Non-emulsion type hair coloring agent

Abstract

To provide a non-emulsion type hair coloring agent which can achieve both a hair coloring effect and improved pigment dispersibility.SOLUTION: The non-emulsion type hair coloring agent of the present invention is characterized by containing (A) a pigment (4 mass% or more in cases where the pigment is iron oxide), (B) a sorbitan fatty acid ester, (C) a film-forming polymer, and (D) ethanol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a non-emulsifying hair colorant that can achieve both a hair coloring effect and improved pigment dispersibility. [Background technology]

[0002] Generally, hair colorants (temporary hair dye compositions) containing inorganic pigments such as carbon black and titanium oxide as colorants are known. These hair colorants temporarily color hair by using a film-forming polymer to fix the pigment to the hair surface. Compared to semi-permanent or permanent hair dyes that use acid or alkali agents, they have the advantage of being able to reduce damage to hair and be easily washed off.

[0003] Hair colorants have been known for some time, such as those described in Patent Document 1. The present invention discloses a composition for dyeing human hair, which contains an organosilicon compound containing a basic functional group, a coloring compound such as a pigment, and a film-forming polymer for the purpose of improving the durability of the color. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2021-523141 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional hair colorants containing a pigment, a film-forming polymer, etc. have had problems such as uneven dyeing due to pigment precipitation, etc. Therefore, it has been difficult to achieve both a hair coloring effect and improved pigment dispersibility, and there has been a problem in that satisfactory performance cannot be achieved. [Means for solving the problem]

[0006] The present invention is based on the discovery that a non-emulsified hair colorant containing a specific pigment, a sorbitan fatty acid ester, a film-forming polymer, and ethanol can achieve both hair coloring effectiveness and improved pigment dispersibility. The mass % values ​​indicating the content of components are values ​​in the formulation, including solubilizers such as organic solvents. Improved dispersibility refers to improvements in both the ability to disperse uniformly and not aggregate, and the ability to reduce sedimentation over time.

[0007] Various aspects for solving the above problems will be described. The non-emulsifying hair colorant of aspect 1 is characterized by containing the following (A) to (D): (A) pigment (however, when the pigment is iron oxide, the content is 4% by mass or more); (B) sorbitan fatty acid ester, (C) a film-forming polymer; (D) Ethanol.

[0008] Aspect 2 is the non-emulsifying hair colorant according to Aspect 1, wherein the HLB value of component (B) is 10 or less. Aspect 3 is the non-emulsifying hair colorant according to Aspect 1 or 2, wherein the component (A) is iron oxide.

[0009] Aspect 4 is the non-emulsifying hair colorant according to any one of Aspects 1 to 3, wherein the component (A) is iron oxide treated with an alkylsilane. [Effects of the Invention]

[0010] The non-emulsified hair colorant of the present invention can achieve both a hair coloring effect and improved pigment dispersibility. DETAILED DESCRIPTION OF THE INVENTION

[0011] One embodiment of the non-emulsifying hair colorant of the present invention will be described below. The non-emulsifying hair colorant of this embodiment contains (A) a pigment, (B) a sorbitan fatty acid ester, (C) a film-forming polymer, and (D) ethanol.

[0012] ((A) Pigment) (A) pigment is a powder used for coloring that is insoluble in water or oil, and the pigment in the present invention is used to color hair. Specific examples of (A) pigment are not particularly limited, and known pigments such as inorganic pigments, organic pigments, dye-resin solid solutions, daylight fluorescent pigments, and natural pigments can be used. These (A) pigments can be used alone or in appropriate combinations of two or more depending on the desired hair color tone.

[0013] Inorganic pigments, also known as mineral pigments, are chemically inorganic pigments. They are made from natural minerals, processed or crushed from natural minerals, or from compounds of zinc, titanium, lead, iron, copper, chromium, and other raw materials. They are light- and heat-resistant and insoluble in organic solvents. There are many types, but they can be categorized by color, including white pigments (e.g., titanium dioxide), red pigments (e.g., red iron oxide), yellow pigments (e.g., yellow lead), green pigments (e.g., emerald green), blue pigments (e.g., cobalt blue), purple pigments (e.g., manganese violet), black pigments (e.g., carbon black), and transparent white pigments (e.g., silica white).

[0014] Specific examples of inorganic pigments are not particularly limited and include, for example, zinc oxide, titanium oxide, chromium oxide, cobalt oxide, iron oxide, chromium hydroxide, aluminum hydroxide, Prussian blue, barium sulfate, hydrous silicate, anhydrous silicic acid, aluminum silicate, talc, kaolin, carmine, mica, magnesium carbonate, bentonite, ultramarine, manganese violet, carbon black, aluminum, copper, gold, mica titanium, etc. Further examples of iron oxide include black iron oxide, yellow iron oxide, red iron oxide, etc.

[0015] Titanium mica may be further subjected to various coating treatments. Specific examples of coated titanium mica include black iron oxide-coated titanium mica, konjou-coated titanium mica, red iron oxide-coated titanium mica, carmine-coated titanium mica, carmine and konjou-coated titanium mica, black iron oxide and carmine-coated titanium mica, black iron oxide and konjou-coated titanium mica, red iron oxide and carmine-coated titanium mica, red iron oxide and black konjou-coated titanium mica, red iron oxide and black iron oxide-coated titanium mica, red iron oxide and konjou-coated titanium mica, and the like.

[0016] Organic pigments are pigments primarily composed of coloring matter made from organic compounds. Organic pigments are broadly divided into organic color pigments, in which the coloring matter itself is insoluble in water, and lake pigments, in which water-soluble dyes are made insoluble by some means, such as the addition of metal salts. Organic pigments have the advantages of a wide range of vivid hues, as well as high coloring power and transparency. Examples of organic pigments include, but are not limited to, Red Nos. 202, 203, 204, 205, 206, 207, 208, 219, 220, 221, 226, 228, 404, and 405; Orange Nos. 203, 204, and 401; Yellow Nos. 4, 205, and 401; and Blue No. 404.

[0017] Daylight fluorescent pigments are a type of fluorescent pigment that are organic. They are characterized by their vivid color under normal light. Their brightness increases when stimulated by light such as ultraviolet light. Specific examples of natural pigments include, but are not limited to, mineral pigments such as clay, natural dye lakes such as madder lake and cochineal lake, azo pigments, and phthalocyanine pigments.

[0018] A hydrophobic treated pigment may be used, in which the surface of the pigment has been subjected to a hydrophobic treatment. A known method can be used for the hydrophobic treatment. Examples of hydrophobic treated pigments include those whose surface has been treated with a silicone compound, a surfactant, an oil, an amino acid compound such as an N-acylamino acid, a fluorine compound, or the like.

[0019] Specific examples of silicone compounds include silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, and methylphenylpolysiloxane; alkylsilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, myristyltrimethoxysilane, cetyltrimethoxysilane, stearyltrimethoxysilane, and caprylyltriethoxysilane; and fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane.

[0020] Among these, iron oxide and iron oxide surface-treated with a silicone compound are preferred, and iron oxide surface-treated with an alkylsilane is more preferred. The lower limit of the content of the (A) pigment other than iron oxide in the non-emulsifying hair colorant is set appropriately depending on the type of pigment, purpose, etc., but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. When the content of the (A) pigment is 0.1% by mass or more, the coloring ability of the (A) pigment to hair can be further improved. On the other hand, the upper limit of the content of the (A) pigment is set appropriately depending on the type of pigment, purpose, etc., but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 15% by mass or less, and most preferably 13% by mass or less. When the content of the (A) pigment is 30% by mass or less, the dispersibility of the (A) pigment in the non-emulsifying hair colorant can be improved.

[0021] When the (A) pigment is iron oxide, the lower limit of the content of the (A) pigment in the non-emulsifying hair colorant is 4% by mass or more, preferably 5% by mass or more, and more preferably 8% by mass or more. When the content of the (A) pigment is 4% by mass or more, coloring properties can be improved. On the other hand, the upper limit of the content of the (A) pigment is appropriately set depending on the type of pigment, purpose, etc., but is preferably 30% by mass or less, more preferably 25% by mass or less. When the content of the (A) pigment is 30% by mass or less, dispersibility of the pigment in the non-emulsifying hair colorant can be improved. Note that ranges that combine the above upper and lower limits are also contemplated.

[0022] ((B) Sorbitan fatty acid ester) The (B) sorbitan fatty acid ester improves the dispersibility of the (A) pigment. The (B) sorbitan fatty acid ester may be a monoester, a diester, or a triester.

[0023] The fatty acid constituting the (B) sorbitan fatty acid ester can be any known fatty acid, and may be a saturated fatty acid or an unsaturated fatty acid. It may also be a linear or branched fatty acid. It may also be a monobasic fatty acid or a polycarboxylic acid (polybasic acid).

[0024] Specific examples of saturated fatty acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid (caproic acid), octylic acid (2-ethylhexanoic acid), octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), and tetracosanoic acid.

[0025] Specific examples of unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, eicosenoic acid, linoleic acid, α-linolenic acid, γ-linolenic acid, and arachidonic acid.

[0026] Specific examples of polyvalent carboxylic acids (polybasic acids) include (1) dibasic acids such as succinic acid, fumaric acid, maleic acid, adipic acid, and sebacic acid; (2) tribasic acids such as aconitic acid; (3) aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid; (4) aromatic tricarboxylic acids such as trimellitic acid; and (5) aromatic tetracarboxylic acids such as pyromellitic acid.

[0027] The alkylene oxide may also be a sorbitan fatty acid ester having a (poly)oxyalkylene structure. The alkylene oxide used as a raw material for forming the (poly)oxyalkylene structure is preferably an alkylene oxide having 2 to 4 carbon atoms. Specific examples of alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The number of moles of alkylene oxide added is appropriately set, but is preferably 0.1 to 40 moles, more preferably 1 to 30 moles. Any combination of the above upper and lower limits is also possible. The number of moles of alkylene oxide added refers to the number of moles of alkylene oxide per mole of the compound to be added in the raw material. One type of alkylene oxide may be used alone, or two or more types of alkylene oxides may be used in appropriate combination. When two or more types of alkylene oxides are used, the addition form may be any of block addition, random addition, or a combination of block addition and random addition, and is not particularly limited.

[0028] The HLB value of the (B) sorbitan fatty acid ester is not particularly limited, but is preferably not more than 10. This configuration can further improve the dispersibility of the (A) pigment. The HLB (hydrophile-lipophile balance) is a numerical value established by W.C. Griffin and assigned to nonionic surfactants. It represents the balance between the strength of the lipophilic group (alkyl group) and the hydrophilic group (ethylene oxide chain). The HLB value is calculated from the emulsification method (see "Handbook - Cosmetics and Pharmaceutical Ingredients" by Nikko Chemicals Co., Ltd. (revised February 1, 1977)). To measure the HLB value, a combination of sorbitan monostearate (e.g., Nikko Chemicals' NIKKOL SS-10, HLB value 4.7) and polyoxyethylene sorbitan monostearate (e.g., Nikko Chemicals' NIKKOL TS-10, HLB value 14.9) is used as surfactant standards. Liquid paraffin is used as the emulsifier. If variations in the liquid paraffin type or lot size are anticipated, measurements should be performed each time. Liquid paraffin is emulsified with the above two types of surfactants to determine the optimal surfactant ratio and the required HLB value of the liquid paraffin (the HLB value at which it is emulsified). The calculation formula is shown in Equation (1).

[0029]

number

[0030] Specific examples of (B) sorbitan fatty acid esters include sorbitan monooleate (HLB: 4.3), sorbitan sesquioleate (HLB: 4.0), sorbitan trioleate (HLB: 1.7), sorbitan monostearate (HLB: 4.7), sorbitan monopalmitate (HLB: 6.7), sorbitan monolaurate (HLB: 8.6), sorbitan coconut oil fatty acid (HLB: 8.6), mono-coconut oil fatty acid POE (addition mole number of alkylene oxide (hereinafter the same) 20) sorbitan (HLB: 16.9), monolaurate POE (6) sorbitan (HLB: 15.5), isostearate POE (20) sorbitan (isostearate PEG-20 sorbitan) (HLB: 15), and the like. Among these, sorbitan monooleate (HLB: 4.3), sorbitan sesquioleate (HLB: 4.0), sorbitan trioleate (HLB: 1.7), sorbitan monostearate (HLB: 4.7), sorbitan monopalmitate (HLB: 6.7), sorbitan monolaurate (HLB: 8.6), and sorbitan coconut oil fatty acid (HLB: 8.6) are preferred, and sorbitan sesquioleate (HLB: 4.0) and sorbitan coconut oil fatty acid (HLB: 8.6) are more preferred.

[0031] In addition, (B) sorbitan fatty acid ester is preferably liquid at room temperature. This configuration eliminates the need for heating during preparation of the non-emulsifying hair colorant, improving mixability and manufacturability. In addition, the stability of the non-emulsifying hair colorant can be further improved.

[0032] The (B) sorbitan fatty acid ester may be contained alone or in combination of two or more kinds. The lower limit of the content of (B) sorbitan fatty acid ester in the non-emulsified hair colorant may be set as appropriate, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more. When the content of (B) sorbitan fatty acid ester is 0.1% by mass or more, the dispersibility of (A) pigment can be further improved. On the other hand, the upper limit of the content of (B) sorbitan fatty acid ester may be set as appropriate, but is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. When the content of (B) sorbitan fatty acid ester is 20% by mass or less, the stability of the non-emulsified hair colorant can be improved. Note that ranges that combine the above upper and lower limits in any combination are also contemplated.

[0033] ((C) Film-forming polymer) Examples of the (C) film-forming polymer include anionic polymers, cationic polymers, nonionic polymers, and amphoteric polymers. The (C) film-forming polymer improves the coloring ability of the (A) pigment on hair. Among these, anionic polymers and amphoteric polymers are preferred, and anionic polymers are more preferred.

[0034] Specific examples of anionic polymers include xanthan gum, carrageenan, sodium alginate, gum arabic, pectin, carboxyvinyl polymer, alkyl acrylate copolymer, alkyl acrylate copolymer AMP, methyl vinyl ether / alkyl maleic anhydride half ester copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid / vinyl neodecanoate copolymer, vinyl acetate / crotonic acid / vinyl propionate copolymer, vinyl acetate / N-vinyl-5-methyl-2-oxazoline copolymer, vinyl acetate / vinyl maleate / isobornyl acrylate copolymer, (alkyl acrylate / diacetone acrylamide) copolymer, (acrylates / diacetone acrylamide) copolymer AMP, (alkyl acrylate / octylacrylamide) copolymer, etc. Among these, (alkyl acrylate / diacetone acrylamide) copolymer is preferred.

[0035] The cationic polymer is not particularly limited, but examples thereof include cationic polysaccharides and cationic polymers containing structural units derived from cationic monomers. The cationic polysaccharides are cationic sugar derivatives in which cationic groups have been added to polysaccharides. Cationic sugar derivatives have a structure in which some of the hydroxyl groups contained in the sugars have been substituted with quaternary nitrogen-containing groups. A preferred quaternary nitrogen-containing group is a quaternary ammonium group. For example, cationic polysaccharides can be obtained by reacting a sugar with a quaternary ammonium salt such as a glycidyl trialkyl ammonium salt or a 3-halogeno-2-hydroxypropyl trialkyl ammonium salt to introduce quaternary ammonium groups into some of the hydroxyl groups of the sugar.

[0036] Examples of the cationic polysaccharides include cationized cellulose, cationized guar gum, cationized tara gum, cationized locust bean gum, cationized cassia, cationized fenugreek gum, and cationized starch.

[0037] The cationized cellulose is a cellulose-based polymer containing cationic groups. It is obtained by partially chemically bonding glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride to hydroxyethyl cellulose. Specific examples include polyquaternium-4 (hydroxyethyl cellulose dimethyldiallylammonium chloride) and polyquaternium-10 (O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride).

[0038] The cationized guar gum is a water-soluble polymer obtained by cationizing guar gum, a polysaccharide in which galactose and mannose are present in a ratio of 1:2, by converting the hydroxylmethyl and hydroxyl groups of the mannose in the main chain and the galactose in the side chain into quaternary ammonium groups. Specific examples include guar hydroxypropyltrimonium chloride and hydroxypropylguar hydroxypropyltrimonium chloride.

[0039] The cationized tara gum is a water-soluble polymer obtained by cationizing tara gum, a polysaccharide in which galactose and mannose are present in a ratio of 1:3. Specific examples include Caesalpinia spinosa hydroxypropyltrimonium chloride.

[0040] The cationized locust bean gum is a water-soluble polymer obtained by cationizing and modifying locust bean gum, a polysaccharide in which galactose and mannose are present in a ratio of 1:4. Specific examples include locust bean hydroxypropyltrimonium chloride.

[0041] The cationized cassia is a water-soluble polymer obtained by cationizing cassia gum, a polysaccharide in which galactose and mannose are present in a ratio of 1:5. Specific examples include cassia hydroxypropyltrimonium chloride.

[0042] The cationized fenugreek gum is a water-soluble polymer obtained by cationizing fenugreek gum, a polysaccharide in which galactose and mannose are present in a 1:1 ratio. Specific examples include fenugreek hydroxypropyltrimonium chloride.

[0043] The cationic starch is a polymer obtained by cationic modification of starch, and specific examples thereof include hydroxypropyltrimonium chloride starch. Examples of cationic monomers in cationic polymers containing structural units derived from the above cationic monomers include dimethyldiallylammonium chloride, diethyldiallylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, sulfate of dimethylaminoethyl diethyl (meth)acrylate (such as diethyl sulfate as the sulfate), 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, (meth)acrylamidopropyltrimethylammonium chloride, ethyltrimethylammonium (meth)acrylate chloride, and (meth)acrylamidopropyllauryldimonium chloride. Here, (meth)acrylamido refers to acrylic acid amide, methacrylic acid amide, or a mixture of acrylic acid amide and methacrylic acid amide. (Meth)acrylic acid refers to acrylic acid, methacrylic acid, or a mixture of acrylic acid and methacrylic acid. (Meth)acryloyl refers to acryloyl group-containing, methacryloyl group-containing, or acryloyl group-containing and methacryloyl group-containing.

[0044] Examples of cationic polymers containing structural units derived from the above-mentioned cationic monomers include polydimethylmethylenepiperidinium chloride such as Polyquaternium-6, dimethyldiallylammonium chloride-acrylamide copolymers such as Polyquaternium-7, vinylpyrrolidone-N,N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate such as Polyquaternium-11, vinylpyrrolidone-methylvinylimidazolium copolymers such as Polyquaternium-16, ethyl[(methacryloyloxy)ethyl]dimethylammonium ethyl sulfate-N,N-dimethylacrylamide-dimethacrylic acid polyethylene glycol copolymers such as Polyquaternium-52, and Polyquaternium-99 (a polymer of a quaternary ammonium salt consisting of butyl methacrylate-2-ethoxyethyl methacrylate and methacryloyloxyethyltrimethylammonium chloride). Among these, polyquaternium-99 (a polymer of a quaternary ammonium salt consisting of butyl methacrylate, 2-ethoxyethyl methacrylate, and methacryloyloxyethyltrimethylammonium chloride) is preferred.

[0045] Specific examples of nonionic polymers include hydroxyethyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, methyl cellulose, highly polymerized polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, vinylpyrrolidone / vinyl acetate copolymer, vinylpyrrolidone / methacrylic acid / methacrylic acid ester copolymer, vinylpyrrolidone / vinyl acetate / alkylaminoacrylate copolymer, vinylpyrrolidone / vinyl acetate / vinyl propionate copolymer, dimethylhydantoin formaldehyde resin, poly(meth)acrylic acid, (meth)acrylic acid copolymer, poly(meth)acrylic acid ester, (meth)acrylic acid ester copolymer, poly(meth)acrylamide, (meth)acrylic acid amide copolymer, dextrin, galactan, pullulan, and the like.

[0046] Specific examples of amphoteric polymers include N-methacryloylethyl N,N-dimethylammonium α-N-methylcarboxybetaine-butyl methacrylate copolymer, (ethyl methacrylate betaine / acrylates) copolymer, hydroxypropyl acrylate-butylaminoethyl methacrylate-octyl acrylate copolymer, dimethyldiallylammonium chloride-acrylic acid copolymer, dimethyldiallylammonium chloride-acrylamide-acrylic acid terpolymer, acrylic acid-methyl acrylate-methacrylamidopropyltrimethylammonium chloride copolymer, and hydroxypropyl acrylate-butylaminoethyl methacrylate-octyl acrylate copolymer. Among these, (ethyl methacrylate betaine / acrylates) copolymer is preferred.

[0047] These film-forming polymers (C) may be contained alone or in combination of two or more. The lower limit of the content of the (C) film-forming polymer in the non-emulsified hair colorant may be set as appropriate, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more. When the content of the (C) film-forming polymer is 0.1% by mass or more, precipitation of the (A) pigment is suppressed and the coloring ability of the (A) pigment to hair can be further improved. On the other hand, the upper limit of the content of the (C) film-forming polymer may be set as appropriate, but is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 15% by mass or less. When the content of the (C) film-forming polymer is 20% by mass or less, the feel to the touch can be improved by improving suppleness, etc. Note that ranges that combine the above upper and lower limits in any combination are also contemplated.

[0048] ((D) Ethanol) (D) Ethanol is incorporated as a solubilizer for non-emulsifying hair colorants. The lower limit of the content of (D) ethanol in the non-emulsified hair colorant is set appropriately, but is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more. When the content of (D) ethanol is 10% by mass or more, quick-drying properties during use can be improved.

[0049] In the non-emulsified hair colorant, the lower limit of the mass ratio (B / A) of the content of the (B) sorbitan fatty acid ester to the content of the (A) pigment can be appropriately set, but is preferably 0.003 or more, more preferably 0.006 or more, and even more preferably 0.01 or more. By setting this mass ratio to 0.003 or more, the dispersibility of the (A) pigment in the non-emulsified hair colorant can be improved. On the other hand, the upper limit of the mass ratio (B / A) of the content of the (B) sorbitan fatty acid ester to the content of the (A) pigment can be appropriately set, but is preferably 100 or less, more preferably 50 or less, and even more preferably 4 or less. By setting this mass ratio to 100 or less, the coloring ability of the (A) pigment to hair can be further improved. Note that ranges obtained by arbitrarily combining the above upper and lower limits are also contemplated.

[0050] In the non-emulsified hair colorant, the lower limit of the mass ratio (B / C) of the content of the (B) sorbitan fatty acid ester to the content of the (C) film-forming polymer can be appropriately set, but is preferably 0.005 or more, more preferably 0.01 or more, and even more preferably 0.03 or more. By setting this mass ratio to 0.005 or more, precipitation of the (A) pigment in the non-emulsified hair colorant can be suppressed, thereby improving the dispersibility of the (A) pigment. Furthermore, the feel of hair can be improved. Meanwhile, the upper limit of the mass ratio (B / C) of the content of the (B) sorbitan fatty acid ester to the content of the (C) film-forming polymer can be appropriately set, but is preferably 100 or less, more preferably 50 or less, and even more preferably 1 or less. Setting this mass ratio to 100 or less can further improve the coloring ability of the (A) pigment to hair. It should be noted that ranges combining the above upper and lower limits are also contemplated.

[0051] In the non-emulsified hair colorant, the upper limit of the mass ratio (B / D) of the content of (B) sorbitan fatty acid ester to the content of (D) ethanol can be appropriately set, but is preferably 1 or less, more preferably 0.07 or less. By setting this mass ratio to 1 or less, quick-drying properties during use can be further improved. Note that ranges that combine the above upper and lower limits are also contemplated.

[0052] (Other ingredients) The non-emulsified hair colorant may further contain, as necessary, ingredients other than those mentioned above, such as solubilizers other than the above-mentioned component (D), oily ingredients, moisturizers, preservatives, plant extracts, herbal extracts, sugars, amino acids, vitamins, fragrances, antioxidants, ultraviolet absorbers, etc., within the scope that does not impair the effects of the present invention.

[0053] The solubilizer is blended, for example, to adjust the properties of the non-emulsified hair colorant. Examples of the solubilizer used include organic solvents (solvents). Specific examples of organic solvents include monohydric alcohols having 4 to 8 carbon atoms and ethylene glycol alkyl ethers. Specific examples of monohydric alcohols having 4 to 8 carbon atoms include n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol. Specific examples of ethylene glycol alkyl ethers include diethylene glycol monoethyl ether (ethyl carbitol) and ethylene glycol mono-n-butyl ether.

[0054] Of these solubilizers, only one may be contained alone, or two or more may be contained in combination. The oily component imparts a moist feeling to hair. Therefore, the non-emulsifying hair colorant may contain an oily component within a range that does not impair the effects of the present invention. Examples of the oily component include wax, higher alcohol, hydrocarbon, ester, silicone, etc.

[0055] Specific examples of waxes include beeswax, candelilla wax, carnauba wax, jojoba oil, lanolin, spermaceti, rice bran wax, sugarcane wax, palm wax, montan wax, cotton wax, bayberry wax, ivotaro wax, kapok wax, shellac wax, etc. Specific examples of higher alcohols include isostearyl alcohol, oleyl alcohol, 2-octyldodecanol, decyltetradecanol, etc.

[0056] Specific examples of hydrocarbons include olefin oligomers, polyisobutene, hydrogenated polyisobutene, mineral oil, squalane, and polybutene. Specific examples of esters include diisopropyl adipate, isopropyl myristate, cetyl octanoate, isononyl isononanoate, octyldodecyl myristate, isopropyl palmitate, stearyl stearate, myristyl myristate, isotridecyl myristate, 2-ethylhexyl palmitate, octyldodecyl ricinoleate, cholesteryl / lanosteryl fatty acids having 10 to 30 carbon atoms, cetyl lactate, lanolin acetate, ethylene glycol di-2-ethylhexanoate, pentaerythritol fatty acid esters, dipentaerythritol fatty acid esters, cetyl caprate, diisostearyl malate, dioctyl succinate, and cetyl 2-ethylhexanoate.

[0057] Specific examples of silicones include dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hydroxyl-terminated dimethylpolysiloxane, highly polymerized silicone, polyether-modified silicone (for example, (PEG / PPG / butylene / dimethicone) copolymer), amino-modified silicone, betaine-modified silicone, alkyl-modified silicone, alkoxy-modified silicone, mercapto-modified silicone, carboxy-modified silicone, and fluorine-modified silicone.

[0058] These oily components may be contained alone or in combination of two or more. Specific examples of preservatives include paraben, methylparaben, sodium benzoate, fetic acid, etc. Specific examples of antioxidants include tocopherol, tocopherol acetate, etc. These other ingredients may be used alone or in combination of two or more.

[0059] The non-emulsified hair colorant is in the form of a non-emulsified liquid when used. The form of use of the non-emulsified hair colorant is not limited, but examples include sprays, pump dispensers, trigger dispensers, manual pump extrusion containers, tube containers, etc. When a spray (atomization) application method is used, examples of propellants include LPG, dimethyl ether, nitrogen, and carbon dioxide. The mixing ratio (mass ratio) of the content liquid to the propellant is appropriately set depending on the type of propellant, etc., but is, for example, 5:95 to 95:5.

[0060] (Effects of this embodiment) The effects of the non-emulsified hair colorant of this embodiment will be described. (1) The non-emulsified hair colorant of this embodiment contains (A) a pigment (however, when the pigment is iron oxide, the content is 4% by mass or more), (B) a sorbitan fatty acid ester, (C) a film-forming polymer, and (D) ethanol. Therefore, it is possible to achieve both a good hair coloring effect and improved pigment dispersibility.

[0061] (2) In particular, (B) sorbitan fatty acid ester can improve the dispersibility and redispersibility of (A) pigment, thereby preventing the precipitation of (A) pigment. Furthermore, the improved stability of the non-emulsified hair colorant suppresses caking, preventing clogging of the container and improving the ease of handling of the product.

[0062] (3) Furthermore, the improved stability of the pigment (A) in the non-emulsified hair colorant allows for a larger amount of the pigment (A) to be incorporated, thereby further improving the hair coloring effect.

[0063] (Example of change) The above embodiment may be modified as follows: The above embodiment and the following modifications may be combined with each other within the scope of technical compatibility.

[0064] The non-emulsifying hair colorant of the above embodiment may be a non-aqueous liquid hair colorant that is substantially free of water. "Substantially free of water" means "free of water as a compounding component" and does not exclude small amounts of water incidental to other compounding components. More specifically, it may contain no water at all, or, even if it contains water incidentally, the content is 1% by mass or less.

[0065] In the above embodiment, the non-emulsified hair colorant is formulated as a single-component formulation in which all of the components constituting the non-emulsified hair colorant are blended together. However, the components may be separated into multiple components, which may be mixed together immediately before use.

[0066] In the above embodiment, monohydric lower alcohols other than ethanol may be used as the organic solvent within a range that does not impair the effects of the present invention. The content of monohydric lower alcohols other than ethanol in the non-emulsified hair colorant is, for example, 5% by mass or less. [Example]

[0067] Next, the above-described embodiment will be described in more detail with reference to examples and comparative examples. Note that the present invention is not limited to the configurations described in the examples section. Test Example 1: Preparation and Evaluation of Non-Emulsifying Hair Colorants The non-emulsified hair colorants according to the Examples and Comparative Examples shown in Table 1 were prepared according to a conventional method. The concentrate obtained by mixing the components was filled into a spray can together with a propellant (DME) in a mass ratio of concentrate:propellant = 26:74.

[0068] With regard to each component shown in the column for component name in each table, the components corresponding to components (A) to (D) of the present invention are indicated by symbols A to D in the left column of the table. The units of the numerical values ​​indicating the content of each component in the tables are % by mass. The symbol b indicates the comparative compound of component B. With regard to the non-emulsifying hair colorants of each Example and Comparative Example in the tables, the column "mass ratio B / A" refers to the mass ratio of the content of component (B) to the content of component (A). The column "mass ratio B / C" refers to the mass ratio of the content of component (B) to the content of component (C). The column "mass ratio B / D" refers to the mass ratio of the content of component (B) to the content of component (D). The triethoxycaprylylsilane-treated iron oxide marked *1 is ALT-BHP-10 manufactured by Miyoshi Chemicals Co., Ltd.

[0069] (Evaluation of non-emulsifying hair colorants) The spray-type non-emulsifying hair colorant according to the Examples and Comparative Examples was evenly applied to 1 g of a gray hair bundle so that 0.1 g of the colorant adhered to the hair, and then the hair was thoroughly dried. The "feel of the hair" was evaluated based on the feel of the resulting hair bundle. After the non-emulsifying hair colorant had dried, the "coloring properties" were evaluated. The "dispersibility" and "quick-drying properties" of the non-emulsifying hair colorant were also evaluated according to the following methods.

[0070] <Method for evaluating dispersibility> 30 g of each non-emulsified hair colorant (undiluted solution) was filled into a pressure-resistant bottle and left to stand in a thermostatic bath at 40°C for one month. After that, the dispersion state of the pigment when manually shaken up and down 10 times and the dispersion state after being left to stand for 3 minutes after shaking were visually evaluated by 10 panelists according to the following criteria.

[0071] The average score of each panelist was calculated, and the evaluation results were determined as follows: an average score of 4.6 or more was "excellent: 5", 3.6 to less than 4.6 was "good: 4", 2.6 to less than 3.6 was "fair: 3", 1.6 to less than 2.6 was "slightly poor: 2", and less than 1.6 was "poor: 1". The results are shown in the "Dispersibility" column in the table below.

[0072] Dispersibility evaluation criteria 5: All pigments are uniformly dispersed, there are no agglomerates, and the dispersion state is maintained even after leaving the material to stand for 3 minutes (very good) 4: Almost uniform dispersion with no pigment agglomerates, and the dispersion state is generally maintained even after leaving it to stand for 3 minutes (good) 3: Disperses, but slight pigment agglomerates are visible, and the dispersion state deteriorates slightly after leaving it for 3 minutes (this does not pose a practical problem) (normal) 2: Poor dispersion, pigment agglomerates are visible, and the dispersion state cannot be maintained after leaving the material to stand for 3 minutes. 1: No dispersion at all, pigment agglomerates are visible, and no dispersion at all after leaving for 3 minutes (very bad) <Evaluation method for coloring> The hair strands to which the non-emulsified hair colorant obtained above had been applied were visually evaluated for coloring properties by 10 panelists based on the following evaluation criteria.

[0073] The average score of each panelist was calculated, and the evaluation results were determined as follows: an average score of 4.6 or more was "excellent: 5", 3.6 to less than 4.6 was "good: 4", 2.6 to less than 3.6 was "fair: 3", 1.6 to less than 2.6 was "slightly poor: 2", and less than 1.6 was "poor: 1". The results are shown in the "Colorability" column in the table below.

[0074] ·Evaluation criteria for colorability 5: When the underlying gray hair color is completely concealed 4: When the underlying gray hair color is slightly affected but concealed 3: When the underlying gray hair color is slightly affected but is mostly concealed 2: When the concealing power is slightly lacking due to the influence of underlying gray hair 1: When the underlying gray hair color is barely concealed, resulting in uneven color <How to evaluate hair feel> The hair strands to which the non-emulsified hair colorant obtained as described above had been applied were subjected to sensory evaluation by 10 panelists to evaluate the feel of the hair based on the following evaluation criteria.

[0075] The average score of each panelist was calculated, and the evaluation results were determined as follows: an average score of 4.6 or more was "excellent: 5", 3.6 to less than 4.6 was "good: 4", 2.6 to less than 3.6 was "fair: 3", 1.6 to less than 2.6 was "slightly poor: 2", and less than 1.6 was "poor: 1". The results are shown in the "Hair feel" column in the table below.

[0076] ·Hair feel evaluation criteria 5: If you don't feel your hair is rough 4: When hair is almost free of coarseness 3: If your hair is not too rough 2: If your hair is slightly rough 1: If your hair is very rough <How to evaluate quick-drying properties> The spray hair colorant compositions of the Examples and Comparative Examples were applied so that 0.1 g adhered to 1 g of hair strand, and then the hair strand was dried for 3 minutes. Immediately afterwards, the hair strand was rubbed with a white cloth and the color transfer to the cloth was visually observed and evaluated by 10 panelists.

[0077] The average of the scores from each panelist was calculated, and the evaluation results were determined as follows: an average of 4.6 points or more was rated as "excellent: 5", 3.6 points or more but less than 4.6 points was rated as "good: 4", 2.6 points or more but less than 3.6 points was rated as "fair: 3", 1.6 points or more but less than 2.6 points was rated as "slightly poor: 2", and less than 1.6 points was rated as "poor: 1". The results are shown in the "Quick-drying" column in the table below.

[0078] Quick-drying evaluation criteria 5: If there is no color transfer at all 4: If there is slight color transfer 3: If there is color transfer 2: If there is significant color transfer 1: If there is severe color transfer

[0079] [Table 1] As shown in Table 1, it was confirmed that each Example achieved evaluations of colorability, dispersibility, hair feel, and quick-drying ability of acceptable or better. (A) Comparative Example 1, which contained less than 4 mass% iron oxide as a pigment, was confirmed to have an inferior evaluation of colorability compared to each Example. (B) Comparative Example 2, which did not contain a sorbitan fatty acid ester, was confirmed to have an inferior evaluation of dispersibility compared to each Example. (C) Comparative Example 3, which did not contain a film-forming polymer, was confirmed to have an inferior evaluation of colorability compared to each Example.

[0080] (Addendum) Next, the technical ideas that can be understood from the above-described embodiment and other examples will be described. (i) The non-emulsifying hair colorant, wherein the (B) sorbitan fatty acid ester is liquid at room temperature.

Claims

1. A non-emulsified hair colorant comprising the following (A) to (D): (A) a pigment (provided that, when the pigment is iron oxide, the amount is 4% by mass or more); (B) sorbitan fatty acid ester, (C) a film-forming polymer; (D) Ethanol.

2. 2. The non-emulsifying hair colorant according to claim 1, wherein the HLB value of component (B) is 10 or less.

3. 2. The non-emulsifying hair colorant according to claim 1, wherein the component (A) is iron oxide.

4. 4. The non-emulsifying hair colorant according to claim 3, wherein component (A) is alkylsilane-treated iron oxide.

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