Dye for dyeing polyolefin fibres using supercritical carbon dioxide

Abstract

The present invention addresses the problem of providing: a dye for dyeing a polyolefin fiber using supercritical carbon dioxide; a method for dyeing a polyolefin fiber using supercritical carbon dioxide; a polyolefin fiber dyed by the dyeing method; and a compound. The dye is capable of dyeing polyolefin fibers to a yellow color at a high concentration, and the dyed product has excellent dyeing fastness such as light resistance, sublimation, washing and the like. Provided are: a dye for dyeing a polyolefin fiber using supercritical carbon dioxide, which contains at least one of the compounds represented by formula (I); a method for dyeing a polyolefin fiber using supercritical carbon dioxide; a polyolefin fiber dyed by the 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, and polyolefin fibers and compounds dyed by the dyeing method. Background Art

[0002] Polyolefin resins such as polypropylene resin and polyethylene resin are crystalline thermoplastic resins with excellent properties such as low cost, easy processability, high strength, high chemical resistance, high scratch 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 high molecular weight compounds composed of hydrocarbons in both the main chain and the side chain. They have low affinity and compatibility with conventional dye compounds and do not have functional groups effective for chemical reactions. Therefore, high-concentration and high-fast dyeing is considered extremely difficult.

[0004] Therefore, most of the colored polyolefin-based resins currently available on the market are those to which a color pigment is added during the production stage of polymer pellets, etc., and then spun, molded, etc. into a desired shape.

[0005] In this coloring method, the color needs to be determined at the initial stage of the resin product manufacturing process. In addition, if accounting is taken into account, it is necessary to produce more than a certain amount of one color, resulting in limited 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 device with the 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 in Hiroshi Yamamoto, Journal of the Fiber Society, 61 (2005), 319-321, polypropylene resin and polyethylene resin are 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 uses of polypropylene resin and polyethylene resin as synthetic fibers are very limited.

[0009] The reason for this is believed to be that, as described above, it is extremely difficult to dye polypropylene resin fibers and polyethylene resin fibers at high concentrations and with high fastness, and the single yarn fineness has to be increased in the only effective coloring method, namely, the solution dyeing method using colored pigments, and the freedom of color selection is limited.

[0010] So far, in order to perform water-based dyeing of polyolefin resin fibers, attempts have been made to change the molecular structure of the dye, and dyes for dyeing polyolefin resin fibers have been proposed in Japanese Patent Publication No. 38-10741, Japanese Patent Publication No. 40-1277, Japanese Patent Publication No. 41-3515, British Patent No. 872,882, U.S. Patent No. 3,536,735, and Japanese Patent Publication No. 2019-203223.

[0011] Japanese Patent Publication No. 38-10741 describes production examples of red dyes and violet dyes obtained by introducing a phenoxy group having an alkyl group or cycloalkyl group having 3 to 12 carbon atoms as a substituent into an anthraquinone dye, and dyeing examples of polypropylene resin fibers using the same.

[0012] However, it is difficult to dye polyolefin resin fibers at high concentrations with these anthraquinone red dyes or anthraquinone violet dyes. Furthermore, regarding the form of the dyes used in dyeing, there are records of using these anthraquinone red dyes after dissolving them in alcohol or acetone as organic solvents, which is difficult to say that they are environmentally friendly. In addition, there is no record of yellow dyes.

[0013] Japanese Patent Gazette No. 40-1277 describes the production of blue dyes obtained by introducing a phenoxy group having an alkyl group, cycloalkyl group or halogen group having 1 to 9 carbon atoms as a substituent into an anthraquinone dye, and examples of dyeing polyester fibers, polyamide fibers and polyolefin resin fibers using the same.

[0014] However, it is difficult to dye polyolefin resin fibers at high concentrations with these anthraquinone blue dyes, and there is no specific record of the dyeing fastness of the obtained dyed products. Furthermore, regarding the form of the dyes used in dyeing, there are records of using these anthraquinone blue dyes after dissolving them in alcohol or acetone as organic solvents, and it is difficult to say that they are environmentally friendly. In addition, there is no record of yellow dyes.

[0015] Japanese Patent Publication No. 41-3515 describes a production example of a blue dye obtained by introducing a phenoxy group having an alkyl group having 1 to 9 carbon atoms or a halogen group as a substituent into an anthraquinone dye and an example of dyeing a polyolefin resin fiber using the same.

[0016] However, it is difficult to dye polyolefin resin fibers at high concentrations with these anthraquinone blue dyes, and there is no specific record of the dyeing fastness of the resulting dyed products. Furthermore, regarding the form of the dyes used in dyeing, there are records of using them after being dissolved in alcohol or acetone as an organic solvent, and it is difficult to say that they are environmentally friendly. In addition, there is no record of yellow dyes.

[0017] British Patent No. 872,882 describes an example of dyeing polyolefin resin fibers using a blue dye obtained by introducing an alkylamino group or a cycloalkylamino group into the α-position of an anthraquinone dye.

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

[0019] U.S. Patent No. 3,536,735 describes a production example of a red dye obtained by introducing a phenoxy group having two substituents selected from sec-butyl, sec-pentyl and tert-pentyl groups into an anthraquinone dye and an example of dyeing polypropylene resin fibers using the same.

[0020] However, it is difficult to dye polyolefin resin fibers at high concentrations with these anthraquinone red dyes, and there is no specific record of the dyeing fastness of the resulting dyed products. Furthermore, regarding the form of the dyes used in dyeing, there are records of using them after being dissolved in dimethylformamide as an organic solvent, etc., and it is difficult to say that they are environmentally friendly. In addition, there is no record of yellow dyes.

[0021] Japanese Patent Application Laid-Open No. 2019-203223 describes a dyeing example in which polypropylene fibers are dyed in water using a disperse dye composition containing an anthraquinone yellow dye, anthraquinone red dye, or anthraquinone blue dye having a long-chain alkyl group.

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

[0023] Japanese Patent Application Laid-Open No. 55-152869 describes the production of monoazo dyes having long-chain alkyl groups and dyeing of fine-denier polyester fibers using the same. However, there is no description of dyeing of polyolefin fibers using the same. In addition, there is no description of yellow dyes.

[0024] In order to improve the dyeability of polyolefin resin fibers, various studies have been conducted on the modification of polyolefin resin fibers.

[0025] As modification techniques, various techniques are known, such as blending of a dyeable resin component such as polyester, copolymerization with a vinyl monomer having a dyeable group, and blending of a dyeing accelerator such as a stearic acid metal salt.

[0026] Although the dyeability of these modified polyolefin-based resin fibers is improved, there is a problem that the strength of the yarn is reduced by the dyeing treatment, and when used for clothing or the like, the strength is insufficient.

[0027] Furthermore, Japanese Patent No. 3253649 describes dyeing a hydrophobic fiber material with various dyes using supercritical carbon dioxide as a dyeing medium as a dyeing method instead of water-based dyeing.

[0028] However, although polypropylene is described as an example of a hydrophobic fiber material, only an example of dyeing a polyester cloth is described in the Examples, and no example of dyeing a polypropylene fiber is described.

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

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

[0031] If a method of dyeing polypropylene resin fibers and polyethylene resin fibers at a high concentration and with high fastness is put into practical use, it will become possible to dye uncolored, small-filament, inexpensive regular yarns without restrictions on the number of colors, and new uses are expected to be developed in fields requiring high design properties such as clothing and vehicle interior materials, to which polypropylene resin fibers and polyethylene resin fibers have not been applied so far. Summary of the invention

[0032] The present invention is a dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising a compound of the following general formula (I).

[0033] [Chemical formula 1]

[0034]

[0035] [In formula (I),

[0036] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0037] 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

[0038] Figure 1 This is a supercritical carbon dioxide dyeing device used in dyeing. DETAILED DESCRIPTION

[0039] 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 into a high-concentration yellow color and has 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 above-mentioned dyeing method.

[0040] The present invention is a dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising a compound represented by the following general formula (I).

[0041] [Chemical formula 2]

[0042]

[0043] [In formula (I),

[0044] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0045] 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.]

[0046] In addition, the present invention provides a method for dyeing polyolefin fibers using supercritical carbon dioxide.

[0047] The method comprises the step of dyeing polyolefin fibers using the dye of the present invention in the presence of supercritical carbon dioxide.

[0048] The present invention also provides a polyolefin fiber dyed by a dyeing method comprising the step of dyeing the polyolefin fiber using the dye of the present invention in the presence of supercritical carbon dioxide.

[0049] Furthermore, the present invention provides a compound represented by the following general formula (I).

[0050] [Chemical formula 3]

[0051]

[0052] [In formula (I),

[0053] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0054] R 2 , R3 , 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.]

[0055] The dye of the present invention can dye polyolefin fibers into high-concentration yellow in the presence of supercritical carbon dioxide, and the dyed product has excellent color fastness such as light resistance, sublimation and washing.

[0056] The present inventors have found that a dye containing the following specific compound has improved affinity for oleophilic polyolefin fibers and dyes polyolefin fibers in a high-concentration yellow in the presence of supercritical carbon dioxide, thereby completing the present invention.

[0057] <Compound of formula (I)>

[0058] The compound of the general formula (I) contained in the dye of the present invention is as follows.

[0059] [Chemical formula 4]

[0060]

[0061] [In formula (I),

[0062] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0063] 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.]

[0064] In the above formula (I), examples of the alkyl group having 8 to 14 carbon atoms include straight-chain alkyl groups such as n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl and n-tetradecyl, and branched-chain alkyl groups such as 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 2-tridecyl and 2-butyloctyl. Among them, the alkyl group having 8 to 14 carbon atoms is preferably a straight-chain or branched-chain alkyl group having 9 to 14 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 10 to 14 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 12 to 14 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 8 to 12 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 9 to 12 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 10 to 12 carbon atoms, preferably a straight-chain or branched-chain alkyl group having 8 to 10 carbon atoms, and preferably a straight-chain or branched-chain alkyl group having 9 to 10 carbon atoms.

[0065] In the above 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 them, 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.

[0066] In the above formula (I), examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and other linear or branched alkoxy groups having 1 to 4 carbon atoms. Among these, an alkoxy group having 4 carbon atoms is preferred.

[0067] <Compounds of Formula (I)>

[0068] [Chemical formula 5]

[0069]

[0070] [In formula (I),

[0071] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0072] 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.]

[0073] In the above formula (I),

[0074] R 1 Preferably it is 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.

[0075] In the above formula (I),

[0076] R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0077] 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,

[0078] It is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0079] Preferably, it is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0080] It is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0081] More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0082] More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0083] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0084] In the above formula (I),

[0085] 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, 2 , R 3 , R 4 , R 5 and R 6It is more preferred that at least one of the groups is a linear or branched alkyl group having 4 carbon atoms.

[0086] In the above formula (I),

[0087] R 2 and R 6 Preferred is a hydrogen atom.

[0088] In the above formula (I),

[0089] R 3 and R 5 Each of them independently is 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.

[0090] In the above formula (I),

[0091] R 4 It is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0092] 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,

[0093] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0094] Preferably, it is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0095] More preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0096] More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0097] More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0098] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0099] In the above formula (I), preferably: R 1 represents an alkyl group having 8 carbon atoms and R 2 , R 3 , R 4 , R 5 and R 6 Compounds containing only hydrogen atoms are excluded.

[0100] In the above formula (I), preferably: R 1 represents an alkyl group having 9 to 14 carbon atoms,

[0101] R 2 , R 3 , R4 , R 5 and R 6 Each 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 above formula (I), preferably: R 1 represents an alkyl group having 10 to 14 carbon atoms,

[0103] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0104] In the above formula (I), preferably: R 1 represents an alkyl group having 9 to 12 carbon atoms,

[0105] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0106] In the above formula (I), preferably: R 1 represents an alkyl group having 10 to 12 carbon atoms,

[0107] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0108] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 12 carbon atoms,

[0109] 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.

[0110] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 10 carbon atoms,

[0111] R 2 , R 3 , R4 , 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.

[0112] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0113] 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,

[0114] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0115] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 12 carbon atoms,

[0116] 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,

[0117] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0118] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 10 carbon atoms,

[0119] 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,

[0120] And R 2 , R 3 , R 4, R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0121] In the above formula (I), preferably: R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0122] R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms,

[0123] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0124] In the above formula (I),

[0125] Preferred are:

[0126] R 1 is an alkyl group having 8 to 14 carbon atoms,

[0127] R 2 and R 6 is a hydrogen atom,

[0128] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0129] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0130] In addition, in the above formula (I), preferably:

[0131] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0132] R 2 and R 6 is a hydrogen atom,

[0133] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0134] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0135] In addition, in the above formula (I), preferably:

[0136] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0137] R 2 and R 6 is a hydrogen atom,

[0138] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0139] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0140] In addition, in the above formula (I), preferably:

[0141] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0142] R 2 and R 6 is a hydrogen atom,

[0143] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0144] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0145] In addition, in the above formula (I), preferably:

[0146] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0147] R 2 and R 6 is a hydrogen atom,

[0148] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0149] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0150] In addition, in the above formula (I), preferably:

[0151] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0152] R 2 and R6 is a hydrogen atom,

[0153] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0154] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0155] In addition, in the above formula (I), preferably:

[0156] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0157] R 2 and R 6 is a hydrogen atom,

[0158] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0159] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0160] In addition, in the above formula (I), preferably:

[0161] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0162] R 2 and R 6 is a hydrogen atom,

[0163] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0164] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0165] In addition, in the above formula (I), preferably:

[0166] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0167] R 2 and R 6 is a hydrogen atom,

[0168] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0169] R4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0170] In addition, in the above formula (I), preferably:

[0171] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0172] R 2 and R 6 is a hydrogen atom,

[0173] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0174] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0175] In addition, in the above formula (I), preferably:

[0176] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0177] R 2 and R 6 is a hydrogen atom,

[0178] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0179] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0180] In addition, in the above formula (I), preferably:

[0181] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0182] R 2 and R 6 is a hydrogen atom,

[0183] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0184] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0185] In addition, in the above formula (I), preferably:

[0186] R1 is an alkyl group having 8 to 10 carbon atoms,

[0187] R 2 and R 6 is a hydrogen atom,

[0188] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0189] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0190] The compound of formula (I) is preferably the following compound, and more preferably a compound of formula (1), (3), (4), (5), (7), (8), (13), (14), (15), (16), or (17).

[0191] [Chemical formula 6]

[0192]

[0193] [Chemical formula 7]

[0194]

[0195] [Chemical formula 8]

[0196]

[0197] The compound of the above formula (I) is a yellow dye compound.

[0198] In the above formula (I) of the above dye,

[0199] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0200] R 1 Preferably it is 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.

[0201] In the above formula (I) of the above dye,

[0202] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0203] R 2 , R 3 , R 4 , R 5 and R6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0204] 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,

[0205] It is preferably a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0206] Preferably, it is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0207] It is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0208] More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0209] More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0210] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0211] In the above formula (I) of the above dye,

[0212] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0213] 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, 2 , R 3 , R 4 , R 5 and R 6 It is more preferred that at least one of the groups is a linear or branched alkyl group having 4 carbon atoms.

[0214] In the above formula (I) of the above dye,

[0215] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0216] R 2 and R 6 Preferred is a hydrogen atom.

[0217] In the above formula (I) of the above dye,

[0218] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0219] R 3 and R 5Each of them independently is 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.

[0220] In the above formula (I) of the above dye,

[0221] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0222] R 4 It is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0223] 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,

[0224] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms,

[0225] Preferably, it is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0226] More preferably, it is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0227] More preferably, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0228] More preferably, it is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 4 carbon atoms,

[0229] More preferably, it is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0230] In the above formula (I) of the above dye,

[0231] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0232] Preferred is: R 1 represents an alkyl group having 8 carbon atoms and R 2 , R 3 , R 4 , R 5 and R 6 Compounds containing only hydrogen atoms are excluded.

[0233] In the above formula (I) of the above dye,

[0234] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0235] R 1 represents an alkyl group having 9 to 14 carbon atoms,

[0236] R 2 , R 3 , R4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0237] In the above formula (I) of the above dye,

[0238] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0239] R 1 represents an alkyl group having 10 to 14 carbon atoms,

[0240] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0241] In the above formula (I) of the above dye,

[0242] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0243] R 1 represents an alkyl group having 9 to 12 carbon atoms,

[0244] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0245] In the above formula (I) of the above dye,

[0246] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0247] R 1 represents an alkyl group having 10 to 12 carbon atoms,

[0248] R 2 , R 3 , R 4 , R 5 and R 6 Each independently represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

[0249] In the above formula (I) of the above dye,

[0250] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0251] R 1 represents an alkyl group having 8 to 12 carbon atoms,

[0252] 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.

[0253] In the above formula (I) of the above dye,

[0254] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0255] R 1 represents an alkyl group having 8 to 10 carbon atoms,

[0256] 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.

[0257] In the above formula (I) of the above dye,

[0258] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0259] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0260] 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,

[0261] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0262] In the above formula (I) of the above dye,

[0263] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0264] R 1 represents an alkyl group having 8 to 12 carbon atoms,

[0265] 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,

[0266] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0267] In the above formula (I) of the above dye,

[0268] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0269] R 1 represents an alkyl group having 8 to 10 carbon atoms,

[0270] 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,

[0271] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkoxy group having 1 to 4 carbon atoms.

[0272] In the above formula (I) of the above dye,

[0273] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0274] R 1 represents an alkyl group having 8 to 14 carbon atoms,

[0275] R 2 , R 3 , R 4 , R 5 and R 6are independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms,

[0276] And R 2 , R 3 , R 4 , R 5 and R 6 At least one of them is an alkyl group having 1 to 4 carbon atoms.

[0277] In the above formula (I) of the above dye,

[0278] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0279] R 1 is an alkyl group having 8 to 14 carbon atoms,

[0280] R 2 and R 6 is a hydrogen atom,

[0281] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0282] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0283] In addition, in the above formula (I) of the above dye,

[0284] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0285] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0286] R 2 and R 6 is a hydrogen atom,

[0287] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0288] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0289] In addition, in the above formula (I) of the above dye,

[0290] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0291] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0292] R 2 and R 6 is a hydrogen atom,

[0293] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0294] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0295] In addition, in the above formula (I) of the above dye,

[0296] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0297] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0298] R 2 and R 6 is a hydrogen atom,

[0299] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0300] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0301] In addition, in the above formula (I) of the above dye,

[0302] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0303] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0304] R 2 and R 6 is a hydrogen atom,

[0305] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0306] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0307] In addition, in the above formula (I) of the above dye,

[0308] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0309] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0310] R 2 and R 6 is a hydrogen atom,

[0311] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0312] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0313] In addition, in the above formula (I) of the above dye,

[0314] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0315] R 1 is an alkyl group having 8 to 12 carbon atoms,

[0316] R 2 and R 6 is a hydrogen atom,

[0317] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0318] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0319] In addition, in the above formula (I) of the above dye,

[0320] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0321] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0322] R 2 and R 6 is a hydrogen atom,

[0323] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0324] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0325] In addition, in the above formula (I) of the above dye,

[0326] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0327] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0328] R 2 and R 6 is a hydrogen atom,

[0329] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0330] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0331] In addition, in the above formula (I) of the above dye,

[0332] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0333] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0334] R 2 and R 6 is a hydrogen atom,

[0335] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0336] R 4 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0337] In addition, in the above formula (I) of the above dye,

[0338] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0339] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0340] R 2 and R 6 is a hydrogen atom,

[0341] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0342] R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0343] In addition, in the above formula (I) of the above dye,

[0344] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0345] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0346] R 2 and R 6 is a hydrogen atom,

[0347] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

[0348] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0349] In addition, in the above formula (I) of the above dye,

[0350] From the viewpoints of dyeing concentration, light fastness, sublimation fastness, etc., preferred are:

[0351] R 1 is an alkyl group having 8 to 10 carbon atoms,

[0352] R 2 and R 6 is a hydrogen atom,

[0353] R 3 and R 5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

[0354] R 4 It is a hydrogen atom, an alkyl group having 4 carbon atoms, or an alkoxy group having 4 carbon atoms.

[0355] From the perspectives of dyeing concentration, light fastness, sublimation fastness, etc.

[0356] The compound of the above-mentioned formula (I) of the above-mentioned dye is preferably the following compound, and more preferably a compound of formula (1), (3), (4), (5), (7), (8), (13), (14), (15), (16), and (17).

[0357] [Chemical formula 9]

[0358]

[0359] [Chemical formula 10]

[0360]

[0361] [Chemical formula 11]

[0362]

[0363] <Method for producing the compound of formula (I)>

[0364] The method for producing the compound represented by the above formula (I) is described.

[0365] [Chemical formula 12]

[0366]

[0367] The compound represented by the above formula (I) is prepared by reacting an aniline derivative represented by the formula (iD) (wherein 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. 1 represents an alkyl group having 8 to 14 carbon atoms) by coupling.

[0368] (i) Diazotization of the compound of formula (iD)

[0369] First, the compound of formula (iD) is diazotized in an inorganic acid or an organic carboxylic acid and in the presence of water added as needed using a nitrosating agent or nitrosylsulfuric acid to obtain a diazo compound. As the organic carboxylic acid used, for example, acetic acid and propionic acid can be listed. In addition, as an inorganic acid, for example, hydrochloric acid, phosphoric acid and sulfuric acid can be listed, preferably sulfuric acid. As the nitrosating agent used, it is a nitrite of an alkali metal, such as sodium nitrite in a solid state or an aqueous solution state. It should be noted that the compound of formula (iD) can be obtained commercially or manufactured by a known method.

[0370] The reaction temperature of diazotization is preferably -10 to 40°C, more preferably 0 to 40°C.

[0371] (ii) Coupling with a compound of formula (iC)

[0372] The compound represented by the above formula (I) is obtained by adding a solution of the diazo compound represented by the above formula (iD) to a solution of the compound represented by the above formula (iC) in N,N-dimethylformamide (DMF), for example, at a temperature range of 0 to 10°C.

[0373] (iii) Method for producing the compound of formula (iC)

[0374] The compound of formula (iC) as a raw material can be produced as follows.

[0375] [Chemical formula 13]

[0376]

[0377] In the absence of solvent, cyanoacetate (such as methyl cyanoacetate) is reacted with R 1 NH 2 (R 1 The alkylamine represented by (represents an alkyl group having 8 to 14 carbon atoms) is reacted with an acetoacetate (such as methyl acetoacetate) in the presence of piperidine to obtain a compound of formula (iC).

[0378] <Dyes for dyeing polyolefin fibers using supercritical carbon dioxide>

[0379] The dye of the present invention has a compound of formula (I).

[0380] The dye of the present invention may further comprise an additive. As the additive, for example, a coloring agent, a dispersant, a filler, a stabilizer, a plasticizer, a crystal nucleating agent, a modifier, a foaming agent, an ultraviolet light absorber, a light stabilizer, an antioxidant, an antibacterial agent, a mildewproof agent, an antistatic agent, a flame retardant, an inorganic filler and an elastomer for improving impact resistance may be listed.

[0381] The polyolefin fiber of the dyed object dyed by the dye of the present invention can be listed as a fiber formed by a polymer selected from homopolymers of α-olefins such as propylene, ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene, copolymers of these α-olefins, or copolymers of other unsaturated monomers copolymerizable with these α-olefins. In addition, the type of copolymer can be listed as a block copolymer, a random copolymer, a graft copolymer, etc. As specific examples of the above-mentioned polymers, polypropylene resins such as propylene homopolymers, propylene-ethylene block copolymers, propylene-ethylene random copolymers, propylene-ethylene-(1-butene) copolymers, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, poly-1-butene, poly-4-methyl-1-pentene, etc. can be listed.

[0382] The above polymers may be used alone or in combination of two or more to form polyolefin fibers.

[0383] The polyolefin fibers are preferably formed of a polypropylene resin and / or a polyethylene resin, and more preferably formed of a polypropylene resin.

[0384] The shape of the polyolefin fiber can be, for example, block (molded product, etc.), film, fiber (cloth (woven fabric, knitted fabric, nonwoven fabric, etc.), yarn (filament yarn, spun yarn, slit yarn, split yarn, etc.), etc.), preferably fiber.

[0385] The polyolefin fibers may be obtained by blending or joining other polymer components with polypropylene resin and / or polyethylene resin. The polyolefin fibers may be obtained by blending or mixing polypropylene fibers with other fibers such as polyester.

[0386] <Dyeing method of polyolefin fibers using supercritical carbon dioxide>

[0387] The present invention is a method for dyeing polyolefin fibers using supercritical carbon dioxide, the method comprising the step of dyeing the polyolefin fibers using the dye of the present invention in the presence of supercritical carbon dioxide. In the above method, supercritical carbon dioxide is used as a dyeing medium.

[0388] The dyeing method using supercritical carbon dioxide as a dyeing medium is compared to a general dyeing method using water as a dyeing medium, because no water is used during dyeing, and no washing process is required, so no waste water is generated, no dyeing auxiliaries are required, the dyeing time is short, and the carbon dioxide as a dyeing medium can be reused, etc., and therefore has attracted attention as an environmentally friendly dyeing method.

[0389] Furthermore, supercritical carbon dioxide is lipophilic, and the dye and polyolefin resin of the present invention are both lipophilic, so the dyeing medium, the dye, and the dyed article each have high affinity, resulting in a high-quality dyed article.

[0390] The dyeing process 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, because the dyeing temperature and dyeing pressure must be above the critical point of carbon dioxide (7.4 MPa at 31°C) as the dyeing medium.

[0391] In the dyeing step, the dyeing temperature is mainly determined by the type of resin of the dyed fiber and is usually in the range of 60 to 180°C, preferably in the range of 80 to 160°C.

[0392] In the dyeing step, the dyeing pressure is mainly determined by the type of resin of the dyed fiber and is generally in the range of about 7.4 to 40.0 MPa, preferably 20 to 30 MPa.

[0393] The dyeing time in the dyeing step is determined by the type of resin of the dyed fiber and the dyeing temperature. The dyeing time is usually about 10 to 120 minutes, preferably 30 to 90 minutes.

[0394] In the dyeing step, the concentration of the dye relative to the fiber depends on the type and processing state of the dyed fiber. When the dyed fiber is fibrous, the concentration of the dye relative to the fiber is 0.1 to 6.0% omf (on the mass of fiber), preferably 0.1 to 4.0% omf.

[0395] In the dyeing method of the present invention, the bath ratio (mass ratio of the dyed material: carbon dioxide) depends on the type of the dyed material and the processing state. The bath ratio is usually 1:2 to 1:100, preferably 1:5 to 1:75. In the case where the dyed material is a polypropylene cloth wound into a suitable cheese yarn, in the dyeing method of the present invention, the bath ratio is relatively low, for example, 1:2 to 1:5.

[0396] <Dyed polyolefin fibers>

[0397] 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 of yellow, and has excellent dyeing fastness such as light resistance, sublimation, and washing. Examples of uses of the polyolefin fiber include clothing, underwear, hats, socks, gloves, sportswear and other clothing products, vehicle interior materials such as seat covers, carpets, curtains, floor mats, sofa covers, cushion covers and other interior decoration products.

[0398] Hereinafter, the present invention will be described in more detail with reference to Examples, but the aspects of the present invention are not limited to these.

[0399] [Example]

[0400] (Synthesis example 1)

[0401] [Synthesis of Yellow Dye Compound (1)]

[0402] The yellow dye compound (1) was produced according to the following scheme.

[0403] [Chemical formula 14]

[0404]

[0405] 1-A. Synthesis of coupling agent compound (C1) and preparation of coupling agent component solution

[0406] (Process 1)

[0407] Methyl cyanoacetate (9.96 g) was mixed with dodecylamine (18.5 g), heated to 90°C and stirred for 4 hours. Methyl acetoacetate (11.6 g) and piperidine (8.52 g) were added dropwise and stirred at 90°C for 4 hours. After cooling to room temperature, the reaction solution was added dropwise to 7.2% hydrochloric acid (100 g), and ethyl acetate (30 g) was added and stirred. The mixture was filtered out, and the filtrate was washed with water to obtain 3-cyano-1-dodecyl-6-hydroxy-4-methyl-2-pyridone represented by formula (C1) as a crude product. 300 g of DMF was added to the reaction mixture, cooled to 5°C, and a coupling agent component solution (C1) containing a compound of formula (C1) was obtained.

[0408] [Chemical formula 15]

[0409]

[0410] 1-B. Preparation of diazo component solution

[0411] (Process 2)

[0412] A 36% sodium nitrite aqueous solution (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 at a temperature in the range of 5 to 10° C. for 1 hour. Aminosulfonic acid (1.84 g) was added to the mixture, and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D1).

[0413] [Chemical formula 16]

[0414]

[0415] 1-C. Synthesis of yellow dye compound (1) by coupling reaction

[0416] (Process 3)

[0417] In the range of 0 to 10°C, the diazo component solution (D1) obtained in the above step 2 was added dropwise to the coupling agent component solution (C1) obtained in the above step 1 over 1 hour to carry out a coupling reaction. After stirring the mixture in the range of 0 to 10°C for 30 minutes, 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 water content became less than 1.0% by mass to obtain a yellow dye compound (29.0 g, yield 60.6%) represented by the following formula (1). The above yellow dye compound was analyzed by LCMS (m / z 479 (M + )) to confirm its structure.

[0418] [Chemical formula 17]

[0419]

[0420] (Synthesis example 2)

[0421] [Synthesis of Yellow Dye Compound (2)]

[0422] The yellow dye compound (2) was produced according to the following scheme.

[0423] [Chemical formula 18]

[0424]

[0425] 2-A. Preparation of diazo component solution

[0426] (Process 1)

[0427] To a mixture of aniline (9.31 g) represented by the following formula (D2) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D2).

[0428] [Chemical formula 19]

[0429]

[0430] 2-B. Synthesis of yellow dye compound (2) by coupling reaction

[0431] (Process 2)

[0432] The same operation as step 3 of Synthesis Example 1 was carried out except that the diazo component solution (D2) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (2) (31.8 g, yield 75.3%). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) to confirm its structure.

[0433] [Chemical formula 20]

[0434]

[0435] (Synthesis example 3)

[0436] [Synthesis of Yellow Dye Compound (3)]

[0437] The yellow dye compound (3) was produced according to the following scheme.

[0438] [Chemical formula 21]

[0439]

[0440] 3-A. Preparation of diazo component solution

[0441] (Process 1)

[0442] To a mixture of p-toluidine (10.7 g) represented by the following formula (D3) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D3).

[0443] [Chemical formula 22]

[0444]

[0445] 3-B. Synthesis of yellow dye compound (3) by coupling reaction

[0446] (Process 2)

[0447] The same operation as step 3 of Synthesis Example 1 was carried out except that the diazo component solution (D3) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (3) (30.0 g, yield 68.8%). The yellow dye compound was analyzed by LCMS (m / z 437 (M + )) to confirm its structure.

[0448] [Chemical formula 23]

[0449]

[0450] [Synthesis of Yellow Dye Compound (4)]

[0451] The yellow dye compound (4) was prepared according to the following scheme.

[0452] [Chemical formula 24]

[0453]

[0454] 4-A. Preparation of diazo component solution

[0455] (Process 1)

[0456] To a mixture of m-toluidine (10.7 g) represented by the following formula (D4) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D4).

[0457] [Chemical formula 25]

[0458]

[0459] 4-B. Synthesis of yellow dye compound (4) by coupling reaction

[0460] (Process 2)

[0461] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D4) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (4) (30.1 g, yield 69.0%). The yellow dye compound was analyzed by LCMS (m / z 437 (M + )) to confirm its structure.

[0462] [Chemical formula 26]

[0463]

[0464] (Synthesis Example 5)

[0465] [Synthesis of Yellow Dye Compound (5)]

[0466] The yellow dye compound (5) was prepared according to the following scheme.

[0467] [Chemical formula 27]

[0468]

[0469] 5-A. Synthesis of coupling agent compound (C2) and preparation of coupling agent component solution

[0470] (Process 1)

[0471] A coupling agent component solution (C2) containing the 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.

[0472] [Chemical formula 28]

[0473]

[0474] 5-B. Synthesis of yellow dye compound (5) by coupling reaction

[0475] (Process 2)

[0476] The same operation as step 3 of Synthesis Example 1 was performed except that coupling agent component solution (C2) was used instead of coupling agent component solution (C1) as coupling agent component solution to obtain a yellow dye compound represented by the following formula (5) (20.5 g, yield 48.5%). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) to confirm its structure.

[0477] [Chemical formula 29]

[0478]

[0479] (Synthesis Example 6)

[0480] [Synthesis of Yellow Dye Compound (6)]

[0481] The yellow dye compound (6) was prepared according to the following scheme.

[0482] [Chemical formula 30]

[0483]

[0484] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D2) was used instead of the diazo component solution (D1) as the diazo component solution, and the coupling agent component solution (C2) was used instead of the coupling agent component solution (C1) as the coupling agent component solution, to obtain a yellow dye compound represented by the following formula (6) (22.5 g, yield 61.3%). The yellow dye compound was analyzed by LCMS (m / z 367 (M + )) to confirm its structure.

[0485] [Chemical formula 31]

[0486]

[0487] (Synthesis Example 7)

[0488] [Synthesis of Yellow Dye Compound (7)]

[0489] The yellow dye compound (7) was prepared according to the following scheme.

[0490] [Chemical formula 32]

[0491]

[0492] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D3) was used instead of the diazo component solution (D1), and the coupling agent component solution (C2) was used instead of the coupling agent component solution (C1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (7) (24.4 g, yield 64.2%). The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) to confirm its structure.

[0493] [Chemical formula 33]

[0494]

[0495] (Synthesis Example 8)

[0496] [Synthesis of Yellow Dye Compound (8)]

[0497] The yellow dye compound (8) was prepared according to the following scheme.

[0498] [Chemical formula 34]

[0499]

[0500] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D4) was used instead of the diazo component solution (D1), and the coupling agent component solution (C2) was used instead of the coupling agent component solution (C1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (8) (22.8 g, yield 60.0%). The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) to confirm its structure.

[0501] [Chemical formula 35]

[0502]

[0503] (Synthesis Example 9)

[0504] [Synthesis of Yellow Dye Compound (9)]

[0505] The yellow dye compound (9) was prepared according to the following scheme.

[0506] [Chemical formula 36]

[0507]

[0508] 9-A. Synthesis of coupling agent compound (C3) and preparation of coupling agent component solution

[0509] (Process 1)

[0510] A coupling agent component solution (C3) containing 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.

[0511] [Chemical formula 37]

[0512]

[0513] 9-B. Synthesis of yellow dye compound (9) by coupling reaction

[0514] (Process 2)

[0515] The same operation as step 3 of Synthesis Example 1 was performed except that coupling agent component solution (C3) was used instead of coupling agent component solution (C1) as coupling agent component solution to obtain a yellow dye compound represented by the following formula (9) (14.6 g, yield 34.6%). The yellow dye compound was analyzed by LCMS (m / z 423 (M + )) to confirm its structure.

[0516] [Chemical formula 38]

[0517]

[0518] (Synthesis Example 10)

[0519] [Synthesis of Yellow Dye Compound (10)]

[0520] The yellow dye compound (10) was prepared according to the following scheme.

[0521] [Chemical formula 39]

[0522]

[0523] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D2) was used instead of the diazo component solution (D1), and the coupling agent component solution (C3) was used instead of the coupling agent component solution (C1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (10) (11.5 g, yield 31.4%). The yellow dye compound was analyzed by LCMS (m / z 367 (M + )) to confirm its structure.

[0524] [Chemical formula 40]

[0525]

[0526] (Synthesis Example 11)

[0527] [Synthesis of Yellow Dye Compound (11)]

[0528] The yellow dye compound (11) was prepared according to the following scheme.

[0529] [Chemical formula 41]

[0530]

[0531] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D3) was used instead of the diazo component solution (D1) as the diazo component solution, and the coupling agent component solution (C3) was used instead of the coupling agent component solution (C1) as the coupling agent component solution, to obtain a yellow dye compound represented by the following formula (11) (14.5 g, yield 38.2%). The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) to confirm its structure.

[0532] [Chemical formula 42]

[0533]

[0534] (Synthesis Example 12)

[0535] [Synthesis of Yellow Dye Compound (12)]

[0536] The yellow dye compound (12) was prepared according to the following scheme.

[0537] [Chemical formula 43]

[0538]

[0539] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D4) was used instead of the diazo component solution (D1), and the coupling agent component solution (C3) was used instead of the coupling agent component solution (C1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (12) (12.2 g, yield 32.1%). The yellow dye compound was analyzed by LCMS (m / z 381 (M + )) to confirm its structure.

[0540] [Chemical formula 44]

[0541]

[0542] (Synthesis Example 13)

[0543] [Synthesis of Yellow Dye Compound (13)]

[0544] The yellow dye compound (13) was prepared according to the following scheme.

[0545] [Chemical formula 45]

[0546]

[0547] 13-A. Synthesis of coupling agent compound (C4) and preparation of coupling agent component solution

[0548] (Process 1)

[0549] A coupling agent component solution (C4) containing the 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.

[0550] [Chemical formula 46]

[0551]

[0552] 13-B. Synthesis of yellow dye compound (13) by coupling reaction

[0553] (Process 2)

[0554] The same operation as step 3 of Synthesis Example 1 was performed except that coupling agent component solution (C4) was used instead of coupling agent component solution (C1) as coupling agent component solution to obtain a yellow dye compound represented by the following formula (13) (32.0 g, yield 71.2%). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) to confirm its structure.

[0555] [Chemical formula 47]

[0556]

[0557] (Synthesis Example 14)

[0558] [Synthesis of Yellow Dye Compound (14)]

[0559] The yellow dye compound (14) was prepared according to the following scheme.

[0560] [Chemical formula 48]

[0561]

[0562] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D4) was used instead of the diazo component solution (D1), and the coupling agent component solution (C4) was used instead of the coupling agent component solution (C1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (14) (29.0 g, yield 71.0%). The yellow dye compound was analyzed by LCMS (m / z 409 (M + )) to confirm its structure.

[0563] [Chemical formula 49]

[0564]

[0565] (Synthesis Example 15)

[0566] [Synthesis of Yellow Dye Compound (15)]

[0567] The yellow dye compound (15) was prepared according to the following scheme.

[0568] [Chemical formula 50]

[0569]

[0570] 15-A. Preparation of Diazo Component Solution

[0571] (Process 1)

[0572] To a mixture of 4-ethylaniline (12.1 g) represented by the following formula (D5) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D5).

[0573] [Chemical formula 51]

[0574]

[0575] 15-B. Synthesis of yellow dye compound (15) by coupling reaction

[0576] (Process 2)

[0577] The same operation as step 3 of Synthesis Example 1 was carried out except that the diazo component solution (D5) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (15) (31.7 g, yield 70.4%). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) to confirm its structure.

[0578] [Chemical formula 52]

[0579]

[0580] (Synthesis Example 16)

[0581] [Synthesis of Yellow Dye Compound (16)]

[0582] The yellow dye compound (16) was prepared according to the following scheme.

[0583] [Chemical formula 53]

[0584]

[0585] 16-A. Preparation of diazo component solution

[0586] (Process 1)

[0587] To a mixture of 3,5-dimethylaniline (12.1 g) represented by the following formula (D6) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D6).

[0588] [Chemical formula 54]

[0589]

[0590] 16-B. Synthesis of yellow dye compound (16) by coupling reaction

[0591] (Process 2)

[0592] The same operation as step 3 of Synthesis Example 1 was performed except that the diazo component solution (D6) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (16) (21.0 g, yield 46.7%). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) to confirm its structure.

[0593] [Chemical formula 55]

[0594]

[0595] (Synthesis Example 17)

[0596] [Synthesis of Yellow Dye Compound (17)]

[0597] The yellow dye compound (17) was prepared according to the following scheme.

[0598] [Chemical formula 56]

[0599]

[0600] 17-A. Preparation of Diazo Component Solution

[0601] (Process 1)

[0602] To a mixture of 3,4-dimethylaniline (12.1 g) represented by the following formula (D7) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D7).

[0603] [Chemical formula 57]

[0604]

[0605] 17-B. Synthesis of yellow dye compound (17) by coupling reaction

[0606] (Process 2)

[0607] The same operation as step 3 of Synthesis Example 1 was carried out except that the diazo component solution (D7) was used instead of the diazo component solution (D1) as the diazo component solution to obtain a yellow dye compound represented by the following formula (17) (33.7 g, yield 74.8%). The yellow dye compound was analyzed by LCMS (m / z 451 (M + )) to confirm its structure.

[0608] [Chemical formula 58]

[0609]

[0610] (Synthesis Example 18)

[0611] [Synthesis of Yellow Dye Compound (18)]

[0612] The yellow dye compound (18) was prepared according to the following scheme.

[0613] [Chemical formula 59]

[0614]

[0615] 18-A. Preparation of Diazo Component Solution

[0616] (Process 1)

[0617] To a mixture of 4-butoxyaniline (16.5 g) represented by the following formula (D8) and 10% hydrochloric acid (140 g), a 36% sodium nitrite aqueous solution (21.1 g) was added dropwise at a temperature in the range of 5 to 10° C., and the mixture was stirred at a temperature in the range of 5 to 10° C. for 1 hour. To the mixture was added sulfamic acid (1.84 g), and the mixture was stirred at a temperature in the range of 5 to 10° C. for 20 minutes to obtain a diazo component solution (D8).

[0618] [Chemical formula 60]

[0619]

[0620] 18-B. Synthesis of yellow dye compound (18) by coupling reaction

[0621] (Process 2)

[0622] In the range of 0 to 10°C, the diazo component solution (D8) obtained in the above step 1 was added dropwise to the coupling agent component solution (C2) over 1 hour to carry out a coupling reaction. After the mixture was stirred in the range of 0 to 10°C for 30 minutes, 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 water content became less than 1.0 wt% to obtain a yellow dye compound (14.6 g, yield 33.3%) represented by the following formula (18). The above yellow dye compound was analyzed by LCMS (m / z 439 (M + )) to confirm its structure.

[0623] [Chemical formula 61]

[0624]

[0625] (Synthesis Example 19)

[0626] [Synthesis of Yellow Dye Compound (19)]

[0627] After adding n-octanoyl chloride (19.5 g) dropwise to a mixture of 5-amino-anthraquinone [9,1-cd] isothiazol-6-one (25.2 g), toluene (120 g) and pyridine (9.49 g), the temperature was raised to 110°C and stirred for 1 hour. After the mixture was cooled to room temperature, methanol (150 g) was added to precipitate. The mixture was filtered out, and the filtrate was washed with methanol and dried at 60°C until the water content became less than 1.0 wt% to obtain a yellow dye compound represented by the following formula (19) (31.8 g, yield 83.9%). The above yellow dye compound was analyzed by LCMS (m / z 379 (M + )) to confirm its structure.

[0628] [Chemical formula 62]

[0629]

[0630] (Synthesis Example 20)

[0631] [Synthesis of Yellow Dye Compound (20)]

[0632] The same operation as in Synthesis Example 19 was carried out except that 2-ethylhexanoyl chloride (19.5 g) was used instead of n-octanoyl chloride to obtain a yellow dye compound represented by the following formula (20) (33.1 g, yield 87.3%). The yellow dye compound was analyzed by LCMS (m / z 379 (M + )) to confirm its structure.

[0633] [Chemical formula 63]

[0634]

[0635] (Synthesis Example 21)

[0636] [Synthesis of Yellow Dye Compound (21)]

[0637] The same operation as in Synthesis Example 19 was carried out except that n-nonanoyl chloride (21.2 g) was used instead of n-octanoyl chloride to obtain a yellow dye compound represented by the following formula (21) (31.0 g, yield 78.9%). The yellow dye compound was analyzed by LCMS (m / z 393 (M + )) to confirm its structure.

[0638] [Chemical formula 64]

[0639]

[0640] (Synthesis Example 22)

[0641] [Synthesis of Yellow Dye Compound (22)]

[0642] A mixture of thionyl chloride (14.3 g) and toluene (20 g) was added dropwise to a mixture of 2-hexyldecanoic acid (30.8 g) and toluene (30 g). A mixture of pyridine (9.49 g) and toluene (30 g) was slowly added dropwise to the mixture over 1 hour, and 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-anthraquinone [9,1-cd] isothiazol-6-one (25.2 g) and toluene (30 g) was added dropwise to the reaction mixture. After the reaction mixture was heated to 110°C and stirred for 2 hours, the solvent was removed from the mixture by vacuum distillation, and methanol (100 g) was added to the residue to precipitate. The mixture was filtered, and the filtrate was washed with methanol and then with water, and dried at 60°C until the water content was 1.0 wt% or less to obtain a yellow dye compound represented by the following formula (22) (36.7 g, yield 74.7%). The yellow dye compound was analyzed by LCMS (m / z 491 (M + )) to confirm its structure.

[0643] [Chemical formula 65]

[0644]

[0645] (Synthesis Example 23)

[0646] [Synthesis of Yellow Dye Compound (23)]

[0647] 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. After the reaction mixture was cooled to room temperature, 100 g of water was added thereto to precipitate a solid. The mixture was filtered out, and the filtrate was washed with methanol and then with water, and dried at 60°C until the water content became less than 1.0 wt %, to obtain a yellow dye compound (11.9 g, yield 92.8%) represented by the following formula (23). The above yellow dye compound was analyzed by LCMS (m / z 482 (M + )) to confirm its structure.

[0648] [Chemical formula 66]

[0649]

[0650] (Synthesis Example 24)

[0651] [Synthesis of Yellow Dye Compound (24)]

[0652] The same operation as in Synthesis Example 23 was carried out except that 1-bromo-2-ethylhexane (7.73 g) was used instead of 1-bromooctane to obtain a yellow dye compound represented by the following formula (24) (11.5 g, yield 89.7%). The yellow dye compound was analyzed by LCMS (m / z 482 (M + )) to confirm its structure.

[0653] [Chemical formula 67]

[0654]

[0655] (Synthesis Example 25)

[0656] [Synthesis of Yellow Dye Compound (25)]

[0657] The same operation as in Synthesis Example 23 was carried out except that 1-bromodecane (9.98 g) was used instead of 1-bromooctane to obtain a yellow dye compound represented by the following formula (25) (14.2 g, yield 99.4%). The yellow dye compound was analyzed by LCMS (m / z 538 (M + )) to confirm its structure.

[0658] [Chemical formula 68]

[0659]

[0660] (Synthesis Example 26)

[0661] [Synthesis of Yellow Dye Compound (26)]

[0662] The same operation as in Synthesis Example 23 was carried out except that 1-bromohexadecane (12.2 g) was used instead of 1-bromooctane to obtain a yellow dye compound represented by the following formula (26) (15.5 g, yield 98.5%). The yellow dye compound was analyzed by LCMS (m / z 594 (M + )) to confirm its structure.

[0663] [Chemical formula 69]

[0664]

[0665] (Synthesis Example 27)

[0666] [Synthesis of Yellow Dye Compound (27)]

[0667] A mixture of thionyl chloride (14.3 g) and toluene (20 g) was added dropwise to a mixture of 2-hexyldecanoic acid (30.8 g) and toluene (30 g). A mixture of pyridine (9.49 g) and toluene (30 g) was slowly added dropwise to the mixture over 1 hour, and 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 1-aminoanthraquinone (22.3 g) and toluene (30 g) was added thereto. After the reaction mixture was heated to 110° C. and stirred for 2 hours, it was cooled to room temperature, 10 g of a 24% aqueous sodium hydroxide solution was added, and 200 g of water was added to extract the organic layer. After washing the extract with saturated brine, the solvent was removed by vacuum distillation, and a precipitate was precipitated by adding methanol (200 g) to the residue. The mixture was filtered out, and the filtrate was washed with methanol and then water, and dried at 60°C until the water content was less than 1.0 wt %, 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 + )) to confirm its structure.

[0668] [Chemical formula 70]

[0669]

[0670] (Synthesis Example 28)

[0671] [Synthesis of Yellow Dye Compound (28)]

[0672] A mixture of thionyl chloride (28.6 g) and toluene (40 g) was added dropwise to a mixture of 2-hexyldecanoic acid (61.6 g) and toluene (60 g). A mixture of pyridine (19.0 g) and toluene (60 g) was slowly added dropwise to the mixture over 1 hour, and the mixture was heated to 110°C and stirred for 1 hour. After the reaction mixture was cooled to room temperature, a mixture of 1,5-diaminoanthraquinone (23.8 g) and toluene (30 g) was added thereto. After the reaction mixture was heated to 110°C and stirred for 2 hours, it was cooled to room temperature, 20 g of a 24% aqueous sodium hydroxide solution was added, and 300 g of water was added to extract the organic layer. After washing the extract with saturated brine, the solvent was distilled off under reduced pressure, and a precipitate was precipitated by adding methanol (300 g) to the residue. The mixture was filtered out, and the filtrate was washed with methanol and then water, and dried at 60°C until the water content was less than 1.0 wt %, 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 + )) to confirm its structure.

[0673] [Chemical formula 71]

[0674]

[0675] (Synthesis Example 29)

[0676] [Synthesis of Yellow Dye Compound (29)]

[0677] 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 out, the filtrate was washed with water, and dried at 60°C until the water content was less than 1.0 wt%. DMF (60 g), triethylamine (8.1 g) and 2-ethylhexylamine (12.4 g) were added to the obtained solid and heated to 90°C and stirred for 2 hours. The mixture was cooled to room temperature, 20 g of 30% sulfuric acid was added, and then 100 g of water was added to precipitate. The mixture was filtered out, and the filtrate was washed with water. Methanol (60 g) was added to the crude product and stirred at 60°C for 30 minutes. After cooling to room temperature, the mixture was filtered out, and the filtrate was washed with methanol and then water, and dried at 60°C until the water content became less than 1.0 wt %, 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 + )) to confirm its structure.

[0678] [Chemical formula 72]

[0679]

[0680] (Synthesis Example 30)

[0681] [Synthesis of Yellow Dye Compound (30)]

[0682] 30-A. Synthesis of coupling agent compound (C5) and preparation of coupling agent component solution

[0683] (Process 1)

[0684] 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. The mixture was filtered out, and the filtrate was washed with water and ethyl acetate. The organic layer was extracted from the filtrate, and after the organic layer was washed with saturated brine, the solvent was removed by reduced pressure distillation to obtain 2-ethylhexylaminobenzoic acid (28.9 g, yield 116%) shown in the following formula (C5a) as a crude product.

[0685] [Chemical formula 73]

[0686]

[0687] (Process 2)

[0688] The mixture of 2-ethylhexylaminobenzoic acid (28.9 g) obtained in the above step 1, acetic anhydride (50 g) and acetic acid (50 g) 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. After the organic layer was washed with saturated brine, the solvent was distilled off under reduced pressure to obtain 4-hydroxy-1-(2-ethylhexyl)quinoline-2-one (36.7 g, yield 134%) shown in the following formula (C5) as a crude product. 100 g of methanol was added to the crude product and cooled to 5 ° C to obtain a coupling agent component solution (C5) containing a compound of formula (C5).

[0689] [Chemical formula 74]

[0690]

[0691] 30-B. Preparation of Diazo Component Solution

[0692] (Process 3)

[0693] 4-Nitroaniline (13.8 g) represented by the following formula (D9) was added to a mixture of concentrated sulfuric acid (34 g) and 43% nitrosylsulfuric acid (29.3 g) at 30 to 35° C., and stirred at the same temperature for 2 hours to obtain a diazo component solution (D9).

[0694] [Chemical formula 75]

[0695]

[0696] 30-C. Synthesis of yellow dye compound (30) by coupling reaction

[0697] (Process 4)

[0698] In the range of 0 to 10°C, triethylamine (120g) was appropriately added while the diazo component solution (D9) obtained in the above step 3 was added dropwise to the coupling agent component solution (C5) obtained in the above step 1 for 1 hour to carry out a coupling reaction. After stirring the mixture in the range of 0 to 10°C for 30 minutes, the product was filtered out from the reaction mixture and washed with methanol and then with water. Methanol (80g) was added to the crude product and stirred at 60°C for 30 minutes. After cooling to room temperature, the mixture was filtered out, and the filtrate was washed with methanol and then with water, and dried at 60°C until the water content became less than 1.0wt%, to obtain a yellow dye compound represented by the following formula (30) (10.2g, yield 24.2%). The above yellow dye compound was analyzed by LCMS (m / z 423 (M + )) to confirm its structure.

[0699] [Chemical formula 76]

[0700]

[0701] Tables 1 and 2 show the dye compounds described in the synthesis examples.

[0702] Table 1

[0703]

[0704] Synthesis example Dye compounds <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> 1 1 <![CDATA[C 12 H 25 ]]> H H <![CDATA[C 4 H 9 ]]> H H 2 2 <![CDATA[C 12 H 25 ]]> H H H H H 3 3 <![CDATA[C 12 H 25 ]]> H H <![CDATA[CH 3 ]]> H H 4 4 <![CDATA[C 12 H 25 ]]> H H H <![CDATA[CH 3 ]]> H 5 5 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[C 4 H 9 ]]> H H 6 6 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H H H H 7 7 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[CH 3 ]]> H H 8 8 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H H <![CDATA[CH 3 ]]> H 9 9 <![CDATA[C 8 H 17 ]]> H H <![CDATA[C 4 H g ]]> H H 10 10 <![CDATA[C 8 H 17 ]]> H H H H H 11 11 <![CDATA[C 8 H 17 ]]> H H <![CDATA[CH 3 ]]> H H 12 12 <![CDATA[C 8 H 17 ]]> H H H <![CDATA[CH 3 ]]> H 13 13 <![CDATA[C 10 H 21 ]]> H H <![CDATA[C 4 H 9 ]]> H H 14 14 <![CDATA[C 10 H 21 ]]> H H H <![CDATA[CH 3 ]]> H 15 15 <![CDATA[C 12 H 25 ]]> H H <![CDATA[C 2 H 5 ]]> H H 16 16 <![CDATA[C 12 H 25 ]]> H <![CDATA[CH 3 ]]> H <![CDATA[CH 3 ]]> H 17 17 <![CDATA[C 12 H 25 ]]> H H <![CDATA[CH 3 ]]> <![CDATA[CH 3 ]]> H 18 18 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[OC 4 H 9 ]]> H H

[0705] Table 2

[0706]

[0707]

[0708] <Dyeing example>

[0709] Using the dye compounds described in Tables 1 and 2, polypropylene cloth or polyethylene cloth was dyed by a supercritical carbon dioxide dyeing method.

[0710] (Supercritical Carbon Dioxide Dyeing of Polypropylene Fabric)

[0711] (Staining example P1)

[0712] The supercritical carbon dioxide dyeing device used in dyeing is shown in Figure 1 middle.

[0713] The dyeing device consists of liquid CO 2The invention is composed of a gas storage cylinder (1), a filter (2), a cooling sleeve (3), a cooler (4), a high-pressure pump (5), a preheater (6), a pressure gauge (7 to 9), a magnetic drive unit (10), a DC motor (11), a safety valve (12, 13), a stop valve (14 to 18), a needle valve (19), and a heater (20).

[0714] The polypropylene cloth is cut and weighed to about 50 to 70 g, and rolled onto a stainless steel drum (21) with punched holes in the order of cotton cloth, polypropylene cloth, and cotton cloth from the inside, and then loosely fixed with cotton yarn. The cotton cloth on the inside is the lining cloth, and the cotton cloth on the outside is the cover cloth.

[0715] A stainless steel drum with the above cloth samples (cotton cloth, polypropylene cloth, cotton cloth) wound around it is fixed in a pressure-resistant stainless steel tank (22), and the yellow dye compound 1 obtained in Synthesis Example 1 is wrapped in a wiping paper in an amount equivalent to 0.3% by mass relative to the mass of the polypropylene cloth, and is placed in the fluid passage on the upper part of the stainless steel drum. The volume of the pressure-resistant stainless steel tank is 2230 cm 3 . Close all valves in the dyeing device and heat to 120°C through the preheater.

[0716] After the dyeing temperature is reached, the stop valves (14) and (16) are opened, and 1.13 kg of liquid carbon dioxide is flowed into the pressure-resistant stainless steel tank using a high-pressure pump via a cooling jacket. Thereafter, the stop valves (14) and (16) are closed, and the liquid is circulated through the impeller and magnetic drive unit at the lower part of the pressure-resistant stainless steel tank. The rotation speed of the magnetic drive unit is 750 rpm, and the circulation direction is from the inside to the outside of the drum.

[0717] After the specified temperature and pressure (120°C, 25MPa) are reached in the pressure-resistant stainless steel tank, the polypropylene cloth is dyed by maintaining these temperature and pressure conditions for 60 minutes. After dyeing, the stop valve (18) is opened and the needle valve is slowly opened to release the carbon dioxide in the pressure-resistant stainless steel tank, so that the pressure in the pressure-resistant stainless steel tank is reduced from 25MPa to atmospheric pressure. The cycle is continued until the critical pressure of carbon dioxide (about 8MPa) is reached. Then, the polypropylene yellow dyed cloth in the pressure-resistant stainless steel tank is taken out.

[0718] (Dyeing examples P2 to P26)

[0719] A polypropylene yellow dyed cloth was obtained by the same dyeing procedure as Dyeing Example P1 except that the yellow dye compound 1 described in Dyeing Example P1 was changed to the 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.

[0720] Table 3

[0721]

[0722] Dyeing example Dye compounds <![CDATA[R 1 ]]> <![CDATA[R 2 ]]> <![CDATA[R 3 ]]> <![CDATA[R 4 ]]> <![CDATA[R 5 ]]> <![CDATA[R 6 ]]> P1 1 <![CDATA[C 12 H 25 ]]> H H <![CDATA[C 4 H 9 ]]> H H P2 2 <![CDATA[C 12 H 25 ]]> H H H H H P3 3 <![CDATA[C 12 H 25 ]]> H H <![CDATA[CH 3 ]]> H H P4 4 <![CDATA[C 12 H 25 ]]> H H H <![CDATA[CH 3 ]]> H P5 5 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[C 4 H 9 ]]> H H P6 6 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H H H H P7 7 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[CH 3 ]]> H H P8 8 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H H <![CDATA[CH 3 ]]> H P9 9 <![CDATA[C 8 H 17 ]]> H H <![CDATA[C 4 H 9 ]]> H H P10 13 <![CDATA[C 10 H 21 ]]> H H <![CDATA[C 4 H 9 ]]> H H P11 14 <![CDATA[C 10 H 21 ]]> H H H <![CDATA[CH 3 ]]> H P12 15 <![CDATA[C 12 H 25 ]]> H H <![CDATA[C 2 H 5 ]]> H H P13 16 <![CDATA[C 12 H 25 ]]> H <![CDATA[CH 3 ]]> H <![CDATA[CH 3 ]]> H P14 17 <![CDATA[C 12 H 25 ]]> H H <![CDATA[CH 3 ]]> <![CDATA[CH 3 ]]> H P15 18 <![CDATA[CH 2 CH(C 2 H 5 )C 4 H 9 ]]> H H <![CDATA[OC 4 H 9 ]]> H H

[0723] Table 4

[0724]

[0725]

[0726] The polypropylene dyed fabrics obtained in Dyeing Examples P1 to P26 were subjected to dyeability evaluation, light fastness test, sublimation fastness test, washing fastness test, perspiration fastness test, friction fastness test, and fastness test to hot pressing.

[0727] (1) Dyeability evaluation

[0728] The dyeability was visually evaluated by Total K / S value, K / S value (measured at the maximum wavelength) obtained by colorimetric measurement of the dyed cloth, and dye residue after dyeing. The colorimetric measurement of the dyed cloth was performed using an integrating sphere spectrophotometer Color-Eye5 (manufactured by GretagMacbeth Co., Ltd.), with the dyed cloth pasted on white paper and observed under a light source of D65 and a 2-degree field of view.

[0729] (2) Light fastness test

[0730] The light fastness test was conducted by the ultraviolet carbon arc lamp method according to JIS L0842: 2004. The test method is outlined 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 at a blackboard temperature of 63±3°C, and then the color fading was determined.

[0731] (3) Sublimation fastness test

[0732] The sublimation fastness test was conducted according to JIS L0854: 2013. The test method is outlined as follows: The dyed cloth was sandwiched between nylon cloths and kept at 120±2° C. for 80 minutes under a load of 12.5 kPa, and then the discoloration and staining of the nylon cloth were determined.

[0733] (4) Washing fastness test

[0734] The washing fastness test was conducted according to JIS L0844:2011 (A-2). The test method is outlined as follows. A multi-fiber interwoven fabric was attached to the dyed fabric, and the fabric was washed for 30 minutes at 50±2°C in the presence of soap, and the discoloration and contamination of the cotton and nylon parts of the multi-fiber interwoven fabric were determined. In addition, the contamination of the residual liquid after washing was determined.

[0735] (5) Sweat fastness test

[0736] The sweat fastness test is conducted according to the method of JIS L0848: 2004. The test method is outlined as follows. A multi-fiber interwoven fabric is attached to the dyed fabric, and the fabric is immersed in acidic artificial sweat or alkaline artificial sweat for 30 minutes. After that, the fabric is kept at 37±2°C for 4 hours under a load of 12.5 kPa, and then dried at 60°C or below to determine whether the fabric is discolored or not, and whether the fabric is contaminated by the cotton and nylon parts of the multi-fiber interwoven fabric.

[0737] (6) Friction fastness test

[0738] The friction fastness test was conducted according to JIS L0849: 2013. The test method is outlined as follows. Using a friction fastness tester RT-300 (manufactured by Daiei Kagaku Seiki Seisakusho), a load of 2N was applied to the dyed cloth with dry cotton cloth or wet cotton cloth and the coloration of the cotton cloth was determined by reciprocating rubbing 100 times.

[0739] (7) Fastness test to heat pressing

[0740] The fastness test to heat pressing is conducted by a method in accordance with JIS L0850:2015 (A-2 drying). The test method is outlined as follows. Dyed cloth is overlapped on cotton cloth, and passed through a 150°C heating plate under a load of 4±1 kPa for 15 seconds, and then the discoloration and staining of the cotton cloth are determined.

[0741] The evaluation results of dyeing examples with the compound of formula (I) are shown in Table 5, and the evaluation results of dyeing examples with dye compounds other than the compound of formula (I) are shown in Table 6.

[0742]

[0743]

[0744] Regarding the dyeing properties of the compound of formula (I), R used in dyeing examples P1 to P15 1 is an alkyl group having 8 to 12 carbon atoms, R 2 , R 3 , R 4 , R 5 and R 6 The compound in which each of the groups independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms has good dyeing properties.

[0745] However, the dyeing properties of the dye compounds other than the compound of formula (I) used in Dyeing Examples P16 to P26 were poor.

[0746] In addition, regarding the fastness of the compound of formula (I), R used in dyeing examples P1 to P15 1 is an alkyl group having 8 to 12 carbon atoms, R 2 , R 3 , R 4 , R 5 and R 6 The compounds each independently representing a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms have good fastness.

[0747] As mentioned above, the present invention is not limited to the above-described embodiment, and forms obtained by appropriately combining or replacing the configurations of the embodiment are also included in the present invention.

[0748] Furthermore, based on the knowledge of those skilled in the art, the combination of the embodiments or the order of the processes may be appropriately rearranged or various design changes may be made to the embodiments, and the embodiments with such modifications may also be included in the scope of the present invention.

[0749] The present invention can be used to dye polyolefin fibers used in clothing such as clothes, underwear, hats, socks, gloves, sportswear, vehicle interior materials such as seat covers, and interior decoration products such as carpets, curtains, floor mats, sofa covers, and cushion covers.

Claims

1. A dye for dyeing polyolefin fibers using supercritical carbon dioxide, comprising a compound of the following general formula (I), In formula (I), R1 represents an alkyl group having 8 to 14 carbon atoms, R2, R3, R4, R5 and R6 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.

2. The dye according to claim 1, wherein As the compound of formula (I), the compound in which R1 represents an alkyl group having 8 carbon atoms and R2, R3, R4, R5 and R6 all represent hydrogen atoms is excluded.

3. The dye according to claim 1 or 2, wherein In the formula (I), R2, R3, R4, R5 and R6 are each independently one 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. The dye according to claim 1 or 2, wherein In the formula (I), R2, R3, R4, R5 and R6 are each independently one 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. The dye according to claim 1 or 2, wherein In the above formula (I), R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

6. The dye according to claim 1 or 2, wherein In the above formula (I), R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

7. The dye according to claim 1, wherein In the formula (I), R1 represents an alkyl group having 9 to 14 carbon atoms, R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

8. The dye according to claim 1, wherein In the formula (I), R1 represents an alkyl group having 8 to 14 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

9. The dye according to claim 1, wherein In the formula (I), R1 represents an alkyl group having 8 to 12 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

10. The dye according to claim 1, wherein In the formula (I), R1 represents an alkyl group having 8 to 10 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

11. The dye according to claim 1, wherein The compound of formula (I) is selected from the compounds represented by the following formulae (1) to (18), 12. A method for dyeing polyolefin fibers using supercritical carbon dioxide, The method comprises the step of dyeing polyolefin fibers using 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 process is performed at 31° C. or higher and under a pressure of 7.4 MPa or higher.

14. The dyeing method according to claim 12 or 13, wherein: The concentration of the dye relative to the fiber ranges from 0.1 to 6.0% omf (on the mass of fiber). 15 . A polyolefin fiber dyed by the dyeing method according to claim 12 .

16. A compound of the following general formula (I), In formula (I), R1 represents an alkyl group having 8 to 14 carbon atoms, R2, R3, R4, R5 and R6 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.

17. The compound according to claim 16, wherein The compound in which R1 represents an alkyl group having 8 carbon atoms and R2, R3, R4, R5 and R6 all represent hydrogen atoms is excluded.

18. The compound according to claim 16 or 17, wherein In the above formula (I), R2, R3, R4, R5 and R6 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 4 carbon atoms.

19. The compound according to claim 16 or 17, wherein In the above formula (I), R2, R3, R4, R5 and R6 each independently represent one 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.

20. The compound according to claim 16 or 17, wherein In the above formula (I), R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

21. The compound according to claim 16 or 17, wherein In the above formula (I), R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms.

22. The compound according to claim 16 or 17, wherein In the formula (I), R1 represents an alkyl group having 9 to 14 carbon atoms, R2, R3, R4, R5 and R6 each independently represent one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 8 carbon atoms.

23. The compound according to claim 16 or 17, wherein In the formula (I), R1 represents an alkyl group having 8 to 14 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

24. The compound according to claim 16 or 17, wherein In the formula (I), R1 represents an alkyl group having 8 to 12 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

25. The compound according to claim 16 or 17, wherein In the formula (I), R1 represents an alkyl group having 8 to 10 carbon atoms, R2, R3, R4, R5 and R6 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, At least one of R2, R3, R4, R5 and R6 is an alkoxy group having 1 to 4 carbon atoms.

26. The compound according to claim 16, wherein The compound of the general formula (I) is selected from the compounds represented by the following formulae (1) to (18),

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