WO2015174343A1

WO2015174343A1 - Hair oil

Info

Publication number: WO2015174343A1
Application number: PCT/JP2015/063322
Authority: WO
Inventors: 坂西裕一
Original assignee: 株式会社ダイセル
Priority date: 2014-05-14
Filing date: 2015-05-08
Publication date: 2015-11-19
Also published as: JPWO2015174343A1; CN106456481A; CN106456481B; JP6578274B2

Abstract

　Provided is a hair oil having excellent spreadability that does not tend to drip when held in the hand. This hair oil contains an oil composition comprising a thickener (A) and an oil (B), and contains 0.5-30.0 wt% of the total oil composition of a compound represented by formula (1) R¹-(CONH-R²)_n (1) (in the formula, R¹ is a group having n number of hydrogen atoms removed from the structural formula of benzene, benzophenone, biphenyl, naphthalene, cyclohexane, or butane; R² is an aliphatic hydrocarbon group having 4 or more carbon atoms; and n is an integer of 3 or higher. n number of R² may be the same or different) as a thickener (A) and 70.0-99.5 wt% of the total oil composition of an oil (B).

Description

Hair oil

The present invention contains an oil composition consisting of a thickener and an oil agent, is hard to dripping when taken in the hand, spreads smoothly when applied to the hair, suppleness, lightness, moist feeling, unity The present invention relates to a hair oil having an effect of imparting ease, luster and the like to hair. This application claims priority of Japanese Patent Application No. 2014-1000039 filed in Japan on May 14, 2014 and Japanese Patent Application No. 2014-241794 filed in Japan on November 28, 2014, the contents of which are hereby incorporated by reference Incorporated into.

Hair oil is a type of cosmetic for hair that is used for the purpose of supplementing the hair with oil, giving it a suppleness, moist feeling, ease of cohesion, luster and the like. Conventionally, vegetable oils such as camellia oil and olive oil, mineral oils such as liquid paraffin, higher fatty acids, silicone oils and the like have been used as hair oils (see Patent Documents 1 and 2 and Non-Patent Document 1).

However, the above-mentioned oil agent has a low viscosity at room temperature, and it has been a problem that it easily drops from between fingers when picked up. As a method for solving this problem, it is conceivable that a thickener is added to moderately thicken the oil agent. However, an oil composition obtained by thickening an oil with a conventional thickener (for example, a polystyrene-hydrogenated polyisoprene block copolymer described in Patent Document 3) is difficult to spread and cannot be applied thinly and uniformly to hair. It was difficult. In addition, Patent Document 4 describes 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) as a gelling agent for hydrophilic or lipophilic compounds.

Japanese Unexamined Patent Publication No. 63-183517 JP-A-1-175923 JP-A-8-59765 JP 2009-155592 A

However, it was found that 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) is difficult to dissolve in the oil agent and it is difficult to use it as a thickener for the oil agent.

Accordingly, an object of the present invention is a hair oil that can be applied to hair to give suppleness, lightness, moist feeling, ease of uniting, glossiness, etc. The object is to provide a hair oil that is hard to fall off and has excellent spreadability.
Another object of the present invention is a hair oil that can be applied to hair to give it suppleness, lightness, moist feeling, ease of cohesion, glossiness, and the like, and is transparent and excellent in aesthetics. It is intended to provide a hair oil that is resistant to dripping when taken on and has excellent spreadability.

As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the following formula (1) can increase the viscosity of an oil agent to an arbitrary viscosity and stably maintain the viscosity, A hair oil containing an oil composition obtained by thickening an oil agent with a compound has a suitable viscosity, so that it is difficult to dripping from between fingers when picked up by hand, has excellent spreadability, and is applied to hair. By doing so, it has been found that suppleness, lightness, moist feeling, ease of grouping, glossiness, and the like can be imparted. The present invention has been completed based on these findings.

That is, this invention is hair oil containing the oil composition which consists of a thickener (A) and an oil agent (B), Comprising: Following formula (1) as a thickener (A)
R ^1- (CONH-R ² ) _n (1)
(In the formula, R ¹ is a group obtained by removing n hydrogen atoms from the structural formula of benzene, benzophenone, biphenyl, naphthalene, cyclohexane, or butane, and R ² is an aliphatic hydrocarbon group having 4 or more carbon atoms. N represents an integer greater than or equal to ^3. n R <2> may be the same and may differ.
A hair oil containing 0.5 to 30.0% by weight of the compound represented by formula (1) and 70.0 to 99.5% by weight of the total amount of the oil agent (B) is provided.

That is, the present invention relates to the following.
[1] A hair oil comprising an oil composition comprising a thickener (A) and an oil agent (B), wherein the thickener (A) is represented by the following formula (1)
R ^1- (CONH-R ² ) _n (1)
(In the formula, R ¹ is a group obtained by removing n hydrogen atoms from the structural formula of benzene, benzophenone, biphenyl, naphthalene, cyclohexane, or butane, and R ² is an aliphatic hydrocarbon group having 4 or more carbon atoms. N represents an integer greater than or equal to ^3. n R <2> may be the same and may differ.
A hair oil comprising 0.5 to 30.0% by weight of the compound represented by the formula (1) and 70.0 to 99.5% by weight of the oil agent (B) based on the total amount of the oil composition.
[2] The hair oil according to [1], wherein all n R ^{2 s} in the formula (1) are the same linear or branched alkyl group having 6 to 12 carbon atoms.
[3] In the formula (1), n R ² are two different groups, one group is a linear or branched alkyl group having 4 to 10 carbon atoms, and the other group is carbon. The hair oil according to [1], which is a linear alkyl group or a linear alkenyl group of formula 16-20.
[4] The oil agent (B) is selected from fats and oils, wax, esters of fatty acids having 8 to 25 carbon atoms and alcohols having 3 to 18 carbon atoms, higher fatty acids, higher alcohols, squalane, petrolatum, hydrocarbon oils, and silicone oils. The hair oil according to any one of [1] to [3], which is at least one kind.
[5] The oil agent (B) is olive oil, lanolin, isopropyl myristate, decyl oleate, cetyl octoate, cetyl 2-ethylhexanoate, glycerin tri-2-ethylhexanoate, lauric acid, oleic acid, cetanol, squalane The hair oil according to any one of [1] to [3], which is at least one selected from petrolatum, petrolatum, isododecane, liquid paraffin, and chain or cyclic silicone oil.
[6] The hair oil according to any one of [1] to [5], wherein the total content of the thickener (A) and the oil agent (B) is 20% by weight or more of the total amount of the hair oil.
[7] The hair oil according to any one of [1] to [6], wherein the viscosity [at 25 ° C., shear rate 10 (1 / s)] is 0.1 to 10 Pa · s.
[8] A method for producing a hair oil, wherein the hair oil according to any one of [1] to [7] is produced through a step of making the thickener (A) and the oil agent (B) compatible.

The hair oil of the present invention has an appropriate viscosity because the compound represented by the above formula (1) is used as a thickener for the oil, and can stably maintain the viscosity. For this reason, the hair oil of the present invention is excellent in usability and spreadability when it is picked up by hand. Moreover, the hair oil of this invention has transparency and is excellent in aesthetics. When the hair oil of the present invention is applied to hair, the hair can be given a suppleness, lightness, moist feeling, ease of grouping, glossiness, and the like.

[Thickener (A)]
The present invention is characterized by using a compound represented by the following formula (1) as a thickener.
R ^1- (CONH-R ² ) _n (1)

In the formula (1), R ¹ is a group obtained by removing n hydrogen atoms from the structural formula of benzene, benzophenone, biphenyl, naphthalene, cyclohexane, or butane, and R ² is an aliphatic hydrocarbon group having 4 or more carbon atoms. It is. n represents an integer of 3 or more (preferably 3 to 4, particularly preferably 4). n R < ² > may be the same and may differ.

R ² is an aliphatic hydrocarbon group having 4 or more carbon atoms. For example, n-butyl, s-butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, myristyl, stearyl, nonadecyl A linear or branched alkyl group having about 4 to 20 carbon atoms (preferably 4 to 18), such as a group; 2-butenyl, 2-pentenyl, isopentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, A linear or branched alkenyl group having about 4 to 20 carbon atoms (preferably 6 to 18) such as 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, oleyl group; butynyl, pentynyl, hexynyl, Linear or branched having about 4 to 20 carbon atoms (preferably 6 to 18) such as octynyl, decynyl, pentadecynyl, octadecynyl group, etc. Jo alkynyl group and the like.

As the compound represented by the formula (1), among them, a compound in which n R ^{2 s} are all the same group or a compound in which n R ^{2 s} are two different groups is an oil agent (B). It is preferable in that it is excellent in solubility and can be thickened while maintaining transparency.

Among the compounds represented by formula (1), the compounds in which n R ^{2 s} are all the same group (R ²¹ ) (wherein R ²¹ represents an aliphatic hydrocarbon group having 4 or more carbon atoms) Of these, compounds in which R ²¹ is a linear or branched alkyl group having about 4 to 20 carbon atoms (preferably 6 to 18, particularly preferably 6 to 12) are preferred.

Of the compounds represented by the formula (1), n R ² are two different groups (R ²¹ and R ²² ) (the R ²¹ and R ²² are different from each other and have 4 or more carbon atoms). As the aliphatic hydrocarbon group, among them, one of R ²¹ and R ²² has about 4 to 20 carbon atoms (preferably 4 to 18, particularly preferably 4 to 15, most preferably 4 to 12, more preferably Preferably, it is a linear or branched alkyl group having 4 to 10), and the other of R ²¹ and R ²² has about 6 to 20 carbon atoms (preferably 12 to 20, particularly preferably 15 to 20 and most preferably. The compound which is a linear alkyl group or a linear alkenyl group of 16 to 20) is preferred.

Among the compounds represented by the formula (1), examples of the compound wherein n is 4 include compounds represented by the following formulas. R ²¹ and R ²² in the following formula are the same as described above. When a plurality of R ²¹ are present in one molecule, they are the same group. The same is true for R ^22. Examples of the compound in which n is an integer other than 4 (for example, n = 3) include compounds corresponding to the compound represented by the following formula.

In the present invention, among the compounds represented by the formula (1), a compound in which n R ² are two different groups is preferable in that it has an excellent viscosity increase over a wide range of solvents.

The molecular weight of the compound represented by the formula (1) of the present invention is, for example, about 500 to 1300, preferably 500 to 1200, particularly preferably 550 to 1100, and most preferably 550 to 1050. When the molecular weight of the compound represented by the formula (1) exceeds the above range, the extensibility of the obtained hair oil tends to be lowered. On the other hand, when the molecular weight of the compound represented by the formula (1) is below the above range, the thickening effect tends to be reduced.

The compound represented by the formula (1) can be produced, for example, by the method 1 or 2 below.
1. Following formula (2)
R ^1- (COOH) _n (2)
(R ¹ and n are the same as above)
A carboxylic acid chloride represented by the formula (1) is reacted with thionyl chloride to obtain a carboxylic acid chloride, and the resulting carboxylic acid chloride is reacted with an amine (R ² —NH ₂ ) (R ² is the same as above). The amine (1) (R ² —NH ₂ ) is reacted with the carboxylic acid anhydride corresponding to the carboxylic acid represented by the formula (2) to obtain an amic acid, and further the amine (2) (R ² —NH ₂ ). , Which may be the same as or different from amine (1)) using a condensing agent

Examples of the carboxylic acid represented by the formula (2) used in the production method 1 include 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid (= pyromellitic acid). ), 2,4,5-benzophenone tricarboxylic acid, 3,4,3′-benzophenone tricarboxylic acid, 3,4,4′-benzophenone tricarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 1 , 1′-biphenyl-2,4,4′-tricarboxylic acid, 1,1′-biphenyl-2,3,3 ′, 4′-tetracarboxylic acid, 1,6,7-naphthalenetricarboxylic acid, 1,2 , 3-Naphthalenetricarboxylic acid, 1,3,8-naphthalenetricarboxylic acid, 1,4,6-naphthalenetricarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, , 4-cyclohexane tricarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, 1,2,4-butane tricarboxylic acid, and 1,2,3,4 butane tetracarboxylic acid.

Examples of the amine (R ² —NH ₂ ) used in the above production method 1 include n-butylamine, s-butylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, myristylamine, stearylamine. An aliphatic hydrocarbon group (preferably a linear or branched alkyl group, alkenyl group, or alkynyl group) wherein R ² is 4 or more (preferably 4 to 20 carbon atoms), such as oleylamine The amine which is) can be mentioned.

The reaction between the carboxylic acid chloride and the amine can be performed, for example, by dropping the carboxylic acid chloride into the system charged with the amine.

The amount of amine used is, for example, about 4 to 8 moles, preferably 4 to 6 moles per mole of carboxylic acid chloride. Here, when two or more different amines are used, a compound in which n R ^{2 s} are two or more different groups among the compounds represented by the formula (1) is obtained.

The reaction between the carboxylic acid chloride and the amine can be carried out in the presence or absence of a solvent. Examples of the solvent include saturated or unsaturated hydrocarbon solvents such as pentane, hexane, heptane, octane and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, chloroform, 1, 2 -Halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, bromobenzene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether; acetonitrile, benzonitrile, etc. Nitrile solvents; sulfoxide solvents such as dimethyl sulfoxide; sulfolane solvents such as sulfolane; amide solvents such as dimethylformamide; high-boiling solvents such as silicone oil. These can be used alone or in combination of two or more.

The amount of the solvent used is, for example, about 50 to 300% by weight with respect to the total amount of carboxylic acid chloride and amine. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

The reaction (= dropping) of carboxylic acid chloride and amine is usually carried out under normal pressure. Further, the atmosphere of the above reaction (= drip) is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature (= temperature at the time of dropping) is, for example, about 30 to 60 ° C. The reaction time (= dropping time) is, for example, about 0.5 to 20 hours. After completion of the reaction (= dropping), an aging step may be provided. When the aging step is provided, the aging temperature is, for example, about 30 to 60 ° C., and the aging time is, for example, about 1 to 5 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

After completion of the reaction, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.

In the above production method 2, for example, an amic acid is formed by charging and aging carboxylic acid anhydride, amine (1) and the following solvent into the system, and then amine (2) and a condensing agent (for example, carbodiimide). Alternatively, the compound represented by the formula (1) can be produced by charging and aging the salt. Here, when two or more different amines are used, a compound in which n R ² are two or more different groups among the compounds represented by the formula (1) of the present invention is obtained.

Examples of the carboxylic acid anhydride include 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 1,1′-biphenyl-2,3,3 ′, 4′-tetracarboxylic acid-2,3: 3 ′, 4′-dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid- 1,8: 4,5-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride, meso-butane-1,2,3,4-tetra Carboxylic dianhydrides and the like can be preferably used.

Examples of the amines (1) and (2) include the same examples as amines that can be used in the above production method 1.

The amount of amine (1) to be used is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of carboxylic anhydride. The amount of amine (2) to be used is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of carboxylic anhydride.

The carbodiimide is represented by the following formula (3).
RN = C = NR ′ (3)
In the above formula (3), as R and R ′, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, and 3 to 8 Member cycloalkyl groups and the like. R and R ′ may be the same or different. R and R ′ may be bonded to each other to form a ring together with a (—N═C═N—) group.

Examples of the linear or branched alkyl group having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, Examples include hexyl, isohexyl, s-hexyl, t-hexyl groups and the like.

Examples of the 3- to 8-membered cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

Examples of the heteroatom-containing substituent include nitrogen atom-containing substituents such as di (C _1-3 ) alkylamino groups such as amino groups and dimethylamino groups.

Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide, and the like. Examples of the carbodiimide salt include hydrochloride (specifically, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride). These can be used alone or in combination of two or more.

The amount of carbodiimide used is, for example, about 2 to 6 moles, preferably 2 to 4 moles per mole of carboxylic anhydride.

As the solvent, it is preferable to use a proton-accepting solvent (for example, pyridine, triethylamine, tributylamine, etc.) excellent in solubility of amic acid. These can be used individually by 1 type or in mixture of 2 or more types.

The amount of the solvent used is, for example, about 50 to 300% by weight, preferably 100 to 250% by weight, based on the total amount of amic acid. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

The above reaction is usually performed under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The aging temperature (reaction temperature) is, for example, about 30 to 70 ° C. The aging time of the carboxylic acid anhydride and the amine is, for example, about 0.5 to 5 hours, and the aging time of the amic acid and the amine is, for example, about 0.5 to 20 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

The compound represented by the formula (1) can self-associate by hydrogen bonding at the amide bond site to form a fibrous self-assembly. Further, the R ² group has an affinity for the oil agent (B). Therefore, by making it compatible with the oil agent (B), it is possible to increase the viscosity of the oil agent (B) moderately and stably over time while maintaining transparency. In particular, when R ² in the formula (1) is two or more different groups, it has appropriate crystallinity, so it can be thickened without being limited to the type of the oil agent (B), and wider A thickening action can be exerted on the range of the oil agent (B). That is, it has a wide range of oil agent selectivity.

[Oil agent (B)]
As the oil agent (B) of the present invention, any oil agent can be used without particular limitation as long as it is capable of imparting suppleness, lightness, moist feeling, ease of grouping, glossiness and the like by applying to the hair. Oils include polar oils, nonpolar oils, and mixtures thereof. An oil agent can be used individually by 1 type or in combination of 2 or more types.

Examples of the polar oil include oils and fats such as olive oil, waxes such as lanolin, esters [isopropyl myristate, decyl oleate, cetyl octanoate, cetyl 2-ethylhexanoate, and glycerin tri-2-ethylhexanoate. An ester of a fatty acid having 8 or more carbon atoms (preferably 8 to 25 carbon atoms) and an alcohol having 3 or more carbon atoms (preferably 3 to 18 carbon atoms, particularly preferably 10 to 16 carbon atoms). [Fatty acids such as lauric acid, oleic acid and the like having 12 or more carbon atoms (preferably, 12 to 25 carbon atoms)], higher alcohols solid at room temperature [such as cetanol and having 12 or more carbon atoms (preferably having 12 to 20 carbon atoms) 25) Alcohol] and the like.

Examples of the nonpolar oil include squalane, petrolatum, hydrocarbon oil (such as isododecane and liquid paraffin), and chain or cyclic silicone oil.

[Hair oil]
The hair oil of this invention contains the oil composition which consists of the said thickener (A) and an oil agent (B).

The oil composition comprising the thickener (A) and the oil agent (B) can be produced, for example, through a step of making the thickener (A) and the oil agent (B) compatible. More specifically, it can be produced by mixing and heating the thickener (A) and the oil agent (B), allowing them to be dissolved, and then cooling. In addition, the thickener (A) is mixed with a part of the oil agent (B), heated and compatible, then cooled, and then mixed with the remaining oil agent (B). Can do.

The combination of the thickener (A) and the oil agent (B) is not particularly limited as long as the thickener (A) and the oil agent (B) are compatible, but from the viewpoint of the minimum gelation concentration, the oil agent (B ) Is mainly a polar oil, the thickener (A) is a fat having at least one R ² in the formula (1) having 13 to 20 carbon atoms (more preferably 13 to 18 carbon atoms). It is preferable to use a compound which is a group hydrocarbon group. When the oil agent (B) is mainly composed of a nonpolar oil, at least one of R ² in the formula (1) has 4 to 12 carbon atoms (more preferably carbon atoms) as the thickener (A). It is preferable to use compounds which are aliphatic hydrocarbon groups 4-10). The “main component” means “contain 80% by weight or more”.

The temperature at the time of the compatibility is appropriately selected depending on the types of the thickener (A) and the oil agent (B), and is not particularly limited, but preferably does not exceed 100 ° C., and the boiling point of the oil agent (B) is 100. When the temperature is not higher than ° C., the boiling point is preferable.

The cooling after the compatibilization is not limited as long as it can be cooled to room temperature (for example, 25 ° C.) or lower, and may be gradually cooled at room temperature, or may be rapidly cooled by ice cooling or the like.

The content of the thickener (A) (when two or more types are contained, the total amount thereof) is 0.5 to 30.0% by weight of the total amount of the oil composition contained in the hair oil, and the lower limit of the above range is preferable. Is 1.0% by weight. The upper limit of the range is preferably 20.0% by weight, particularly preferably 10.0% by weight, and most preferably 5.0% by weight. By blending the thickener (A) in the above range, it is possible to impart an appropriate viscosity to the oil agent (B), and it is possible to obtain a hair oil that is resistant to dripping when picked up and has excellent spreadability. . On the other hand, when the content of the thickener (A) is below the above range, it tends to be difficult to stably maintain the viscosity of the hair oil. Moreover, even if content of a thickener (A) exceeds the said range, an advantageous effect is difficult to be acquired and there exists a tendency for the extensibility of hair oil to fall.

The hair oil of the present invention may contain other thickeners in addition to the thickener (A), but the proportion of the thickener (A) in the total thickener contained in the hair oil is, for example, It is 30% by weight or more, preferably 50% by weight or more, particularly preferably 70% by weight or more, and most preferably 85% or more. The upper limit of the proportion of the thickener (A) is 100% by weight. When the ratio of another thickener exceeds the said range, there exists a tendency for the effect of this invention to become difficult to be acquired. The “thickener” in the present invention is a concept including a thickener that imparts viscosity, a gelling agent that gels, and a stabilizer that uniformly stabilizes the components of the composition.

The content of the oil agent (B) (when two or more are contained, the total amount thereof) is 70.0 to 99.5% by weight of the total amount of the oil composition contained in the hair oil, and the lower limit of the above range is preferably 80 0.0% by weight, particularly preferably 90.0% by weight. The upper limit of the range is preferably 99.0% by weight. The hair oil containing the oil agent (B) in the above range is excellent in spreadability while stably maintaining an appropriate viscosity, and imparts suppleness, lightness, moist feeling, ease of cohesion, luster and the like to the hair. be able to.

The hair oil of the present invention contains the above oil composition in an amount of, for example, 20% by weight or more (preferably 30% by weight or more, particularly preferably 50% by weight or more, most preferably 80% by weight or more). The upper limit of the content of the oil composition is 100% by weight of the total amount of hair oil. The water content in the hair oil of the present invention is, for example, 1% by weight or less, preferably 0.2% by weight or less. In addition to the oil composition, the hair oil of the present invention may contain one or more components that are used in normal hair cosmetics as long as the effects of the present invention are not impaired. The component may be either an aqueous component or a non-aqueous component, but is preferably a non-aqueous component. Examples of the components include oily components other than the oil agent (B), surfactants, polyhydric alcohols, chelating agents, antibacterial agents, antioxidants, viscosity modifiers, astringents, antidandruff agents, hair restorers, ultraviolet rays. Examples include absorbents, colorants (pigments such as dyes and pigments), fragrances, cosmetic ingredients (vitamins, etc.), aerosol propellants and the like.

The hair oil of the present invention has an appropriate viscosity, and its viscosity [at 25 ° C., at a shear rate of 10 (1 / s)] is, for example, in the range of 0.1 to 10 Pa · s, preferably 0.5 to 5 Pa · s. Can be selected as appropriate. When the viscosity exceeds the above range, the spreadability tends to be difficult to obtain. On the other hand, if the viscosity is below the above range, it tends to be difficult to prevent dripping when the hair oil is picked up. In addition, adjustment of a viscosity can be performed by adjusting content of a thickener (A) within the said range.

The hair oil of the present invention may be in any state such as liquid, gel or multiphase. Moreover, it can also be set as mist form, aerosol form, etc. by the combination with a container.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Preparation Example 1 (Thickener (1): Synthesis of 1,2,4,5-benzenetetracarboxylic acid tetra (hexylamide))
Chloroform 20 mL and hexylamine 3.6 g (0.036 mol) were charged into a 100 mL four-neck separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple, and the system temperature was set to 40 ° C. .
Thereafter, a 10 mL chloroform solution of 3 g (0.009 mol) of pyromellitic acid tetrachloride was added dropwise over 2 hours, followed by further aging for 2 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a white wet powder. The obtained wet powder was recrystallized from CHCl ₃ / CH ₃ OH (70/30 (v / v)), and 1,2,4,5-benzenetetracarboxylic acid tetra (hexylamide) (molecular weight: 586). Was obtained (yield: 67%). The structure of the reaction product was confirmed by ¹ H-NMR.

Preparation Example 2 (Thickener (2): Synthesis of 1,2,4,5-benzenetetracarboxylic acid tetra (octylamide))
Tetra (octylamide) 1,2,4,5-benzenetetracarboxylic acid (molecular weight: 699) in the same manner as in Preparation Example 1, except that 4.8 g (0.036 mol) of octylamine was used instead of hexylamine 3.7 g (yield: 59%) was obtained.

Preparation Example 3 (Thickener (3): Synthesis of 1,2,4,5-benzenetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide))
20 mL of pyridine, 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple 3.0 g (0.014 mol) of the product and 7.4 g (0.028 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 3.6 g (0.028 mol) of 2-ethylhexylamine and 7.0 g (0.056 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was recrystallized from CHCl ₃ / CH ₃ OH (70/30 (v / v)) to obtain 1,2,4,5-benzenetetracarboxylic acid di (2-ethylhexylamide) di (oleyl). Amide) (molecular weight: 975) [1,2,4,5-benzenetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (oleylamide) and 1,2,4,5 -Mixture of benzenetetracarboxylic acid-1,5-di (2-ethylhexylamide) -2,4-di (oleylamide)] was obtained (yield: 51%).

Preparation Example 4 (Thickener (4): Synthesis of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetra (dodecylamide))
A 100 mL four-neck separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple was charged with 20 mL of chloroform and 11.4 g (0.062 mol) of dodecylamine. The system temperature was set to 50 ° C., and a 10 mL chloroform solution of 4.97 g (0.011 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetrachloride was added dropwise over 0.5 hours. Aged for time. Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was recrystallized with CHCl ₃ / CH ₃ OH (70/30 (v / v)), and 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetra (dodecylamide) (molecular weight: 923) was obtained (yield: 27%).

Preparation Example 5 (Thickener (5): Synthesis of 1,2,3,4-butanetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide))
20 mL of pyridine, 1,2,3,4-butanetetracarboxylic acid-1,2: 3,4-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple 4.2 g (0.021 mol) of the product and 11.3 g (0.042 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 5.4 g (0.042 mol) of 2-ethylhexylamine and 5.8 g (0.048 mol) of diisopropylcarbodiimide were charged, followed by further aging for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was recrystallized from CHCl ₃ / CH ₃ OH (70/30 (v / v)) to obtain 1,2,3,4-butanetetracarboxylic acid di (2-ethylhexylamide) di (oleyl). Amide) (molecular weight: 1024.95) [1,2,3,4-butanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,3-di (oleylamide) and 1,2,3 , 4-butanetetracarboxylic acid-1,3-di (2-ethylhexylamide) -2,4-di (oleylamide)] was obtained (yield: 83%).

Preparation Example 6 (Thickener (6): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (n-butylamide) di (oleylamide))
20 mL of pyridine, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple 4.5 g (0.02 mol) of the product and 10.7 g (0.04 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 2.9 g (0.02 mol) of n-butylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was recrystallized from CHCl ₃ / CH ₃ OH (70/30 (v / v)) to obtain 1,2,4,5-cyclohexanetetracarboxylic acid di (n-butylamide) di (oleylamide). ) (Molecular weight: 869.43) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (n-butylamide) -2,5-di (oleylamide) and 1,2,4,5 -11.6 g of a mixture of cyclohexanetetracarboxylic acid-1,5-di (n-butylamide) -2,4-di (oleylamide)] (yield: 67%).

Preparation Example 7 (Thickener (7): Synthesis of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide))
A 100 mL four-neck separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple was charged with 20 mL of pyridine, 2.97 g (0.017 mol) of 1,2,3-propanetricarboxylic acid, and 7.0 g of diisopropylcarbodiimide. (0.056 mol) was added, the system temperature was set to 50 ° C., and the mixture was aged for 3 hours.
Further, 5.7 g (0.051 mol) of 2-methylcyclohexylamine was added and aged for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. The obtained wet powder was washed with acetone to obtain 4.7 g of 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) (yield: 61%).

Example 1
2 parts by weight of the thickener (1) obtained in Preparation Example 1 and 98 parts by weight of isododecane are mixed, heated and stirred at 80 ° C. to dissolve them, and then cooled to 25 ° C. to obtain an oil composition (1) (Viscosity at 2.4 ° C., shear rate 10 (1 / s): 2.4 Pa · s) was obtained, and hair oil (1) comprising the oil composition (1) was obtained.
The obtained hair oil (1) was evaluated for usability, spreadability, and transparency by the following methods.

Examples 2-8, Comparative Examples 1-6
A hair oil was obtained in the same manner as in Example 1 except that the prescription (unit: parts by weight) shown in the following table was changed, and these were evaluated in the same manner as in Example 1.

<Evaluation method>
(1) Evaluation of usability and spreadability Sensory evaluation was performed by 10 panelists specializing in sensory testing.
Specifically, the hair was washed with shampoo (trade name “Revul”, manufactured by Japan Gateway Co., Ltd.), rinsed well, and then semi-dried with a dryer. Then, 5 g of each hair oil obtained in Examples and Comparative Examples was picked up and adjusted to the hair, usability of hair oil (difficulty of sagging when taken in hand), and spreadability (smooth extension) ) Was evaluated in five stages using the following evaluation criteria to obtain a score.
Evaluation criteria Very good: 5 points Good: 4 points Normal: 3 points Bad: 2 points Very bad: 1 point

Judgment was made from the average value of the obtained scores using the following criteria.
Criteria ◎: 4 points or more ○: 3 points or more, less than 4 points △: 2 points or more, less than 3 points ×: Less than 2 points

(2) Evaluation of transparency About each hair oil obtained by the Example and the comparative example, transparency was judged visually and transparency was evaluated according to the following reference | standard.
Evaluation criteria ◎: Transparent ○: Translucent △: Cloudy ×: Two-phase separation

Isododecane: Trade name “Permethyl 99A”, manufactured by Nippon Koken Kogyo Co., Ltd. Liquid paraffin: Trade name “Molesco White P-100”, manufactured by MORESCO Corporation Cetyl octanoate: Trade name “CEH”, Higher Alcohol Industry Co., Ltd. Made

The hair oil of the present invention was a hair oil having excellent usability, spreadability, and transparency. On the other hand, when the thickener of the present invention was not used, it was easy to drop from between fingers, and usability was poor. Further, in the hair oil using the conventionally known thickener (7) (1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide)), the thickener was not dissolved in any oil agent. The thickening effect could not be obtained. Therefore, it was easy to drop from between the fingers and the usability was poor. Moreover, it was inferior also in the point of transparency.

The hair oil of the present invention has an appropriate viscosity and can stably maintain the viscosity. For this reason, the hair oil of the present invention is excellent in usability and spreadability when it is picked up by hand. Moreover, the hair oil of this invention has transparency and is excellent in aesthetics. When the hair oil of the present invention is applied to hair, the hair can be given a suppleness, lightness, moist feeling, ease of grouping, glossiness, and the like.

Claims

A hair oil comprising an oil composition comprising a thickener (A) and an oil agent (B), wherein the thickener (A) is represented by the following formula (1)
R 1- (CONH-R 2 ) n (1)
(In the formula, R 1 is a group obtained by removing n hydrogen atoms from the structural formula of benzene, benzophenone, biphenyl, naphthalene, cyclohexane, or butane, and R 2 is an aliphatic hydrocarbon group having 4 or more carbon atoms. N represents an integer greater than or equal to 3. n R <2> may be the same and may differ.
A hair oil comprising 0.5 to 30.0% by weight of the compound represented by the formula (1) and 70.0 to 99.5% by weight of the oil agent (B) based on the total amount of the oil composition.