JP5782295B2 - Hair cosmetics - Google Patents

Description

  In recent years, an increasing number of consumers are using hot hair-styling tools such as hair irons (flat irons, curling irons, etc.) and irons for the purpose of making hairstyles desired and more convenient. The frequency of use is also increasing. Some hair-styling tools such as curling irons and irons can be set to temperatures of 120 to 180 ° C for general household use and 200 to 220 ° C or higher for barbershops. When using these hot hair styling devices, the hair will be exposed to higher temperatures than

  For this reason, a technique using saccharides has been proposed as a means for protecting hair from damage caused by high-temperature hairdressing instruments such as a hair iron and a trowel or repairing hair damage. For example, Patent Document 1 discloses a technique that uses a reducing sugar to suppress a decrease in tensile strength due to high-temperature heating. Patent Document 2 discloses a method for maintaining the tensile strength by protecting the α structure of a hair protein using a monosaccharide having 3 to 5 carbon atoms. Patent Document 3 mentions long-term use of a high-temperature styling device as an example of the cause of hair damage. By using a disaccharide, a chain saturated diacid, and a guanidinium salt in combination, the hair is more easily handled. Disclosure about technology

JP 2010-95472 A JP 2008-163037 A JP 2010-77138 A

  In Patent Documents 1 and 2, it is reported that, after the hair is immersed in the composition for a long time, the heat treatment with a high-temperature heating apparatus has a tensile strength reduction suppressing effect. However, when the inventor evaluated the techniques of Patent Documents 1 and 2 repeatedly using high-temperature hairdressing equipment under conditions close to the actual usage conditions of consumers, the effect of suppressing tensile strength was insufficient. . The technique of Patent Document 3 is also insufficient in effect when it is applied to hair under conditions close to the actual use conditions of consumers and repeated use of high-temperature heating equipment.

  Here, the present inventor newly discovered that heat denaturation of hair proteins is accumulated by repeated use of a high-temperature hairdressing instrument, thereby causing undulation and curling after hair washing and drying. When the techniques of Patent Documents 1 to 3 were evaluated from the viewpoint of suppressing the occurrence of this undulation, it was newly found that these techniques hardly provide the effect of suppressing the undulation.

  The above suggests that new hair damage that has not been known so far has occurred as a result of the accumulation of thermal denaturation of hair proteins by repeated high-temperature heat treatment.

  On the other hand, poly (N-acylalkylenimine) -modified polysiloxanes are known to have performances that are superior in hair setability, set durability, and feel after styling compared to conventional film-forming resins. However, when used in combination with saccharides, the saccharide and the poly (N-acylalkylenimine) -modified polysiloxane are not compatible with each other, so that the film formed on the hair during hair styling is not uniformly formed. There is a problem that the setability, the set sustainability, and the smoothness of the hair when used are reduced.

  In other words, by repeatedly using high temperature hairdressing instruments such as hair irons and irons, the swell and drying of the hair after washing and drying is suppressed, and the setability and set durability during hairstyling using a high temperature hairdressing apparatus It is an object of the present invention to provide a technique that is high and excellent in all hair feel.

The present invention comprises the following components (A) to (C), the mass ratio (A) / (C) of the components (A) and (C) is 0.01 to 2, and the pH of the composition is The present invention provides a hair cosmetic composition that is 2.0 to 4.5.
(A): Disaccharide in which two glucose molecules are linked via a glycosidic bond
(B): a monocarboxylic acid having 2 to 6 carbon atoms and a pKa of 3 to 4, or a di- or tricarboxylic acid having a pKa ₁ of 3 to 4
(C): at least two silicon atoms of the organopolysiloxane segment [segment (a)] constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and n represents 2 or 3.)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments [segment (b)] composed of repeating units represented by:
The weight average molecular weight of segment (a) is 7,000 to 100,000,
The number average molecular weight of the segment (b) is 1,200-5,500;
The mass ratio (a / b) of segment (a) to segment (b) is 35 / 65-60 / 40,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1,300-5,500,
Organopolysiloxane

  The present invention also provides a hair styling method comprising the steps of applying the above-described hair cosmetic composition to hair and heating the temperature of the hair to 100 ° C. or higher.

  The hair cosmetic composition of the present invention can suppress the occurrence of undulation and curling of the hair after washing and drying that occurs when a high-temperature heating device is repeatedly used. Property and set durability are high, and smoothness of hair is excellent.

[Component (A): a disaccharide in which two molecules of glucose are linked via a glycosidic bond]
The disaccharide in which two glucose molecules of component (A) are linked via glycosidic bonds penetrates into the hair and interacts with the internal protein, so that the structure of the internal protein of the hair is stable even when heated with a hair iron or the like. By maintaining at, it is possible to impart resistance to the accumulation of high temperature heat denaturation to the hair. However, since disaccharides and poly (N-acylalkylenimine) -modified polysiloxanes are not compatible with each other, when these are used in combination, hair iron set properties, set durability, and smoothness of hair after setting are reduced. was there.

  In order to solve this problem, the inventors have considered that it is necessary not only to increase the permeability of disaccharides into hair, but also to strengthen the interaction itself between disaccharides and hair internal proteins. According to the present invention, by combining a disaccharide in which two molecules of component (A) glucose are linked via a glycosidic bond and a specific carboxylic acid of component (B), and further adjusting the pH to a range of 2.0 to 4.5. The high heat resistance of the disaccharide of component (A) can be increased, and the occurrence of swells and curls after washing and drying due to repeated use of high-temperature hairdressing equipment can be suppressed.

  Specific examples of disaccharides in which two molecules of component (A) glucose are linked via glycosidic bonds include trehalose (α1-α1 linkage), cordose (α1,2 linkage), nigerose (α1,3 linkage), maltose ( α1,4 bond), isomaltose (α1,6 bond), isotrehalose (β1-β1 bond), sophorose (β1,2 bond), laminaribiose (β1,3 bond), cellobiose (β1,4 bond), Examples include gentiobiose (β1,6 bond) and neotrehalose (β1-α1 bond), and trehalose and maltose are particularly preferable from the viewpoint of easy availability.

  Sugars include sugar alcohols, monosaccharides, disaccharides, trisaccharides, oligosaccharides, polysaccharides, etc., but in the present invention, from the viewpoint of penetration into hair and the strength of interaction with hair proteins. Uses the specific disaccharides described above. Sugar alcohols and monosaccharides can easily penetrate into the hair due to their low molecular weight, but they have weak interactions with proteins inside the hair, while trisaccharides, oligosaccharides and polysaccharides have high molecular weights and are difficult to penetrate inside the hair. Therefore, it is not preferable. Among disaccharides, the disaccharide composed of two molecules of glucose (component (A)) has a strong interaction with hair internal proteins, and hair swells and curls occur due to the accumulation of heat denaturation of hair proteins. The effect which suppresses is high.

  The content of the component (A) in the hair cosmetic composition of the present invention is preferably 0.01 to 6% by mass from the viewpoint of achieving both swell after hair washing and drying, curling suppression, high setability, and set sustainability. Furthermore, 0.1-3 mass%, Furthermore, 0.2-2 mass% is preferable.

[Component (B): Specific carboxylic acid]
Is the number of carbon atoms of component (B) is 2-6, di- or tricarboxylic acids monocarboxylic acid or pKa ₁ having a pKa of 3 to 4 is 3-4, the interaction of the component (A) and the hair internal protein It is presumed that the effect of strengthening and suppressing the occurrence of hair undulation and curling due to the accumulation of heat denaturation of hair proteins is improved. Specific examples of the component (B) include glycolic acid (carbon number 2, pKa = 3.88), lactic acid (carbon number 3, pKa = 3.86), malic acid (carbon number 4, pKa ₁ = 3.46), tartaric acid (carbon number) 4, pKa ₁ = 3.04), citric acid (6 carbon atoms, pKa ₁ = 3.15), which improves hair iron set properties and is excellent in smoothness of hair after styling, glycolic acid, lactic acid, apple Acid is preferred.

  Moreover, a component (B) can be used individually or in combination of 2 or more types. Here, the content of the component (B) in the hair cosmetic composition of the present invention increases the effect of suppressing the occurrence of hair swell and curl due to the accumulation of heat denaturation of hair proteins, repairs cavities inside the hair From the viewpoint of simultaneously achieving all the effects of achieving high setting properties and sustainability, 0.01 to 10% by mass is preferable, 0.05 to 5% by mass, and further 0.15 to 3% by mass is preferable.

  The hair cosmetic composition of the present invention has a pH of 2.0 to 4.5 as the composition, preferably 3.0 to 4.0. By setting it within this range, it is considered that the component (A) can permeate into the site inside the hair to be reached without damage, and the interaction between the component (A) and the hair can be strengthened. Here, the pH can be controlled by adjusting the blending amount of the component (B) or by using a normal pH adjuster.

Typical pH adjusters used in addition to component (B) include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and β-naphthalenesulfonic acid; acetic acid (carbon number 2, pKa = 4.76), propionic acid (carbon number 3, pKa = 4.87), succinic acid (carbon number 4, pKa ₁ = 4.21), the pKa ₁ of adipic acid (number of carbon atoms 6, pKa ₁ = 4.42) Organic acids that are not 3-4 are mentioned. However, even without adjusting the mono- or tricarboxylic acid of component (B) to the above pH range only with these normal pH adjusting agents, hair undulation and curl due to the accumulation of heat denaturation of hair proteins can be prevented. The effect of suppressing generation and the effect of repairing cavities inside the hair cannot be obtained sufficiently.

[Component (C): Organopolysiloxane]
In the organopolysiloxane of component (C), the poly (N-acylalkylenimine) segment composed of the repeating unit represented by the general formula (1) is at least 2 of the silicon atoms of the organopolysiloxane segment constituting the main chain. In addition, it has a unique structure that is bonded at a predetermined interval and at a predetermined ratio through an alkylene group containing a hetero atom. That is, a highly hydrophilic poly (N-acylalkyleneimine) segment and a highly lipophilic organopolysiloxane segment are present at a specific ratio, and a poly (N-acylalkyleneimine) segment is present at a specific interval.

  The poly (N-acylalkylenimine) segment can be bonded to any silicon atom constituting the organopolysiloxane segment via an alkylene group containing a hetero atom, except for both ends. It is preferable that it is bonded to the above silicon atom via the alkylene group, and it is more preferable that it is bonded to two or more silicon atoms excluding both ends via the alkylene group.

The alkylene group containing a hetero atom functions as a linking group for the poly (N-acylalkylenimine) segment. Examples of the alkylene group include C2-C20 alkylene groups containing 1 to 3 nitrogen atoms, oxygen atoms or sulfur atoms, and are represented by any of the following formulas (i) to (viii). The group represented by any one of the following formulas (i) to (iii) is more preferable. In the formula, An ⁻ represents a counter ion of a quaternary ammonium salt, for example, ethyl sulfate ion, methyl sulfate ion, chloride ion, iodide ion, sulfate ion, p-toluenesulfonate ion, perchlorate ion. Is exemplified.

In the general formula (1), which is a repeating unit constituting the poly (N-acylalkylenimine) segment, the alkyl group having 1 to 22 carbon atoms in R ¹ is, for example, linear or branched having 1 to 22 carbon atoms. Or a cyclic alkyl group, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl Examples include a group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group, nonadecyl group, eicosyl group, docosyl group and the like. Among these, from the viewpoint of high solubility in water and lower alcohols, an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further 1 to 3 carbon atoms is preferable.

  Examples of the aralkyl group include aralkyl groups having 7 to 15 carbon atoms, and specific examples include a benzyl group, a phenethyl group, a trityl group, a naphthylmethyl group, and an anthracenylmethyl group. Among them, an aralkyl group having 7 to 14 carbon atoms, and more preferably 7 to 10 carbon atoms is preferable.

  Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and specific examples include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group. An aryl group having 6 to 12 carbon atoms, more preferably 6 to 9 carbon atoms is preferable.

Among these, R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.

  The mass ratio (a / b) between the organopolysiloxane segment (a) and the poly (N-acylalkyleneimine) segment (b) is solubility / dispersibility in a solvent and ease of shaping during hairdressing. From the viewpoint of being particularly suitable for the hair styling method of the present invention by combining the feel of the hair after hair styling and the setting power for holding the hair that has been laid for a long time in a balanced manner, it is 35 / 65-60 / 40. , Preferably 42/58 to 58/42, more preferably 45/55 to 55/45, still more preferably 47/53 to 53/47.

In the present specification, the mass ratio (a / b) is determined by dissolving 5% by mass of the organopolysiloxane of the present invention in deuterated chloroform and analyzing it by nuclear magnetic resonance ( ¹ H-NMR) analysis. The value obtained from the integral ratio of the alkyl group or phenyl group of the above and the methylene group in the poly (N-acylalkylenimine) segment can be used.

  The weight average molecular weight (MWg) of the organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments (hereinafter sometimes referred to as “molecular weight between graft points”) is 1,300 to 5,500, preferably Is from 1,600 to 3,500, more preferably from 1,800 to 3,200, still more preferably from 2,000 to 3,000.

In the present specification, “an organopolysiloxane segment between adjacent poly (N-acylalkyleneimine) segments” means an organopolysiloxane of a poly (N-acylalkyleneimine) segment as shown in the following formula (2): A portion surrounded by a broken line between two points from a bonding point (bonding point α) to a segment to a bonding point (bonding point β) of a poly (N-acylalkyleneimine) segment adjacent thereto. A segment composed of an R ² SiO unit, one R ⁶ , and y + 1 (R ² ) ₂ SiO units. The “poly (N-acylalkylenimine) segment” refers to —W—R ⁷ bonded to the above R ⁶ .

In the general formula (2), each R ² independently represents an alkyl group having 1 to 22 carbon atoms or a phenyl group, R ⁶ represents an alkylene group containing a hetero atom, and —W—R ⁷ represents poly (N— An acylalkylenimine) segment, R ⁷ represents a residue of a polymerization initiator, and y represents a positive number.

  The molecular weight MWg between graft points is the weight average molecular weight of the portion surrounded by the broken line in the general formula (2), but the mass of the organopolysiloxane segment per mole of the poly (N-acylalkylenimine) segment (g / mol).

  The molecular weight (MWox) of the poly (N-acylalkylenimine) segment can be calculated from the molecular weight of N-acylalkylenimine units and the degree of polymerization, or can be measured by gel permeation chromatography (GPC) measurement method described later. In the present invention, the number average molecular weight measured by the GPC measurement method is used. The MWox of component (C) is 1,200-5,500, preferably 1,600-3,500, more preferably 1,800-3,200, and still more preferably 2,000-3,000. This makes it possible to give a firm shape when styling hair using a high-temperature heating device, and to be elastic enough to maintain the style of the hair at normal temperatures (near room temperature) where people live. And a good feel can be imparted. Moreover, the component (C) can be dissolved in a polar solvent such as water or a lower alcohol.

  The molecular weight MWg between the graft points can be determined by the following formula (I) using the content (Csi) of the organopolysiloxane segment constituting the main chain.

  The weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain is 7,000 to 100,000. From the viewpoint of solubility in polar solvents such as water and ease of handling after dissolution, preferably 10,000 to 80,000, More preferably, it is 20,000-60,000, More preferably, it is 30,000-50,000. Since MWsi has a common skeleton with the modified organopolysiloxane that is the raw material compound, MWsi is substantially the same as the weight average molecular weight of the modified organopolysiloxane that is the raw material compound. The average molecular weight of the modified organopolysiloxane that is a raw material compound is measured by GPC under the following measurement conditions and is converted to polystyrene.

Column: Super HZ4000 + Super HZ2000 (manufactured by Tosoh Corporation)
Eluent: 1 mM triethylamine / THF
Flow rate: 0.35mL / min
Column temperature: 40 ° C
Detector: UV
Sample: 50 μL

  The weight average molecular weight (MWt) of the component (C) organopolysiloxane is preferably 10,000 to 200,000, more preferably 30,000 to 100,000, and still more preferably 50,000 to 70,000. Thereby, a good touch can be imparted to the hair, and in addition, solubility in polar solvents such as water becomes excellent. Moreover, both styling of set property and set sustainability can be further improved. In the present invention, MWt can be determined from the weight average molecular weight of the modified organopolysiloxane that is the raw material compound and the above-mentioned mass ratio (a / b).

Next, a method for producing the organopolysiloxane of component (C) will be described.
The organopolysiloxane of component (C) is, for example, the following general formula (3)

[Wherein, R ² is as defined above, and R ³ and R ⁴ each represent the same group as R ² , or the following formulas (ix) to (xiv)

R ⁵ represents a monovalent group represented by any one of the above formulas (ix) to (xiv), d represents an integer of 89 to 1332, e represents an integer of 2 to 77. ]
Modified organopolysiloxane represented by the following general formula (4)

[Wherein, R ¹ and n are as defined above. ]
And a terminal reactive poly (N-acylalkylenimine) obtained by ring-opening polymerization of a cyclic imino ether represented by the following formula (hereinafter referred to as “cyclic imino ether (4)”).

  As the modified organopolysiloxane of the general formula (3) (hereinafter referred to as “modified organopolysiloxane (3)”), the functional group equivalent is preferably 1,700 to 3,500, more preferably 1,800 to 3,200, still more preferably 2,000 to 3,000. And having a weight average molecular weight of preferably 7,000 to 100,000, more preferably 10,000 to 80,000, still more preferably 30,000 to 50,000. The weight average molecular weight of the modified organopolysiloxane (3) as the raw material is substantially the same as the weight average molecular weight (MWsi) of the organopolysiloxane segment constituting the main chain.

  The terminal reactive poly (N-acylalkylenimine) is preferably adjusted to have a molecular weight of 1,200 to 5,500, preferably 1,600 to 3,500, more preferably 1,800 to 3,200, and still more preferably 2,000 to 3,000. This is substantially the same as the molecular weight (MWox) of the aforementioned poly (N-acylalkylenimine) segment.

  A polymerization initiator can be used for the ring-opening polymerization of the cyclic imino ether (4). As the polymerization initiator, a compound having strong electrophilic reactivity, for example, a strong acid such as benzenesulfonic acid alkyl ester, p-toluenesulfonic acid alkyl ester, trifluoromethanesulfonic acid alkyl ester, trifluoroacetic acid alkyl ester, sulfuric acid dialkyl ester, etc. Alkyl esters can be used, and among them, dialkyl sulfate is preferably used. The amount of the polymerization initiator used is usually 1 mol of the polymerization initiator with respect to 2 to 100 mol of the cyclic imino ether (4).

  Examples of the polymerization solvent include acetates such as ethyl acetate and propyl acetate, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, halogen solvents such as chloroform and methylene chloride, acetonitrile. , Nitrile solvents such as benzonitrile, aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, etc., among which acetates are preferred Is done. The amount of the solvent used is usually 0.2 to 20 with respect to the mass of the cyclic imino ether (4).

  The polymerization temperature is usually 30 to 170 ° C., preferably 40 to 150 ° C., and the polymerization time is usually 1 to 60 hours, although it is not uniform depending on the polymerization temperature and the like.

  When, for example, 2-substituted-2-oxazoline is used as the cyclic imino ether (4), a poly (N-acylethyleneimine) of n = 2 in the general formula (1) is obtained, and 2-substituted-dihydro When 2-oxazine is used, poly (N-acylpropyleneimine) having n = 3 in the general formula (1) can be obtained.

  Examples of a method for connecting poly (N-acylalkylenimine) and the organopolysiloxane segment include the following methods.

1) A method of reacting a terminally reactive poly (N-acylalkyleneimine) obtained by living polymerization of a cyclic imino ether with a modified organopolysiloxane represented by the general formula (3) 2) between a carboxy group and a hydroxyl group Formation reaction of ester by condensation 3) Formation reaction of amide by condensation of carboxy group and amino group 4) Secondary, tertiary or quaternary ammonium of alkyl halide group and primary, secondary or tertiary amino group 5) Addition reaction of vinyl group to organopolysiloxane having Si-H group 6) β-hydroxyamine formation reaction of epoxy group and amino group

  Above all, the method 1) can easily control the degree of polymerization by the amount of the cyclic iminoether (4) and the polymerization initiator used as shown in the following theoretical formula (II), and moreover than ordinary radical polymerization. It is most effective in that a substantially monodispersed poly (N-acylalkylenimine) having a narrow molecular weight distribution can be obtained.

  Preferable examples of the component (C) organopolysiloxane include poly (N-formylethyleneimine) organosiloxane, poly (N-acetylethyleneimine) organosiloxane, poly (N-propionylethyleneimine) organosiloxane, and the like. .

  The organopolysiloxane of component (C) can be used alone or in combination of two or more, and the content thereof is based on the total mass of the hair cosmetic from the viewpoint of hair setability and set durability. Preferably, it is 0.01-50 mass%, More preferably, it is 0.05-30 mass%, More preferably, it is 0.1-20 mass%, More preferably, it is 0.5-10 mass%.

  The mass ratio (A) / (C) of the component (A) to the component (C) in the hair cosmetic composition of the present invention suppresses the occurrence of hair swell and curl due to the accumulation of heat denaturation of hair proteins. From the viewpoint of excellent setability during hair styling using a high-temperature hair styling device, set sustainability, and hair feel, (A) / (C) = 0.01 to 2, preferably 0.05 to 1.5, More preferably, it is 0.1-1.

[Component (D): Surfactant]
The hair cosmetic composition of the present invention can contain a surfactant as the component (D) from the viewpoints of system stability including solvent solubilization, dispersibility and the like, and improvement in feel. As the surfactant, any of cationic surfactants, nonionic surfactants, amphoteric surfactants and anionic surfactants can be used, and among these, from the viewpoint of hair feel, cationic surfactants and Nonionic surfactants are particularly preferred.

  As the cationic surfactant that can be used here, quaternary ammonium salts, amidoamines, etheramines and the like are generally used.

  Examples of the quaternary ammonium salt include quaternary ammonium salts represented by the following general formula (5).

[In the formula, R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, but at the same time, they do not become a hydrogen atom or a benzyl group, and at least one of them has 8 or more carbon atoms. It is an alkyl group. R ¹⁰ and R ¹¹ represent an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group, or a polyoxyethylene group having a total addition mole number of 10 or less, and An ⁻ represents an anion. ]
Specific examples of the quaternary ammonium salt of the formula (5) include those described in JP-A-2007-186474, for example.

  Further, the quaternary ammonium salt includes an ether type quaternary ammonium salt represented by the general formula (6).

[Wherein R ¹² represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ^{13 to} R ¹⁵ represent an alkyl group, benzyl group or — (DO ) _c H (DO represents an alkyleneoxy group having 2 to 4 carbon atoms, c represents an average addition mole number of 1 to 6, c pieces of DO may be the same or different, and the arrangement thereof is arbitrary. ) And An ⁻ represents an anion. ]

  Specific examples of the ether type quaternary ammonium salt of the general formula (6) include those described in JP-A-2007-186474, for example.

  As the quaternary ammonium salt, a mono long chain alkyl quaternary ammonium salt is preferable, and specifically, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylbenzalkonium chloride, etc. In particular, stearyltrimethylammonium chloride and behenyltrimethylammonium chloride are preferable.

  Examples of amidoamines include compounds represented by general formula (7).

[Wherein, R ¹⁶ represents a linear or branched alkyl group or alkenyl group having 11 to 23 carbon atoms, R ¹⁷ represents the same or different hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and f represents 2 Represents an integer of ~ 4. ]

  Specific examples of the amidoamine of the general formula (7) include those described in JP 2007-186474 A and JP 2008-297262 A, for example.

  Examples of ether amines include compounds represented by general formula (8).

(In the formula, R ¹⁸ represents a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, and R ¹⁹ is the same or different alkyl group or group having 1 to 6 carbon atoms-(AO) _g. H (AO represents an alkyleneoxy group having 2 to 4 carbon atoms, g represents a number of 1 to 6, and g AOs may be the same or different, and the arrangement thereof is arbitrary).

  Specific examples of the ether amine of the general formula (8) include those described in JP-A-2008-297262.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether and polyoxyethylene / polyoxypropylene alkyl ether are more preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series. Of these, betaine surfactants such as alkyldimethylaminoacetic acid betaine and fatty acid amidopropyl betaine are preferred, and fatty acid amidopropyl betaine is preferred. The fatty acid amidopropyl betaine preferably has an acyl group having 8 to 18 carbon atoms and more preferably 10 to 16 carbon atoms. Among them, amide propyl betaine laurate, palm kernel fatty acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, etc. preferable.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. Counter ions of the anionic residue of the surfactant include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; alkanol group having 2 or 3 carbon atoms Alkanolamine having 1 to 3 (for example, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Examples of the counter ion of the cationic residue include halide ions such as chloride ion, bromide ion and iodide ion, methosulphate ion and saccharinate ion.

  The surfactant of component (D) can be used alone or in combination of two or more. From the viewpoint of the stability of the system including solubilization of the solvent, emulsification of the oil, etc., its content is determined according to the present invention. 0.01-30 mass% in hair cosmetics, Especially 0.05-20 mass% are preferable.

[Component (E): Organic solvent]
Moreover, the hair cosmetic composition of the present invention can further contain an organic solvent selected from the following (e1) to (e5) as a preferable component from the viewpoint of stabilization of the composition.

  (e1) Compound represented by general formula (9)

[In the formula, R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a group R ²¹ —Ph—R ²² — (R ²¹ ; a hydrogen atom, a methyl group or a methoxy group, R ²² ; a bond or a carbon number. 1-3 represents a saturated or unsaturated divalent hydrocarbon group, Ph; paraphenylene group), E represents a bond or a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, and Y and Z represent Each independently represents a hydrogen atom or a hydroxyl group, and p and q each independently represents an integer of 0 to 5. However, when p = q = 0, Z is a hydroxyl group, and R ²⁰ is neither a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, nor a group R ²¹ —Ph—. ]
(e2) N-alkylpyrrolidone or N-alkenylpyrrolidone having an alkyl or alkenyl group having 1 to 18 carbon atoms bonded to a nitrogen atom
(e3) C2-C4 alkylene carbonate
(e4) Polypropylene glycol having a number average molecular weight of 100 to 1,000
(e5) Lactone or cyclic ketone represented by general formula (10), (11) or (12)

[Wherein, X represents a methylene group or an oxygen atom, R ²³ and R ²⁴ represent different substituents, and a and b each independently represent 0 or 1. ]

Among the organic solvents, (e1) includes C ₄ -C ₆ linear or branched aliphatic alcohols such as butanol and isobutanol, ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, benzyl Alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, triethylene glycol monoethyl Examples include ether and triethylene glycol monobutyl ether.

  Examples of (e2) include N-methylpyrrolidone, N-octylpyrrolidone, N-laurylpyrrolidone and the like.

  Examples of (e3) include ethylene carbonate and propylene carbonate.

  The polypropylene glycol having a number average molecular weight of 100 to 1,000 in (e4) is preferably one having a number average molecular weight of 300 to 500. Here, the number average molecular weight refers to the number average molecular weight in terms of polystyrene measured by GPC.

In (e5), R ²³ and R ²⁴ in the general formulas (10) to (12) are linear, branched or cyclic alkyl groups, hydroxyl groups, sulfonic acid groups, phosphoric acid groups, carboxy groups, and phenyl groups. , A sulfoalkyl group, an alkyl phosphate group, a carboxyalkyl group and the like are preferable, among which a linear or branched alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. preferable. These groups are preferably substituted at the γ-position in the case of γ-lactone and at the δ-position in the case of δ-lactone (that is, the methylene adjacent to the heterooxygen atom). When it is desired to increase the water solubility of the compounds (10) to (12), R ²³ or R ²⁴ has an acidic group such as a sulfonic acid group, a phosphoric acid group or a carboxy group, or an alkyl group substituted with these. Is preferred. Among (e5), examples of the lactone include γ-butyrolactone, γ-caprolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, δ-heptanolactone, and the like, from the viewpoint of lactone stability. Γ-lactone, γ-butyrolactone and γ-caprolactone are preferred. Among (e5), examples of the cyclic ketone include cyclopentanone, cyclohexanone, cycloheptanone, 4-methylcycloheptanone and the like.

  The above organic solvents may be used in combination of two or more, and the total content thereof is an effect of improving elasticity and stiffness after shampooing, an effect of improving the softness and cohesion of hair, an improvement effect (improving elasticity, In addition to improving moisture resistance, etc., 0.01-40% by mass in the hair cosmetic composition of the present invention is preferable, and 0.05-10 % By mass, more preferably 0.1 to 5% by mass.

[Polyhydric alcohol]
Furthermore, the hair cosmetic composition of the present invention can contain a polyhydric alcohol other than the organic solvent. The polyhydric alcohol contributes to solubilization and stable dispersion of the organic solvent, and works synergistically with the organic solvent to promote improvement of gloss and hair modification effects. Examples of the polyhydric alcohol include ethylene glycol, glycerin and sorbitol, and glycerin is preferable. Polyhydric alcohol can be used individually or in combination of 2 or more types, and the content is 0.01-10 mass% in the hair cosmetics of this invention, Furthermore, 0.1-5 mass% is preferable.

[Set polymer]
The hair cosmetic composition of the present invention can contain a set polymer in order to further improve the setability and the set holding power and to improve the slipperiness of the hair.

  Examples of the set polymer include those shown in the following 1) to 8), and they can be used alone or in combination of two or more.

1) Vinylpyrrolidone-based polymer Polyvinylpyrrolidone Commercially available products include Rubiscol K12, K30 (above BASF), PVP K15, K30 (above GAF) and the like.

Vinyl pyrrolidone / vinyl acetate copolymer Commercially available products include Rubiscol VA28, VA73 (above BASF), PVP / VA E-735, S-630 (above GAF).

Vinyl pyrrolidone / vinyl acetate / vinyl propionate terpolymer A commercially available product is Rubiscol VAP343 (manufactured by BASF).

Vinyl pyrrolidone / alkylamino acrylate copolymer Commercially available products include rubiflex (manufactured by BASF), copolymers 845, 937 and 958 (manufactured by GAF).

Vinylpyrrolidone / acrylate / (meth) acrylic acid copolymer Commercially available products include Rubyflex VBM35 (manufactured by BASF).

Vinyl pyrrolidone / alkylamino acrylate / vinyl caprolactam copolymer As a commercial product, copolymer VC-713 (manufactured by GAF) and the like can be mentioned.

2) Acid vinyl ether polymer Methyl vinyl ether / maleic anhydride alkyl half ester copolymer Commercially available products include GANTREZ ES-225, ES-425, SP-215 (manufactured by GAF).

3) Acidic polyvinyl acetate polymer Vinyl acetate / crotonic acid copolymer Commercially available products include Resin 28-1310 (National Starch), Ruby Set CA66 (BASF).

Vinyl acetate / crotonic acid / vinyl neodecanoate copolymer Commercially available products include Resin 28-2930 (manufactured by National Starch).

Vinyl acetate / crotonic acid / vinyl propionate copolymer Rubiset CAP (manufactured by BASF) and the like are listed as commercial products.

4) Acid acrylic polymer (Meth) acrylic acid / (meth) acrylic ester copolymer Commercially available products include Plus Size L53P (manufactured by Kyoyo Chemical Co., Ltd.), Diamond (Mitsubishi Yuka Co., Ltd.), etc. Can be mentioned.

Acrylic acid / acrylic acid alkyl ester / alkyl acrylamide copolymer Examples of commercially available products include Ultrahold 8 (manufactured by BASF) and Amphomer V-42 (manufactured by National Starch).

5) Amphoteric acrylic polymer (meth) acrylethyl betaine / (meth) acrylic acid alkyl ester copolymer For example, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine and (meth) Examples thereof include copolymers with alkyl crylate and the like, and commercially available products include Yuka Former M-75, SM (manufactured by Mitsubishi Yuka Co., Ltd.) and the like.

Acrylic acid alkyl ester / butyl aminoethyl methacrylate / octyl amide acrylate copolymer For example, octyl acrylamide / acrylate / butyl aminoethyl methacrylate copolymer and the like are exemplified, and as a commercial product, Anformer 28-4910 (National Starch Co., Ltd.) Manufactured) and the like.

6) Basic acrylic polymer Acrylamide / acrylic ester copolymer For example, those described in Examples of JP-A-2-809911 and JP-A-8-291206 can be mentioned.

7) Cellulose derivative Cationic cellulose derivative Examples of commercially available products include Cellcoat H-100 and L-200 (manufactured by National Starch).

8) Chitin / chitosan derivative Hydroxypropyl chitosan Examples of commercially available products include chitofilmer (manufactured by Ichimaru Falcos).
Carboxymethylchitin, carboxymethylchitosan, chitosan and monovalent acids such as pyrrolidone carboxylic acid, lactic acid, glycolic acid or salts with divalent acids such as adipic acid, succinic acid, etc. Examples include Kitemer L (lactate) (manufactured by Union Carbide).

  Among these set polymers, set polymers selected from acrylic polymers and vinylpyrrolidone polymers are particularly preferable. The content of the set polymer is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and particularly preferably 0.3 to 5% by mass, based on the total mass of the hair cosmetic.

[Conditioning ingredients]
In order to further improve the conditioning effect, the hair cosmetic composition of the present invention can contain a conditioning component selected from oils and silicones other than the organopolysiloxane component (C).

  Oils are used to improve the feeling of hair unity after drying. Oils include hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, α-olefin oligomer, liquid paraffin and cycloparaffin; castor oil, cacao oil, mink oil, avocado oil, olive oil, etc. Glycerides; waxes such as beeswax, whale wax, lanolin, microcrystalline wax, ceresin wax, carnauba wax; higher alcohols such as cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol; myristic acid Octyldodecyl, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, isononanoic acid Esters such as tridecyl; higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearyl acid, isopalmitic acid; cholesterol, petrolatum, cholesteryl iso Examples thereof include solid fats such as stearate and sphingolipids; jojoba oil, isostearyl glyceryl ether, polyoxypropylene butyl ether, and the like. Among these, branched hydrocarbons such as squalene, squalane, liquid isoparaffin, light liquid isoparaffin, heavy liquid isoparaffin, and α-olefin oligomer are preferable.

  The content of the oil agent is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and further 0.5 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of good unity and no stickiness. Is preferred.

  Silicones other than the component (C) of the present invention include dimethylpolysiloxane, polyether-modified silicone, amino-modified silicone, carboxy-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, aliphatic alcohol-modified silicone, Examples include epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, and alkyl-modified silicone. Of these, dimethylpolysiloxane, polyether-modified silicone, and amino-modified silicone are preferable.

Dimethylpolysiloxane can impart good lubricity to hair, polyether-modified silicone can impart smoothness to hair, and amino-modified silicone can impart moist feeling to hair. . In the present invention, various silicones can be used alone or in combination of two or more depending on the desired performance. Dimethylpolysiloxane can be used from a viscosity of about 5 mm ² / s to a viscosity of about 10 million mm ² / s, which is often supplied as an emulsion, depending on the desired feel. mm ² / s, further preferably those of 50,000 to 1,000 ten thousand mm ² / s.

  The polyether-modified silicone may be a silicone having a polyoxyalkylene group, and examples of the group constituting the polyoxyalkylene group include an oxyethylene group and an oxypropylene group. More specifically, for example, KF-6015, KF-945A, KF-6005, KF-6009, KF-6013, KF-6019, KF-6029, KF-6017, KF-6043, KF-353A, KF- 354A, KF-355A (Shin-Etsu Chemical Co., Ltd.), FZ-2404, SS-2805, FZ-2411, FZ-2412, SH3771M, SH3772M, SH3773M, SH3775M, SH3749, SS-280X series, BY22-008M, BY11 -030, BY25-337 (above, manufactured by Toray Dow Corning).

  As the amino-modified silicone, those having an average molecular weight of about 3,000 to 100,000 and described in the third edition of the PCPC Dictionary (US, Personal Care Products Council Dictionary) under the name Amodimethicone are preferable. Commercially available products include SM 8704C, 2-8035 Cationic Emulsion (Toray Dow Corning), KT 1989, XS65-C0032 (Momentive), 8500 Conditioning Agent, DOW CORNING TORAY SS-3588, DOW CORNING TORAY SILSTYLE 104 (Toray Dow Corning).

  The content of the silicones is preferably 0.05 to 20% by mass, more preferably 0.1 to 10% by mass, and further 0.5 to 5% by mass in the hair cosmetic composition of the present invention from the viewpoint of fingering and non-stickiness. % Is preferred.

[Other solvents]
Moreover, in the hair cosmetic composition of the present invention, water, C ₁ -C ₃ linear or branched, are used as a solvent from the viewpoint of hair setability, good usability, and dissolution promotion when preparing the hair cosmetic composition. Saturated or unsaturated alcohols can be included. These can be used alone or in combination of two or more. Among these, water, ethanol, and isopropanol are preferable, and water and ethanol are more preferable. The total content of water and C ₁ -C ₃ alcohol is preferably 0.1 to 98% by mass, more preferably 1 to 90% by mass, and still more preferably 5 to 60% by mass, based on the total mass of the hair cosmetic. is there.

[Optional ingredients]
In addition to the above-mentioned components, the hair cosmetic of the present invention can be appropriately blended with components used in ordinary hair cosmetics depending on the purpose, application, dosage form, and the like. Such components include, for example, anti-dandruff agents such as zinc pyrithione and octopirox; vitamin agents; fungicides such as triclosan and trichlorocarban; anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate; methylparaben, butylparaben and the like Preservatives; chelating agents; moisturizers such as panthenol; colorants such as dyes and pigments; viscosity modifiers such as hydroxyethylcellulose, methylcellulose, polyethylene glycol, clay minerals; pH of organic acids, sodium hydroxide, potassium hydroxide, etc. Conditioning agents; plant extracts; pearlizing agents; fragrances; dyes; ultraviolet absorbers; antioxidants; and others described in ENCYCLOPEDIA OF SHAMPOO INGREDIENTS (MICELLE PRESS) Components and the like.

  The hair cosmetic composition of the present invention can be prepared into various dosage forms according to a conventional method. For example, it is not only a liquid composition such as mist, lotion, tonic, but also a gel, paste, cream, wax, etc. It can be set as a solid composition.

[Hair shaping method]
The method of performing hairdressing using the hair cosmetic composition of the present invention is, for example, as follows. First, the hair cosmetic composition of the present invention is applied to the hair, and after the hair is heated and shaped using a high-temperature hairdressing device in which the temperature of the heating part is set to 100 ° C. or higher, the temperature of the hair is cooled to less than 100 ° C. Thus, the shaped hairstyle can be fixed. The heating temperature of the hair with the hot hair styling device is preferably 100 to 220 ° C, more preferably 120 to 200 ° C. Usually, since there is substantially no difference between the temperature of the heating part of the high-temperature hairdressing device and the temperature of the heated hair, hereinafter, the temperature of the heating part of the high-temperature hairdressing device was used as the heating temperature of the hair.

  In the present invention, “shaping” the hair means changing the shape of the hair itself. Specifically, adding curls or waves to straight hair, straightening curled or waved hair, changing the curl or wave of curled or waved hair, etc. Included.

  In the present invention, the “high-temperature hair styling device” is not only a straight iron, a curling iron, a curling iron, but also a wave iron, a waffle iron, or other name, or an iron or iron that performs heat treatment in contact with hair. All of the appliances. In addition, not only appliances used in general households where the upper limit of the set temperature is about 180 ° C., but also all appliances used in barber / beauty shops that can be set to temperatures of 200 to 220 ° C. or higher.

  In the present invention, “cooling” is a concept including not only lowering the temperature consciously (for example, applying cool air) but also lowering the temperature naturally by the ambient temperature such as leaving it alone. Accordingly, the “cooling” also includes a decrease in temperature due to natural drying.

  The means for applying (applying) the hair cosmetic composition of the present invention to the hair is not uniform depending on the type of the dosage form, but it is usually used for application using spray, mist, etc., application by hand, and a combination of both. You can do it.

  Moreover, the timing of applying the hair cosmetic composition of the present invention to hair is applied to wet hair such as after washing, towel drying, etc., applied to semi-dry hair in the middle of drying, and dried after drying. Although it may be applied to the hair in a state, it may be applied to the hair at any timing. Moreover, the hair cosmetic composition of the present invention is applied to the hair at least once after washing the hair and heating and shaping the hair at a hair temperature of 100 ° C. or higher using a high-temperature hairdressing instrument.

  The amount of application (application) of the hair cosmetic composition of the present invention to the hair is not uniform depending on the dosage form and the properties of the agent, but is usually 0.001 to 3, preferably more than a bath ratio with respect to the weight of the hair. 0.005 to 1, more preferably 0.01 to 0.5.

  In addition, the applied hair cosmetic is not rinsed between the time when the hair cosmetic of the present invention is applied to the hair and the time when the hair is heated and shaped at a hair temperature of 100 ° C. or higher using a high-temperature hairdressing device. However, either rinsing or flowing may be used, but from the viewpoint of suppressing the occurrence of hair swell and curl caused by repeated use of a high-temperature hair styling device, heating using a high-temperature hair styling device, setability when shaping, From the viewpoint of improving set sustainability and hair feel, it is preferable not to rinse.

  In addition, if the hair is dried after applying the hair cosmetic composition of the present invention to the hair and heating and shaping the hair at a hair temperature of 100 ° C. or higher using a high-temperature hairdressing instrument, The process can be completed in a short time, and as a result, the time required for the entire hairdressing can be shortened. Drying after applying the hair cosmetic can be performed by natural drying, heating, or the like.

  The time for heating and shaping the hair using a high-temperature hair styling device is preferably 0.01 seconds to 1 minute, from the viewpoint of further reducing the accumulation of heat denaturation in the hair while obtaining high setability and set durability. More preferably, it is 0.1 second-30 seconds, More preferably, it is 0.1 second-20 seconds.

Synthesis example 1
Diethyl sulfate (6.17 g, 0.04 mol) and 2-ethyl-2-oxazoline (93.8 g, 0.947 mol) were dissolved in dehydrated ethyl acetate (203 g), heated under reflux for 8 hours under a nitrogen atmosphere, and terminal-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 2500. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (190 g, yield 95%). The final product had an organopolysiloxane segment content of 50 mass% and a weight average molecular weight of 60000. As a result of neutralization titration with hydrochloric acid using methanol as a solvent, it was found that about 20 mol% of amino groups remained.

Synthesis example 2
6.17 g (0.04 mol) of diethyl sulfate and 106.6 g (1.075 mol) of 2-ethyl-2-oxazoline were dissolved in 229 g of dehydrated ethyl acetate, heated under reflux for 8 hours under a nitrogen atmosphere, and terminal-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 2800. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (200 g, 94% yield).

Synthesis example 3
Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 75.7 g (0.763 mol) of 2-ethyl-2-oxazoline in 166 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2000. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (169 g, yield 93%).

Synthesis example 4
Dissolve 3.08 g (0.02 mol) of diethyl sulfate and 96.9 g (0.978 mol) of 2-ethyl-2-oxazoline in 203 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 5000. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 40000, amine equivalent 3800) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (188 g, yield 94%).

Synthesis example 5
6.17 g (0.04 mol) of diethyl sulfate and 116.1 g (1.171 mol) of 2-ethyl-2-oxazoline were dissolved in 248 g of dehydrated ethyl acetate, heated under reflux for 8 hours under a nitrogen atmosphere, and terminal-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 3000. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (204 g, yield 92%).

Synthesis Example 6
Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 102.2 g (1.031 mol) of 2-ethyl-2-oxazoline in 220 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2700. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (194 g, yield 93%).

Synthesis example 7
Dissolve 6.17 g (0.04 mol) of diethyl sulfate and 86.1 g (0.869 mol) of 2-ethyl-2-oxazoline in 187 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2300. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (179 g, yield 93%).

Synthesis example 8
Dissolve 12.78 g (0.0829 mol) of diethyl sulfate and 246.6 g (2.488 mol) of 2-ethyl-2-oxazoline in 519 g of dehydrated ethyl acetate, and heat to reflux for 15 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 3100. A 33% ethyl acetate solution of 166.7 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2010) was added all at once and heated to reflux for 12 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (422 g, yield 99%).

Synthesis Example 9
Dissolve 5.92 g (0.038 mol) of diethyl sulfate and 60.7 g (0.613 mol) of 2-ethyl-2-oxazoline in 135 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 1700. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 1980) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow solid (158 g, yield 95%).

Synthesis example 10
Diethyl sulfate (6.17 g, 0.04 mol) and 2-ethyl-2-oxazoline (50.1 g, 0.505 mol) were dissolved in dehydrated ethyl acetate (114 g) and heated under reflux for 8 hours under a nitrogen atmosphere to terminate terminal reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 1400. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 32000, amine equivalent 1900) was added all at once and heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubbery semi-solid (152 g, yield 97%).

Synthesis example 11
Diethyl sulfate (6.17 g, 0.04 mol) and 2-ethyl-2-oxazoline (34.7 g, 0.35 mol) were dissolved in dehydrated ethyl acetate (83 g), heated under reflux for 8 hours under a nitrogen atmosphere, and end-reactive poly (N-propionylethylene). Imine) was synthesized. The number average molecular weight measured by GPC was 1000. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 30000, amine equivalent 2000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a pale yellow rubbery semi-solid (141 g, yield 97%).

Synthesis example 12
Dissolve 0.77 g (0.005 mol) of diethyl sulfate and 12.9 g (0.13 mol) of 2-ethyl-2-oxazoline in 28 g of dehydrated ethyl acetate, and heat to reflux for 8 hours under a nitrogen atmosphere. End-reactive poly (N-propionylethylene) Imine) was synthesized. The number average molecular weight measured by GPC was 2700. A 33% ethyl acetate solution of 100 g of side chain primary aminopropyl-modified polydimethylsiloxane (weight average molecular weight 100000, amine equivalent 20000) was added all at once, and the mixture was heated to reflux for 10 hours. The reaction mixture was concentrated under reduced pressure to obtain an N-propionylethyleneimine / dimethylsiloxane copolymer as a colorless solid (108 g, yield 95%).

  The details of the organopolysiloxanes obtained in Synthesis Examples 1 to 12 are summarized in Table 1.

Example 1, Comparative Examples 1-3
According to the description in Patent Documents 1 to 3, hair cosmetics of Comparative Examples 1 to 3 shown in Table 1 were prepared. Moreover, according to a conventional method, the hair cosmetics of Example 1 shown in Table 2 were prepared.

[Test 1] -Heat swell suppression effect- (Suppression effect of swell generation by repeated iron heating)
1. Bleach treatment [Bleach agent: soft foam bleach (trade name) manufactured by Kao Corporation, bath ratio (ratio of the mass of the agent to be applied to the hair mass): 1.0, agent mixing ratio (1 agent / 2 agents): 4/6] Using a Japanese woman's hair that has been performed once, make a hair bundle with a hair weight of 0.5 g and a length of 25 cm.
Using the hair bundles prepared in 2.1, repeat the following flow up to 12 times, repeat the process up to 12 times, determine the pass / fail status according to the criteria for the shape of the hair bundle after drying, and display the results. This is shown in FIG.

(flow)
A) Agent application → Iron heating → Hair washing → Drying B) Observation of hair shape (confirmation of waviness / curly hair)

  The application of the agent in the above flow was performed under conditions where water, Comparative Examples 1 to 3 in Table 2, or Example 1 in Table 3 was applied to the hair bundle at a bath ratio of 0.05 and then allowed to stand for 30 seconds.

  Iron heating in the above flow is done by setting the temperature so that the average plate temperature is 200 ° C when measured in a closed state with a thermocouple sandwiched between the heating plates of the flat iron. The hair bundle was averagely heated while sliding the plate from the root side toward the hair tip at a speed of 20 cm / 10 s.

  For the hair washing in the above flow, after rinsing the hair with water at 40 ° C for 30 seconds, apply plain shampoo (Laureth-1 ammonium sulfate 10 mass% aqueous solution) at a bath ratio of 0.2 and foam for 30 seconds, and finally plain shampoo for 30 seconds Rinse the agent, then apply plain rinse (2.0% cetanol, 5% propylene glycol, 2.7% distearyldimonium chloride, 0.75% stearyltrimonium chloride, 89.55% water) at a bath ratio of 0.2. The sample was allowed to stand for 30 seconds and then rinsed for 30 seconds.

  Drying in the above flow was performed with warm air from a dryer, and in order to confirm the original shape of the hair, setting by brushing or combing was not performed during drying.

(Criteria)
Three professional hairdressers observed hair bundles and made the following determinations.
3: All three hairdressers evaluated that no hair swells, curly hairs, or hair bundles spread.
2: Two out of three hairdressers evaluated that no swell, curly hair, or spread of hair bundles occurred.
1: One out of three hairdressers evaluated that no swell, curly hair, or spread of hair bundles occurred.
0: All three hairdressers evaluated that hair swells / curly hairs and hair bundles had spread.

[Test 2] -Tensile test of hair-
About the hair before the test 1 of the test and the hair which repeated the process up to n times, using a tensile tester (TG-500N manufactured by Minebea Co., Ltd.), a tensile test in water was performed to measure the breaking strength.
The rate of change in the breaking strength of the hair was calculated using the following formula, and pass / fail was determined according to the criteria, and the results are shown in Table 4. In addition, the average value of 10 samplings (N = 10) was used as the value of the change rate.
Rate of change in breaking strength = [(breaking strength of hair before treatment) − (breaking strength of hair after treatment n)] / (breaking strength of hair before treatment)

(Criteria)
Pass: The breaking strength change rate is less than 10%. Fail: The breaking strength change rate is 10% or more.

Examples 1-19, Comparative Examples 4-20
The hair cosmetics of Examples 1 to 19 and Comparative Examples 4 to 20 were evaluated as follows.
<Heat swell suppression effect>
According to the same method as in Test 1 described above, Flow A (repeated up to 12 treatments) was performed using each hair cosmetic. The shape of the hair bundle after drying was determined according to the same evaluation criteria by three professional hairdressers observing the hair bundle.

[Test 3] -Set test using an iron-
A hair bundle of virgin hair (Japanese female hair not subjected to chemical treatment such as hair coloring and bleaching) having a length of 30 cm and a weight of 6 g was used for evaluation.
After 0.6 g of spray water was applied to the hair bundle, 0.2 g of each sample was applied, and the comb was passed 5 times on the front and back with a ring comb manufactured by DELRIN. Next, after the hair bundle was completely dried with a dryer, five professional panelists wrapped the hair around a Kreuz iron (model number: J72010M) set at a temperature of 150 ° C and held it for 10 seconds. After that, the iron was removed. After being removed, the hair bundle is placed in a room temperature environment, so that the temperature of the hair bundle soon reaches room temperature.
After this series of treatments was completed, sensory evaluation and comprehensive evaluation were performed according to the following criteria. Each evaluation showed the average value of the panel evaluation of 5 persons.

〔Evaluation criteria〕
<Setability>
In Test 3 above, the degree of fading on the hair bundle after removing the iron was visually evaluated according to the following criteria.
5: Very good 4: Good 3: Normal 2: Bad 1: Very bad

<Set sustainability>
In an environment of a temperature of 30 ° C. and a relative humidity of 80%, the hair bundle after completion of the series of treatments in the test 3 was hung and allowed to stand. When left to stand for 15 minutes, the degree of change of the shaped part before and after being left was evaluated visually (hydrogen bonds strongly related to hair shape retention are quickly bonded when the amount of moisture in the air is large. In order to alleviate, leaving for 15 minutes in an environment with a temperature of 30 ° C and a relative humidity of 80% is equivalent to leaving it in an environment with a temperature of 25 ° C and a relative humidity of 40% for 12 hours.

5: Very sustainability 4: Slightly sustainability 3: Neither can be said 2: Slightly low sustainability 1: Very low sustainability

<Smoothness of hair>
In the test 3, the feel (smoothness) when the shaped part was gripped by hand was subjected to sensory evaluation according to the following criteria.

5: Smooth 4: Slightly smooth 3: Not good 2: Slightly smooth 1: Not smooth

  Examples 1 to 19 are superior to Comparative Examples 1 to 20 in all of the effects of suppressing thermal undulation, setability during hair styling with a high-temperature hair styling device, set sustainability, and hair feel.

Example 20 hair mist (prescription adjustment)
The following hair mist (pH 3.7) is prepared according to a conventional method.
(mass%)
Trehalose 0.50
Malic acid 1.25
Lactic acid 1.25
Organopolysiloxane of Synthesis Example 1 1.00
Benzyl alcohol 0.20
Torides-9 (* 1) 0.40
Polyquaternium-11 (* 2) 0.18
Cetrimonium chloride 0.23
Lanolin fatty acid (* 3) 0.10
Bismethoxypropylamide isodocosane (* 4) 0.10
Highly polymerized methylpolysiloxane emulsion (* 5) 3.50
Ethanol 15
Oxybenzone-9 (* 6) 0.05
EDTA-2Na 0.05
Honey 0.01
Royal Jelly Extract 0.01
Sodium hydroxide appropriate amount *
Perfume appropriate amount water balance
* 1: Softanol 90 (manufactured by Nippon Shokubai Co., Ltd.)
* 2: Guffcut 734 (ISP)
* 3: 18MEA (Croda)
* 4: BRS661 (manufactured by Kao)
* 5: BY22-060 (Toray Dow Corning)
* 6: Yubinar DS49 (BASF)
* Amount to make pH = 3.7

[Hair shaping method]
Spray the dry hair with the hair mist of Example 20 so that the entire hair is moist (approx. 0.5-6 g), apply it by hand, and then heat it with a hair iron at 100-200 ° C without rinsing. Perform hair styling.

Example 21 Out bath treatment The following out bath treatment (pH 3.7) is prepared according to a conventional method.
(mass%)
Stearoxypropyldimethylamine (* 7) 0.25
Behentrimonium chloride (* 8) 0.4
PEG-40 hydrogenated castor oil (* 9) 0.24
Cetearyl alcohol 2.8
Glycerin 5
Benzyl alcohol 0.2
Dipyropropylene glycol 2
Trehalose 0.5
Lactic acid 0.65
Malic acid 0.75
Polyorganosiloxane of Synthesis Example 1 0.5
Isopropyl palmitate 1.5
Hydrogenated polydecene (* 10) 2
Lanolin fatty acid (* 3) 0.2
Dimethicone 0.6
Isododecane 1.4
Phenoxyethanol 0.4
Sodium hydroxide appropriate amount *
Water balance
* 7: Farmin DM E-80 (Kao Corporation)
* 8: Cotamine 2285E-E (Kao Corporation)
* 9: Emanon CH-40 (manufactured by Kao Corporation)
* 10: SILKFLO 364 NF (made by LIPO CHEMICALS, INC)
* Amount to make pH = 3.7

[Hair shaping method]
After washing the hair and applying it to the hair after towel drying (approx. 0.5-6g) by hand, drying the hair without rinsing, heating it with a hair iron at 100-200 ° C, and shaping the hair I do.

Example 22 Hair foam The following hair foam stock solution (pH 3.7) is prepared. Fill the aerosol solution with 50% by mass of the hair foam stock solution and make a valve. Next, 50% by mass of liquefied petroleum gas is filled to obtain a hair foam.
(mass%)
Trehalose 1.0
Malic acid 0.15
Lactic acid 2.0
Benzyl alcohol 0.2
1,3-butylene glycol 1.0
Polyorganosiloxane of Synthesis Example 1 2.0
Trehalose 1.0
Polyquaternium-11 (* 2) 5.0
Stearyltrimonium chloride 0.4
Torides-9 (* 1) 1.0
Ethanol 10.0
Sodium hydroxide appropriate amount *
Fragrance Appropriate amount Purified water balance ※ Amount to make pH = 3.7

[Hair shaping method]
The hair foam of Example 22 is applied to the hair in a semi-dry state (about 0.5 to 6 g), dried with a dryer, and then heated and shaped with a hair iron at 120 to 180 ° C.

Example 23 Hair wax The following hair wax (pH 3.7) is prepared according to a conventional method.
(mass%)
Trehalose 0.5
Malic acid 0.1
Polyorganosiloxane of Synthesis Example 2 0.5
Diisostearyl malate 2.0
Mineral oil 6.0
Glycerin 8.0
Polysorbate 60 (* 7) 4.5
Cetanol (* 8) 6.0
Methyl polysiloxane (* 9) 2.0
Stearic acid 4.0
PEG-65M (* 10) 0.15
Polyvinylpyrrolidone (* 11) 0.6
Sorbitol 9.0
Carbomer (* 12) 0.1
Methyl paraoxybenzoate 0.4
Benzyl alcohol 0.1
Ethanol 3.0
Sodium hydroxide appropriate amount *
Perfume appropriate amount water balance
* 7: Leodoll TW-S120V (Kao Corporation)
* 8: Calcoal 6780 (manufactured by Kao Corporation)
* 9: Silicone SH200C FLUID 10cs (Toray Dow Corning)
* 10: Alcox E-100 (Myosei Chemical Co., Ltd.)
* 11: Rubiscol K30 powder (BASF)
* 12: Carbopol # 981 (Lubrizol Advanced Materials Inc)
* Amount to make pH = 3.7

[Hair shaping method]
An amount (about 0.5 g to 6 g) of the hair wax of Example 23 applied to the entire hair is applied to the dry hair, and then heated and shaped with a 120 to 180 ° C. hair iron.

Example 24 Hair conditioner The hair conditioner (pH 3.3) shown below is prepared according to a conventional method.
(mass%)
Stearoxypropyldimethylamine (* 7) 1.75
Stearamidopropyldimethylamine (* 17) 0.2
Stearyl alcohol 3.6
Isopropyl palmitate 0.15
Dimethicone (* 18) 2
Amino-modified siloxane emulsion (* 19) 0.5
Amino polyether-modified silicone (* 20) 0.1
Lanolin fatty acid (* 3) 0.1
Polyorganosiloxane of Synthesis Example 4 1
Trehalose 0.7
Lactic acid 1.4
Glycolic acid 0.14
Hydrolyzed conchiolin solution (* 21) 0.002
Camellia oil 0.001
Seaweed extract (* 22) 0.01
Hydroxyethyl cellulose (* 23) 0.1
Perfume appropriate amount water balance
* 17: NIKKOL Amidoamine MPS (Nikko Chemicals)
* 18: Silicone KHS-3 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 19: Silicone SM8704C (manufactured by Toray Dow Corning)
* 20: SILSTYLE 201 (Toray Dow Corning)
* 21: Promois Pearl P (Seiwa Kasei)
* 22: Falco Rex Hibamata K (Ichimaru Falcos)
* 23: HEC Daicel SE850K (manufactured by Daicel Chemical Industries)

[Hair shaping method]
After applying the hair conditioner of Example 24 over the entire hair (about 1 to 6 g) to the damp hair after rinsing with shampoo, rinse with warm water at a suitable temperature. After drying the hair, heat and shape with a hair iron at 120-160 ° C.

Example 25 Hair Treatment The following hair treatment (pH 3.3) is prepared according to a conventional method.
(mass%)
Stearoxypropyltrimonium chloride (* 24) 7.42
Stearamidopropyldimethylamine (* 17) 0.24
Cetrimonium chloride (* 25) 1.5
Stearyl alcohol 3.2
Cetanol 3.2
Sodium naphthalene sulfonate 0.7
Lanolin fatty acid (* 3) 0.25
(Hydroxystearic acid / stearic acid / rosin acid)
Dipentaerythrityl (* 26) 0.2
Isopropyl palmitate 0.5
Paraffin 0.5
Dimethicone (* 19) 2
Amino polyether-modified silicone (* 20) 0.05
Dipropylene glycol 1.4
Benzyl alcohol 0.8
Trehalose 2
Polyorganosiloxane 2 of Synthesis Example 2
Lactic acid 0.7
Hydroxyethyl cellulose (* 27) 0.1
Perfume appropriate amount water balance
* 24: Cotamin E-80K (Kao Corporation)
* 25: Cotamin 60W (manufactured by Kao Corporation)
* 26: Cosmall 168AR (Nisshin Oillio)
* 27: HEC Daicel SE850K (manufactured by Daicel Chemical Industries)

[Hair shaping method]
After applying the hair treatment of Example 25 over the entire hair (about 1 to 6 g) to the damp hair after shampooing, it was held for 5 minutes. Rinse with hot water of appropriate temperature, dry the hair, and heat and shape with a hair iron at 100-180 ° C.

Example 26 Shampoo The following shampoo (pH 3.9) is prepared according to a conventional method.
(mass%)
Ammonium laureth sulfate 12
Lauryl hydroxysultain (* 28) 5.7
PPG-3 caprylyl ether 1
Myristyl alcohol 0.4
Guar hydroxypropyltrimonium chloride (* 29) 0.4
Polyquaternium-7 (* 30) 0.2
Glycol distearate (* 31) 2
Polypropylene glycol (* 32) 1.5
Benzyl alcohol 0.3
Trehalose 1.0
Malic acid 0.75
Polyorganosiloxane of Synthesis Example 3 1.5
P-Toluenesulfonic acid 0.5
Glycylglycine 0.05
Sunflower oil 0.04
Novara extract 0.001
Perfume proper amount Hydroxide K proper amount *
Water balance
* 28: Anhitoal 20HD (Kao Corporation)
* 29: Jaguar C17 (made by Rhodia)
* 30: Marcote 550 (Nalco)
* 31: Pegnol EDS-98K (manufactured by Toho Chemical Industry Co., Ltd.)
* 32: Adeka Car Pole DL-30 (made by ADEKA)
* Amount to make pH = 3.9

[Hair shaping method]
After moistening the hair with hot water of appropriate temperature, the shampoo of Example 26 is applied to the whole hair (about 1 to 6 g), foamed and washed, and then rinsed with hot water of appropriate temperature. After drying, heat and style the hair with a 120-160 ° C curling iron.

Claims (5)

Component (A) is contained in an amount of 0.2 to 6% by mass, component (B) is contained in an amount of 0.01 to 3% by mass, and component (C) is contained in an amount of 0.5 to 50% by mass. ) / (C) is 0.01 to 2, and the pH of the composition is 2.0 to 4.5 .
(A): Disaccharide in which two glucose molecules are linked via a glycosidic bond
(B): a monocarboxylic acid having 2 to 6 carbon atoms and a pKa of 3 to 4, or a di- or tricarboxylic acid having a pKa ₁ of 3 to 4
(C): at least two silicon atoms of the organopolysiloxane segment [segment (a)] constituting the main chain, via an alkylene group containing a hetero atom, the following general formula (1);

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aralkyl group or an aryl group, and n represents 2 or 3.)
An organopolysiloxane formed by bonding poly (N-acylalkylenimine) segments [segment (b)] composed of repeating units represented by:
The weight average molecular weight of segment (a) is 7,000 to 100,000,
The number average molecular weight of the segment (b) is 1,200-5,500;
The mass ratio (a / b) of segment (a) to segment (b) is 35 / 65-60 / 40,
The weight average molecular weight of the organopolysiloxane segment between adjacent poly (N-acylalkylenimine) segments is 1,300-5,500,
Organopolysiloxane   The hair cosmetic composition according to claim 1, wherein component (A) is selected from trehalose and maltose.   The hair cosmetic composition according to claim 1 or 2, wherein the component (B) is selected from glycolic acid, lactic acid and malic acid.   Hair cosmetics given in any 1 paragraph of Claims 1-3 whose content of an ingredient (A) is 0.01-6 mass%. A hair styling method comprising a step of applying the hair cosmetic composition according to any one of claims 1 to 4 to hair and heating the temperature of the hair to 100 ° C or higher.