitrarily changed according to the equipment performance of the distillation tower, the kettle efficiency, the recovery amount, etc., and there are no particular restrictions as long as the TCDDM composition of the composition specified in the present invention can be obtained.

[0139] The bottom liquid of the distillation column obtained by such distillation purification can be further subjected to simple distillation at 0.1 to 10 kPa and 140 to 250° C. Such distillation purification can generally obtain a TCDDM composition having a TCDDM purity of 98% or more at a high yield.

[0140] <Ultraviolet curable composition>

[0141] The ultraviolet curable composition of the present invention is an ultraviolet curable composition derived from the TCDDM composition of the present invention.

[0142] More specifically, the ultraviolet curable composition of the present invention is a UV curable composition synthesized using the TCDDM composition of the present invention as a raw material. More specifically, the ultraviolet curable composition of the present invention is a UV curable composition synthesized using the tricyclodecane dimethanols contained in the TCDDM composition of the present invention as a raw material.

[0143] The method for producing the ultraviolet curable composition is not particularly limited and can be carried out according to a conventional method. Generally, it is desirable to use the tricyclodecane dimethanols in the TCDDM composition as a raw material and as a derivative such as a di(meth)acrylate derivative or a urethane acrylate.

[0144] Both hydroxyl groups of the tricyclodecane dimethanols contained in the TCDDM composition may be used for the reaction, or one of the hydroxyl groups may be reacted and the other hydroxyl group may remain. In this case, the remaining hydroxyl group may be appropriately converted into a functional group suitable for the application by organic synthesis techniques.

[0145] Specific examples of methods for producing di(meth)acrylate derivatives from TCDDM using a TCDDM composition as a raw material include a method of reacting (meth)acrylic acid with TCDDM, a method of subjecting TCDDM to an ester exchange reaction with a (meth)acrylic ester, and a method of reacting a (meth)acrylic acid halide such as (meth)acryloyl chloride with TCDDM.

[0146] The reaction conditions and the like in each of the above-mentioned production methods are as follows.

[0147] When (meth)acrylic acid or (meth)acrylic acid ester is used to produce a di(meth)acrylic acid ester derivative, the reaction can be accelerated by using a catalyst and continuously removing the generated water or lower alcohol to the outside of the system.

[0148] As the above-mentioned catalyst, for example, known catalysts as esterification catalysts such as sulfuric acid, p-toluenesulfonic acid, boron trifluoride, and organotin compounds can be listed, and any catalyst selected from these can be used. From the perspective of reducing the load on the manufacturing device and reducing the catalyst cost, the amount of the catalyst used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrate.

[0149] When a (meth)acrylic acid halide is used to produce a di(meth)acrylate derivative, the reaction is preferably carried out in the presence of a basic compound, and a catalyst may be used to accelerate the reaction.

[0150] Examples of the alkaline compound include tertiary amines such as triethylamine and N-ethyldiisopropylamine; phosphates such as potassium phosphate and sodium phosphate; carbonates such as potassium carbonate and sodium carbonate; hydroxides such as potassium hydroxide and sodium hydroxide, and other compounds known as alkaline compounds, which can be selected and used. The amount of the alkaline compound used is preferably 1.0 to 6.0 equivalents relative to 1 equivalent of the halide of acrylic acid or methacrylic acid from the perspective of reducing the load on the manufacturing device and reducing the cost of raw materials.

[0151] As the above-mentioned catalyst, for example, known catalysts for esterification reaction of acid chlorides such as pyridines such as N,N-dimethyl-4-aminopyridine, imidazoles such as N-methylimidazole, and tertiary amines such as triethylenediamine can be listed, and any catalyst can be selected from these for use. From the perspective of reducing the load on the manufacturing device and reducing the catalyst cost, the amount of the catalyst used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrate.

[0152] In each of the above production methods, a polymerization inhibitor is preferably added to prevent thermal polymerization of (meth)acrylic acid, (meth)acrylic acid ester, or (meth)acrylic acid halide.

[0153] Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, copper salts, phenothiazine, p-phenylenediamine, phenyl-β-naphthylamine, etc. From the perspective of reducing the influence on catalytic activity and side reactions, the amount of the polymerization inhibitor used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrate.

[0154] The reaction temperature in each of the above-mentioned production methods is preferably -20 to 120° C., more preferably 0 to 100° C., from the viewpoint of shortening the reaction time and preventing polymerization. The reaction time is preferably 1 to 20 hours.

[0155] A solvent may be used in the reaction in each of the above-mentioned production methods.

[0156] The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, and cyclooctane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, and dioxane; ketones such as methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate; nitriles such as acetonitrile; acyclic or cyclic amides such as dimethylformamide and N-methylpyrrolidone; acyclic or cyclic sulfoxides or sulfones such as dimethyl sulfoxide; etc. These solvents may be used alone or in combination of two or more.

[0157] The structure of the urethane acrylate made from the TCDDM composition is not particularly limited as long as it is an acrylic acid or methacrylic acid ester derivative containing a urethane bond.

[0158] As a method for manufacturing urethane acrylate from TCDDM using TCDDM as a raw material, specifically, it is desirable to react the TCDDM composition, a polyisocyanate compound and a monohydroxy acrylate compound in the presence of a catalyst. In addition, for the purpose of adjusting the performance of the cured product, a polyol compound other than the TCDDM composition may also be further added.

[0159] From the viewpoint of the hardness and heat resistance of the cured product, the content of the TCDDM composition is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more relative to the total mass of the reaction matrix as the urethane acrylate raw material. On the other hand, the upper limit of the above-mentioned content is not particularly limited, and the higher the better.

[0160] As the above-mentioned polyisocyanate compound, for example, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, norbornene methane diisocyanate and their hydride, pentamethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, etc. can be listed. Their ureate bodies, adducts, biuret bodies can be used, and dimers and trimers can also be used. They can be used alone or in combination of two or more.

[0161] In the monohydroxy acrylate compound, the structural site where the hydroxyl group and the acryloyloxy group are bonded is preferably composed of three or more carbon atoms. Examples of such compounds include acrylate compounds of aliphatic polyols having 3 or more carbon atoms, such as hydroxypropyl acrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, di-trimethylolpropane triacrylate, and dipentaerythritol pentaacrylate; (poly)oxyalkylene modified products having (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into the molecular structure of the above acrylate compounds; lactone modified products having (poly)lactone structures introduced into the molecular structure of the above acrylate compounds; isocyanuric acid diacrylate; (poly)oxyalkylene modified products having (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains introduced into the molecular structure of isocyanuric acid diacrylate; and lactone modified products having (poly)lactone structures introduced into the molecular structure of isocyanuric acid diacrylate. In addition, a methacrylate compound obtained by replacing the acrylate in the above compound group with a methacrylate may be used. These may be used alone or in combination of two or more.

[0162] Examples of polyol compounds other than the TCDDM composition include straight-chain diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, and 1,6-hexanediol; and branched diols such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and dimer diol. Chain diols, diols having an ether group such as diethylene glycol and propylene glycol, diols having an alicyclic structure such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, diols having an aromatic group such as xylene glycol, 1,4-dihydroxyethylbenzene, 4,4'-methylenebis(hydroxyethylbenzene), polyols such as glycerol, trimethylolpropane, pentaerythritol, polyether polyols, polyester polyols, polycarbonate polyols, etc. These polyol compounds may be used alone or in combination of two or more.

[0163] Examples of the catalyst include organic tin compounds such as dibutyltin dilaurate, trimethyltin hydroxide, and tetra-n-butyltin; organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate; metal salts such as zinc octylate, tin octylate, cobalt naphthenate, stannous chloride, and tin chloride; and amine catalysts such as triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N',N'-tetramethyl-1,3-butanediamine, and N-ethylmorpholine.

[0164] In order to prevent thermal polymerization of the monohydroxyacrylate compound or the like, it is preferred to add a polymerization inhibitor.

[0165] The above-mentioned polymerization inhibitor is not particularly limited as long as it does not hinder the reaction, and examples thereof include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, copper salts, phenothiazine, p-phenylenediamine, phenyl-β-naphthylamine, etc. From the perspective of reducing the influence on catalytic activity and side reactions, the amount of the polymerization inhibitor used is preferably 10 to 100,000 ppm relative to the total mass of the reaction substrate.

[0166] The reaction temperature in the above production method is preferably 30 to 120° C., more preferably 40 to 100° C., from the viewpoint of shortening the reaction time and preventing polymerization. The reaction time is preferably 1 to 10 hours.

[0167] A solvent may be used in the reaction in each of the above-mentioned production methods.

[0168] The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; aliphatic hydrocarbons such as heptane, octane, nonane, decane, cyclohexane, and cyclooctane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, and trifluoromethylbenzene; ethers such as diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, and dioxane; ketones such as methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate; nitriles such as acetonitrile; acyclic or cyclic amides such as dimethylformamide and N-methylpyrrolidone; acyclic or cyclic sulfoxides or sulfones such as dimethyl sulfoxide; etc. These solvents may be used alone or in combination of two or more.

[0169] The ultraviolet curable composition of the present invention is synthesized using the TCDDM composition of the present invention as a raw material, and therefore can be controlled to be high viscosity without damaging the performance originally required by the ultraviolet curable composition, and has excellent coating stability. Therefore, the ultraviolet curable composition of the present invention can be suitably used for hard coating materials, antifouling coating materials, resist materials, inkjet inks, 3D printer materials, etc.

[0170] In applications such as resists, a method is used in which the above-mentioned ultraviolet curable composition is applied to a substrate by screen printing or flexographic printing and then cured. From the viewpoints of being able to apply the composition thinly and evenly, being able to apply the composition in a thick deposit, and being able to print fine patterns on the substrate with high precision, the ultraviolet curable composition is required to have a high viscosity.

[0171] In applications such as inkjet printing of hard coatings and antifouling coatings, a method of applying the above-mentioned ultraviolet curable composition on a substrate by a coater method, a sprayer method, or a dispenser method and curing the composition is used. From the viewpoint of accurately and quantitatively ejecting the ultraviolet curable composition, a high viscosity is required for the ultraviolet curable composition.

[0172] As mentioned above, the ultraviolet curable composition of the present invention is derived from the TCDDM composition, and the above-mentioned TCDDM composition is mainly composed of three different mirror image isomers of the bonding position of the hydroxymethyl group, and the crystallinity is adjusted by appropriately controlling the isomer ratio, and it is not easy to draw and the handling property is excellent. Therefore, the ultraviolet curable composition of the present invention becomes high viscosity, and the coating stability and the coating stability are excellent. Further, since it is not necessary to coordinate the viscosity increaser for high viscosity, there is no problem that the performance required by the ultraviolet curable composition is impaired. Due to these situations, the ultraviolet curable composition of the present invention can be suitably used for the purposes of hard coating materials, antifouling coating materials, resist materials, inkjet inks and 3D printer materials.

[0173] <Polymer composition>

[0174] The polymer composition of the present invention is a polymer composition derived from the TCDDM composition of the present invention, or a polymer composition derived from the ultraviolet curable composition of the present invention.

[0175] More specifically, the polymer composition of the present invention is a composition obtained by polymerizing the TCDDM composition of the present invention or a composition containing the TCDDM composition, and contains a polymer containing a structural unit derived from tricyclodecane dimethanol in the TCDDM composition. Alternatively, the polymer composition of the present invention is a composition containing a polymer obtained by polymerizing the ultraviolet curable composition of the present invention.

[0176] One embodiment of the polymer composition of the present invention may be the polymer composition itself, or a composition obtained by adding or removing a solvent such as water or an organic solvent in an appropriate amount in order to further adjust the solid content concentration, or a composition obtained by removing the solvent and drying to form a solid substance. It may also be a polymer composition obtained by further removing impurities and refining from a composition containing a polymer obtained by polymerization, or a composition obtained by further adding appropriate additives such as a storage stabilizer (ultraviolet absorber, antioxidant, etc.), a colorant, an antistatic agent, a lubricant, a filler, a flame retardant, a foaming agent, etc. as needed within a range that does not affect the performance of the above-mentioned polymer obtained by polymerization.

[0177] That is, the polymer composition of the present invention may contain a polymer obtained by polymerizing the TCDDM composition of the present invention or the ultraviolet curable composition of the present invention, and its form, component composition, etc. are not particularly limited.

[0178] As another embodiment of the polymer composition, specifically, at least one selected from the group consisting of polyester resins, epoxy resins, acrylate resins, polycarbonate resins, and polyurethane resins can be cited.

[0179] In the present invention, the polyester resin refers to a resin having polyethylene polymers such as polyethylene terephthalate (PET) as a main component. The polyethylene polymer is not particularly limited, and for example, refers to a polymer containing structural units derived from a polyol mainly composed of diols and structural units derived from terephthalic acid compounds, and containing structural units derived from tricyclodecane dimethanols in the TCDDM composition of the present invention.

[0180] In the present invention, the epoxy resin refers to a resin having an epoxy polymer as a main component. The epoxy polymer is not particularly limited, and examples thereof include a polymer containing a structural unit derived from a bisphenol compound and a structural unit derived from epichlorohydrin, and containing a structural unit derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0181] In the present invention, the acrylic resin refers to a resin having an acrylic polymer as a main component. The acrylic polymer is not particularly limited, and examples thereof include a polymer containing a structural unit derived from (meth) acrylic acid or a structural unit derived from a (meth) acrylic acid derivative, and containing a structural unit derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0182] In the present invention, the polycarbonate resin refers to a resin having a polycarbonate polymer as a main component. The polycarbonate polymer is not particularly limited, and examples thereof include a polymer containing a structural unit derived from a bisphenol compound, a structural unit derived from phosgene (phosgene) or a structural unit derived from diphenyl carbonate and a structural unit derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0183] In the present invention, the polyurethane resin refers to a resin having a polyurethane polymer as a main component. The polyurethane polymer is not particularly limited, and examples thereof include a polymer containing a structural unit derived from a polyol mainly composed of a diol and a structural unit derived from a difunctional isocyanate, and containing a structural unit derived from tricyclodecane dimethanol in the TCDDM composition of the present invention.

[0184] Example

[0185] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0186] The compounds used in Examples and Comparative Examples are as follows.

[0187] ·Dicyclopentadiene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0188] · Rhodium dicarbonyl acetylacetonate (manufactured by NE Chemcat Co., Ltd.)

[0189] ·Tris(2,4-di-tert-butylphenyl)phosphite (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0190] ·Methylcyclohexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0191] Ruthenium-supported carbon (dry basis Ru content 5%, water content 56%) (trade name: Ru / C, manufactured by NE Chemcat Co., Ltd.)

[0192] · Powdered activated carbon (trade name: Special Egret, manufactured by Osaka Gas Chemical Co., Ltd.)

[0193] Evaluations in Examples and Comparative Examples were performed by the following methods.

[0194] <Determination of Xa, Xb, Xc and Xt>

[0195] For the TCDDM compositions obtained in the examples and comparative examples, gas chromatography was used to calculate the peak area Xa of chiral compound A, the peak area Xb of chiral compound B, the peak area Xc of chiral compound C, and the total peak area Xt of TCDDM by the following steps.

[0196] (Gas chromatography analysis conditions)

[0197] Measuring device: GC-2025 (manufactured by Shimadzu Corporation)

[0198] Carrier gas: Helium, linear velocity 30cm / sec

[0199] Column: DB-1 (manufactured by Agilent Technologies, length 30 m × inner diameter 0.25 mm × film thickness 1.00 μm)

[0200] Temperature (heating conditions): 160°C → 5°C / min → 300°C (holding time 2 minutes)

[0201] Inlet temperature: 200℃

[0202] Ion source temperature: 300°C

[0203] Sample volume: 0.3 μL

[0204] Split ratio: 1:30

[0205] Detector: FID

[0206] The gas chromatogram of the TCDDM composition obtained in Example 3 described below is shown in Figure 1 .

[0207] The peak ("peak 1") with the dissolution time between 14.88 minutes and 15.03 minutes and labeled (1) is the peak of the chiral compound A in the TCDDM composition.

[0208] The peak ("peak 2") with the dissolution time between 15.03 minutes and 15.18 minutes and labeled (2) is the peak of the chiral compound B in the TCDDM composition.

[0209] The peak ("peak 3") with the dissolution time between 15.38 minutes and 15.56 minutes and labeled (3) is the peak of the chiral compound C in the TCDDM composition.

[0210] Small peaks without labels are peaks of other TCDDM isomers.

[0211] The peak area Xa, the peak area Xb, the peak area Xc, and the peak area Xt are determined according to the following procedure.

[0212] For the obtained gas chromatogram, the area between the base line and the gas chromatogram curve within the range of elution time 14.88 to 15.90 minutes was defined as Xt.

[0213] For the obtained gas chromatogram, the area between the base line and the gas chromatogram curve within the range of elution time 14.88 to 15.03 minutes was defined as Xa.

[0214] For the obtained gas chromatogram, the area between the base line and the gas chromatogram curve within the range of elution time 15.03 to 15.18 minutes was defined as Xb.

[0215] For the obtained gas chromatogram, the area between the base line and the gas chromatogram curve within the range of elution time 15.38 to 15.56 minutes was defined as Xc.

[0216] <Quality Analysis of TCDDM Composition>

[0217] The m / z and fragment pattern of the TCDDM compositions obtained in Examples and Comparative Examples were measured by gas chromatography-mass spectrometry according to the following procedures.

[0218] (Gas chromatography mass analysis conditions)

[0219] Measuring device: GCMS-QP2010Ultra (manufactured by Shimadzu Corporation)

[0220] Carrier gas: Helium, linear velocity 40 cm / sec

[0221] Column: BPX-5 (manufactured by Trajan Scientific and Medical, length 60 m × inner diameter 0.32 mm × film thickness 0.25 μm)

[0222] Temperature (heating conditions): 160°C → 5°C / min → 300°C (holding time 2 minutes)

[0223] Vaporization chamber temperature: 200℃

[0224] Ion source temperature: 250°C

[0225] MS interface temperature: 300°C

[0226] Injection volume: 0.5 μL

[0227] Split ratio: 1:30

[0228] <Evaluation of handling performance>

[0229] As an index of the handling properties of the TCDDM compositions obtained in Examples and Comparative Examples, the stringiness when the tip of a glass rod was immersed 10 mm in a test solution at room temperature (20° C.) and then lifted 10 cm was evaluated according to the following criteria.

[0230] (Judgment Criteria)

[0231] A: No stringiness was observed.

[0232] B: Stringiness was exhibited, but the string broke immediately.

[0233] C: Stringiness is exhibited, and the string remains without being broken.

[0234] [Reference Example 1]

[0235] <Hydroformylation reaction>

[0236] In a 20L autoclave reactor, 2.51g of Rh(acac)(CO)2 and 188.6g of tri(2,4-di-tert-butylphenyl)phosphite as raw material compounds of a hydroformylation reaction catalyst were weighed under a nitrogen atmosphere, and 3.9kg of methylcyclohexane as an organic solvent was added, and the temperature of the reaction liquid in the reactor was raised to 70°C while stirring at 120rpm. Then, a mixed gas of hydrogen and carbon monoxide (hydrogen: carbon monoxide = 1:1 (molar ratio)) was quickly introduced through a gas introduction valve so that the pressure in the reactor became 5MPaG. While maintaining this pressure, the temperature of the reaction liquid was raised to 100°C, and 4.9kg of dicyclopentadiene as a raw material compound was further fed over 5 hours, and the mixture was further reacted for 3 hours. During the reaction, the mixed gas was continuously introduced into the reactor in an amount consumed by the reaction while the pressure in the reactor was maintained at 5MPaG.

[0237] After the reaction was completed, the reaction liquid in the reactor was cooled to room temperature, and the residual gas in the reactor was released to obtain 12.5 kg of hydroformylation reaction product liquid. The amount of dicyclopentadiene as a raw material compound contained in the reaction liquid before the reaction and the amount of tricyclodecane dicarboxaldehyde as a product in the reaction product liquid after the reaction were analyzed by gas chromatography to determine the yield of tricyclodecane dicarboxaldehyde. The yield was 99%.

[0238] <Extraction operation>

[0239] 3.77 kg of methanol and 2.0 kg of water were added to 12.5 kg of the obtained hydroformylation reaction product liquid, and the mixture was stirred for 30 minutes under a nitrogen atmosphere. Then, the mixture was allowed to stand for 30 minutes to separate into two phases and perform an extraction operation. 0.4 kg of methylcyclohexane was added to the obtained lower phase (a1), and the mixture was stirred for 30 minutes. Then, the mixture was allowed to stand for 30 minutes to separate into two phases and perform an extraction operation, thereby obtaining 13.8 kg of the lower phase (a2).

[0240] The composition of the obtained lower phase (a2) was analyzed by gas chromatography. The composition was 47% by mass of tricyclodecanedicarboxaldehyde, 27% by mass of methanol, 14% by mass of water, 7% by mass of methylcyclohexane, and 5% by mass of other components.

[0241] <Hydrogen reduction reaction>

[0242] In an autoclave reactor with a content of 20 L, 13.8 kg of the lower phase (a2) obtained by the above-mentioned extraction operation and 0.14 kg of ruthenium-supported carbon were loaded, and the temperature of the reaction solution in the reactor was raised to 160° C. while stirring at 120 rpm. Then, hydrogen was pressed into the reactor using a gas introduction valve so that the pressure in the reactor became 5 MPaG, and the reaction was carried out for 8 hours while maintaining the pressure and the temperature of the reaction solution. During the reaction, the mixed gas of the amount consumed by the reaction was continuously introduced into the reactor to maintain the pressure in the reactor at 5 MPaG.

[0243] After the reaction was completed, the reaction solution in the reactor was cooled to room temperature, and the residual gas in the reactor was released. The ruthenium-supported carbon was separated by filtering using a 5 μm filter to obtain 14.5 kg of the reaction product. The amount of tricyclodecane dicarboxaldehyde as a raw material compound contained in the reaction solution before the reaction and the amount of TCDDM as a product in the reaction product solution after the reaction were analyzed by gas chromatography. The yield of TCDDM was 94%.

[0244] The Ru concentration of the reaction product liquid analyzed by fluorescent X-ray analysis was 36 mass ppm, and the pH was 7.

[0245] [Example 1]

[0246] 1.90 kg of the hydrogenation reduction reaction product liquid obtained in Reference Example 1 was loaded into an intermittent distillation tower equivalent to 20 stages of regular packing, and 1.03 kg of light boiling components with the solvent as the main component were distilled off, and the TCDDM composition was distilled out at 0.4 kPa and 185 ° C, and recovered in the order of primary distillation and main distillation. As the main distillation, the recovered amount of the TCDDM composition was 0.36 kg. For the obtained TCDDM composition, the component ratios of chiral compound A, chiral compound B and chiral compound C, and the handleability were evaluated. The evaluation results are shown in Table 1.

[0247] [Example 2]

[0248] The hydroreduction reaction product liquid obtained in Reference Example 1 was subjected to simple distillation at 0.3 kPa and 210° C. to obtain a TCDDM composition. The obtained TCDDM composition was evaluated for the component ratio of chiral compound A, chiral compound B, and chiral compound C, and the handling properties. The evaluation results are shown in Table 1.

[0249] [Example 3]

[0250] Powdered activated carbon was added to 1.00 kg of the hydrogenation reduction reaction product solution obtained in Reference Example 1 so that the content concentration became 1% by mass, and stirred at room temperature for 3 hours. Then, the stirred reaction product solution was filtered to remove the powdered activated carbon, and 0.95 kg of activated carbon treatment solution was obtained. The Ru concentration of the activated carbon treatment solution analyzed by fluorescent X-ray analysis was 3.5 mass ppm.

[0251] 0.12 kg of the activated carbon treated liquid was charged into a batch distillation tower equivalent to 20 stages of structured packing, and after the solvent was distilled off, distillation was performed at 0.6 kPa, 185 ° C, and a reflux ratio of 30 until 17 g was distilled out. Further, 0.01 kg of the obtained bottom liquid was simply distilled at 0.3 kPa and 210 ° C to obtain 0.01 kg of TCDDM composition. The component ratios of chiral compound A, chiral compound B, and chiral compound C, and the handleability of the obtained TCDDM composition were evaluated. The evaluation results are shown in Table 1.

[0252] [Comparative Example 1]

[0253] The component ratios of chiral compound A, chiral compound B, and chiral compound C, and the handling properties of a commercially available TCDDM composition (1) (product name: TCD Alcohol DM, manufactured by OQ Chemicals) were evaluated.

[0254] [Comparative Example 2]

[0255] The component ratios of chiral compound A, chiral compound B, and chiral compound C, and the handling properties of a commercially available TCDDM composition (2) (manufactured by Tokyo Chemical Industry Co., Ltd.) were evaluated. The evaluation results are shown in Table 1.

[0256] [Comparative Example 3]

[0257] The component ratios of chiral compound A, chiral compound B, and chiral compound C, and the handling properties of a commercially available TCDDM composition (3) (manufactured by Merck) were evaluated. The evaluation results are shown in Table 1.

[0258] The TCDDM compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were subjected to gas chromatography mass spectrometry by the above method to measure m / z and fragment patterns. The results confirmed that Peaks 1 to 3 all showed m / z and fragment patterns equivalent to TCDDM.

[0259] Representative fragments observed are described below.

[0260] MS(EI): 178([M-18]+), 165, 147, 119, 105, 91, 81, 67

[0261] [Table 1]

[0262]

[0263] The TCDDM compositions obtained in Examples 1 to 3 have a high component ratio of the chiral compound C and excellent crystallinity as compositions, so they are less likely to cause stringing and have excellent handleability.

[0264] Since the TCDDM compositions of Comparative Examples 1 to 3 contained a low proportion of the chiral compound C, they were prone to stringing and had poor handling properties.

[0265] Although the present invention has been described in detail using specific embodiments, it will be apparent to one skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.

[0266] This application is based on Japanese patent application No. 2022-042785 filed on March 17, 2022, and the entire contents are incorporated herein by reference.

Claims

1. A tricyclodecane dimethanol composition, which is a composition comprising tricyclodecane dimethanols, The tricyclodecane dimethanols include a chiral compound A in which one mirror image isomer is represented by the following formula (I), a chiral compound B in which one mirror image isomer is represented by the following formula (II), and a chiral compound C in which one mirror image isomer is represented by the following formula (III). In the composition, the sum of the peak area Xc of the gas chromatogram of the chiral compound C and the peak area Xt of the gas chromatogram of the tricyclodecane dimethanols detected by gas chromatography satisfies Xc / Xt≥0.35, [Chemistry 1] 2. The tricyclodecane dimethanol composition according to claim 1, wherein The peak area Xb of the gas chromatogram of the chiral compound B detected by gas chromatography and the Xc satisfy Xc / Xb≥1.

00.

3. The tricyclodecane dimethanol composition according to claim 1, wherein The peak area Xa of the gas chromatogram of the chiral compound A detected by gas chromatography, the peak area Xb of the gas chromatogram of the chiral compound B, and Xc satisfy Xc / (Xa+Xb)≥0.

60.

4. The tricyclodecane dimethanol composition according to claim 1, wherein The peak area Xa of the gas chromatogram of the chiral compound A detected by gas chromatography and the Xt satisfy Xa / Xt≤0.

27.

5. The tricyclodecane dimethanol composition according to claim 1, wherein The peak area Xb of the gas chromatogram of the chiral compound B detected by gas chromatography and the Xt satisfy Xb / Xt≤0.

32. 6 . An ultraviolet curable composition derived from the tricyclodecane dimethanol composition according to claim 1 . 7 . The ultraviolet curable composition according to claim 6 , which is used for any one of a hard coating material, an antifouling coating material, a resist material, an inkjet ink, and a material for a 3D printer.

8. A polymer composition derived from the tricyclodecane dimethanol composition according to any one of claims 1 to 5. 9 . The polymer composition according to claim 8 , which is at least one selected from the group consisting of polyester resins, epoxy resins, acrylate resins, polycarbonate resins, and polyurethane resins.

10. A polymer composition derived from the ultraviolet curable composition according to claim 6.

11. The method for producing the tricyclodecane dimethanol composition according to any one of claims 1 to 5, comprising: The invention relates to a step of obtaining tricyclodecane dicarboxaldehydes by hydroformylating dicyclopentadiene; obtaining a crude reaction liquid containing tricyclodecane dimethanol by reducing the tricyclodecane dicarboxaldehydes; and obtaining a tricyclodecane dimethanol composition by distilling and purifying the crude reaction liquid.

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