Dye for dyeing polyolefin fibers using supercritical carbon dioxide

Abstract

The present invention addresses the problem of providing: a dye for dyeing a polyolefin fiber by using supercritical carbon dioxide, the dye being capable of dyeing a polyolefin fiber with a high concentration of yellow and yielding a dyed product having excellent color fastness to light, sublimation, washing, etc.; a dyeing method for dyeing a polyolefin fiber by using supercritical carbon dioxide; a polyolefin fiber dyed by said dyeing method; and a compound. Provided are: a dye for dyeing a polyolefin fiber by using supercritical carbon dioxide, the dye including at least one compound of formula (I); a dyeing method for dyeing a polyolefin fiber by using supercritical carbon dioxide; a polyolefin fiber dyed by said dyeing method; and a compound.

Description

[Technical field]

[0001] The present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, a method for dyeing polyolefin fibers using supercritical carbon dioxide, polyolefin fibers dyed by the dyeing method, and a compound. [Background technology]

[0002] Polyolefin resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins that have excellent properties such as low cost, ease of processability, high strength, high chemical resistance, high abrasion resistance, high bending resistance, light weight, low moisture absorption, low thermal conductivity, high antistatic properties, and recyclability.

[0003] On the other hand, polyolefin resins are polymeric compounds in which both the main chain and side chain are made of hydrocarbons, and because of these reasons, they have low affinity and compatibility with conventional dye compounds and do not have functional groups that are effective in chemical reactions, and for other reasons, it has been considered extremely difficult to dye them with high concentration and high fastness.

[0004] For this reason, most of the colored polyolefin resins currently on the market are made by adding colored pigments during the production stage of polymer pellets, etc., and then spinning and molding the resin into a desired shape.

[0005] This coloring method requires that the color be determined at an early stage of the resin product manufacturing process, and in order to be profitable, a certain amount of each color must be produced, which limits the freedom of color selection.

[0006] Furthermore, when changing the color of a resin product, a process is required to replace the colored resin of the previous color remaining in the resin product manufacturing equipment with colored resin of the next color, which generates a large amount of waste resin and causes problems such as wasting time and energy.

[0007] As described by Hiroshi Yamamoto in Sen-i-Gakkaishi Journal, 61 (2005), 319-321, polypropylene resin and polyethylene resin are one of the four major general-purpose synthetic resins, along with polyvinyl chloride resin and polystyrene resin, and are used in a wide range of fields.

[0008] However, the applications of polypropylene resin and polyethylene resin as synthetic fibers are very limited.

[0009] The reason for this is believed to be that, as mentioned above, it is extremely difficult to dye polypropylene resin fibers and polyethylene resin fibers with high concentration and high fastness, and the only effective coloring method, the dope coloring method using colored pigments, necessitates a large single yarn fineness and limits the freedom of color selection.

[0010] In the past, attempts have been made to change the molecular structure of dyes in order to dye polyolefin-based resin fibers in an aqueous system, and dyes for dyeing polyolefin-based resin fibers are proposed in JP-B-10741 / 1963, JP-B-1277 / 1965, JP-B-41-3515, GB Patent No. 872,882, U.S. Patent No. 3,536,735, and JP-A-2019-203223.

[0011] Japanese Patent Publication No. 1963-10741 describes examples of producing red and purple dyes in which a phenoxy group having an alkyl or cycloalkyl group having 3 to 12 carbon atoms as a substituent is introduced into an anthraquinone dye, and examples of dyeing polypropylene resin fibers with them.

[0012] However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone red dyes or anthraquinone purple dyes. Furthermore, with regard to the form of the dyes used for dyeing, there is a description that these anthraquinone red dyes are dissolved in organic solvents such as alcohol or acetone before use, which is not environmentally friendly. In addition, there is no description about yellow dyes.

[0013] Japanese Patent Publication No. 40-1277 describes examples of producing blue dyes in which a phenoxy group having an alkyl group, a cycloalkyl group or a halogeno group having 1 to 9 carbon atoms as a substituent is introduced into an anthraquinone dye, and examples of dyeing polyester fibers, polyamide fibers and polyolefin resin fibers using the dyes.

[0014] However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description of the color fastness of the dyed products obtained. Furthermore, with regard to the form of the dye when used for dyeing, there is a description that these anthraquinone blue dyes are dissolved in organic solvents such as alcohol or acetone before use, which is hardly environmentally friendly. In addition, there is no description of yellow dyes.

[0015] Japanese Patent Publication No. 41-3515 describes examples of producing blue dyes in which a phenoxy group having an alkyl group having 1 to 9 carbon atoms or a halogeno group as a substituent is introduced into an anthraquinone dye, and examples of dyeing polyolefin resin fibers using the dyes.

[0016] However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description of the color fastness of the dyed products obtained. Furthermore, with regard to the form of the dye when used for dyeing, there is a description that the dye is dissolved in an organic solvent such as alcohol or acetone before use, which is hardly environmentally friendly. Furthermore, there is no description of a yellow dye.

[0017] British Patent Specification No. 872,882 describes an example of dyeing polyolefin resin fibers using a blue dye in which an alkylamino group or a cycloalkylamino group has been introduced at the α-position of an anthraquinone dye.

[0018] However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone blue dyes, and there is no specific description of the color fastness of the dyed products obtained. In addition, there is no description of yellow dyes.

[0019] U.S. Pat. No. 3,536,735 describes examples of producing red dyes in which a phenoxy group having two substituents selected from a sec-butyl group, a sec-pentyl group, and a tert-pentyl group is introduced into an anthraquinone dye, and examples of dyeing polypropylene resin fibers with the dyes.

[0020] However, it is difficult to dye polyolefin resin fibers at high concentration with these anthraquinone red dyes, and there is no specific description of the color fastness of the dyed products obtained. Furthermore, with regard to the form of the dye when used for dyeing, there is a description that the dye is dissolved in dimethylformamide, an organic solvent, before use, which is hardly environmentally friendly. Furthermore, there is no description of the yellow dye.

[0021] JP 2019-203223 A describes a dyeing example in which polypropylene fibers are dyed in water using a disperse dye composition containing an anthraquinone yellow dye, an anthraquinone red dye, or an anthraquinone blue dye having a long-chain alkyl group.

[0022] However, it is difficult to dye polypropylene fibers at high concentration with the described anthraquinone yellow dyes having long chain alkyl groups.

[0023] JP-A-55-152869 describes examples of producing monoazo dyes having long-chain alkyl groups and examples of dyeing fine denier polyester fibers using the dyes. However, it does not describe examples of dyeing polyolefin fibers using the dyes. In addition, there is no description of yellow dyes.

[0024] Furthermore, in order to improve the dyeability of polyolefin resin fibers, various studies have been conducted on modifying the properties of polyolefin resin fibers.

[0025] As modification techniques, various techniques are known, such as blending of dyeable resin components such as polyester, copolymerization with vinyl monomers having dyeable groups, blending of dyeing accelerators such as metal stearates, and the like.

[0026] Although the dyeability of these modified polyolefin resin fibers has been improved, the strength of the yarn is reduced by the dyeing treatment, resulting in a problem of insufficient strength when used in clothing and the like.

[0027] Incidentally, Japanese Patent No. 3253649 describes a dyeing method as an alternative to aqueous dyeing, in which supercritical carbon dioxide is used as a dyeing medium to dye hydrophobic fiber materials with various dyes.

[0028] However, although polypropylene is mentioned as an example of a hydrophobic fiber material, only examples of dyeing polyester fabric are mentioned in the examples, and no examples of dyeing polypropylene fibers are mentioned.

[0029] Japanese Patent No. 6721172 describes the use of supercritical carbon dioxide as a dyeing medium to dye polypropylene fibers, which are polyolefin fibers, with an anthraquinone blue dye, an anthraquinone yellow dye, an anthraquinone red dye, or a mixture of these dyes.

[0030] However, it is difficult to dye polypropylene fibers at high concentration with the described anthraquinone yellow dyes.

[0031] When a method for dyeing polypropylene resin fibers and polyethylene resin fibers with high concentration and high fastness is put into practical use, it will be possible to color inexpensive, uncolored, small single yarn fineness regular yarns with no limit on the number of colors, which is expected to lead to new applications in fields where high design properties are required, such as clothing and vehicle interior materials, where polypropylene resin fibers and polyethylene resin fibers have not been used until now. Summary of the Invention

[0032] The present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which comprises a compound represented by the following general formula (I).

[0033] [ka]

[0034] [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. [Brief description of the drawings]

[0035] [Figure 1] The supercritical carbon dioxide dyeing apparatus used for dyeing is shown. Detailed Description of the Invention

[0036] Therefore, an object of the present invention is to provide a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which can dye polyolefin fibers in a high-concentration yellow and give dyed products with excellent color fastness to light, sublimation, washing, etc.; a method for dyeing polyolefin fibers using supercritical carbon dioxide; and polyolefin fibers and compounds dyed by the dyeing method.

[0037] The present invention relates to a dye for dyeing polyolefin fibers using supercritical carbon dioxide, which contains a compound represented by the following general formula (I).

[0038] [ka]

[0039] [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0040] The present invention also provides a method for dyeing polyolefin fibers using supercritical carbon dioxide, comprising the steps of: A process is provided which comprises the step of dyeing polyolefin fibres in the presence of supercritical carbon dioxide with the dye of the present invention.

[0041] The present invention also provides a polyolefin fiber dyed by a dyeing method comprising a step of dyeing a polyolefin fiber with the dye of the present invention in the presence of supercritical carbon dioxide.

[0042] The present invention also provides a compound represented by the following general formula (I):

[0043] [ka]

[0044] [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5, and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0045] The dye of the present invention is capable of dyeing polyolefin fibers in a high-concentration yellow in the presence of supercritical carbon dioxide, and the dyed product has excellent color fastness to light, sublimation, washing, etc.

[0046] The present inventors have discovered that a dye containing the following specific compound has improved affinity for lipophilic polyolefin fibers and dyes polyolefin fibers in a high concentration yellow in the presence of supercritical carbon dioxide, and have completed the present invention.

[0047] <Compound of formula (I)> The compounds of the general formula (I) included in the dye of the present invention are as follows:

[0048] [ka]

[0049] [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0050] In the formula (I), examples of the alkyl group having 8 to 14 carbon atoms include linear alkyl groups such as n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, and n-tetradecyl group, and branched alkyl groups such as 2-ethylhexyl group, 1,1,3,3-tetramethylbutyl group, 2-tridecyl group, and 2-butyloctyl group. Among these, as the alkyl group having 8 to 14 carbon atoms, a linear or branched chain alkyl group having 9 to 14 carbon atoms is preferable, a linear or branched chain alkyl group having 10 to 14 carbon atoms is preferable, a linear or branched chain alkyl group having 12 to 14 carbon atoms is preferable, a linear or branched chain alkyl group having 8 to 12 carbon atoms is preferable, a linear or branched chain alkyl group having 9 to 12 carbon atoms is preferable, a linear or branched chain alkyl group having 10 to 12 carbon atoms is preferable, a linear or branched chain alkyl group having 8 to 10 carbon atoms is preferable, and a linear or branched chain alkyl group having 9 to 10 carbon atoms is preferable.

[0051] In the formula (I), examples of the alkyl group having 1 to 8 carbon atoms include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, 2-methylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 1-ethyl-1-methylpropyl. Among these, linear or branched alkyl groups having 1 to 4 carbon atoms are preferred, and linear or branched alkyl groups having 4 carbon atoms are more preferred.

[0052] In the formula (I), examples of the alkoxy group having 1 to 4 carbon atoms include linear or branched alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, etc. Among these, an alkoxy group having 4 carbon atoms is preferred.

[0053] <Compound of general formula (I)>

[0054] [ka]

[0055] [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0056] In the formula (I), R 1 is preferably an alkyl group having 9 to 14 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, preferably an alkyl group having 12 to 14 carbon atoms, preferably an alkyl group having 8 to 12 carbon atoms, preferably an alkyl group having 9 to 12 carbon atoms, preferably an alkyl group having 10 to 12 carbon atoms, preferably an alkyl group having 8 to 10 carbon atoms, and preferably an alkyl group having 9 to 10 carbon atoms.

[0057] In the formula (I), R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, It is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. It is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. It is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms. More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0058] In the formula (I), R 2 、R 3 、R 4 、R 5 、and R 6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and at least one of R 2 、R 3 、R 4 、R 5 、and R 6 is more preferably a linear or branched alkyl group having 4 carbon atoms.

[0059] In the formula (I), R 2 and R 6 are preferably hydrogen atoms.

[0060] In the formula (I), R 3 and R 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0061] In the formula (I), R 4is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, More preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms. More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0062] In the formula (I), R 1 represents an alkyl group having 8 carbon atoms, and R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable to exclude compounds in which all represent hydrogen atoms.

[0063] In the formula (I), R 1 represents an alkyl group having 9 to 14 carbon atoms, R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0064] In the formula (I), R 1 represents an alkyl group having 10 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0065] In the formula (I), R 1 represents an alkyl group having 9 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0066] In the formula (I), R 1 represents an alkyl group having 10 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0067] In the formula (I), R 1 represents an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable that each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0068] In the formula (I), R 1 represents an alkyl group having 8 to 10 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable that each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0069] In the formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0070] In the formula (I), R 1 represents an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0071] In the formula (I), R 1 represents an alkyl group having 8 to 10 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0072] In the formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of these is preferably an alkyl group having 1 to 4 carbon atoms.

[0073] In the formula (I), R 1 is an alkyl group having 8 to 14 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0074] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0075] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0076] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0077] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0078] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0079] In addition, in the formula (I), R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0080] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0081] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0082] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0083] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0084] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0085] In addition, in the formula (I), R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0086] The compound of formula (I) is preferably the following compound, and more preferably the compound of formula (1), (3), (4), (5), (7), (8), (13), (14), (15), (16), or (17).

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] The compound of formula (I) is a yellow dye compound.

[0091] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1is preferably an alkyl group having 9 to 14 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, preferably an alkyl group having 12 to 14 carbon atoms, preferably an alkyl group having 8 to 12 carbon atoms, preferably an alkyl group having 9 to 12 carbon atoms, preferably an alkyl group having 10 to 12 carbon atoms, preferably an alkyl group having 8 to 10 carbon atoms, and preferably an alkyl group having 9 to 10 carbon atoms.

[0092] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms; More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms. It is more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0093] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 2 , R 3 , R 4 , R 5 , and R 6 are each preferably independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 2 , R3 , R 4 , R 5 , and R 6 It is more preferable that at least one of them is a linear or branched alkyl group having 4 carbon atoms.

[0094] In the formula (I) of the dye, From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 2 and R 6 are preferably hydrogen atoms.

[0095] In the formula (I) of the dye, From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 3 and R 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0096] In the formula (I) of the dye, From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms, still more preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0097] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 carbon atoms, and R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable to exclude compounds in which all represent hydrogen atoms.

[0098] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 9 to 14 carbon atoms, R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0099] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 10 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0100] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 9 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0101] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 10 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 Each of the groups preferably independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0102] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable that each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0103] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 10 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 It is preferable that each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

[0104] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0105] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0106] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 10 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of them is preferably an alkoxy group having 1 to 4 carbon atoms.

[0107] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of these is preferably an alkyl group having 1 to 4 carbon atoms.

[0108] In the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 14 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0109] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0110] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0111] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0112] In addition, in the formula (I) of the dye, From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 are hydrogen atoms, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0113] Also, in the formula (I) of the dye, from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 are hydrogen atoms, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0114] Also, in the formula (I) of the dye, from the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., R 1 is an alkyl group having 8 to 12 carbon atoms, R 2 and R 6 are hydrogen atoms, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0115] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0116] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0117] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0118] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0119] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0120] In addition, in the formula (I) of the dye, From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. R 1 is an alkyl group having 8 to 10 carbon atoms, R 2 and R 6 is a hydrogen atom, R 3 and R 5are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 4 is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0121] The compound of formula (I) of the dye is From the viewpoint of dyeing density, light fastness, sublimation fastness, etc. The following compounds are preferred, and the compounds of formulae (1), (3), (4), (5), (7), (8), (13), (14), (15), (16), and (17) are more preferred.

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] <Method for producing the compound of formula (I)> A method for producing the compound represented by the above formula (I) will be described.

[0126] [ka]

[0127] The compound represented by formula (I) is an aniline derivative represented by formula (iD) (wherein R 2 , R 3 , R 4 , R 5 , and R 6each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.) and a compound represented by formula (iC) (wherein R 1 represents an alkyl group having 8 to 14 carbon atoms) can be obtained by coupling.

[0128] (i) Diazotization of a compound of formula (iD) First, the compound of formula (iD) is diazotized in a mineral acid or an organic carboxylic acid, optionally in the presence of added water, using a nitrosating agent or nitrosylsulfuric acid to obtain a diazo compound. Examples of the organic carboxylic acid used include acetic acid and propionic acid. Examples of the mineral acid used include hydrochloric acid, phosphoric acid, and sulfuric acid, preferably sulfuric acid. The nitrosating agent used is an alkali metal nitrite, for example, sodium nitrite in a solid state or in an aqueous solution state. The compound of formula (iD) may be commercially available or may be prepared by a known method.

[0129] The reaction temperature for diazotization is preferably -10 to 40°C, more preferably 0 to 40°C.

[0130] (ii) Coupling with a compound of formula (iC) A solution of the diazo compound of formula (iD) is added to a solution of the compound of formula (iC) in N,N-dimethylformamide (DMF) at a temperature in the range of, for example, 0 to 10° C. to obtain the compound of formula (I).

[0131] (iii) Method for preparing the compound of formula (iC) The starting compound of formula (iC) can be produced as follows.

[0132] [ka]

[0133] Under solvent-free conditions, cyanoacetate (e.g., methyl cyanoacetate) is converted to R1 NH 2 (R 1 represents an alkyl group having 8 to 14 carbon atoms), and then reacting with an acetoacetate (for example, methyl acetoacetate) in the presence of piperidine to obtain a compound of formula (iC).

[0134] <Dye for dyeing polyolefin fiber using supercritical carbon dioxide> The dyes of the present invention have the formula (I).

[0135] The dye of the present invention may further contain additives, such as auxiliary colorants, dispersants, fillers, stabilizers, plasticizers, crystal nucleating agents, modifiers, foaming agents, UV absorbers, light stabilizers, antioxidants, antibacterial agents, fungicides, antistatic agents, flame retardants, inorganic fillers, and elastomers for improving impact resistance.

[0136] The polyolefin fiber of the dyed article to be dyed with the dye of the present invention may be, for example, a fiber formed from a polymer selected from homopolymers of α-olefins such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, etc., copolymers of these α-olefins, or copolymers of these α-olefins with other unsaturated monomers copolymerizable therewith. The types of copolymers include, for example, block copolymers, random copolymers, graft copolymers, etc. Specific examples of the polymers include polypropylene-based resins such as propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, and propylene-ethylene-(1-butene) copolymers, polyethylene-based resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymers, and ethylene-ethyl acrylate copolymers, poly-1-butene, poly-4-methyl-1-pentene, etc.

[0137] The above polymers may be used alone or in combination to form the polyolefin fibers.

[0138] The polyolefin fibers are preferably made of a polypropylene-based resin and / or a polyethylene-based resin, and more preferably made of a polypropylene-based resin.

[0139] The polyolefin fiber may be in any shape, for example, a block (molded product, etc.), a film, a fiber (cloth (woven fabric, knitted fabric, nonwoven fabric, etc.), thread (filament yarn, spun yarn, slit yarn, split yarn, etc.), etc.), and is preferably in a fiber shape.

[0140] The polyolefin fiber may be a fiber formed by blending other polymer components with polypropylene resin and / or polyethylene resin, bonding, etc. The polyolefin fiber may be a fiber obtained by blending or blending polypropylene fiber with other fibers such as polyester.

[0141] <Method of dyeing polyolefin fiber using supercritical carbon dioxide> The present invention relates to a method for dyeing polyolefin fibers using supercritical carbon dioxide, which comprises a step of dyeing polyolefin fibers in the presence of supercritical carbon dioxide using the dye of the present invention. In the method, supercritical carbon dioxide is used as a dyeing medium.

[0142] A dyeing method using supercritical carbon dioxide as a dyeing medium is attracting attention as an environmentally friendly dyeing method because, compared with a general dyeing method that uses water as a dyeing medium, it does not use water during dyeing, does not require a washing step, and therefore does not generate wastewater, does not require dyeing auxiliaries, takes a short dyeing time, and allows the reuse of carbon dioxide as a dyeing medium.

[0143] In addition, supercritical carbon dioxide is lipophilic, and both the dye and the polyolefin resin of the present invention are lipophilic, so that the affinity between the dyeing medium, the dye, and the item to be dyed is high, resulting in high-quality dyed items.

[0144] The dyeing step in the method for dyeing polyolefin fibers using supercritical carbon dioxide of the present invention is preferably carried out at a temperature of 31° C. or higher and a pressure of 7.4 MPa or higher. This is because the dyeing temperature and dyeing pressure must be equal to or higher than the critical point (7.4 MPa at 31° C.) of carbon dioxide, which is the dyeing medium.

[0145] In the dyeing process, the dyeing temperature is mainly determined by the type of resin of the fiber to be dyed, and is usually in the range of 60 to 180°C, preferably in the range of 80 to 160°C.

[0146] In the dyeing process, the dyeing pressure is mainly determined by the type of resin of the dyed fiber, and is usually in the range of about 7.4 to 40.0 MPa, preferably 20 to 30 MPa.

[0147] The dyeing time in the dyeing step is determined by the type of resin of the dyed fiber and the dyeing temperature, and is usually about 10 to 120 minutes, preferably 30 to 90 minutes.

[0148] In the dyeing process, the concentration of the dye on the fiber depends on the type and processing state of the fiber to be dyed. When the fiber to be dyed is fibrous, the concentration of the dye on the fiber is 0.1 to 6.0% omf (on the mass of fiber), preferably 0.1 to 4.0% omf.

[0149] In the dyeing method of the present invention, the liquor ratio (mass ratio of material to be dyed: carbon dioxide) depends on the type of material to be dyed and its processing state. The liquor ratio is usually 1:2 to 1:100, preferably 1:5 to 1:75. When the material to be dyed is a polypropylene cloth wrapped in a suitable cheesecloth, the liquor ratio in the dyeing method of the present invention is relatively low, for example, 1:2 to 1:5.

[0150] <Dyed polyolefin fiber> The present invention provides a polyolefin fiber dyed by the dyeing method of the present invention. The dyed polyolefin fiber is dyed to a high concentration, particularly to a high concentration yellow, and has excellent color fastness to light, sublimation, washing, etc. Applications of the polyolefin fiber include, for example, clothing, underwear, hats, socks, gloves, sportswear, and other clothing items, vehicle interior materials such as seat covers, and interior goods such as carpets, curtains, mats, sofa covers, and cushion covers.

[0151] The present invention will be described in more detail below with reference to examples, but the aspects of the present invention are not limited to these.

[0152] [Example] (Synthesis Example 1) [Synthesis of yellow dye compound (1)] The yellow dye compound (1) was produced according to the following scheme.

[0153] [ka]

[0154] 1-A. Synthesis of coupler compound (C1) and preparation of coupler component solutions (Process 1) Methyl cyanoacetate (9.96g) and dodecylamine (18.5g) were mixed, heated to 90°C, and stirred for 4 hours. Methyl acetoacetate (11.6g) and piperidine (8.52g) were added dropwise, and the mixture was stirred at 90°C for 4 hours. After cooling to room temperature, the reaction solution was added dropwise to 7.2% hydrochloric acid (100g), and ethyl acetate (30g) was added and stirred. This mixture was filtered, and the filtered product was washed with water to obtain 3-cyano-1-dodecyl-6-hydroxy-4-methyl-2-pyridone represented by formula (C1) as a crude product. 300g of DMF was added to this reaction mixture, and the mixture was cooled to 5°C to obtain a coupler component solution (C1) consisting of the compound of formula (C1).

[0155] [ka]

[0156] 1-B. Preparation of diazo component solutions (Process 2) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 4-butylaniline (14.9 g) represented by the following formula (D1) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D1).

[0157] [ka]

[0158] 1-C. Synthesis of yellow dye compound (1) by coupling reaction (Step 3) The diazo component solution (D1) obtained in the step 2 was added dropwise to the coupler component solution (C1) obtained in the step 1 over a period of 1 hour at a temperature in the range of 0 to 10°C, to carry out a coupling reaction. This mixture was stirred at a temperature in the range of 0 to 10°C for 30 minutes, and then 500 g of water was added. The product was filtered out from the reaction mixture, washed with water, and dried at 60°C until the moisture content was 1.0 mass% or less, to obtain a yellow dye compound represented by the following formula (1) (29.0 g, yield 60.6%). The yellow dye compound was analyzed by LCMS (m / z 479 (M + )) confirmed its structure.

[0159] [ka]

[0160] (Synthesis Example 2) [Synthesis of yellow dye compound (2)] The yellow dye compound (2) was produced according to the following scheme.

[0161] [ka]

[0162] 2-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of aniline (9.31 g) represented by the following formula (D2) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D2).

[0163] [ka]

[0164] 2-B. Synthesis of yellow dye compound (2) by coupling reaction (Process 2) A yellow dye compound (31.8 g, yield 75.3%) represented by the following formula (2) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D2) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) confirmed its structure.

[0165] [ka]

[0166] (Synthesis Example 3) [Synthesis of yellow dye compound (3)] The yellow dye compound (3) was produced according to the following scheme.

[0167] [ka]

[0168] 3-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of p-toluidine (10.7 g) represented by the following formula (D3) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D3).

[0169] [ka]

[0170] 3-B. Synthesis of yellow dye compound (3) by coupling reaction (Process 2) A yellow dye compound (30.0 g, yield 68.8%) represented by the following formula (3) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D3) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 437 (M + )) confirmed its structure.

[0171] [ka]

[0172] (Synthesis Example 4) [Synthesis of yellow dye compound (4)] The yellow dye compound (4) was produced according to the following scheme.

[0173] [ka]

[0174] 4-A. Preparation of diazo component solutions (Process 1) A 36% aqueous sodium nitrite solution (21.1 g) was added dropwise to a mixture of m-toluidine (10.7 g) represented by the following formula (D4) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D4).

[0175] [ka]

[0176] 4-B. Synthesis of yellow dye compound (4) by coupling reaction (Process 2) A yellow dye compound (30.1 g, yield 69.0%) represented by the following formula (4) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 437 (M + )) confirmed its structure.

[0177] [ka]

[0178] (Synthesis Example 5) [Synthesis of yellow dye compound (5)] The yellow dye compound (5) was prepared according to the following scheme.

[0179] [ka]

[0180] 5-A. Synthesis of coupler compound (C2) and preparation of coupler component solutions (Process 1) A coupler component solution (C2) composed of a compound of formula (C2) was obtained in the same manner as in step 1 of Synthesis example 1, except that 2-ethylhexylamine (12.9 g) was used instead of dodecylamine.

[0181] [ka]

[0182] 5-B. Synthesis of yellow dye compound (5) by coupling reaction (Process 2) A yellow dye compound (20.5 g, yield 48.5%) represented by the following formula (5) was obtained in the same manner as in step 3 of Synthesis Example 1, except that coupler component solution (C2) was used instead of coupler component solution (C1). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) confirmed its structure.

[0183] [ka]

[0184] (Synthesis Example 6) [Synthesis of yellow dye compound (6)] The yellow dye compound (6) was prepared according to the following scheme.

[0185] [ka]

[0186] A yellow dye compound (22.5 g, yield 61.3%) represented by the following formula (6) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D2) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 367 (M + )) confirmed its structure.

[0187] [ka]

[0188] (Synthesis Example 7) [Synthesis of yellow dye compound (7)] The yellow dye compound (7) was prepared according to the following scheme.

[0189] [ka]

[0190] A yellow dye compound represented by the following formula (7) (24.4 g, yield 64.2%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D3) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) confirmed its structure.

[0191] [ka]

[0192] (Synthesis Example 8) [Synthesis of yellow dye compound (8)] The yellow dye compound (8) was prepared according to the following scheme.

[0193] [ka]

[0194] A yellow dye compound represented by the following formula (8) (22.8 g, yield 60.0%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C2) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) confirmed its structure.

[0195] [ka]

[0196] (Synthesis Example 9) [Synthesis of yellow dye compound (9)] The yellow dye compound (9) was prepared according to the following scheme.

[0197] [ka]

[0198] 9-A. Synthesis of coupler compound (C3) and preparation of coupler component solutions (Process 1) A coupler component solution (C3) composed of a compound of formula (C3) was obtained in the same manner as in step 1 of Synthesis example 1, except that octylamine (12.9 g) was used instead of dodecylamine.

[0199] [ka]

[0200] 9-B. Synthesis of yellow dye compound (9) by coupling reaction (Process 2) A yellow dye compound represented by the following formula (9) (14.6 g, yield 34.6%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that coupler component solution (C3) was used instead of coupler component solution (C1). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) confirmed its structure.

[0201] [ka]

[0202] (Synthesis Example 10) [Synthesis of yellow dye compound (10)] The yellow dye compound (10) was prepared according to the following scheme.

[0203] [ka]

[0204] A yellow dye compound represented by the following formula (10) (11.5 g, yield 31.4%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D2) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 367 (M + )) confirmed its structure.

[0205] [ka]

[0206] (Synthesis Example 11) [Synthesis of yellow dye compound (11)] The yellow dye compound (11) was prepared according to the following scheme.

[0207] [ka]

[0208] A yellow dye compound represented by the following formula (11) (14.5 g, yield 38.2%) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D3) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) confirmed its structure.

[0209] [ka]

[0210] (Synthesis Example 12) [Synthesis of yellow dye compound (12)] The yellow dye compound (12) was prepared according to the following scheme.

[0211] [ka]

[0212] A yellow dye compound (12.2 g, yield 32.1%) represented by the following formula (12) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution, and coupler component solution (C3) was used instead of coupler component solution (C1) as the coupler component solution. The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) confirmed its structure.

[0213] [ka]

[0214] (Synthesis Example 13) [Synthesis of yellow dye compound (13)] The yellow dye compound (13) was prepared according to the following scheme.

[0215] [ka]

[0216] 13-A. Synthesis of coupler compound (C4) and preparation of coupler component solutions (Process 1) A coupler component solution (C4) composed of a compound of formula (C4) was obtained in the same manner as in Step 1 of Synthesis Example 1, except that 1-aminodecane (15.7 g) was used instead of dodecylamine.

[0217] [Chemical formula]

[0218] 13-B. Synthesis of Yellow Dye Compound (13) by Coupling Reaction (Step 2) A yellow dye compound (32.0 g, yield 71.2%) represented by the following formula (13) was obtained in the same manner as in Step 3 of Synthesis Example 1, except that coupler component solution (C4) was used instead of coupler component solution (C1) as the coupler component solution. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 451 (M + ))

[0219] [Chemical formula]

[0220] (Synthesis Example 14) [Synthesis of Yellow Dye Compound (14)] The yellow dye compound (14) was produced according to the following scheme

[0221] [Chemical formula]

[0222] A yellow dye compound (29.0 g, yield 71.0%) represented by the following formula (14) was obtained in the same manner as in Step 3 of Synthesis Example 1, except that diazo component solution (D4) was used instead of diazo component solution (D1) as the diazo component solution and coupler component solution (C4) was used instead of coupler component solution (C1) as the coupler component solution. The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 409 (M + ))

[0223] [Chemical formula]

[0224] (Synthesis Example 15) [Synthesis of yellow dye compound (15)] The yellow dye compound (15) was prepared according to the following scheme.

[0225] [ka]

[0226] 15-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 4-ethylaniline (12.1 g) represented by the following formula (D5) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D5).

[0227] [ka]

[0228] 15-B. Synthesis of yellow dye compound (15) by coupling reaction (Process 2) A yellow dye compound (31.7 g, yield 70.4%) represented by the following formula (15) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D5) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) confirmed its structure.

[0229] [ka]

[0230] (Synthesis Example 16) [Synthesis of yellow dye compound (16)] The yellow dye compound (16) was prepared according to the following scheme.

[0231] [ka]

[0232] 16-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 3,5-dimethylaniline (12.1 g) represented by the following formula (D6) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D6).

[0233] [ka]

[0234] 16-B. Synthesis of yellow dye compound (16) by coupling reaction (Process 2) A yellow dye compound (21.0 g, yield 46.7%) represented by the following formula (16) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D6) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) confirmed its structure.

[0235] [ka]

[0236] (Synthesis Example 17) [Synthesis of yellow dye compound (17)] The yellow dye compound (17) was prepared according to the following scheme.

[0237] [ka]

[0238] 17-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 3,4-dimethylaniline (12.1 g) represented by the following formula (D7) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D7).

[0239] [ka]

[0240] 17-B. Synthesis of yellow dye compound (17) by coupling reaction (Process 2) A yellow dye compound (33.7 g, yield 74.8%) represented by the following formula (17) was obtained in the same manner as in step 3 of Synthesis Example 1, except that diazo component solution (D7) was used instead of diazo component solution (D1). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) confirmed its structure.

[0241] [ka]

[0242] (Synthesis Example 18) [Synthesis of yellow dye compound (18)] The yellow dye compound (18) was prepared according to the following scheme.

[0243] [ka]

[0244] 18-A. Preparation of diazo component solutions (Process 1) A 36% aqueous solution of sodium nitrite (21.1 g) was added dropwise to a mixture of 4-butoxyaniline (16.5 g) represented by the following formula (D8) and 10% hydrochloric acid (140 g) at a temperature in the range of 5 to 10° C., and the mixture was stirred for 1 hour at a temperature in the range of 5 to 10° C. Sulfamic acid (1.84 g) was added to the mixture, and the mixture was stirred for 20 minutes at a temperature in the range of 5 to 10° C., to obtain a diazo component solution (D8).

[0245] [ka]

[0246] 18-B. Synthesis of yellow dye compound (18) by coupling reaction (Process 2) The diazo component solution (D8) obtained in step 1 was added dropwise to the coupler component solution (C2) over 1 hour at a temperature in the range of 0 to 10°C to carry out a coupling reaction. This mixture was stirred at a temperature in the range of 0 to 10°C for 30 minutes, and then 500 g of water was added. The product was filtered from the reaction mixture, washed with water, and dried at 60°C until the moisture content was 1.0 wt% or less to obtain a yellow dye compound represented by the following formula (18) (14.6 g, yield 33.3%). The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 439 (M+)).

[0247] [ka]

[0248] (Synthesis Example 19) [Synthesis of yellow dye compound (19)] To a mixture of 5-amino-anthra[9,1-cd]isothiazol-6-one (25.2 g), toluene (120 g), and pyridine (9.49 g), n-octanoyl chloride (19.5 g) was added dropwise, and the mixture was heated to 110° C. and stirred for 1 hour. After cooling the mixture to room temperature, methanol (150 g) was added to precipitate. The mixture was filtered, and the filtered product was washed with methanol and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (19) (31.8 g, yield 83.9%). The yellow dye compound was analyzed by LCMS (m / z 379 (M + )) confirmed its structure.

[0249] [ka]

[0250] (Synthesis Example 20) [Synthesis of yellow dye compound (20)] A yellow dye compound (33.1 g, 87.3% yield) represented by the following formula (20) was obtained in the same manner as in Synthesis Example 19, except that 2-ethylhexanoyl chloride (19.5 g) was used instead of n-octanoyl chloride. The yellow dye compound was analyzed by LCMS (m / z 379 (M + )) confirmed its structure.

[0251] [ka]

[0252] (Synthesis Example 21) [Synthesis of yellow dye compound (21)] A yellow dye compound (31.0 g, yield 78.9%) represented by the following formula (21) was obtained in the same manner as in Synthesis Example 19, except that n-nonanoyl chloride (21.2 g) was used instead of n-octanoyl chloride. The yellow dye compound was analyzed by LCMS (m / z 393 (M + )) confirmed its structure.

[0253] [ka]

[0254] (Synthesis Example 22) [Synthesis of yellow dye compound (22)] A mixture of thionyl chloride (14.3g) and toluene (20g) was added dropwise to a mixture of 2-hexyldecanoic acid (30.8g) and toluene (30g). A mixture of pyridine (9.49g) and toluene (30g) was slowly added dropwise to this mixture over 1 hour, then the mixture was heated to 110°C and stirred for 1 hour. After the reaction mixture was cooled to room temperature, a mixture of 5-amino-anthra[9,1-cd]isothiazol-6-one (25.2g) and toluene (30g) was added dropwise to the reaction mixture. The reaction mixture was heated to 110°C and stirred for 2 hours, after which the solvent was removed from the mixture by vacuum distillation, and methanol (100g) was added to the residue to precipitate. The mixture was filtered, the filtered product was washed with methanol and then with water, and dried at 60°C until the moisture content was 1.0wt% or less, to obtain a yellow dye compound represented by the following formula (22) (36.7g, yield 74.7%). The yellow dye compound was analyzed by LCMS (m / z 491(M + )) confirmed its structure.

[0255] [ka]

[0256] (Synthesis Example 23) [Synthesis of yellow dye compound (23)] A mixture of 4-(anilino)-3-nitro-N-phenylbenzenesulfonamide (9.84 g), DMF (15.7 g), potassium carbonate (3.68 g), and 1-bromooctane (7.73 g) was heated to 80° C. and stirred for 2 hours. The reaction mixture was cooled to room temperature, and 100 g of water was added thereto to precipitate a solid. The mixture was filtered, and the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (23) (11.9 g, yield 92.8%). The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 482 (M+)).

[0257] [ka]

[0258] (Synthesis Example 24) [Synthesis of yellow dye compound (24)] A yellow dye compound (11.5 g, 89.7% yield) represented by the following formula (24) was obtained in the same manner as in Synthesis Example 23, except that 1-bromo-2-ethylhexane (7.73 g) was used instead of 1-bromooctane. The yellow dye compound was analyzed by LCMS (m / z 482 (M + )) confirmed its structure.

[0259] [ka]

[0260] (Synthesis Example 25) [Synthesis of yellow dye compound (25)] A yellow dye compound (14.2 g, 99.4% yield) represented by the following formula (25) was obtained in the same manner as in Synthesis Example 23, except that 1-bromododecane (9.98 g) was used instead of 1-bromooctane. The yellow dye compound was analyzed by LCMS (m / z 538 (M + )) confirmed its structure.

[0261] [ka]

[0262] (Synthesis Example 26) [Synthesis of yellow dye compound (26)] A yellow dye compound (15.5 g, 98.5% yield) represented by the following formula (26) was obtained in the same manner as in Synthesis Example 23, except that 1-bromohexadecane (12.2 g) was used instead of 1-bromooctane. The yellow dye compound was analyzed by LCMS (m / z 594 (M + )) confirmed its structure.

[0263] [ka]

[0264] (Synthesis Example 27) [Synthesis of yellow dye compound (27)] A mixture of thionyl chloride (14.3g) and toluene (20g) was added dropwise to a mixture of 2-hexyldecanoic acid (30.8g) and toluene (30g). A mixture of pyridine (9.49g) and toluene (30g) was slowly added dropwise to this mixture over 1 hour, then the mixture was heated to 110°C and stirred for 1 hour. The reaction mixture was cooled to room temperature, and then a mixture of 1-aminoanthraquinone (22.3g) and toluene (30g) was added thereto. The reaction mixture was heated to 110°C and stirred for 2 hours, then cooled to room temperature, and 10g of 24% aqueous sodium hydroxide was added, followed by the addition of 200g of water to extract the organic layer. This extract was washed with saturated saline, and the solvent was removed under reduced pressure, and methanol (200g) was added to the residue to precipitate. The mixture was filtered, and the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (27) (41.0 g, yield 88.7%). The yellow dye compound was analyzed by LCMS (m / z 462 (M + )) confirmed its structure.

[0265] [ka]

[0266] (Synthesis Example 28) [Synthesis of yellow dye compound (28)] A mixture of thionyl chloride (28.6g) and toluene (40g) was added dropwise to a mixture of 2-hexyldecanoic acid (61.6g) and toluene (60g). A mixture of pyridine (19.0g) and toluene (60g) was slowly added dropwise to this mixture over 1 hour, then the mixture was heated to 110°C and stirred for 1 hour. The reaction mixture was cooled to room temperature, and a mixture of 1,5-diaminoanthraquinone (23.8g) and toluene (30g) was added thereto. The reaction mixture was heated to 110°C and stirred for 2 hours, then cooled to room temperature, and 20g of 24% aqueous sodium hydroxide was added, followed by the addition of 300g of water to extract the organic layer. This extract was washed with saturated saline, and the solvent was removed under reduced pressure, and methanol (300g) was added to the residue to precipitate. The mixture was filtered, and the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (28) (22.6 g, yield 31.6%). The yellow dye compound was analyzed by LCMS (m / z 715 (M + )) confirmed its structure.

[0267] [ka]

[0268] (Synthesis Example 29) [Synthesis of yellow dye compound (29)] A mixture of 1-aminoanthraquinone (22.3 g), cyanuric chloride (18.4 g), and N-methyl-2-pyrrolidone (NMP) (100 g) was heated to 60°C and stirred for 2 hours. The reaction mixture was cooled to room temperature, and 200 g of water was added to precipitate. The mixture was filtered, the filtered product was washed with water, and dried at 60°C until the moisture content was 1.0 wt% or less. DMF (60 g), triethylamine (8.1 g), and 2-ethylhexylamine (12.4 g) were added to the obtained solid, and the mixture was heated to 90°C and stirred for 2 hours. The mixture was cooled to room temperature, and 20 g of 30% sulfuric acid was added, followed by 100 g of water to precipitate. The mixture was filtered, and the filtered product was washed with water. Methanol (60 g) was added to this crude product, and the mixture was stirred at 60°C for 30 minutes. After cooling to room temperature, the mixture was filtered, the filtered product was washed with methanol and then with water, and dried at 60° C. until the moisture content was 1.0 wt % or less to obtain a yellow dye compound represented by the following formula (29) (14.4 g, yield 25.9%). The yellow dye compound was analyzed by LCMS (m / z 557 (M + )) confirmed its structure.

[0269] [ka]

[0270] (Synthesis Example 30) [Synthesis of yellow dye compound (30)] 30-A. Synthesis of coupler compound (C5) and preparation of coupler component solutions (Process 1) A mixture of 2-chlorobenzoic acid (15.6 g), potassium carbonate (13.8 g), copper chloride (300 mg), DMF (80 g), and ethylhexylamine (15.5 g) was heated to 100° C. and stirred for 16 hours. The reaction mixture was cooled to room temperature, and 50 g of 30% sulfuric acid, 100 g of water, and 200 g of ethyl acetate were added. This mixture was filtered, and the filtered product was washed with water and ethyl acetate. An organic layer was extracted from this filtrate, and the organic layer was washed with saturated saline, and the solvent was distilled off under reduced pressure to obtain 2-ethylhexylaminobenzoic acid (28.9 g, yield 116%) represented by the following formula (C5a) as a crude product.

[0271] [ka]

[0272] (Process 2) The mixture of 2-ethylhexylaminobenzoic acid (28.9 g), acetic anhydride (50 g), and acetic acid (50 g) obtained in the above step 1 was heated to 110° C. and stirred for 7 hours. After the reaction mixture was cooled to room temperature, 200 g of water and 200 g of ethyl acetate were added to extract the organic layer, which was washed with saturated saline, and the solvent was distilled off under reduced pressure to obtain 4-hydroxy-1-(2-ethylhexyl)quinolin-2-one (36.7 g, yield 134%) represented by the following formula (C5) as a crude product. 100 g of methanol was added to this crude product and cooled to 5° C. to obtain a coupler component solution (C5) consisting of the compound of formula (C5).

[0273] [ka]

[0274] 30-B. Preparation of diazo component solutions (Step 3) To a mixture of concentrated sulfuric acid (34 g) and 43% nitrosylsulfuric acid (29.3 g), 4-nitroaniline (13.8 g) represented by the following formula (D9) was added at a temperature in the range of 30 to 35°C, and the mixture was stirred at the same temperature for 2 hours to obtain a diazo component solution (D9).

[0275] [ka]

[0276] 30-C. Synthesis of yellow dye compound (30) by coupling reaction (Step 4) The diazo component solution (D9) obtained in the step 3 was added dropwise to the coupler component solution (C5) obtained in the step 1 over 1 hour while appropriately adding triethylamine (120 g) within the range of 0 to 10 °C to conduct a coupling reaction. After stirring this mixture within the range of 0 to 10 °C for 30 minutes, the product was filtered off from this reaction mixture and washed with methanol and then with water. Methanol (80 g) was added to this crude product and stirred at 60 °C for 30 minutes. After cooling to room temperature, this mixture was filtered off, the filtrate was washed with methanol and then with water, and dried at 60 °C until the water content became 1.0 wt% or less to obtain a yellow dye compound (10.2 g, yield 24.2%) represented by the following formula (30). The structure of the yellow dye compound was confirmed by LCMS analysis (m / z 423 (M + ))

[0277] [Chemical formula]

[0278] The dye compounds described in the synthesis examples are shown in Tables 1 to 2.

[0279] [Table 1]

[0280] [Table 2] TIFF0007681368000079.tif181154

[0281] [Dyeing example] Using the dye compounds described in Tables 1 to 2, polypropylene fabric or polyethylene fabric was dyed by a supercritical carbon dioxide dyeing method.

[0282] (Supercritical carbon dioxide dyeing of polypropylene fabric) (Dyeing example P1) The supercritical carbon dioxide dyeing apparatus used for dyeing is shown in Figure 1. The dyeing apparatus is liquid CO2 It consists of a cylinder (1), a filter (2), a cooling jacket (3), a cooler (4), a high-pressure pump (5), a preheater (6), pressure gauges (7 to 9), a magnetic drive unit (10), a DC motor (11), safety valves (12, 13), stop valves (14 to 18), a needle valve (19), and a heater (20).

[0283] The polypropylene cloth was cut into pieces of about 50 to 70 g, weighed, and wound around a stainless steel cylinder (21) with punched holes in the order of cotton cloth, polypropylene cloth, and cotton cloth from the inside, and then loosely secured with cotton thread. The inner cotton cloth was the undercloth, and the outer cotton cloth was the cover cloth.

[0284] A stainless steel cylinder wrapped with the above-mentioned fabric samples (cotton fabric, polypropylene fabric, cotton fabric) was fixed to a pressure-resistant stainless steel tank (22), and the yellow dye compound 1 obtained in Synthesis Example 1, equivalent to 0.3% by mass relative to the mass of the polypropylene fabric, was wrapped in a paper wipe and placed in the fluid passage at the top of the stainless steel cylinder. The volume of the pressure-resistant stainless steel tank was 2230 cm. 3 All valves in the dyeing equipment were closed, and the equipment was heated to 120°C using a preheater.

[0285] After the dyeing temperature was reached, the stop valves (14) and (16) were opened, and 1.13 kg of liquid carbon dioxide was introduced into the pressure-resistant stainless steel tank using a high-pressure pump connected via a cooling jacket. After that, the stop valves (14) and (16) were closed, and the liquid was circulated by the impeller and magnetic drive unit at the bottom of the pressure-resistant stainless steel tank. The rotation speed of the magnetic drive unit was 750 rpm, and the circulation direction was from the inside to the outside of the cylinder.

[0286] After the pressure-resistant stainless steel tank reached the specified temperature and pressure (120°C, 25 MPa), these temperature and pressure conditions were maintained for 60 minutes to dye the polypropylene fabric. After dyeing, the stop valve (18) was opened and the needle valve was gradually opened to release the carbon dioxide in the pressure-resistant stainless steel tank, lowering the pressure in the tank from 25 MPa to atmospheric pressure. Circulation continued until the critical pressure of carbon dioxide (approximately 8 MPa) was reached. The yellow-dyed polypropylene fabric was then removed from the pressure-resistant stainless steel tank.

[0287] (Staining examples P2 to P26) A yellow dyed polypropylene fabric was obtained by the same dyeing procedure as in Dyeing Example P1, except that the yellow dye compound 1 described in Dyeing Example P1 was changed to a dye compound described in Tables 1 and 2. The dye compounds used in Dyeing Examples P1 to P26 are shown in Tables 3 and 4.

[0288] [Table 3]

[0289] [Table 4] TIFF0007681368000082.tif148156

[0290] The dyed polypropylene fabrics obtained in Dyeing Examples P1 to P26 were subjected to dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, sweat fastness test, friction fastness test, and hot pressing fastness test.

[0291] (1) Dyeability evaluation The dyeability was evaluated by measuring the color of the dyed fabric, using the Total K / S value, the K / S value (measured at the maximum wavelength), and visual inspection of the dye residue after dyeing. The color of the dyed fabric was measured using an integrating sphere spectrophotometer Color-Eye 5 (GretagMacbeth) with the dyed fabric glued onto white paper, using an observation light source of D65 and a 2-degree visual field.

[0292] (2) Light fastness test The light fastness test was performed using the ultraviolet carbon arc lamp method in accordance with JIS L0842: 2004. The outline of the test method is as follows: Using an ultraviolet fade meter U48 (manufactured by Suga Test Instruments Co., Ltd.), the dyed fabric was exposed to light for 20 hours under the condition of a black panel temperature of 63±3°C, and then the discoloration was judged.

[0293] (3) Sublimation fastness test The sublimation fastness test was conducted according to JIS L0854:2013. The outline of the test method is as follows: The dyed fabric was sandwiched between nylon fabrics and held at 120±2°C for 80 minutes under a load of 12.5kPa, after which discoloration and staining of the nylon fabric were evaluated.

[0294] (4) Washing fastness test The washing fastness test was conducted according to JIS L0844:2011 (A-2). The outline of the test method is as follows. A multi-woven fabric was attached to the dyed fabric, and it was washed for 30 minutes at 50±2℃ in the presence of soap, and the discoloration and the staining of the cotton and nylon parts of the multi-woven fabric were judged. The staining of the residual liquid after washing was also judged.

[0295] (5) Sweat fastness test The sweat fastness test was conducted according to JIS L0848:2004. The outline of the test method is as follows: A multi-woven fabric was attached to the dyed fabric, and it was immersed in acidic artificial sweat or alkaline artificial sweat for 30 minutes, and then it was held at 37±2℃ for 4 hours under a load of 12.5kPa, and then it was dried at 60℃ or less, and the discoloration and the staining of the cotton and nylon parts of the multi-woven fabric were judged.

[0296] (6) Rubbing fastness test The friction fastness test was conducted according to JIS L0849:2013. The outline of the test method is as follows: Using a friction fastness tester RT-300 (manufactured by Daiei Scientific Instruments Co., Ltd.), the dyed fabric was rubbed back and forth 100 times with dry cotton fabric or wet cotton fabric under a load of 2N, and the coloring of the cotton fabric was judged.

[0297] (7) Fastness test against hot pressing The fastness test for hot pressing was conducted according to JIS L0850:2015 (A-2, dry). The outline of the test method is as follows: The dyed fabric was placed on top of the cotton fabric, and the fabric was held for 15 seconds under a load of 4±1kPa on a 150℃ heating plate, after which discoloration and staining of the cotton fabric were evaluated.

[0298] Table 5 shows the evaluation results for dyeing examples using the compound of formula (I), and Table 6 shows the evaluation results for dyeing examples using dye compounds other than the compound of formula (I).

[0299] [Table 5]

[0300] [Table 6]

[0301] Regarding the dyeing properties of the compound of formula (I), the R used in dyeing examples P1 to P15 was 1 is an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 The dyeing properties of the compounds in which each of the groups is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms were good.

[0302] However, the dyeing properties of the dye compounds other than the compound of formula (I) used in Dyeing Examples P16 to P26 were poor.

[0303] In addition, the fastness of each compound of formula (I) was measured using the R 1 is an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, the fastness of each of the compounds was good.

[0304] As described above, the present invention is not limited to the above-described embodiment, and suitable combinations or substitutions of the configurations of the embodiment are also included in the present invention.

[0305] In addition, it is possible to appropriately rearrange the combinations and order of steps in the embodiments based on the knowledge of a person skilled in the art, and to make modifications to the embodiments such as various design changes, and embodiments to which such modifications have been made are also within the scope of the present invention.

[0306] The present invention can be utilized for dyeing polyolefin fibers used in clothing such as clothes, underwear, hats, socks, gloves, and sportswear, vehicle interior materials such as seat covers, and interior goods such as carpets, curtains, mats, sofa covers, and cushion covers.

Claims

1. A dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising a compound represented by the following general formula (I) (excluding compounds in which the polyolefin fibers are polyethylene fibers, R 1 represents an alkyl group having 12 carbon atoms, R 2 , R 3 , R 5 , and R 6 represent hydrogen atoms, and R 4 represents an alkyl group having 4 carbon atoms): 【Chemical 77】 [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

2. As the compound of formula (I), R 1 represents an alkyl group having 8 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 Excluding compounds where all are hydrogen atoms. The dye of claim 1.

3. In the formula (I), R 2 , R 3 , R 4 , R 5 , and R 6 The dye according to claim 1 , wherein each of the groups is independently a member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 4 carbon atoms.

4. In the formula (I), R 2 , R 3 , R 4 , R 5 , and R 6 2. The dye of claim 1, wherein each independently is a member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

5. In the formula (I), R 2 , R 3 , R 4 , R 5 , and R 6 2. The dye of claim 1, wherein each independently represents a member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

6. In the formula (I), R 2 , R 3 , R 4 , R 5 , and R 6 2. The dye of claim 1, wherein each independently represents a member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

7. In the formula (I), R 1 represents an alkyl group having 9 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 2. The dye of claim 1, wherein each independently represents a member selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

8. In the formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the above is an alkoxy group having 1 to 4 carbon atoms. The dye of claim 1.

9. In the formula (I), R 1 represents an alkyl group having 8 to 12 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the above is an alkoxy group having 1 to 4 carbon atoms. The dye of claim 1.

10. In the formula (I), R 1 represents an alkyl group having 8 to 10 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 At least one of the above is an alkoxy group having 1 to 4 carbon atoms. The dye of claim 1.

11. 2. The dye according to claim 1, wherein the compound of formula (I) is selected from the compounds represented by the following formulas (2) to (18): 【Chemical 78】 【Chemical 79】 【Chemistry 80】

12. A method for dyeing polyolefin fibers using supercritical carbon dioxide, comprising the steps of: A method comprising the step of dyeing polyolefin fibers with the dye according to any one of claims 1 to 11 in the presence of supercritical carbon dioxide.

13. The dyeing method according to claim 12, wherein the dyeing step is carried out at 31° C. or higher and at a pressure of 7.4 MPa or higher.

14. 13. The method of claim 12, wherein the concentration of the dye on the fiber ranges from 0.1 to 6.0% o.m.f. (on the mass of fiber).

15. A polyolefin fiber dyed by the dyeing method according to claim 12.

16. A compound represented by the following general formula (I-1): 【Chemistry 81】 [In formula (I-1), R 1-1 represents an alkyl group having 12 to 14 carbon atoms; R 2-1 , R 3-1 , R 4-1 , R 5-1 , and R 6-1 each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 2 to 4 carbon atoms; R 2-1 , R 3-1 , R 4-1 , R 5-1 , and R 6-1 At least one of the groups is an alkyl group having 2 carbon atoms.

17. In the formula (I-1), R 2-1 , R 3-1 , R 4-1 , R 5-1 , and R 6-1 each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 2 carbon atoms; R 2-1 , R 3-1 , R 4-1 , R 5-1 , and R 6-1 The compound according to claim 16, wherein at least one of the following is an alkyl group having 2 carbon atoms:

18. A compound represented by the following general formula (I-2): 【Chemistry 82】 [In formula (I-2), R 1-2 represents a branched alkyl group having 8 carbon atoms, R 2-2 , R 3-2 , R 5-2 and R 6-2 represents a hydrogen atom, R 4-2 represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

19. In the formula (I-2), R 4-2 19. The compound according to claim 18, wherein: represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

20. A compound represented by the following general formula (I-3): 【Chemistry 83】 [In formula (I-3), R 1-3 represents an alkyl group having 10 carbon atoms, R 2-3 , R 3-3 , R 4-3 , R 5-3 and R 6-3 are each independently selected from a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 2-3 , R 3-3 , R 4-3 , R 5-3 and R 6-3 At least one of the groups is an alkyl group having 4 carbon atoms.

21. A compound represented by the following general formula (I-4): 【Chemistry 84】 [In formula (I-4), R 1-4 represents an alkyl group having 8 to 14 carbon atoms; R 2-4 and R 6-4 represents a hydrogen atom, R 3-4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; R 5-4 represents an alkyl group having one carbon atom, R 4-4 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

22. In the formula (I-4), R 3-4 The compound according to claim 21, wherein represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

23. In the formula (I-4), R 3-4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 5-4 represents an alkyl group having one carbon atom, R 4-4 22. The compound according to claim 21, wherein represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

24. A compound represented by the following general formula (I-5): 【Chemistry 85】 [In formula (I-5), R 1-5 represents a branched alkyl group having 8 to 14 carbon atoms, R 2-5 , R 3-5 , R 4-5 , R 5-5 , and R 6-5 are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms; R 2-5 , R 3-5 , R 4-5 , R 5-5 , and R 6-5 At least one of the groups is an alkoxy group having 1 to 4 carbon atoms.

25. In the formula (I-5), R 1-5 represents a branched alkyl group having 8 to 12 carbon atoms; 25. The compound of claim 24.

26. In the formula (I-5), R 1-5 represents a branched alkyl group having 8 to 10 carbon atoms; 25. The compound of claim 24.

27. A compound represented by a formula selected from the group consisting of the following formulas (4), (5), (7), (8), and (12) to (18): 【Chemistry 86】 【Chemistry 87】 【Chemistry 88】

28. A dye for dyeing polypropylene fibers using supercritical carbon dioxide, comprising a compound of the following general formula (I): 【Chemistry 89】 [In formula (I), R 1 represents an alkyl group having 8 to 14 carbon atoms; R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

29. A method for dyeing polypropylene fibers using supercritical carbon dioxide, comprising the steps of:

29. A process comprising the step of dyeing polypropylene fibres in the presence of supercritical carbon dioxide with the dye according to claim 28.

30. The dyeing method according to claim 29, wherein the dyeing step is carried out at 31° C. or higher and at a pressure of 7.4 MPa or higher.

31. 30. The method of claim 29, wherein the concentration of the dye on the fiber ranges from 0.1 to 6.0% o.m.f. (on the mass of fiber).

32. Polypropylene fiber dyed by the dyeing method described in claim 29.

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