Composition for dyeing

Abstract

To provide a composition for dyeing containing at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, exhibiting excellent dyeing effects at a pH of 6.0 or higher.SOLUTION: A dyeing composition according to the present invention comprises: at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin; and at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, and exhibits a pH of 6.0 or higher.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dye composition containing at least one dye selected from the group consisting of crocin, salts of crocin, crocetin, and salts of crocetin. [Background technology]

[0002] Hair coloring products using synthetic dyes are mainstream for dyeing hair. However, due to concerns about damage to hair and allergic reactions, hair coloring compositions using safer natural pigments have been attracting attention in recent years.

[0003] Gardenia pigment is a natural pigment obtained from the fruit of Gardenia augusta Merrill or Gardenia jasminoides Ellis, which belongs to the Rubiaceae family, and is available in three colors: blue, red, and yellow, depending on the manufacturing method. Gardenia yellow pigment is mainly composed of crocin and / or crocetin, and is generally obtained by extracting Gardenia fruit with water or aqueous ethanol. It is widely used as a food coloring agent and is also sometimes used as a hair dye.

[0004] For example, Patent Document 1 proposes a hair coloring composition containing (iii) gardenia yellow pigment which contains 13-cis-crocetin and may or may not contain all-trans-crocetin, and in the case where all-trans-crocetin is contained, the peak area of ​​13-cis-crocetin when analyzed by HPLC is set to 1 when the peak area of ​​all-trans-crocetin is set to 1. Patent Document 1 also describes that by using the gardenia yellow pigment (iii) directly as a dye, fixation to hair is improved and an excellent hair coloring effect can be obtained without using a dyeing auxiliary. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2018 / 181008 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional hair coloring compositions containing gardenia yellow pigment only provide sufficient hair dyeing effects under acidic conditions of about pH 5.0 or less, and do not provide sufficient hair dyeing effects under weakly acidic, neutral, or alkaline conditions of pH 6.0 or more. This limits the pH of the hair coloring composition, and there is a problem in that it is not possible to expand the variety of hair dyes.

[0007] The present invention aims to provide a dyeing composition which contains at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, and which provides an excellent dyeing effect at a pH of 6.0 or higher. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems and have found that a dyeing composition that provides excellent dyeing results at pH 6.0 or higher can be obtained by blending at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin with at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts. The present invention was completed through further research based on this finding.

[0009] That is, the present invention provides the following aspects. Item 1. A dyeing composition comprising at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, and at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, and having a pH of 6.0 or higher. Item 2. The dyeing composition according to Item 1, wherein the amine is at least one selected from the group consisting of acyclic monoamines and cyclic amines. Item 3. The dyeing composition according to Item 2, wherein the non-cyclic monoamine is a non-cyclic aliphatic monoamine. Item 4. The dyeing composition according to any one of Items 1 to 3, wherein the ammonium salt is a non-cyclic ammonium salt. Item 5. The dyeing composition according to Item 4, wherein the non-cyclic ammonium salt is a non-cyclic aliphatic ammonium salt. Item 6. The dyeing composition according to Item 5, wherein the acyclic aliphatic ammonium salt is a acyclic aliphatic quaternary ammonium salt. Item 7. The dyeing composition according to any one of Items 1 to 6, wherein the content of the nitrogen-containing compound is 0.01 to 10% by mass. Item 8. The dye composition according to any one of Items 1 to 7, which is a hair coloring composition. Item 9. The dyeing composition according to Item 8, which is used for dyeing gray hair. Item 10. A hair dyeing method, comprising dyeing hair with the dyeing composition according to any one of items 1 to 9. Item 11. A hair dyeing method, comprising dyeing an animal fiber with the dyeing composition according to any one of items 1 to 7. Effect of the Invention

[0010] The dyeing composition of the present invention contains at least one pigment selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, as well as at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, and therefore has an excellent dyeing effect at a pH of 6.0 or higher, and therefore has the advantage that it can be used in a pH range that cannot be adopted by conventional dyeing compositions containing gardenia yellow pigment (e.g., hair coloring compositions).

[0011] Furthermore, according to the dye composition of the present invention, at least one pigment selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin is blended with at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, thereby achieving good hair dyeability. This allows the amount of dyeing auxiliaries used in the past to be reduced or to be omitted, thereby suppressing damage to the hair and scalp and suppressing dyeing of the skin, etc., during hair dyeing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] 1. Dyeing composition The dyeing composition of the present invention is characterized in that it contains at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, and at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, and has a pH of 6 or more. Since the dyeing composition of the present invention contains the nitrogen-containing compound together with the dye, it has an excellent dyeing effect at a pH of 6.0 or more. The dyeing composition of the present invention will be described in detail below.

[0013] Although the dye composition of the present invention contains at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, the mechanism by which excellent dyeing effect can be obtained at pH 6.0 or higher is not clear, but is thought to be as follows. For example, the isoelectric point of the hair surface is 3.9, and the inside of the hair is basically hydrophobic. Gardenia yellow pigment, which is mainly composed of crocin and / or crocetin, has an isoelectric point of about 4.0, and therefore is hydrophobic under acidic conditions. Under acidic conditions, the hair surface is weakly positively charged, but gardenia yellow pigment is hydrophobic, so there is little electrostatic repulsion and gardenia yellow pigment is easily penetrating into the inside of the hair, which is thought to facilitate dyeing inside the hair. However, when the pH of the dye composition is outside the isoelectric point of gardenia yellow pigment, for example, under basic conditions, both hair and gardenia yellow pigment are negatively charged, which generates electrostatic repulsion and makes it difficult to penetrate into the inside of the hair, making it difficult to dye inside the hair. As a result, it is considered that the dyeing effect is not sufficient. On the other hand, for example, under basic conditions, when at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin coexists with the nitrogen-containing compound, they are attracted to each other by electrostatic interaction, and the dye becomes hydrophobic under the influence of the hydrophobic group of the nitrogen-containing compound. As a result, it is considered that the dye easily penetrates into the inside of the hair even under basic conditions, and dyeing easily occurs inside the hair, so that an excellent dyeing effect is obtained. However, the above-mentioned mechanism of action is merely speculation, and the present invention is not limited to the above-mentioned mechanism of action.

[0014] <Dye> The dye composition of the present invention contains at least one colorant selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin. Crocin and crocetin are carotenoid colorants, and are contained in, for example, the fruit of Gardenia augusta Merrill or Gardenia jasminoides Ellis (Rubiaceae) and the stigma of saffron (Crocus sativus (Iridaceae)).

[0015] The method for extracting crocin or crocetin from plant base is not particularly limited, and examples thereof include known methods such as extraction from crushed dried gardenia fruit using water or alcohol (e.g., methanol, ethanol, etc.), or a mixture thereof.

[0016] Crocetin may also be obtained by hydrolyzing crocin. In the case of hydrolysis of crocin with an alkali, crocetin can usually be precipitated by adding an appropriate amount of an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, or an organic acid such as citric acid, to the reaction solution after completion of the hydrolysis to adjust the pH to 4.0 or less, preferably 1.0 to 3.0. The mixture in which crocetin has been precipitated can then be centrifuged or filtered to recover crocetin as a paste-like solid. The obtained crocetin may be further treated by washing or the like.

[0017] The salts of crocin and crocetin are not particularly limited, and examples thereof include alkali metal salts such as sodium salts and potassium salts, and alkaline earth metal salts such as magnesium salts and calcium salts.

[0018] The dye composition of the present invention preferably contains gardenia yellow pigment as the coloring matter. Gardenia yellow pigment is not particularly limited, and known pigments containing crocin and / or crocetin as the main components can be used, for example, pigments used as food colorants. Gardenia yellow pigment is defined in the 9th edition of the Official Specification of Food Additives (Ministry of Health, Labour and Welfare of Japan) as "This product is obtained from the fruit of Gardenia jasminoides J. Ellis (Gardenia augusta Merr.) and contains crocin and crocetin as the main components. It may contain dextrin or lactose." In the present invention, gardenia yellow pigment may be one that meets the above definition.

[0019] The gardenia yellow pigment used in the present invention preferably contains 13-cis-crocetin and may or may not contain all-trans-crocetin. When it contains all-trans-crocetin, it is preferable that the peak area of ​​13-cis-crocetin is 1 or more when the peak area of ​​all-trans-crocetin is set to 1 when analyzed by HPLC. Hereinafter, the peak area of ​​13-cis-crocetin when the peak area of ​​all-trans-crocetin is set to 1 when analyzed by HPLC is sometimes simply referred to as "peak area ratio (13-cis / all-trans)". By using such a gardenia yellow pigment, it becomes possible to dye hair and animal fibers a uniform yellow color. The gardenia yellow pigment may contain crocin.

[0020] In the present invention, "all-trans-crocetin" refers to a compound in which all of the double bonds in crocetin are in the trans configuration and which has the following structure. [ka]

[0021] In addition, "13-cis-crocetin" refers to a compound in which the double bonds at the 13th and 14th positions of crocetin are cis-type and has the following structure. [ka]

[0022] In the present invention, the peak area ratio (13-cis / All-trans) is determined by performing HPLC analysis under conditions that enable separation of all-trans-crocetin and 13-cis-crocetin, determining the peak areas of both, and calculating the peak area of ​​13-cis-crocetin when the peak area of ​​all-trans-crocetin is set to 1. Specifically, a column of Inertsil ODS-3 5μm 4.6×250mm (GL Science) was used, and a solvent was used, using solution A (1% (v / v) acetic acid) and solution B (acetonitrile), at a flow rate of 1ml / min, with a column temperature of 40°C, and time-programmed so that the ratio of solution B was 20% at 0 min, 80% at 20 min, 80% at 30 min, 20% at 30.01 min, and 20% at 40 min, and a photodiode array (PDA) was used as a detector. The peak area of ​​13-cis-crocetin was calculated by dividing the peak area of ​​13-cis-crocetin by the peak area of ​​all-trans-crocetin in a chromatogram produced at an absorbance of 417.0 nm. The peak area ratio (13-cis / All-trans) was determined by dividing the peak area of ​​13-cis-crocetin by the peak area of ​​all-trans-crocetin. This value increases as the amount of all-trans-crocetin decreases.

[0023] From the viewpoint of further improving the fixation to hair and animal fibers, the gardenia yellow pigment used in the present invention preferably has a peak area ratio (13-cis / All-trans) of 1 to 10,000, more preferably 1 to 5,000, even more preferably 1.5 to 3,000, still more preferably 1.5 to 2,000, even more preferably 1.5 to 1,000, still more preferably 1.5 to 500, particularly preferably 1.8 to 100, and most preferably 1.8 to 15.

[0024] At present, the molar absorptivity of 13-cis-crocetin is unknown. However, considering that the molar absorptivity of cis-crocin:trans-crocin is approximately 63350:approximately 89000=approximately 0.7:1 (J.Agric.FoodChem,2008,56,1627-1637), the molar absorptivity of 13-cis-crocetin is also considered to be significantly smaller than that of all-trans-crocetin. Therefore, even if the peak area of ​​all-trans-crocetin and the peak area of ​​13-cis-crocetin are 1:1, the ratio of the amounts is not 1:1, and it is estimated that 13-cis-crocetin is significantly more abundant.

[0025] The method for producing gardenia yellow pigment having the above-mentioned properties is not particularly limited as long as it provides a product having the above-mentioned properties, but a suitable example includes a method including a step of hydrolyzing crocin in a crocin-containing extract obtained from the fruit of Gardenia jasmine (Rubiaceae) to obtain a crocetin-containing mixed solution (the mixed solution contains both 13-cis-crocetin and all-trans-crocetin), and a step of removing all-trans-crocetin from the obtained crocetin-containing mixed solution. Specific conditions for such a method for producing gardenia yellow pigment are disclosed in JP 2011-168649 A and the like, and may be set in accordance with the known content.

[0026] In the dye composition of the present invention, the content of the pigment (or the Gardenia Yellow pigment) may be appropriately set depending on the product form of the dye composition, the color depth to be imparted to hair and animal fibers, etc. 10% 1cm is preferably 0.1 or more, more preferably 0.1 to 40, further preferably 0.5 to 30, and particularly preferably 1.0 to 20. 10% 1cm" is a unit of color intensity of a pigment, and refers to the value obtained by converting the absorbance at the maximum absorption wavelength measured in a reliable concentration range using an absorptiometer with a cell with an optical path length of 1 cm into a value for a 10% by weight solution. The maximum absorption wavelength of Gardenia Yellow Pigment (crocetin type) is around 420 nm, so the color value E of Gardenia Yellow Pigment having the above characteristics is 10% 1cm can be determined by identifying a maximum absorption wavelength near 420 nm and measuring the absorbance at that wavelength, but if there is no maximum absorption wavelength, it is sufficient to measure the absorbance at 420 nm. In measuring the color value of Gardenia Yellow, a 0.5% (w / v) aqueous solution of trisodium phosphate is used as the dilution solvent for the dye solution used to measure absorbance.

[0027] In the dye composition of the present invention, the content of the pigment (or the gardenia yellow pigment) (the total content when two or more kinds of the pigments are contained) is preferably 0.005% by mass or more, more preferably 0.005 to 40% by mass, even more preferably 0.01 to 30% by mass, still more preferably 0.1 to 30% by mass, and particularly preferably 0.2 to 20% by mass. In the dye composition of the present invention, crocin may be converted to crocetin by hydrolysis.

[0028] <Nitrogen-containing compounds> The dye composition of the present invention contains at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts together with the colorant (or the gardenia yellow pigment). The nitrogen-containing compound is blended to change the colorant (or the gardenia yellow pigment), which usually exhibits a sufficient dyeing effect only under acidic conditions of about pH 5.0 or less, into the colorant (or the gardenia yellow pigment), which exhibits a sufficient dyeing effect at pH 6.0 or more.

[0029] [Amine] The amine used in the present invention is not particularly limited as long as it can change the above-mentioned dye (or the above-mentioned gardenia yellow dye) that usually exhibits a sufficient dyeing effect only under acidic conditions of about pH 5.0 or less into the above-mentioned dye (or the above-mentioned gardenia yellow dye) that exhibits a sufficient dyeing effect at pH 6.0 or more, and may be a monoamine or diamine, or a polyamine such as a triamine or tetraamine, or may be an acyclic amine (meaning an amine that is not cyclic), or may be a cyclic amine (meaning an amine in which at least one of the atoms constituting the ring is a nitrogen atom). From the viewpoint of further improving the dyeing effect of the dye composition at pH 6.0 or more, the amine used in the present invention is preferably at least one selected from the group consisting of acyclic monoamines and cyclic amines. In the present invention, the acyclic monoamine means an amine that has one amino group in the molecule and is not cyclic.

[0030] The non-cyclic monoamine is not particularly limited, and examples thereof include those represented by the general formula: NH 1 Primary monoamines represented by the general formula: NHR 1 R 2 and secondary monoamines represented by the general formula: NR 1 R 2 R 3 These may be used alone or in combination of two or more. 1 , R 2 , and R 3 are each independently an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. In the present invention, the aliphatic hydrocarbon group means a chain aliphatic hydrocarbon group.

[0031] The aliphatic hydrocarbon group is not particularly limited, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched. The number of carbon atoms of the aliphatic hydrocarbon group (however, if the group has a substituent, the number of carbon atoms of the substituent is included) is not particularly limited, but from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, it is preferably 1 to 24, more preferably 2 to 22, even more preferably 4 to 18, and particularly preferably 6 to 15. The alicyclic hydrocarbon group is not particularly limited, and may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the alicyclic hydrocarbon group (however, if the group has a substituent, the number of carbon atoms of the substituent is included) is not particularly limited, but from the viewpoint, it is preferably 5 to 20, more preferably 6 to 18, and even more preferably 6 to 15. The aromatic hydrocarbon group is not particularly limited, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group (including the number of carbon atoms in the substituent when the aromatic hydrocarbon group has a substituent) is not particularly limited, but from the above-mentioned viewpoints, it is preferably 6 to 20, more preferably 6 to 18, and even more preferably 6 to 15. The aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a substituent such as an alkyl group, an alkenyl group, a halogen atom, a hydroxy group, an alkoxy group, or a carbonyl group.

[0032] In each of the above general formulas, R 1 , R 2 , and R 3are preferably aliphatic hydrocarbon groups, more preferably each independently an aliphatic hydrocarbon group having the above carbon number, and even more preferably each independently a saturated aliphatic hydrocarbon group having the above carbon number, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher. That is, the non-cyclic monoamine is preferably a non-cyclic aliphatic monoamine, more preferably a non-cyclic saturated aliphatic monoamine. In the present invention, the non-cyclic aliphatic monoamine means an amine having one amino group in the molecule, in which all the substituents bonded to the nitrogen atom of the amino group are aliphatic hydrocarbon groups, and which is not cyclic. In the present invention, the non-cyclic saturated aliphatic monoamine means an amine having one amino group in the molecule, in which all the substituents bonded to the nitrogen atom of the amino group are saturated aliphatic hydrocarbon groups, and which is not cyclic. In addition, the total carbon number of the non-cyclic monoamine is preferably 4 to 60, more preferably 6 to 50, even more preferably 6 to 45, even more preferably 6 to 40, and particularly preferably 6 to 30, from the viewpoint of the above.

[0033] Examples of the primary monoamine include aliphatic primary monoamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, laurylamine, tridodecylamine, myristylamine, pentadecylamine, hexadecylamine, stearylamine, behenylamine, allylamine, and oleylamine; alicyclic primary monoamines such as cyclohexylamine, 3,3,5-trimethylcyclohexylamine, cycloheptylamine, cyclooctylamine, norbornylamine, bornylamine, dicyclopentanylamine, and amantadine; and aromatic primary monoamines such as aniline, 2,4,6-trimethylaniline, toluidine, naphthylamine, anisidine, and benzylamine. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or more, the aliphatic primary monoamine is preferable. That is, the non-cyclic monoamine is preferably an aliphatic primary monoamine, more preferably a saturated aliphatic primary monoamine. In the present invention, the aliphatic primary monoamine means an amine having one amino group in the molecule, and one substituent bonded to the nitrogen atom of the amino group is an aliphatic hydrocarbon group. In the present invention, the saturated aliphatic primary monoamine means an amine having one amino group in the molecule, and one substituent bonded to the nitrogen atom of the amino group is a saturated aliphatic hydrocarbon group.

[0034] Examples of the secondary monoamines include aliphatic secondary monoamines such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, dilaurylamine, dimyristylamine, dipentadecylamine, dihexadecylamine, distearylamine, methylbutylamine, ethylpropylamine, and ethylisopropylamine; Examples of the non-cyclic monoamine include alicyclic secondary monoamines having at least one alicyclic hydrocarbon group, such as diphenylamine, dicycloheptylamine, cycloheptylmethylamine, cycloheptylethylamine, dicyclooctylamine, cyclooctylmethylamine, and cyclooctylethylamine; and aromatic secondary monoamines having at least one aromatic hydrocarbon group, such as diphenylamine, phenylmethylamine, phenylethylamine, phenylbutylamine, phenylhexylamine, N-methylbenzylamine, N-ethylbenzylamine, and ditolylamine. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, the aliphatic secondary monoamine is preferred. That is, the non-cyclic monoamine is preferably a non-cyclic aliphatic secondary monoamine, and more preferably a non-cyclic saturated aliphatic secondary monoamine. In the present invention, the non-cyclic aliphatic secondary monoamine means an amine having one amino group in the molecule, in which the two substituents bonded to the nitrogen atom of the amino group are all aliphatic hydrocarbon groups, and which are not cyclic. In the present invention, the non-cyclic saturated aliphatic secondary monoamine refers to an amine having one amino group in the molecule, in which two substituents bonded to the nitrogen atom of the amino group are all saturated aliphatic hydrocarbon groups, and which is not cyclic. In one embodiment of the non-cyclic aliphatic secondary monoamine, the two aliphatic hydrocarbon groups are the same aliphatic hydrocarbon group, and the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 to 12, more preferably 4 to 10, and even more preferably 4 to 8.

[0035] Examples of the tertiary monoamines include aliphatic tertiary monoamines such as trimethylamine, triethylamine, tributylamine, tripentylamine, triisopentylamine, trihexylamine, trioctylamine, dimethylethylamine, diethylmethylamine, diisopropylethylamine, and N,N-dimethylbutylamine; tricyclohexylamine, N,N-dimethylcyclohexylamine, N,N-diethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-dicyclohexylethylamine, and N,N-dicyclohexylethylamine. amine, alicyclic tertiary monoamine having at least one alicyclic hydrocarbon group such as tricyclohexylamine; aromatic tertiary monoamine having at least one aromatic hydrocarbon group such as triphenylamine, tritolylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, N,N-dibenzylmethylamine, tribenzylamine, N,N-dimethyl-4-methylbenzylamine, N,N-dimethylphenylamine, N,N-diethylphenylamine, and N,N-diphenylmethylamine. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, the aliphatic tertiary monoamine is preferred. That is, the non-cyclic monoamine is preferably a non-cyclic aliphatic tertiary monoamine, more preferably a non-cyclic saturated aliphatic tertiary monoamine. In the present invention, the non-cyclic aliphatic tertiary monoamine means an amine having one amino group in the molecule, all three substituents bonded to the nitrogen atom of the amino group being aliphatic hydrocarbon groups, and not cyclic. In the present invention, the non-cyclic saturated aliphatic tertiary monoamine means an amine having one amino group in the molecule, all three substituents bonded to the nitrogen atom of the amino group being saturated aliphatic hydrocarbon groups, and not cyclic. In one embodiment of the non-cyclic aliphatic tertiary monoamine, all three aliphatic hydrocarbon groups are the same aliphatic hydrocarbon group, and the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 to 10, more preferably 4 to 8, and even more preferably 4 to 6.

[0036] The cyclic amine is not particularly limited, and examples thereof include cyclic amines in which at least one of the atoms constituting the aliphatic ring is a nitrogen atom (hereinafter also referred to as "heterocyclic aliphatic amines"), and cyclic amines in which at least one of the atoms constituting the aromatic ring is a nitrogen atom (hereinafter also referred to as "heterocyclic aromatic amines").

[0037] The heterocyclic aliphatic amine is not particularly limited, and examples thereof include azetidine, pyrrolidine, piperidine, piperazine, morpholine, and quinuclidine. The heterocyclic aliphatic amine may have one or more substituents such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic group, a halogen atom, a carboxy group, a hydroxy group, an alkoxy group, a carbonyl group, an amino group, an azo group, a sulfo group, and a group combining two or more of these. Specific examples of the heterocyclic aliphatic amine having a substituent include 1-piperidinepropionic acid, minoxidil, and pyrrolidinyldiaminopyrimidine oxide. The heterocyclic aliphatic amine may be used alone or in combination of two or more.

[0038] The heterocyclic aromatic amine is not particularly limited, and examples thereof include 5-membered heterocyclic aromatic amines such as pyrrole, pyrazole, imidazole, oxazole, isoxazole, thiazole, isothiazole, and triazole; 6-membered heterocyclic aromatic amines such as pyridine, pyridazine, pyrimidine, pyrazine, and triazine; and polycyclic heterocyclic aromatic amines such as quinoline, isoquinoline, quinazoline, phthalazine, pteridine, indole, isoindole, benzimidazole, indazole, benzoxazole, benzothiazole, benzotriazole, and purine. The heterocyclic aromatic amine may have one or more substituents such as an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heteroaromatic group, a halogen atom, a carboxy group, a hydroxy group, an alkoxy group, a carbonyl group, an amino group, an azo group, a sulfo group, and a group obtained by combining two or more of these. Specific examples of the heterocyclic aromatic amine having a substituent include 2-phenylbenzimidazole-5-sulfonic acid, glutamylamidoethylindole, oxyquinoline sulfate, 2,6-diamino-3-((pyridin-3-yl)azo)pyridine, and 2,4-diaminopyridine. One type of heterocyclic aromatic amine may be used, or two or more types may be used in combination.

[0039] [Ammonium salts] The ammonium salt used in the present invention is not particularly limited as long as it can change the above-mentioned colorant (or the above-mentioned gardenia yellow pigment) that exhibits a sufficient dyeing effect only under acidic conditions of about pH 5.0 or less into the above-mentioned colorant (or the above-mentioned gardenia yellow pigment) that exhibits a sufficient dyeing effect at pH 6.0 or more, and may be a non-cyclic ammonium salt or a cyclic ammonium salt. In the present invention, the non-cyclic ammonium salt means an ammonium salt in which the ammonium is not cyclic, and the cyclic ammonium salt means an ammonium salt in which the ammonium is cyclic. The ammonium salt used in the present invention is preferably a non-cyclic ammonium salt from the viewpoint of further improving the dyeing effect of the dye composition at pH 6.0 or more.

[0040] Examples of the non-cyclic ammonium salt include those represented by the general formula: [NHR 1 ] + X - Primary ammonium salts represented by the general formula: [NHR 1 R 2 ] + X - A secondary ammonium salt represented by the general formula: [NHR 1 R 2 R 3 ] + X - and tertiary ammonium salts represented by the general formula: [NR 1 R 2 R 3 R 4 ] + X - These may be used alone or in combination of two or more. 1 , R 2 , R 3 , and R 4 are each independently an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.

[0041] The aliphatic hydrocarbon group is not particularly limited, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be linear or branched. The number of carbon atoms of the aliphatic hydrocarbon group (however, if the group has a substituent, the number of carbon atoms of the substituent is included) is not particularly limited, but from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, it is preferably 1 to 24, more preferably 2 to 22, even more preferably 4 to 20, and particularly preferably 6 to 18. The alicyclic hydrocarbon group is not particularly limited, and may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the alicyclic hydrocarbon group (however, if the group has a substituent, the number of carbon atoms of the substituent is included) is not particularly limited, but from the viewpoint, it is preferably 5 to 20, more preferably 6 to 18, and even more preferably 6 to 15. The aromatic hydrocarbon group is not particularly limited, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group (including the number of carbon atoms in the substituent when the aromatic hydrocarbon group has a substituent) is not particularly limited, but from the above-mentioned viewpoints, it is preferably 6 to 20, more preferably 6 to 18, and even more preferably 6 to 15. The aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may have a substituent such as an alkyl group, an alkenyl group, a halogen atom, a hydroxy group, an alkoxy group, or a carbonyl group.

[0042] In each of the above general formulas, R 1 , R 2 , R 3 , and R 4are preferably aliphatic hydrocarbon groups, more preferably each independently an aliphatic hydrocarbon group having the above carbon number, and even more preferably each independently a saturated aliphatic hydrocarbon group having the above carbon number, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher. That is, the non-cyclic ammonium salt is preferably a non-cyclic aliphatic ammonium salt, more preferably a non-cyclic saturated aliphatic ammonium salt. In the present invention, the non-cyclic aliphatic ammonium salt means an ammonium salt in which the ammonium is not cyclic and all the substituents bonded to the nitrogen atom of the ammonium are aliphatic hydrocarbon groups. In the present invention, the non-cyclic saturated aliphatic ammonium salt means an ammonium salt in which the ammonium is not cyclic and all the substituents bonded to the nitrogen atom of the ammonium are saturated aliphatic hydrocarbon groups. In addition, the total carbon number of the non-cyclic ammonium salt is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 25, and particularly preferably 10 to 22, from the viewpoints mentioned above.

[0043] Examples of the ammonium constituting the primary ammonium salt include aliphatic primary ammonium such as methylammonium, ethylammonium, propylammonium, isopropylammonium, butylammonium, pentylammonium, hexylammonium, heptylammonium, octylammonium, nonylammonium, decylammonium, undecylammonium, laurylammonium, tridodecylammonium, myristylammonium, pentadecylammonium, hexadecylammonium, stearylammonium, and behenylammonium; alicyclic primary ammonium such as cyclohexylammonium, cycloheptylammonium, and cyclooctylammonium; aromatic primary ammonium such as phenylammonium, benzylammonium, and phenethylammonium. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, the aliphatic primary ammonium is preferred. That is, the non-cyclic ammonium salt is preferably an aliphatic primary ammonium salt, more preferably a saturated aliphatic primary ammonium salt. In the present invention, the aliphatic primary ammonium salt refers to an ammonium salt in which one substituent bonded to the nitrogen atom of ammonium is an aliphatic hydrocarbon group. In the present invention, the saturated aliphatic primary ammonium salt refers to an ammonium salt in which one substituent bonded to the nitrogen atom of ammonium is a saturated aliphatic hydrocarbon group.

[0044] Examples of the ammonium constituting the secondary ammonium salt include dimethylammonium, diethylammonium, methylethylammonium, dipropylammonium, methylpropylammonium, ethylpropylammonium, diisopropylammonium, methylisopropylammonium, Aliphatic secondary ammonium such as ethylisopropylammonium, dibutylammonium, methylbutylammonium, ethylbutylammonium, dipentylammonium, dihexylammonium, diheptylammonium, dioctylammonium, dinonylammonium, didecylammonium, diundecylammonium, dilaurylammonium, ditridodecylammonium, dimyristylammonium, dipentadecylammonium, dihexadecylammonium, and distearylammonium; alicyclic secondary ammonium having at least one alicyclic hydrocarbon group such as dicyclopentylammonium, cyclopentylbutylammonium, dicyclohexylammonium, cyclohexylmethylammonium, cyclohexylethylammonium, cyclohexylbutylammonium, dicycloheptylammonium, and dicyclooctylammonium; aromatic secondary ammonium having at least one aromatic hydrocarbon group such as diphenylammonium, phenylmethylammonium, phenylethylammonium, and dibenzylammonium. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or more, the aliphatic secondary ammonium salt is preferable. That is, the non-cyclic ammonium salt is preferably a non-cyclic aliphatic secondary ammonium salt, more preferably a non-cyclic saturated aliphatic secondary ammonium salt. In the present invention, the non-cyclic aliphatic secondary ammonium salt means an ammonium salt in which the ammonium is not cyclic and all two substituents bonded to the nitrogen atom of the ammonium are aliphatic hydrocarbon groups. In the present invention, the non-cyclic saturated aliphatic secondary ammonium salt means an ammonium salt in which the ammonium is not cyclic and all two substituents bonded to the nitrogen atom of the ammonium are saturated aliphatic hydrocarbon groups.In one embodiment of the non-cyclic aliphatic secondary ammonium salt, the two aliphatic hydrocarbon groups are the same aliphatic hydrocarbon group, and the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 to 12, more preferably 4 to 10, and even more preferably 4 to 8.

[0045] Examples of the ammonium constituting the tertiary ammonium salt include aliphatic tertiary ammonium such as trimethylammonium, triethylammonium, tributylammonium, trihexylammonium, trioctylammonium, dimethylethylammonium, and diethylmethylammonium; alicyclic tertiary ammonium having at least one alicyclic hydrocarbon group such as tricyclohexylammonium, cyclohexyldimethylammonium, and cyclohexyldiethylammonium; aromatic tertiary ammonium having at least one aromatic hydrocarbon group such as triphenylammonium, diphenylmethylammonium, diphenylethylammonium, and tribenzylammonium. These may be used alone or in combination of two or more. Among these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, the aliphatic tertiary ammonium is preferred. That is, the non-cyclic ammonium salt is preferably a non-cyclic aliphatic tertiary ammonium salt, and more preferably a non-cyclic saturated aliphatic tertiary ammonium salt. In the present invention, the non-cyclic aliphatic tertiary ammonium salt means an ammonium salt in which the ammonium is not cyclic and all three substituents bonded to the nitrogen atom of the ammonium are aliphatic hydrocarbon groups. In the present invention, the non-cyclic saturated aliphatic tertiary ammonium salt refers to an ammonium salt in which the ammonium is not cyclic and all three substituents bonded to the nitrogen atom of the ammonium are saturated aliphatic hydrocarbon groups. In one embodiment of the non-cyclic aliphatic tertiary ammonium salt, all three aliphatic hydrocarbon groups are the same aliphatic hydrocarbon group, and the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 to 10, more preferably 4 to 8, and even more preferably 4 to 6.

[0046] Examples of ammonium constituting the quaternary ammonium salt include tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetrahexylammonium, tetraoctylammonium, hexyltrimethylammonium, cyclohexyltrimethylammonium, hexyltriethylammonium, cyclohexyltriethylammonium, octyltrimethylammonium, octyltriethylammonium, hexyldimethyloctylammonium, dimethyldioctylammonium, diethyldioctylammonium, lauryltrimethylammonium, lauryltriethylammonium, dilauryldimethylammonium, dilauryldiethylammonium, stearyltrimethylammonium, stearyltriethylammonium, distearyldimethylammonium, and distearyldiethylammonium. Aliphatic quaternary ammonium such as ethylammonium and behentrimonium; alicyclic quaternary ammonium having at least one alicyclic hydrocarbon group such as cyclohexyltrimethylammonium, cyclohexyltriethylammonium, cyclohexyltributylammonium, cyclopentyltributylammonium, dicyclohexylmethylethylammonium, tricyclopentylethylammonium, and tetracyclohexylammonium; aromatic quaternary ammonium having at least one aromatic hydrocarbon group such as phenyltrimethylammonium, phenyltributylammonium, benzyltrimethylammonium, benzyltriethylammonium, dodecyldimethylbenzylammonium, tetraphenylammonium, tetrabenzylammonium, and tetranaphthylammonium. These may be used alone or in combination of two or more. Of these, from the viewpoint of further improving the dyeing effect of the dyeing composition at pH 6.0 or higher, the aliphatic quaternary ammonium is preferred. That is, the non-cyclic ammonium salt is preferably a non-cyclic aliphatic quaternary ammonium salt, more preferably a non-cyclic saturated aliphatic quaternary ammonium salt.In the present invention, the non-cyclic aliphatic quaternary ammonium salt refers to an ammonium salt in which the ammonium is not cyclic and all four substituents bonded to the nitrogen atom of the ammonium are aliphatic hydrocarbon groups. In the present invention, the non-cyclic saturated aliphatic quaternary ammonium salt refers to an ammonium salt in which the ammonium is not cyclic and all four substituents bonded to the nitrogen atom of the ammonium are saturated aliphatic hydrocarbon groups. In one embodiment of the non-cyclic aliphatic quaternary ammonium salt, all four aliphatic hydrocarbon groups are the same aliphatic hydrocarbon group, and the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 to 10, more preferably 4 to 8, and even more preferably 4 to 6.

[0047] X in the above general formula - The counter anion is not particularly limited and may be, for example, a halogen ion (F - , Cl - , Br - , and I - Examples of the anion include carboxylate anions (anions of carboxylic acids having 1 to 7 carbon atoms (e.g., formic acid, acetic acid, and propionic acid)), sulfonate ions (anions of sulfonic acids having 1 to 20 carbon atoms (e.g., methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid)), phosphate ions (anions of phosphoric acid and phosphoric acid group-containing compounds having 1 to 10 carbon atoms), thiocyanate ions, perchlorate ions, sulfate ions, nitrate ions, and inorganic acids. Among these, preferred are halogen ions, and more preferred are Cl ions. - Or Br - It is.

[0048] Examples of the ammonium constituting the cyclic ammonium salt include cyclic ammonium in which at least one of the atoms constituting the aliphatic ring is a nitrogen atom, such as piperidinium, pyrrolidinium, pyrrolinium, morpholinium, piperazinium, and derivatives having these skeletons (for example, those having the above skeleton and hydrogen atoms in the skeleton are substituted with substituents such as alkyl groups, alkenyl groups, aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups); and cyclic ammonium in which at least one of the atoms constituting the aromatic ring is a nitrogen atom, such as pyridinium, picolinium, quinolinium, isoquinolinium, and derivatives having these skeletons (for example, those having the above skeleton and hydrogen atoms in the skeleton are substituted with substituents such as alkyl groups, alkenyl groups, aryl groups, halogen atoms, hydroxyl groups, and alkoxy groups). Examples of the counter anion constituting the cyclic ammonium salt include the above counter anions. These may be used alone or in combination of two or more.

[0049] In the dye composition of the present invention, the content of the nitrogen-containing compound may be appropriately set depending on the content of the pigment (or the gardenia yellow pigment), but is usually about 0.005 to 14 mass %, and from the viewpoint of further improving the dyeing effect of the dye composition at pH 6.0 or higher, it is preferably 0.01 to 10 mass %, more preferably 0.05 to 10 mass %.

[0050] In the dye composition of the present invention, the content of the nitrogen-containing compound is usually about 0.005 to 14 parts by mass per part by mass of the pigment (or the Gardenia Yellow pigment) (1 part by mass in total when two or more kinds of the pigments are contained), and from the viewpoint of further improving the dyeing effect of the dye composition at pH 6.0 or higher, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 10 parts by mass.

[0051] <Penetration enhancer (dyeing aid)> The dyeing composition of the present invention has high fixation to hair and animal fibers and has an excellent dyeing effect even without the use of a penetration enhancer, so the dyeing composition of the present invention does not need to contain a penetration enhancer, but may contain a penetration enhancer in order to further improve the dyeability of the dye on hair and animal fibers by further promoting the penetration into hair and animal fibers.

[0052] The penetration enhancer may be any that can enhance the penetration of the direct dye into the hair and animal fibers, and examples thereof include aromatic alcohols such as benzyl alcohol, 2-phenylethyl alcohol, cinnamyl alcohol, phenylpropanol, α-methylbenzyl alcohol, dimethylbenzyl carbinol, benzyloxyethanol, phenoxyethanol, and p-anisyl alcohol; lower monohydric alcohols such as ethanol and isopropanol; polyhydric alcohols such as ethylene glycol, propylene glycol, and 1,3-butylene glycol; alkylene carbonates such as ethylene carbonate and propylene carbonate, etc. These penetration enhancers may be used alone or in combination of two or more.

[0053] The content of the penetration enhancer in the dyeing composition of the present invention is not particularly limited, and may be, for example, 0 to 10% by mass, preferably 0 to 5.0% by mass, and more preferably 0 to 0.4% by mass. In conventional hair coloring compositions using direct dyes, the content of the penetration enhancer is usually set to 0.5% by mass or more when the penetration enhancer is blended, but the dyeing composition of the present invention has high hair dyeing properties, so the content of the penetration enhancer can be set to 0% by mass or a small amount, and safety concerns due to the blending of the penetration enhancer can be eliminated or reduced.

[0054] <Reducing agent (dyeing auxiliary)> The dye composition of the present invention may not contain a reducing agent, but may contain a reducing agent in order to further improve the dyeability of the dye on hair and animal fibers.

[0055] The type of reducing agent is not particularly limited, and examples thereof include sulfites such as sodium sulfite and sodium hydrogen sulfite, sodium L-ascorbate, compounds having a thiol group, etc. These reducing agents may be used alone or in combination of two or more.

[0056] The content of the reducing agent in the dyeing composition of the present invention is not particularly limited, and may be, for example, 0 to 1 mass%, preferably 0 to 0.8 mass%, and more preferably 0 to 0.2 mass%. In conventional hair coloring compositions using direct dyes, the content of the reducing agent is usually set to 0.3 mass% or more when the reducing agent is blended, but the dyeing composition of the present invention has high hair dyeing properties, so the content of the penetration promoter can be set to 0 mass% or a small amount, and safety concerns due to the blending of the reducing agent can be eliminated or reduced.

[0057] <Alkaline agent (dyeing auxiliary)> The dye composition of the present invention may not contain an alkaline agent, but may contain an alkaline agent in order to open the cuticle and thereby further improve the dyeability of the dye on hair and animal fibers.

[0058] The type of alkaline agent is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkanolamines and salts thereof such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, isopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and 2-amino-2-hydroxymethyl-1,3-propanediol; ammonia and salts thereof; alkanediamines and salts thereof such as 1,3-propanediamine; and carbonates such as guanidine carbonate, guanidine hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and lithium carbonate. These alkaline agents may be used alone or in combination of two or more.

[0059] The content of the alkaline agent in the dyeing composition of the present invention is not particularly limited and may be appropriately set so as to satisfy the pH range described below, for example, 0 to 1.5% by mass, preferably 0 to 1.0% by mass, and more preferably 0 to 0.4% by mass. In conventional hair coloring compositions using direct dyes, the content of an alkaline agent is usually set to 0.5% by mass or more when it is blended, but the dyeing composition of the present invention has high hair dyeing properties, so the content of the alkaline agent can be set to 0% by mass or a small amount, and safety concerns due to the blending of an alkaline agent can be eliminated or reduced.

[0060] <Other ingredients> The dye composition of the present invention may contain, as necessary, direct dyes such as acid dyes, natural dyes, nitro dyes, and disperse dyes; reactive dyes such as oxidation dyes, etc. Whether or not such other dyes are blended may be determined depending on the color tone to be imparted to hair, etc.

[0061] In addition, the dyeing composition of the present invention may contain other components that are commonly used in dyeing agents in addition to the above-mentioned components. Such components include, for example, higher alcohols, silicones, hydrocarbons, waxes, animal and vegetable oils and fats, higher fatty acids, organic solvents, thickeners, organic acids, cationic surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, cationic polymers, anionic polymers, amphoteric polymers, proteins, protein hydrolysates, amino acids, preservatives, chelating agents, stabilizers, antioxidants, antibacterial agents, moisturizers, pH adjusters, animal extracts, plant extracts, yeast extracts, vitamins, pigments, fragrances, ultraviolet absorbers, hair growth components, hair nourishing components, and dandruff prevention components. The content of these components can be appropriately set according to the type of components used, the product form of the dyeing composition, etc.

[0062] <ph> The dyeing composition of the present invention is characterized by having a pH of 6.0 or more. Conventional dyeing compositions containing Gardenia Yellow Pigment cannot provide sufficient dyeing effect unless the dyeing composition is in an acidic condition of about pH 5.0 or less. However, the dyeing composition of the present invention contains at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts together with the coloring matter (or the Gardenia Yellow Pigment) and can provide excellent dyeing effect at pH 6.0 or more. The pH of the dyeing composition of the present invention is preferably 6.0 to 12.0, more preferably 6.5 to 11.5, even more preferably 7.0 to 11.0, even more preferably 7.0 to 10.0, and particularly preferably 7.0 to 9.0, from the viewpoint of further improving the dyeing effect while suppressing damage to hair, animal fibers, or scalp. In the present invention, the pH is a value at 25°C.

[0063] The pH of the dye composition of the present invention can be adjusted, for example, by using a pH adjuster.The pH adjuster is not particularly limited, but can be, for example, inorganic bases such as potassium hydroxide, sodium hydroxide, sodium carbonate, etc.; organic bases such as triethanolamine, diisopropanolamine, triisopropanolamine, etc.; inorganic acids such as hydrochloric acid, sulfuric acid, etc.; organic acids such as lactic acid, sodium lactate, citric acid, sodium citrate, succinic acid, sodium succinate, etc.

[0064] <Applicable objects, product types, etc.> The dyeing composition of the present invention is used for dyeing hair and animal fibers, such as wool, goat hair, and silk.

[0065] The dyeing composition of the present invention is preferably a hair coloring composition. The hair coloring composition of the present invention may be applied to any hair, such as white hair, black hair, brown hair, and blonde hair, but white hair is a suitable target for application because the hair coloring composition of the present invention is likely to produce a hair dyeing effect. The hair coloring composition of the present invention may also be a shampoo, rinse, conditioner, or hair milk. The hair coloring composition of the present invention may also be incorporated into a shampoo, rinse, conditioner, or hair milk.

[0066] The hair coloring composition of the present invention may be in any product form, such as a permanent hair dye or a semi-permanent hair dye, with semi-permanent hair dye being preferred.

[0067] A permanent hair dye is a hair dye that uses a reactive dye such as an oxidation dye (classified as a quasi-drug in Japan). When the hair coloring composition of the present invention is made into a permanent hair dye product, the above-mentioned pigment (or the above-mentioned gardenia yellow pigment) is used as the dye, and a reactive dye such as an oxidation dye is blended to form a formulation.

[0068] A semi-permanent hair dye is a hair dye that uses a direct dye (in Japan, it is classified as a cosmetic product). When the hair coloring composition of the present invention is made into a semi-permanent hair dye product, the above-mentioned pigment (or the above-mentioned gardenia yellow pigment) is used as a direct dye, and other direct dyes may be added as necessary to form the formulation.

[0069] 2. Hair dyeing method To dye hair or animal fibers using the dyeing composition of the present invention, a method may be used according to the product form of the dyeing composition, for example, by applying the composition to the hair or animal fibers to be dyed, leaving it for a predetermined time, and then rinsing with water or the like. If necessary, it may be rinsed with a detergent such as shampoo. The temperature conditions for dyeing hair using the dyeing composition of the present invention are not particularly limited, but the higher the temperature during dyeing, the better the dyeing effect tends to be, so the temperature conditions may be appropriately set according to the composition of the dyeing composition, the color depth to be imparted to the hair or animal fibers, and the like. EXAMPLES

[0070] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0071] 1. Production of Gardenia Yellow Pigment 2500g of 50% (v / v) ethanol aqueous solution was added to 2500g of crushed dried gardenia fruit, and the mixture was stirred at 60°C for 1 hour to extract. An appropriate amount of 50% (v / v) ethanol aqueous solution was added to the residue again for secondary extraction, and the combined extract was used as a crocin-containing extract. The resulting crocin-containing extract was concentrated under reduced pressure to obtain a crocin-containing concentrated extract with a color value of 500. 450g of the crocin-containing concentrated extract with a color value of 500 was diluted with 2050g of water to obtain 2500g of a crocin-containing liquid with a color value of 90. A 10% by mass potassium hydroxide aqueous solution was added to the crocin-containing liquid to adjust the pH to 12.0. The mixture was stirred at 35°C for 20 hours to hydrolyze crocin and convert it to crocetin. Thereafter, concentrated hydrochloric acid was added, the pH was adjusted to 3.0, and the mixture was stirred for 60 minutes to precipitate crocetin. The precipitated crocetin was collected as a crude crocetin cake using a filter press. This crude crocetin cake was washed with water until no acid remained. 50 g of the washed crocetin cake was dispersed in 500 g of water, and 10 wt % aqueous potassium hydroxide solution was added to adjust the pH to 12.0. The mixture was stirred for 30 minutes to dissolve the crocetin cake, yielding a crocetin-containing alkaline mixture. Concentrated hydrochloric acid was added to this crocetin-containing alkaline mixture, and the pH was adjusted to 7.7 to obtain a crocetin-containing weakly alkaline mixture. The adjusted crocetin-containing weakly alkaline mixture was promptly filtered again with a filter press to obtain a gardenia yellow pigment-containing liquid (13-cis-crocetin-rich filtrate). The cake at this stage was a trans-crocetin-rich cake, and by drying and pulverizing this cake, a trans-crocetin-rich crocetin powder could be obtained. Hydrochloric acid was added to the gardenia yellow pigment-containing liquid (13-cis-crocetin-rich filtrate) and the pH was adjusted to 3.0 to cause precipitation. The cake obtained by the filter press was dried to obtain Gardenia Yellow powder (crocetin powder with high 13-cis-crocetin content).

[0072] 2. Analysis of Gardenia Yellow Pigment The obtained gardenia yellow pigment powder was analyzed by high performance liquid chromatography (HPLC) under the following conditions to determine the ratio of the peak areas of all-trans-crocin and 13-cis-crocin (peak area ratio (13-cis / All-trans)). As a result, the peak area ratio (13-cis / All-trans) of the obtained gardenia yellow pigment powder was 5.7. <HPLC Conditions> Column: Inertsil ODS-3 5μm 4.6×250mm (manufactured by GL Sciences Inc.) Solvent: Solution A: 1% (v / v) acetic acid, Solution B: acetonitrile Flow rate: 1 ml / min Column temperature: 40°C Detector: Photodiode array (PDA) (417.0 nm) Time program: Time B solution concentration 0 min 20% 20 min 80% 30 min 80% 30.01 min 20% 40 min 20%

[0073] 3. Preparation of Staining Solution Comparative Example 1 The prepared gardenia yellow pigment powder was added to an aqueous solution containing benzyl alcohol and ethanol and dissolved, and then the pH was adjusted using 0.1% hydrochloric acid and 0.1% aqueous sodium hydroxide solution to prepare staining solutions with pH values of 7.0, 9.0, and 11.0. The content of each component is as shown in Table 1. The pH was measured at 25°C using a pH meter (manufactured by Horiba, Ltd., product name: Desktop pH Meter F-52).

[0074] Examples 1 to 23 The prepared Gardenia Yellow powder was added to and dissolved in an aqueous solution containing benzyl alcohol and ethanol, and each amine or ammonium salt shown in Table 2 below was added and stirred, and then the pH was adjusted using 0.1% hydrochloric acid and 0.1% sodium hydroxide aqueous solution to prepare staining solutions with pH 7.0, 9.0, and 11.0. The contents of each component are as shown in Tables 1 and 2. The pH was measured at 25° C. using a pH meter (manufactured by Horiba Ltd., product name: benchtop pH meter F-52).

[0075] 4. Hair dye test A 1 g bundle of goat hair moistened with water was soaked in 2 mL of each of the dye solutions of Comparative Example 1 and Examples 1 to 23, and after 10 minutes it was washed with running water and dried with a hair dryer to obtain each dyed hair bundle. The b-values ​​of each dyed hair bundle and undyed hair bundle not treated with the dye solution were measured using a two-dimensional colorimeter (PPLB-400A, Paparabou Co., Ltd.), and the colors were expressed using the Hunter Lab color system. Here, the Hunter Lab color system is a color system that forms a color solid consisting of an orthogonal coordinate system consisting of an a-axis and a b-axis indicating chromaticity, and an L-axis perpendicular to the a-axis, and an increase in the b-value on the positive side indicates an increase in yellowness, and an increase on the negative side indicates an increase in blueness. In addition, 2 mL of a washing solution prepared by diluting a shampoo having the composition shown in Table 3 below 10 times with deionized water was applied to each dyed hair bundle, and after 2 minutes, the bundle was washed with running water and dried with a hair dryer. This shampoo washing treatment was performed once. After the shampoo washing treatment, the b value was measured in the same manner as above. The results are shown in Table 2 below.

[0076] [Table 1]

[0077] [Table 2]

[0078] [Table 3]

[0079] As shown in Table 2, the dye solutions of Examples 1 to 23 contain amines or ammonium salts, and therefore the b value of the dyed hair bundle before shampooing is higher than that of the dye solution of Comparative Example 1, which does not contain amines or ammonium salts, and it was confirmed that the dye solution has excellent dyeing effect at pH 7.0 to 11.0. It was also confirmed that the dye solutions of Examples 1 to 23 can maintain high dyeing effect even when the dyed hair bundle is shampooed. Furthermore, when the dye solution of Comparative Example 1 is compared with the dye solutions of Examples 13 to 17, it is found that the dyeing effect is very excellent when the concentration of the ammonium salt is 0.01 to 10 mass%.

[0080] 5. Preparation of hair coloring treatment and hair dyeing test Example 24, Comparative Example 2 Hair coloring treatments with a pH of 8.18 were prepared with the composition shown in Table 4 below. Then, 2 mL of each of the hair coloring treatments of Example 24 and Comparative Example 2 was applied to 1 g of a goat hair bundle moistened with water, and after 10 minutes, the hair bundle was washed with running water and dried with a hair dryer to obtain each dyed hair bundle. The b-values ​​of each dyed hair bundle and an undyed hair bundle that was not treated with a hair coloring treatment were measured using a two-dimensional colorimeter (PPLB-400A, Paparabou Co., Ltd.), and the colors were expressed using the Hunter Lab color system. The results are shown in Table 5 below.

[0081] [Table 4]

[0082] [Table 5]

[0083] As shown in Table 5, since the hair coloring treatment of Example 24 contains ammonium salt, the b value of the dyed hair strand after dyeing was higher than that of the hair coloring treatment of Comparative Example 2, which does not contain ammonium salt, and it was confirmed that the dyeing effect was superior.

[0084] 6. Preparation of hair coloring milk and hair dyeing test Example 25, Comparative Example 3 A hair coloring milk with a pH of 8.19 was prepared with the composition shown in Table 6. Then, 2 mL of each of the hair coloring milks of Example 25 and Comparative Example 3 was applied to 1 g of a goat hair bundle moistened with water, and after 10 minutes, the bundle was washed with running water and dried with a hair dryer to obtain each dyed hair bundle. The b-values ​​of each dyed hair bundle and an undyed hair bundle that was not treated with the hair coloring milk were measured using a two-dimensional colorimeter (PPLB-400A, Paparabou Co., Ltd.), and the colors were expressed using the Hunter Lab color system. The results are shown in Table 7 below.

[0085] [Table 6]

[0086] [Table 7]

[0087] As shown in Table 7, since the hair coloring milk of Example 25 contains ammonium salt, the b value of the dyed hair strand after dyeing was higher than that of the hair coloring milk of Comparison Example 3, which does not contain ammonium salt, and it was confirmed that the dyeing effect was superior.

[0088] 7. Preparation of dye solution and wool dyeing test Example 26, Comparative Example 4 A dyeing solution with a pH of 7.0 was prepared with the composition shown in Table 8 below. Then, 2 mL of each of the dyeing solutions of Example 26 and Comparative Example 4 was applied to a 1 g bundle of sheep's wool moistened with water, and after 10 minutes, the bundle was washed with running water and dried with a dryer to obtain each dyed bundle. The b-values ​​of each dyed hair bundle and an undyed hair bundle that was not treated with the dye solution were measured using a two-dimensional colorimeter (PPLB-400A, Paparabou Co., Ltd.), and the colors were expressed using the Hunter Lab color system. The results are shown in Table 9 below.

[0089] [Table 8]

[0090] [Table 9]

[0091] As shown in Table 9, since the dyeing solution of Example 26 contains an ammonium salt, the b value of the dyed hair bundle after dyeing was higher than that of the dyeing solution of Comparative Example 4 which does not contain an ammonium salt, and it was confirmed that the dyeing effect is excellent even for wool.< / ph>

Claims

1. A dyeing composition comprising at least one dye selected from the group consisting of crocin, a salt of crocin, crocetin, and a salt of crocetin, and at least one nitrogen-containing compound selected from the group consisting of amines and ammonium salts, and having a pH of 6.0 or higher.

2. 2. The dye composition according to claim 1, wherein the amine is at least one selected from the group consisting of acyclic monoamines and cyclic amines.

3. 3. The dye composition according to claim 2, wherein the acyclic monoamine is an acyclic aliphatic monoamine.

4. 2. The dye composition according to claim 1, wherein the ammonium salt is an acyclic ammonium salt.

5. 5. The dye composition according to claim 4, wherein the non-cyclic ammonium salt is a non-cyclic aliphatic ammonium salt.

6. 6. The dye composition according to claim 5, wherein the acyclic aliphatic ammonium salt is a acyclic aliphatic quaternary ammonium salt.

7. 2. The dye composition according to claim 1, wherein the content of the nitrogen-containing compound is from 0.01 to 10% by mass.

8. 2. The dye composition of claim 1 which is a hair coloring composition.

9. The dye composition according to claim 8, which is used for dyeing gray hair.

10. A hair dyeing method, comprising dyeing hair with the dyeing composition according to any one of claims 1 to 9.

11. A method for dyeing animal fibers, comprising dyeing the animal fibers with the dye composition according to any one of claims 1 to 7.

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